IMPP-2 2015 - Dipartimento di Scienze e Tecnologie Chimiche

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IMPP-2 2015 - Dipartimento di Scienze e Tecnologie Chimiche
IMPP-2 2015
The I talian Meeting on
P orphyrins and P hthalocyanines-2
6 – 8 July, 2015
Rome
IMPP-2 2015
The Italian Meeting on
Porphyrins and Phthalocyanines-2
6 – 8 July 2015
CNR-Aula Marconi
P.le Aldo Moro 7, 00185 Rome
Abstract Book
2
Contents
Welcome
5
General Information
7
Scientific Programme
9
Oral Communications
13
Posters
47
List of Participants
63
3
Sponsors
4
Welcome to IMPP-2 2015
Every two years the Italian porphyrinoid community meets to share, collaborate
and discuss all aspects of porphyrinoid science at the 'Italian Meeting on
Porphyrins and Phthalocyanines'. The organising committee, in conjunction with
the delegates, decided to convene this conference in Rome due to its convenient
proximity thus making it easier for all representatives to attend.
The meeting has reached its second edition and we trust that this union of
porphyrinoid minds will bring multiple benefits:
Organisation: The primary purpose of this gathering is to consolidate and
streamline our porphyrinoid community to create unity within our field and within
Italy and, by doing so, we create a united front in the international scientific
society of porphyrinoids.
Knowledge: Sharing knowledge could lead to new opportunities and new
opportunities could lead us to greater progress and success.
Collaboration: Bringing together the best of Italian expertise could be the key to
higher quality research ideas and results. As a community we should share our
resources and our intellectual capital to ensure excellent quality output. In addition,
there is the advantage of collective financial resources as well as greater strength in
tendering for local and international funding.
Cross-bordering: Interdisciplinary scientific sharing could expand the scope of our
research thus opening doors to new prospects for fruitfull scientific projects.
Friendship: Last but not least, we hope that IMPP will be the place to create new
friendships as well as build on new ones, giving opportunity to grow human and
scientific partnerships!
Benvenuti a Roma!!
The Organising Committie
5
Maps of
Meeting Venue and Social Event
Ristorante “Al Chiostro”
Social Dinner
6
General Information
LOCATION
The conference takes place at CNR-Aula Marconi (P.le Aldo Moro 7, 00185
Rome) located near the Rome Termini train station.
From the rail station Roma-Termini you go to Piazza dei Cinquecento, take the bus
492 (direction: Stazione Tiburtina) and after 6 stops you reach Via dei Marrucini
bus stop. Then, you walk for 100 meters to arrive at piazzale Aldo Moro, 7.
ORAL AND FLASH COMMUNICATIONS
The lecture hall is equipped with a projector and Windows computers. Microsoft
Power Point facilities will be available. Memory key is preferred instead of a
personal laptop computer.
POSTER PRESENTATIONS
The poster section will take place on Tuesday 7th at 12:40 during the lunch time.
A number has been assigned to each poster and it will appear on the allotted poster
place. All posters will be on view throughout the conference.
SOCIAL EVENTS
The Social Dinner will take place on Tuesday 7th at 20:30 in ‘Ristorante Al
Chiostro’, Via Paolina, 31 -Roma.
7
8
Scientific Program
MONDAY AFTERNOON, 6th JULY
12:00
14:00
Registration
Opening Ceremony
Chairperson: Roberto Paolesse
14:20
M.L. Naitana ([email protected])
Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma “Tor Vergata”
A New Sulfonation Strategy for Corroles: the Key Role of Phosphorus
14:40
S. Banfi ([email protected])
Dipartimento di Scienze Teoriche ed Applicate (DiSTA), Università degli Studi dell’Insubria
Fotosensibilizzatori Cationici Antitumorali e Antibatterici
15:00
S. Belviso ([email protected])
Dipartimento di Scienze, Università della Basilicata
Thioalkyl-Porphyrazines for Electronic Materials
15:20
C. D. Calvano ([email protected])
Dipartimento di Chimica e Centro Interdipartiment. di Ricerca S.M.A.R.T., Università degli Studi di Bari
Characterization of Cyclic Tetrapyrroles and Related Compounds by Maldi TOF/TOF Mass
Spectroscopy
15:40
D. M. Carminati ([email protected])
Dipartimento di Chimica, Università degli Studi di Milano
Synthesis of Iron(III) Porphyrin Complexes to Promote the Regioselective Cyclopropanation of
Olefins”
16:00 Coffee Break
Chairperson: Maria Elena Fragalà
16:20
M. A. Castriciano ([email protected])
I.S.M.N. – C.N.R. Dipartimento di Scienze Chimiche, Università di Messina
Composite Nafion and Speek-Porphyrin Membranes
16:40
D. Monti ([email protected])
Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma “Tor Vergata”
Effect of Chiral Surfactants on the Sterespecific Aggregation of Chiral Amphiphilic Porphyrin
Derivatives
17:00
A. D’Urso ([email protected])
INSTM UdR - Dipartimento di Scienze Chimiche, Università di Catania
Supramolecular Porphyrins Systems: Chiroptical Probe, Building Block for Multicomponent
Arrays and Chiral Assemblyes
17:20
G. Manca ([email protected])
Istituto di Chimica dei Composti OrganoMetallici, ICCOM-CNR, Firenze
Mechanistic Investigation of the Ruthenium Porphyrin Catalysed Aziridination of Olefins by
Aryl Azides
9
TUESDAY MORNING, 7th JULY
Chairperson: Alessandro D’Urso
9:00
L. Monsù Scolaro ([email protected])
I.S.M.N. – C.N.R. Dipartimento di Scienze Chimiche, Università di Messina
Reversible Aggregation/Deaggregation of Porphyrin J-Aggregates Induced by Silver(I) Cations
9:20
M. Gobbo ([email protected])
Dipartimento di Scienze Chimiche, Università di Padova
Chiral Assemblies of Porphyrins Linked to -Helical Peptides is Controlled by the
Stereochemistry of the First Amino Acid
9:40
E. Iengo ([email protected])
Dipartimento di Scienze Chimiche e Farmaceutiche, Università di Trieste
Tetrahedral Arrays of Metallo-Porphyrins
10:00
M.E. Fragalà ([email protected])
INSTM UdR - Dipartimento di Scienze Chimiche, Università di Catania
Spontaneous Deposition of Water-Soluble Porphyrins on Glass: a Big Challenge or a “Green”
Opportunity?”
10:20
G. Smulevich ([email protected])
Dipartimento di Chimica “Ugo Schiff”, Firenze
Conformational Changes of Cardiolipin-Bound Cytochrome C: a Spectroscopic Study
10:40
Coffee Break
Chairperson: Sara Nardis
11:00
M. Stefanelli ([email protected])
Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma “Tor Vergata”
-Alkynylcorrole Derivatives via Stille Cross-Coupling Reaction
11:20
P. Mineo ([email protected])
Dipartimento di Scienze Chimiche, Università di Catania
Action of an Asymmetric Heat Source on the Mirror-Symmetry Breaking of Porphyrin
Aggregates
11:40
A. Mazzaglia ([email protected])
I.S.M.N. – C.N.R. Dipartimento di Scienze Chimiche, Università di Messina
Cyclodextrins/Porphyrinoids Supramolecular Assemblies Tailored by Receptor Targeting Groups
as Potentially Cell-Selective Nano-Phototherapeutics
12:00
M. Bischetti ([email protected])
Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma “Tor Vergata”
Mesoscopic Structures by Langmuir-Blodgett Deposition of Steroid-Porphyrins
12:20
C. Di Natale ([email protected])
Dipartimento di Ingegneria Elettronica, Università di Roma “Tor Vergata”
Photo-Assisted Chemical Sensors Based on Porphyrins Coated ZnO
12:40
Lunch Break / Poster Session
10
TUESDAY AFTERNOON, 7th JULY
Chairperson: Roberto Purrello
14:00
B. Berionni Berna ([email protected])
Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma “Tor Vergata”
Expanded Corroles by  -Fused Aromatic Rings
14:20
P. Galloni ([email protected])
Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma “Tor Vergata”
Assessment in Electronic Interactions in Mono-Oxidated Tetraferrocenylporphyrins
14:40
E. Reddi ([email protected])
Dipartimento di Biologia, Università di Padova
Porphyrins and Antimicrobial Peptides for Photodynamic Therapy of Cancer”
15:00
N. Russo ([email protected])
Dipartimento di Chimica e Tecnologie Chimiche, Università della Calabria
Photodynamic Therapy: Good News from Computational Approaches
15:20
P. Tagliatesta ([email protected])
Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma “Tor Vergata”
Synthesis and Characterization of New Ferrocene, Porphyrin and C60 Triads, Connected by
Triple Bonds”
15:40
Coffee Break
16:00
Round Table: Valutazione, finanziamento e didattica: quale futuro per l’Università
20:30
Social Dinner, Ristorante “Al Chiostro”, Via Paolina, 31 - Rome
11
WEDNESDAY MORNING, 8th JULY
Chairperson: Maria Pia Donzello
9:00
E. Gallo ([email protected])
Dipartimento di Chimica, Università degli Studi di Milano
Ruthenium Porphyrin Complexes as Efficient Catalysts of Biological Aza-Derivatives
9:20
F. Tessore ([email protected])
Dipartimento di Chimica, Università degli Studi di Milano
The Fascinating World of  -Pyrrolic Substituted Zn(II)-Tetraarylporphyrinates for
Dye-Sensitized Solar Cells”
9:40
M. Trotta ([email protected])
IPCF-CNR, Università degli Studi di Bari
Photosynthetic Bacteria Play Heavy Metals
10:00
E. Viola ([email protected])
Dipartimento di Chimica, Università di Roma “La Sapienza”
Porphyrazines in Combined Photo - and Chemio- Anticancer Therapies: Recent Results in
Water Solution”
10:20
G. Zanotti ([email protected])
CNR – ISM, Roma
Fluorescence Enhancement in an Unsymmetrically-Substituted Copper Phthalocyanine
10:40
Coffee Break
Chairperson: Emma Gallo
11:00
A. Peluso ([email protected])
Dipartimento di Chimica e Biologia, Università di Salerno
Genetrating Function Approach to the Calculation of Spectral Band Shapes
11:20
M. Di Valentin ([email protected])
Dipartimento di Scienze Chimiche, Università di Padova
The Porphyrin in the Triplet State as a Potential Spin Label for Nanometer Distance
Measurements by EPR Spectroscopy
11:40
M.E. Crestoni ([email protected])
Dipartimento di Chimica e Tecnologie del Farmaco, Università di Roma “La Sapienza”
Metal-Oxo Porphyrin Complexes: Catalytic Intermediates in the Gas Phase
12:00
L. Guidoni ([email protected])
Dipartimento di Scienze Fisiche e Chimiche, Università degli Studi dell’Aquila
The Special Pair of Chlorophylls in Photosynthesis. Insights by Computer Simulations
12:20
Conclusions and Perspectives
12
ORAL COMMUNICATIONS
13
OC01
A NEW SULFONATION STRATEGY FOR CORROLES: THE KEY ROLE
OF PHOSPHORUS
Mario NAITANA, Fabrizio CAROLEO, Sara NARDIS, Roberto PAOLESSE
Department of Chemical Science and Technologies, University Of Rome Tor Vergata, Via della Ricerca
Scientifica 1, 00133 Rome, Italy.
[email protected]
One of the most interesting features of porphyrins is represented by the possibility of modulating
their properties and reactivity exploiting, for instance, a wide coordination chemistry developed
through the years 1.
In these last few years, the relatively new member of this family of molecules, corrole, has been
the main character for a sort of “gold rush”, with the main goal to synthesize metal and main
group complexes and enrich the macrocycle with new functional groups.
In particular non-metals complexes of amphiphilic porphyrinoid have obtained high attention,
due to their biological and optical properties, which are very promising for the utilization in
different technology fields, such as dyes for photodynamic therapy, solar cells, supramolecular
chemistry and organic catalysis 2.
One of the main route to obtain an amphiphlic porphyrinoid is the sulfonation reaction with the
best example of this strategy given by 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (TPPS4).
Therefore all the applications that have involved the use of the TPPS4 are enough to justify the
efforts that are involving the synthesis of analogues corrole derivatives3.
In this work we present a novel and efficient strategy to obtain new sulfonato corrole derivatives,
showing peculiar properties that can be exploited in all the fields that have made TPPS 4 very
popular.
N OCH3
N
P
O3S
N
OH
SO3
______________
References:
1. Aviv-Harel, I.; Gross, Z. Coord. Chem. Rev, 2011, 7, 717.
2. Aviv-Harel, I.; Gross, Z. Chem. Eur. J, 2009, 15, 8382.
3. Naitana, M. L.; Nardis, S.; Lentini, S.; Cicero, D.; Paolesse, R. J. Porphyrins and Phtalocyanines, 2015, 19, 1.
14
OC02
FOTOSENSIBILIZZATORI CATIONICI ANTITUMORALI E
ANTIBATTERICI
1
1
1
1
Stefano BANFI , Enrico CARUSO , Viviana ORLANDI , Paola BARBIERI , Amedea MANFREDI
2
1
Dipartimento di Scienze Teoriche ed Applicate (DiSTA), Università degli Studi dell’Insubria, via
2
JH Dunant, 3 – Varese. Dipartimento di Chimica, Università Statale di Milano, Via Golgi 19 – Milano
La terapia fotodinamica (PDT) è una metodologia di cura applicabile contro i tumori solidi o per
debellare le infezioni batteriche localizzate. Il processo richiede la somministrazione di un
fotosensibilizzante (PS), in modo che possa raggiungere efficacemente la zona malata, seguita da
irraggiamento della zona interessata con una radiazione elettromagnetica a bassa energia, cioè
luce visibile. Il PS assorbe l’energia della radiazione e la trasmette all’ossigeno molecolare che
in questo modo genera radicali dell’ossigeno (ROS) e ossigeno singoletto (1O2). Entrambe queste
specie sono forti ossidanti che attaccano le molecole organiche presenti nelle vicinanze così
causando la morte della cellula.
Nel nostro laboratorio ci occupiamo di due classi di PS, le porfirine e i borodipirrometeni
(BODIPY), di cui la prima è una delle famiglie di molecole storicamente più studiata nella
terapia fotodinamica che trova applicazione a livello clinico mentre la seconda comprende
fotosensibilizzanti che stanno riscontrando un discreto interesse in vitro per la loro applicazione
nella PDT.
In questo convegno presentiamo due recenti risultati del nostro lavoro di ricerca. Il primo
riguarda porfirine diariliche simmetriche (dicationiche), la cui struttura è stata ideata con
l’obiettivo di facilitarne la somministrazione oltre alla possibilità di applicare lo stesso PS sia in
campo antitumorale che in campo antibatterico semplicemente modificando le condizioni
sperimentali quali iltempo di incubazione e di illuminazione.
Le molecole sintetizzate sono state testate in vitro su cellule tumorali del colon (HCT116) in
differenti condizioni sperimentali di incubazione e di illuminazione. In seguito sono state
eseguite prove preliminari di attività fotodinamica su due ceppi batterici, uno Gram negativo
(Escherichia coli) e uno Gram positivo (Staphilococcus aureus).
Il secondo lavoro riguarda lo studio dell’attività fotodinamica antibatterica ottenuta per azione
combinata di un BODIPY cationico con polimeri policationici appartenenti alla famiglia delle
poliammidoammine (PAA), quest’ultimi caratterizzati da un numero crescente di cariche in
funzione del peso molecolare del polimero stesso.
Per questo studio si sono scelti gli stessi ceppi batterici modello indicati sopra. Nella valutazione
dell’efficacia del trattamento si è preso in considerazione: 1) la fototossicità del BODIPY da
solo; 2) la tossicità intrinseca dei polimeri e 3) la fototossicità ottenuta in presenza di entrambe le
molecole.
15
OC03
THIOALKYL-PORPHYRAZINES FOR ELECTRONIC MATERIALS
Sandra BELVISO
Dipartimento di Scienze - Università della Basilicata, via dell'Ateneo Lucano 10, I-85100, Potenza, IT
[email protected]
Our research is mainly directed to the synthesis and characterization of porphyrazines,
tetrapyrrole macrocycles which are “structural hybrids” of the more well known porphyrins and
phthalocyanines. In particular we are studying symmetrically and non-symmetrically substituted
thioalkyl-porphyrazines for applications in material chemistry. Thanks to the presence of the
sulfur atoms on the peripheral positions these molecules display discotic columnar mesophases1
and peculiar spectroscopic and electrochemical properties, such as an UV-visible spectrum with
very broad and intense absorption bands, well overlapping the solar emission spectrum.
Moreover, the possibility to selectively remove one thioalkyl chain in these macrocycles 2 has
allowed to disclose a new procedure for the synthesis of non-symmetrically substituted thioalkylporphyrazines from the symmetric parent. This opened the way to the easy insertion on the
macrocycle periphery of substituents suitable to tune its spectroscopic and self-aggregation
properties, as well as HOMO-LUMO values.3 In particular, mono-aryl substituted derivatives
provided unconventional “push-pull” systems suitable for non-linear optics.3 Taking into account
the great interest of tetrapyrrole macrocycles as light acceptors in organic photovoltaic (OPV)
devices, our recent studies focused on the synthesis of novel thioalkyl-porphyrazine dyes for
either dye-sensitized (DSSC) or bulk heterojunction (BHJ) solar cells. To this end, perfluorinated
thio-alkylporphyrazines endowed with liquid-crystalline and spectro-electrochemical properties
interesting for potential applications in electronic materials were prepared.4 Moreover, the
insertion of a pyrene unit on the macrocycle periphery provided a dye able to interact non
covalently with acceptor systems like carbon nanotubes (SWNTs) and graphene, making these
molecules promising chromophoric/donor units for OPV. Preliminary experiments on
photoconduction of nanohybrids of 1-pyrene-thioalkyl-porphyrazine with both SWNTs and
graphene nanoflakes (GNF) have been carried out.
______________
References:
1. Belviso, S.; Ricciardi, G.; Lelj, F. J. Mater. Chem. 2000, 10, 297.
2. a) Belviso, S. ; Ricciardi, G. ; Lelj, F. ; Monsù Scolaro, L. ; Bencini, A. ; Carbonera, C. J. Chem. Soc., Dalton
Trans., 2001, 1143. b) Belviso, S.; Giugliano, A.; Amati, M.; Ricciardi, G.; Lelj, F.; Monsù Scolaro, L. Dalton
Trans. 2004, 305.
3. a) Belviso, S.; Amati, M.; De Bonis, M.; Lelj, F. Mol. Cryst., Liq. Cryst. 2008, 481, 56. b) Belviso, S.; Amati, M.;
Rossano, R.; Crispini, A.; Lelj, F. Dalton Trans. 2015, 44, 2191.
4. Belviso, S.; Cammarota, F.; Rossano, R.; Lelj, F. Tetrahedron 2015, submitted.
16
OC04
CHARACTERIZATION OF CYCLIC TETRAPYRROLES AND RELATED
COMPOUNDS BY MALDI TOF/TOF MASS SPECTROSCOPY
C.D. CALVANO
1,2
3
3
1
1,2
, M. TROTTA , F. ITALIANO , G. VENTURA , T.R.I. CATALDI , F. PALMISANO
1
1,2
2
Dipartimento di Chimica & Centro Interdipartimentale di Ricerca S.M.A.R.T. - Università degli Studi di
3
Bari Aldo Moro, Via Orabona 4, 70126 Bari, Italy CNR, Istituto per i Processi Chimico-Fisici, Sezione di
Bari, Via Orabona, 4, 70126 Bari, Italy
[email protected]
Tetrapyrrole derivatives are a large family of molecules containing four pyrrole rings held
together by direct covalent bonds or by one-carbon bridges with a resultant linear or cyclic
structure. The most common macrocycles, usually coordinating a metal ion into the conjugated
ring system, include porphyrins (e.g., hemes), chlorins (e.g., pheophytins, chlorophylls and
bacteriochlorophylls), corrins (e.g., cobalamins, vitamins B12), and phthalocyanines (Figure 1).
These macrocyclic substructures are present in many natural compounds as green pigments in
chloroplasts of algae, plants and bacteria (chlorophylls or bacteriochlorophylls) [1, 2] or red
pigments in hemoglobin, myoglobin (heme b) and cytochrome c (heme c) [3]. Porphyrins,
phthalocyanines, and corroles complexes are also efficient catalysts for many reactions [4, 5].
A
B
C
D
Figure 1. Structures of basic tetrapyrrole macrocycle for (A) porphyrins, (B) chlorins, (C) corrins and (D)
phthalocyanines.
High performance liquid chromatography coupled with mass spectrometry (LC-MS) is a
versatile tool to investigate and identify cyclic tetrapyrroles and closely related compounds [6]
even if, due to the necessary sample treatment, it could be less suitable for routine analyses of
large numbers of samples. Fast and selective identification of these compounds may be
accomplished by matrix-assisted laser desorption ionization (MALDI) time-of-flight (ToF) MS
because of well-recognized features, such as rapid and easy sample preparation, tolerance to
salts, and high sensitivity. Yet, the analysis of cyclic tetrapyrrole-derivatives by MALDI-MS
technique has not been fully established. Considering that proton affinities and ionization energy
of a MALDI matrix affect energy transfer involved in proton- and electron-transfer, a possible
way to successfully attain structural information on these compounds may be the choice of a
proton-transfer or an electron-transfer matrix [7], depending on the nature of the metal cation
and/or the surrounding substituents. Here, we report the characterization of some representative
cyclic tetrapyrrole-derivatives by MALDI-ToF/ToF MS analyses, including chlorophylls (a and
b), bacteriochlorophylls, vitamins B12, etc., upon proper matrix selection.
References:
1. Ballschmiter K, Katz JJ. Nature, 1968, 220, 1231.
2. Scheer, H. Chlorophylls and bacteriochlorophylls: biochemistry, biophysics, functions and applications, 2006, 25, 1.
3. Kim T, Lee J, Kim J. Int. J. Mass Spectrom., 2015, 376, 13.
4. Costas, M. Coord. Chem. , 2011, 225, 2912.
5. Sorokin, A. B. Chem. Rev., 2013, 113, 8152.
6. Luo X, Chen B, Ding L, Tang F, Yao S. Anal. Chim. Acta, 2006, 562,185.
7. Calvano CD, Ventura G, Cataldi TRI, Palmisano F. Anal. Bioanal. Chem., 2015, doi: 10.1007/s00216-015-87289.
17
OC05
SYNTHESIS OF IRON(III) PORPHYRIN COMPLEXES TO PROMOTE
THE REGIOSELECTIVE CYCLOPROPANATION OF OLEFINS.
1
1
2
2
Daniela M. CARMINATI, Daniela INTRIERI, Stéphane LE GAC, Bernard BOITREL, Emma GALLO
1
1
2
Università degli Studi di Milano, Milan, Italy. Institut des Sciences Chimiques de Rennes, UMR CNRS
6226, Université de Rennes 1, France,
e-mail: [email protected]
Cyclopropanes are important three-member carbon rings which often represent the active part in
biological and/or pharmaceutical compounds.1-2 Catalytic diastereo- and enantioselective olefin
cyclopropanations have been extensively explored and among all the available synthetic
methodologies to synthesise cyclopropanes, the one pot reaction of diazocompounds with olefins
represents a sustainable and atom-efficient strategy due to the formation of N2 as the only
stoichiometric by-product.
Considering that metal porphyrins represent
a very competent and stereoselective class of
catalysts, we are currently studying the
catalytic activity of iron derivatives which
display a good sustainability for the
presence of the eco-friendly, cheap and very
efficient metal centre.
Thus, we synthesised the new iron(III)
complex 1Fe starting from the porphyrin
ligand 13 (scheme 1) which has one C2 axis
within the porphyrin plane and exhibits an
open space on each side for the substrate
access. Complex 1Fe demonstrated a very
high catalytic activity in cyclopropanations
which occurred with excellent transdiastereoselectivities (94-99%).
Since positive data, we employed ligand 1 to
synthesise the chiral derivative 2, which
shows a steric chiral bulk surrounding the Ncore of the porphyrin. The free porphyrin 2
was then reacted with iron bromide, in the
presence of methanol, to yield the relative
iron(III) complex 2Fe (scheme 1) which was completely characterised.4 Complex 2Fe showed a
very high catalytic efficiency; excellent trans-diastereoselectivities, good enantioselectivities and
outstanding TON and TOF values were observed in the reaction of cyclopropanation of several
olefins by differently substituted diazo compounds (scheme 1).4
References:
1. C. A. Carson, M. A. Kerr, Chem. Soc. Rev. 2009, 38, 3051-3060.
2. A. K. Kumar, Int. J. Pharm. Pharm. Sci. 2013, 5, 467-472.
3. A. Didier, L. Michaudet, D. Ricard, V. Baveux-Chambenoît, P. Richard, B. Boitrel, Eur. J. Org. Chem. 2001,
1927-1926.
4. D. Intrieri, S. Le Gac, A. Caselli, E. Rose, B. Boitrel, E. Gallo, Chem. Commun. 2014, 50, 1811-1813.
18
OC06
CHIRALITY IN PORPHYRIN AGGREGATES
1
1
2
Maria Angela CASTRICIANO, Roberto ZAGAMI, Mario SAMPERI, Andrea ROMEO,
1,2
SCOLARO
1,2
Luigi MONSU’
1
Istituto per lo Studio dei Materiali Nanostrutturati, c/o Dipartimento di Scienze Chimiche, V.le F. Stagno
2
D'Alcontres n.31, 98166 Messina, Italy. Dipartimento di Scienze Chimiche, University of Messina, V.le F.
Stagno D'Alcontres n.31, 98166 Messina, Italy.
[email protected]
Reports of optical activity for assemblies of achiral entities in the absence of templates were
greeted at first with skepticism. However, now that these findings have been confirmed,
considerable attention has been focused on this phenomenon. The possibility that what is being
observed in these systems is a spontaneous mirror-symmetry breaking has led to speculation
about the relationship of these processes to those responsible for the ubiquitous homochirality in
our universe. Achiral chromophores, especially porphyrins, have been of some considerable
importance for such symmetry-breaking studies due to their rich spectral properties and their
ability (under appropriate conditions) to self-assemble into chiral supramolecular structures. In
particular, meso-tetrakis4-sulfonatophenyl (TPPS) and aryl-substituted porphyrins have been
widely used as starting materials. TPPS J-aggregates, obtained in aqueous solution in the absence
of any added chiral templating agent, show an unpredictable chirality, resulting in controversial
proposals for their basis. Recently, we demonstrated the fundamental role of kinetic parameters
in the expression and transmission of chirality in this supramolecular system.1 Whatever the
source of the chiral bias promoting such symmetry breaking, the rate of the aggregation process
leading to the formation of J-aggregates strongly affects the size of these nanoassemblies and the
chiral induction.
With the aim to resolve some of the confounding issues still open in literature related to
the TPPS J-aggregate optical activity, here we report on detailed kinetic investigation on selfassembly processes induced by different inorganic achiral acid in the absence of an added chiral
template and in presence of various chiral acids opportunely selected to have variability in terms
of structure and strength. The results obtained have allowed to gain important information in the
field of supramolecular architectures, highlighting the importance of the role of experimental
parameters such as concentration and/or mixing order of the reagents. We anticipate that,
depending on the overall rate of the process, a distinctive kinetic difference, together with a
difference variance in the extent of the chiral transfer, is evident for the various acids and strictly
connected with medium properties.
______________
References:
1. Romeo, A.; Castriciano, M.A.; Occhiuto, I.; Zagami, R.; Pasternack, R.F.; Monsù Scolaro, L. J. Am. Chem. Soc.
2014, 136, 40-43.
19
OC08
SUPRAMOLECULAR PORPHYRINS SYSTEMS: CHIROPTICAL PROBE,
BUILDING BLOCK FOR MULTICOMPONENT ARRAYS AND CHIRAL
ASSEMBLYES
Alessandro D’URSO, Maria Elena FRAGALA’, Roberto PURRELLO
University of Catania, Viale A. Doria 6, 95125 Catania, Italy.
[email protected]
Porphyrins are quite versatile molecules successfully used in many fields: from nanotechnology
to biomedicine. These hetero-aromatic macrocycles present remarkable electronic properties
which bring to attractive spectroscopic features. The non-covalent interactions of water-soluble
achiral porphyrins with chiral templates have been exploited to transfer, detect and/or amplify
the matrix handedness.
As chiral templates we used biopolymers such aminoacid or DNA sequences, even if more
challenging was the induction of chirality with single molecules as Ruthenium phenantroline.
Interestingly, for some of such systems the chiral memory phenomenon has been observed.1
Porphyrins are used also as chiroptical probe for polynucleotides conformation. Cationic and
anionic metalloporphyrins, have shown to be excellent chiroptical probes for detecting Z-DNA
(an intriguing DNA structure which vital role in vivo is still unknown) not only in
polynucleotides entirely converted in Z form but also under highly competitive conditions as in
BZB sequence.2
We are involved also in non-covalent syntheses of multi-porphyrin supramolecular species in
aqueous solution.3 In particular, calixarene–porphyrin species represents concrete evidence of a
quantitative complexation, governed by precise hierarchical rules, which together with a rational
functionalization of the molecular components leads to supramolecular entities of well-defined
and tunable stoichiometry.
Herein, we will propose an overview of our recent developments in porphyrin systems
mentioned above.
______________
References:
1. a) Mammana A.; D’Urso A.; Lauceri R.; Purrello R. J. Am. Chem. Soc. 2007, 129, 8062–8063; b) Randazzo R.;
Mammana A.; D’Urso A.; Lauceri R.; Purrello R. Angew. Chem. 2008, 120, 10027–10030.
2. a) Balaz M.; De Napoli M.; Holmes A.E.; Mammana A.; Nakanishi K.; Berova N.; Purrello R. Angew Chem Int
Ed 2005, 44, 4006-4009; b) D'Urso A.; Choi J.K.; Shabbir-Hussain M.; Ngwa F.N.; Lambousis M.I,.; Purrello
R.; Balaz M. Biochem Biophys Res Comm 2010, 397,329–332;
d) D'Urso A.; Mammana A.; Balaz M.; Holmes
A.E.; Berova N.; Lauceri R.; Purrello R. J Am Chem Soc 2009, 131, 2046–2047; e) D'Urso A.; Holmes A.E.;
Berova N.; Balaz M.; Purrello R. Chem As J 2011, 6, 3104–3109; f) Holmes A.E.; Choi J.K.; Francis J.; D’Urso
A.; Balaz M. J Inorg Biochem, 2012, 110, 18–20.
3. D’Urso A., Fragalà M. E.; Purrello R. Chem. Commun., 2012, 48, 8165–8176.
20
OC09
MECHANISTIC INVESTIGATION OF THE RUTHENIUM PORPHYRIN
CATALYSED AZIRIDINATION OF OLEFINS BY ARYL AZIDES
a
b
Emma GALLO , Gabriele MANCA , Carlo MEALLI
a
b
b
Dep. of Chemistry, University of Milan, Via Golgi 19, I-20133 Milan (Italy). Istituto di Chimica dei
Composti OrganoMetallici, ICCOM-CNR, Via Madonna del Piano 10, I-50019 Sesto Fiorentino.
[email protected]
Aziridines are important building blocks in organic synthesis because their highly
strained three-membered ring affords an epoxide-like reactivity through an easy C-N
bond cleavage. 1 The relevant biological activity of these heterocycles, which are present
in several natural compounds and antitumor/antimicrobial agents 2 suggests their usage as
precursors of important aza-compounds. Hence, efficient aziridine synthetic strategies
have become of importance.
A mechanism for the aziridination of olefins by aryl azides (ArN 3), promoted by
ruthenium(II) porphyrin complexes, is proposed on the basis of a combined
experimental/theoretical approach. Aryl azides are efficient nitrogen sources with the
eco-friendly N 2 elimination. All the recorded data support the involvement of a monoimido ruthenium complex as the active intermediate in the transfer of the nitrene moiety
“ArN” to the olefin. The DFT study highlights the importance of an accessible triplet
ground state of the intermediate ruthenium mono-imido complex [Ru](NR)(CO) to allow
the evolution of the aziridination process in presence of an olefin. A similar intermediate
has been recognized by us to play a central role also in the amination reactions in
presence of organic azides and olefin with a hydrogen atoms. 3 The diradical mono-imido
nitrogen is able to transfer spin density to the olefin carbon atom, providing a metastable
triplet N-C-C open chain, which is the subject of a triplet  singlet, before the final
achievement of three-membered ring. The analysis of Minimum Energy Crossing Point
(MECP) has been also provided.
The selectivity of the azidirination vs. the uncatalysed triazoline formation has been also
addressed in terms of electronic features of the porphyrin ligand and olefin/azide
catalytic ratio.
______________
References:
1.a) Sweeney, J. B. Chem. Soc. Rev., 2002, 31, 247; b) Hu, X. E., Tetrahedron, 2004, 60, 2701; c) Sweeney, J. B.;
Yudin, A., Aziridines and Epoxides in Organic Synthesis, Wiley-VCH Verlag GmbH & Co. KGaA, 2006.
2. a) Ismail, F. M. D.; Levitsky, D. O.; Dembitsky, V. M., Eur. J. Med. Chem., 2009, 44, 3373; b) Tsuchida, T. ;
Sawa, R.; Takahashi, Y.; Inuma, H.; Sawa, H.; Naganawa, H.; Takeuchi, T., J. Antibiot., 1995, 48, 1148.
3. Manca, G.; Gallo, E.; Intrieri, D.; Mealli, C., ACS Catal., 2014, 4, 823.
21
OC10
REVERSIBLE AGGREGATION/DEAGGREGATION OF PORPHYRIN
J-AGGREGATES INDUCED BY SILVER(I) CATIONS
1
2
2
Ilaria Giuseppina OCCHIUTO, Mariachiara TRAPANI, Maria Rosaria PLUTINO, Giovanna DE LUCA,
1,2
Luigi MONSU’ SCOLARO
3
1
Dipartimento di Scienze Chimiche, University of Messina, V.le F. Stagno D'Alcontres n.31, 98166
2
Messina, Italy. Istituto per lo Studio dei Materiali Nanostrutturati, c/o Dipartimento di Scienze Chimiche.
3
V.le F. Stagno D'Alcontres n.31, 98166 Messina, Italy. Dipartimento di Scienze del Farmaco e dei
Prodotti per la Salute, University of Messina, V.le Annunziata, 98166 Messina, Italy.
[email protected]
Porphyrin J-aggregates have been largely investigated due to their remarkable structural,
electronic and chiral properties. Much of these studies have been carried out on water soluble
tetra-anionic tetrakis(4-sulfonato-phenyl)porphyrin (H2TPPS4). In the presence of added salts or
at high acid concentration the diacid H4TPPS4 self-assembles into J-aggregates stabilized
primarily by electrostatic interactions between the positive protonated core of the macrocycle
and the negatively charged sulfonate groups of adjacent porphyrins.
The kinetics of supramolecular assembling of these nanoaggregates are characterized by a
sigmoidal profile with an initial lag period.1 Detailed kinetic studies on the reverse reaction for
J-aggregates , i.e. the disassembly process, are far less frequent. Quite recently, we reported that
for the metallation of the acidic form of H2TPPS4 (di-anionic H4TPPS4) by copper(II), the order
of reagent mixing determines the rate and mechanism of CuTPPS 4 formation. When copper salts
are added last, the kinetic profile is fit as a (pseudo)-first order process. However, J-aggregates
of the di-anionic H4TPPS4 porphyrin are rapidly formed at pH ~ 3 when copper(II) salts are
incorporated in solution prior to porphyrin addition. The subsequent metallation of the porphyrin
units leads to the disassembling of these arrays via a pseudo-zero order kinetic profile,
suggesting an attack of the metal ion at the rims of the nanostructure.2
Here we report on the aggregation of H4TPPS4 under acidic pH in the presence of excess
silver(I) ions. The formed J-aggregates under light irradiation undergo to the formation of the
silver(II) metal derivative of the porphyrin, that in the dark slowly interconverts back to the
J-aggregated species. Based on previous literature reports,3 a mechanism has been proposed.
______________
References:
1. Micali, N.; Mallamace, F.; Romeo, A.; Purrello, R.; Scolaro, L. M. J. Phys. Chem. B 2000, 104, 5897−5904.
2. Occhiuto, I.; De Luca, G.; Trapani, M.; Monsù Scolaro, L. and Pasternack, R.F. Inorg. Chem., 2012, 51,
10074−10076.
3. Krishnamurthy, M. Inorg. Chem. 1978, 17, 2242.
22
OC11
CHIRAL ASSEMBLIES OF PORPHYRINS LINKED TO α-HELICAL
PEPTIDES IS CONTROLLED BY THE STEREOCHEMISTRY OF THE
FIRST AMINO ACID
Francesca BISCAGLIA, Elisa FREZZA, Alberta FERRARINI, Marina GOBBO
Department of Chemical Sciences – University of Padua
[email protected]
Supramolecular assemblies of porphyrins have been received increasing interest in recent years
due to potential applications in optoelectronic and photovoltaic devices as models of the light
harvesting complexes and redox enzymes in living systems.
Achiral porphyrins can self-assembly in chiral supramolecular aggregates under the influence of
different stimuli as complexation with chiral guest, mechanical effects (such as swirling, stirring)
or aggregation on chiral templates such as helical peptides and DNA.1 In the last few years the
synthesis of several porphyrin-peptide conjugates,2-3 for studies in photodynamic therapy,
allowed us to observe aggregation behavior of these compounds in water-organic mixture,
suggesting that the peptide secondary structure can influence growing of chiral aggregates.
In particular the conjugate between meso-tetraphenylporphyrin and the α-helical peptide
[Leu21]magainin (see the sequence below) self-assemblies in water in chiral supramolecular
aggregates, as suggested by the CD spectrum that shows an intense positive couplet in the
porphyrin region, with a zero point crossing at 422 nm. The reproducible sign of the Cotton
effect suggests a preferential right-handed twist between porphyrins in aggregates. By
synthetizing two model peptides, adopting in organic solvent right-handed or left-handed helical
conformation, and their porphyrin conjugates, we found that chiral preferences exhibit by
supramolecular aggregates are independent by the screw sense of the α-helical peptide. On the
contrary, alanine scan on selected positions of the magainin sequence pointed at the importance
of the first amino acid residue, connecting the peptide to the porphyrin system, in determining
chiral preferences of supramolecular aggregates. This result could shed light on assembling of
natural peptide-containing porphyrin systems.
______________
References:
1. D’Urso, A.; Fragalà, M. E.; Purrello, R.; Chem. Commun. 2012, 48, 8165-8176.
2. Dosselli,R., Tampieri, C., Ruiz-Gonzalez,.R, De Munari, S, Ragàs,.S, Sánchez-García, D, Agut, M, Nonell, S,
Reddi, E., Gobbo, M. J. Med. Chem. 2013 , 56, 1052-1063.
3. Dosselli, R.;
,. R. ; Moret,. F. ; Agnolon,. V. ; Compagnin, C.; Mognato,. M.; Sella,. V. ; Agut,. M.
; Nonell,. S. ; Gobbo, M.;. Reddi , E. J. Med. Chem. 2014 , 57, 1403-14153.
23
OC12
TETRAHEDRAL ARRAYS OF METALLO-PORPHYRINS
a
b
c
c
Alessandra LUISA, Nicola DEMITRI, Giacomo BERGAMINI, Marianna MARCHINI, Massimo
c
c
a
BARONCINI, Paola CERONI, Elisabetta IENGO
a
Dep. Chemical and Pharmaceutical Sciences, University of Trieste, Via L. Giorgieri 1, 34127 Trieste (IT);
b
Elettra – Sincrotrone Trieste, S.S. 14 Km 163.5 in Area Science Park, 34149 Basovizza Trieste (IT);
c
Dep. of Chemistry “G. Ciamician” and Interuniversity Center for the Chemical Conversion of Solar
Energy, University of Bologna, Via Selmi 2, 40126 Bologna (IT).
[email protected]
Artificial photosystems mimicking the natural occurring ones [1] play a prominent role in the
contemporary research [2]. In particular, the study of multichromophoric systems with a shapepersistent arrangement of the chromophores has gained increasing relevance since new
properties may emerge from the interaction between the spatially organized units. The group of
Anderson has very elegantly achieved the template-directed synthesis of fully conjugated zincporphyrin nanorings (containing up to twelve Zn-porphyrin units), by axial coordination of
appropriate oligo-pyridyl scaffolds to the zinc centers of linear Zn-porphyrin oligomers,
followed by covalent coupling and removal of the templating scaffold [3].
Herein, we describe two
H O acetone
H
CH
novel
rutheniumCH
py
porphyrin tetra-cationic
py
Ph Ph py
py
arrays
obtained
by
D
= 5.9510 cm s
coordination of four Rur = 11.6 Å
porphyrin units to the
+4
pyridylpyridinium arms
of a tetrahedral core
(Figure). The arrays, that
differs in the substituents
on the Ru-porphyrins,
have
been
fully
characterized in solution
and, in one case, also in
the solid state (X-ray
δ (ppm)
structure).
The dendritic core serves as scaffold, but most importantly it posses unique luminescent
properties on its own, deriving from the rigid spatial arrangement of the four pyridylpyridinium
units [4]. Modulation of the emission and electrochemical properties of the peripheral Ruporphyrins and of the core unit within the arrays, with respect to those of the parent components
and/or of smaller model compounds, and possible inter-component photo-induced processes
occurring between the peripheral and the inner chromophores, have also been investigated.
2
meso
3
2
2
1
3
4
1
2
coeff
-6
2
-1
Diffusion Coeffcient (cm2 s-1)
h
______________
References:
1. In “Electron Transfer in Chemistry” Balzani, V., Ed.; Wiley-VCH: Weinheim (Germany) 2001: Gust, D. et al.
Vol. III, Part 2, Chapter 2, pp 273−336 and Fukuzumi, S. et al. Vol. II, Part 2, Chapter 8, pp 927−966.
2. Scholes, G. D.; Fleming, G. R.; Olaya-Castro, A.; van Grondelle, R. Nat. Chem., 2011, 3, 763.
3. O’Sullivan, M. C.; Sprafke, J. K.; Kondratuk, D. V.; Rinfray, C.; Claridge, T. D. W.; Saywell, A.; Blunt, M. O;
O’Shea, J. N.; Beton, P. H; Malfois, M; Anderson, H. L. Nature, 2011, 469, 72.
4. Bergamini, G.; Fermi, A.; Marchini, M.; Locritani, M.; Credi, A.; Venturi, M.; Negri, F.; Ceroni, P.; Baroncini,
M. Chem. Eur. J., 2014, 20, 7054.
24
OC13
SPONTANEOUS DEPOSITION OF WATER-SOLUBLE PORPHYRINS
ON GLASS: A BIG CHALLENGE OR A “GREEN” OPPORTUNITY?
Maria Elena FRAGALÀ, Alessandro D’URSO, Domenico A. CRISTALDI, Rosalba RANDAZZO and
Roberto PURRELLO
Università di Catania, Dipartimento di Scienze Chimiche and INSTM UdR Catania Viale A. Doria 6, 95100
Catania, Italy
Porphyrins represent a multitopic class of chromophores largely used as functional overlayer in
hybrid organic-inorganic materials. These versatile macrocycles, in fact, are often grafted to
inorganic nanostructures for applications in sensing, energetics, medicine, catalysis and many
other technological fields.
An interesting functional aspect of porphyrins is their dichotomous behaviour: in fact, by a
proper derivatization of periphery (meso and beta positions) it is possible to make them water
soluble despite the intrinsic solvophobic nature. Accordingly, porphyrin based supramolecular
chemistry in aqueous solutions paves the wave to a plethora of noncovalent self-assembled
architectures with specific optical, electronic and chemical properties. Since chemistry in water
represents, nowadays, an eco-friendly and harmless synthetic and material fabrication approach
we focus our efforts in optimization and control of noncovalent surface functionalization
strategies to graft porphyrin overlayers onto inorganic surfaces. In fact, immobilization of
porphyrin onto surface of inorganic materials and nanostructures has become a fundamental
process in the development of advanced devices.
Aware of the importance of electrostatic and related interaction in formation of supramolecular
assemblies, we remark the importance of the porphyrin chemistry in solution- and its associated
hierarchical rules- to trigger the spontaneous deposition of water soluble porphyrin derivatives
on oppositely charged surface as well as to determine the layer stability and process reliability.
The possibility to control spontaneous deposition process in a reproducible manner represents an
easier and greener alternative to covalent approaches extensively used to develop functional
materials and systems.
25
OC14
CONFORMATIONAL CHANGES OF CARDIOLIPIN-BOUND
CYTOCHROME C: A SPECTROSCOPIC STUDY
Lisa MILAZZO, Lorenzo TOGNACCINI, Barry D. HOWES, and Giulietta SMULEVICH
Dipartimento di Chimica “Ugo Schiff”, Via della Lastruccia 3-13, Sesto Fiorentino (Fi).
[email protected]
Interaction of cytochrome c (Cyt c) with cardiolipin (CL) is important for its apoptotic function.
CL binding activates a peroxidase function in Cyt c by promoting protein unfolding.
Peroxidation of CL decreases the strength of the Cyt c-CL interaction, facilitating protein
detachment from the mitochondrial membrane leading to initiation of apoptosis (1,2).
Many attempts have been made to obtain a consistent structural description of the CL-bound Cyt
c species; however, the protein conformational heterogeneity has hindered the analysis of the
different forms. A consensus view is that upon formation of the Cyt c-CL complex the Fe-Met80
coordination is ruptured followed by changes in heme ligation. Using different approaches, it has
been concluded that i) His33, His26 or water (3), ii) Lys or OH- (4) can replace Met80, or iii)
that both His-Fe-His and Lys-Fe-His species can be formed in the complex (5). The puzzling
disparity in binding modes may be due to the different experimental conditions used (6). In the
present work we have studied the interaction using horse heart Cyt c which, unlike yeast Cyt c,
has pro-apoptotic activity (7). Ferric Cyt c has been titrated with bovine CL. The final complex,
corresponding to a CL/Cyt c ratio of 30:1, is characterized by the disappearance of the 695 nm
CT, the presence of a new band at 625 nm, and the overall blue shift of the electronic absorption
spectrum compared to the native Cyt c. These changes, together with a curve-fitting analysis of
the corresponding resonance Raman (RR) spectra, indicate that upon complexation the lack of
the Met80 ligand gives rise to the formation of at least four different forms: two minor HS
species (a 5-coordinated HS and an aquo 6-coordinated HS) and two misligated forms. A His-FeHis species is the first misligated state to be formed, at low CL concentration (when the CT at
695 nm, indication of the presence of the Fe-Met ligation, is still present in the UV-Vis spectra),
followed by the formation of a Lys-Fe-His species, for higher CL ratios. In the final complex, the
proximal Fe-His bond is strong, as suggested by the fairly high RR frequency of the (Fe-Im)
stretching bond, whereas the distal cavity is open, since CO binds to the Fe atom in an upright
conformation with no polar interactions with the distal residues.
In agreement with previously reported UV-RR data (8), we suggest that the first event of the
interaction between Cyt c and CL is the rupture of the critical His26-Pro44 hydrogen-bond.
Pro44 bridges the 20s and the 40s -loops in the polypeptide chain stabilizing the protein
tertiary conformation. This event induces increased flexibility of the Met80-containing loop,
disrupting the Met80-heme ligation followed by the formation of the His-Fe-His species.
Subsequently, a nearby Lys residue possibly binds the heme.
______________
References:
1. Kagan V.E.; Tyurin, V.A.; Jiang, J.; Tyurina, Y.Y.; Ritov, V.B.; Amoscato, A.A.; Osipov, A. N., Belikova, N.
A., Kapralov, A.A., Kini, V., Vlasova, I. I., Zhao, Q., et al., Nat. Chem .Biol., 2005, 1, 223.
2.Ott, M.; Robertson, J.D.; Gogvadze, V.; Zhivotovsky, B.; Orrenius, S. PNAS, 2002, 99, 1259.
3. Oellerich, S.; Wackerbarth, H.; Hildebrandt, P.,. Eur. Biophys J., 2003, 32, 599.
4. Bradley, J.M.; Silkstone, G.; Wilson, M.T.; Cheesman, M.R.; Butt, J.N. J. Am. Chem. Soc., 2011, 133, 19676.
5. Sinibaldi, F.; Howes, B.D.; Droghetti, E.; Polticelli, F.; Piro, M.C.; Di Pierro, D.; Fiorucci, L.; Coletta, M.;
Smulevich, G., Santucci, R.. Biochemistry, 2013, 52, 4578.
6. Muenzner, J.; Pletneva, E.V. Chemistry and Physics of Lipids 2014, 179, 57.
7. Kluck R.M.; Ellerby L.M.; Ellerby H.M.; Naiem S.; Yaffe M.P.; Margoliash E.; Bredesen D.; Grant
Mauk A.; Sherma F.; Newmeyer D.D. J. Biol. Chem. 2000, 275, 16127.
8. Balakrishnan, G.; Hu, Y.; Spiro, T. G. J. Am. Chem. Soc., 2012, 134, 19061.
26
OC15
β-ALKYNYLCORROLE DERIVATIVES VIA STILLE CROSS-COUPLING
REACTION
a
a
b
a
b
Manuela STEFANELLI , Mario Luigi NAITANA , Marco CHIARINI , Sara NARDIS , Antonella RICCI ,
b
a
Claudio LO STERZO , Roberto PAOLESSE
a
Dipartimento di Scienze e Tecnologie Chimiche Università di Roma “Tor Vergata” Via della Ricerca
b
Scientifica snc, 00133 Roma, Italy E-mail:[email protected] Facoltà di Bioscienze e
Tecnologie Agro-Alimentari e Ambientali, Università degli Studi di Teramo, Via Carlo R. Lerici 1,
64023 Mosciano Sant’Angelo (Teramo), Italy
The remarkable photophysical and photochemical properties exhibited by corroles accounted for
their potential use as photo- and electro-active building blocks in the realization of
multicomponent arrays where these tetrapyrroles and other cromophores or electron acceptors
are linked.1Frequently, synthetic methodologies for the peripheral functionalization of corrole
macrocycle are developed
with the aim to further
amplify these appealing
features,
for
example
allowing for the introduction
of functional groups that
increase
the
electronic
conjugation along the corrole
skeleton. Regarding this,
recently we have been
interested to the insertion of
alkynyl groups at the corrole
β-pyrrolic positions, they
being commonly used in the
organic synthetic materials
fabrication, where high
exciton
and
electron
coupling between the units
are
required.2
The
alkynylation
of
corrole
periphery can be performed
by metal-catalyzed reactions
on halogenated corrole derivatives. We have recently developed a bromination protocol leading
selectively to a silver 3,17-dibrominated corrolate in very high yield. This compound gave entry
to both free base and the corresponding copper complex, which were used as substrates for the
cross coupling reactions tested. Although unsatisfactory results were obtained applying the
Sonogashira reaction conditions, the use of Stille methodology allowed the achievement of the
novel β-alkynylcorrole derivatives reported in Figure from good to excellent yields. These
studies are extremely important in corrole field and will be discussed in detail during this
communication.
______________
References:
1. Flamigni, L; Gryko, D.T., Chem. Soc. Rev., 2009, 38, 1635.
2. Bottari G.; Diaz, D.D; Torres, T., J. Porphyrins Phtalocyanines, 2006, 10, 1083.b) Tanaka, T.; Osuka, A., Chem.
Soc. Rev., 2015, 44, 943.
27
OC16
ACTION OF AN ASYMMETRIC HEAT SOURCE ON THE MIRRORSYMMETRY BREAKING OF PORPHYRIN AGGREGATES
a,b
CD (mdeg)
a
b
b
a
Placido MINEO , Norberto MICALI , Valentina VILLARI , Emilio SCAMPORRINO
b
Dipartimento di Scienze Chimiche, Università di Catania, Viale Andrea Doria 6, I-95125 Catania. CNRIPCF Istituto per i Processi Chimico-Fisici, Viale F. Stagno d’Alcontres 37, I-98158,Messina.
[email protected]
The spontaneous symmetry breaking (SSB) is one of the most strange and exciting natural
phenomenon. It, from the macroscopic to the microscopic world, finds an evidence (often
without any plausible explanation) in several scientific fields, as for example: in astronomy, the
spiral galaxies have, generally, a left-handed motion; in nuclear physic, the β-particles, emitted
from radioactive nuclei, have an intrinsic asymmetry; in biochemistry, L-amino acids and Dsugars are the essential elements of the origin of the life. For a simple approach to the study of
the mirror-symmetry breaking, the aggregation of non-chiral molecules should be considered.
Commonly used dyes can be some water soluble porphyrinic systems which exhibit some
peculiar properties: i) a high molar absorption; ii) a water solubility, generally due to the
presence of suitable charged peripheral groups or peripheral hydrophilic branches; iii) a
capability to form self-assembled systems that can be tuned acting on the solution properties.
The self-aggregation of porphyrin systems can lead to the formation of H-type and/or J-type
structures, whose formation can be easily evidenced by examining the visible region of their
extinction spectra. However, these mesoscopic aggregates, generated from achiral buildingblocks, should not show chiral properties because the aggregation process, generally, is a
random phenomenon leading to an achiral or racemic mixture. Nevertheless, it has been shown
that the mirror-symmetry of a such system can be
100
"broken" by means of an enantiomeric enrichment
Figure 1
induced by a chemical (through chiral templates)
50
heating [email protected] C
and/or a physical (through asymmetric fields)
perturbation. Surprisingly, in several cases, also
0
without the application of an external perturbation, the
appearance of a CD signal, in correspondence of
-50
cooling [email protected] C
porphyrin H- or/and J-band, has been observed.
Concerning this, we have recently demonstrated1 that,
-100
in a stagnant aqueous solution, a self-assembled
360
380
400
420
440
460
480
500
achiral porphyrin can exhibit an induced
l (nm)
supramolecular chirality, if subjected to a weak
temperature gradient able to give rise to a thermophoretic chiral force, inducing an enantiomeric
enrichment with the appearance of circular dichroism signals, as consequence of an unexpected
asymmetric external force.
In the present communication, we show that, in a stagnant water solution of porphyrin-based
molecular aggregates, the symmetry breaking, caused by a temperature gradient (due to an
asymmetric heat source), can be controlled in sign. In particular, the optical activity (evidenced
by CD signal) can be increased and reversed only acting on the thermal ramp direction (Figure
1). These data can be considered a further evidence about the origin of mirror-symmetry
breaking phenomena, suggesting as also weak natural events could be responsible of a chirality
selection in animal and vegetal environment.
_____________
References:
1. Mineo, P.; Villari, V.; Scamporrino, E.; and Micali, N. Soft Matter, 2014, 10 (1), 44-47.
28
OC17
CYCLODEXTRINS/PORPHYRINOIDS SUPRAMOLECULAR
ASSEMBLIES TAILORED BY RECEPTOR TARGETING GROUPS AS
POTENTIALLY CELL-SELECTIVE NANO-PHOTOTHERAPEUTICS
1
2
2
3
Giuseppe SORTINO , Anna PIPERNO , Angela SCALA , Valentina RAPOZZI , Luigi MONSU’
1,2
1
SCOLARO and Antonino MAZZAGLIA
1
CNR-Istituto per lo studio dei Materiali Nanostrutturati, CNR-ISMN c/o Dip. di Scienze Chimiche, dell’
2
Università di Messina, Viale Ferdinando Stagno D’Alcontres 31, 98166, Messina, Italy. Dip. di Scienze
3
Chimiche, Università di Messina, Viale Ferdinando Stagno D’Alcontres 31, 98166, Messina, Italy. Dip. di
Scienze Mediche e Biologiche, Università di Udine, P.le Kolbe 4, 33100 Udine, Italy
[email protected]
Over the past two decades, scientists focused their interests on design of novel nanotherapeutic
tools, prompt to actively deliver drugs in tumor tissue. One of the most used strategies relies on
the functionalization of carrier system with receptor targeting groups such as folate, antibody,
saccharides and peptides. Folate receptor-α (FR-α) is over-expressed in different cancer cell
lines, thus the modification of nanosystem with folate group, represents a well-established
strategy for tumor targeting. Cyclodextrins (CyDs), a well-known class of macrocyclic carriers,
have been modified with folate group to deliver anticancer drug in (FR-α) cell positive.1 Here,
we exploit the host−guest interaction of non ionic amphiphilic cyclodextrins (ACyDs, SC6OH)2
with a folate–adamantanyl derivative (Ada-Fol) to design a novel tailored drug delivery system.
Ada-Fol was newly synthesized by coupling of the adamantanyl-carboxylate and the carboxylic group of folic acid to a diamine spacer, and characterized by 1H-NMR and MALDIMS. Nanoassemblies of [email protected] loaded with Pheophorbide (Pheo),3 a photosensitiser
with high PDT efficacy were produced and fully characterized. [email protected] system has
been prepared by adding PBS (10 mM, pH 7.4) to a mixed (organic) film of SC6OH and AdaFol at 2.5:1 SC6OH/Ada-Fol molar ratio. This dispersion has been used to dissolve Pheo at
2.5:1:1 SC6OH:Ada-Fol:Pheo molar ratio. Pheo-loaded [email protected] nanoassemblies were
investigated by complementary techniques such as UV-Vis, steady-state fluorescence and
characterized to elucidate size, drug loading and to get insight on the sites of entrapped
photosensitizer interaction. In order to verify the biological properties, we have begun to
evaluate in vitro the effectiveness of [email protected]/Pheo on cell growth on different breast
cancer cell lines (MCF-7, MD-231). Preliminary data indicate that the nanoassemblies, upon
light irradiation, inhibit cell proliferation depending on the expression of folate receptor. Other
biological studies in this direction are in due course.
Webpage:http://www.ismn.cnr.it/index.php?option=com_cnrprofile&view=profile&profileid=73
5&lang=it
______________
References:
1. Onodera, R.; Motoyama, K.; Okamatsu, A.; Higashi, T.; Arima, H.; Scientific Reports .2013, 3, 1104.
2. Mazzaglia, A.; Bondì M. L.; Scala, A.; Zito, F.; Barbieri, G.; Crea, F.; Vianelli, G.; Mineo, P.; Fiore, T.; Pellerito,
C.; Pellerito, L.; Costa. M. A. Biomacromolecules, 2013, 14, 3820.
3. Rapozzi ,V.; Zorzet, S.; Zacchigna, M.,; Drioli, S.; Xodo, L. Invest. new drugs, 2013; 31, 192.
29
OC18
MESOSCOPIC STRUCTURES BY LANGMUIR-BLODGETT
DEPOSITION OF STEROID-PORPHYRINS
a
a
a
b
Martina BISCHETTI, Raffaella LETTIERI, Antonio PALLESCHI, Ernesto PLACIDI, Lenka CARDOVA,
c
a
a
Pavel DRASAR, Donato MONTI, Mariano VENANZI
a
c
b
Dept. of Chemical Sciences and Technologies, and CNR-ISM, Dept. of Physics, University of Rome
b
‘Tor Vergata’, 00133 Rome (Italy). Institute of Chemical Technology, 166 28, Praha, Czech Republic
[email protected]
Porphyrin aggregation is primarily dictated by non-covalent and non-specific interactions
established between the large macrocycles (π-π and London dispersion). However, the presence
of substituents with particular chemical and structural characteristics can modulate the extent and
type of noncovalent interactions.1 Exploiting hierarchical self-assembly, porphyrin aggregation
can be driven to generate ordered nano- and meso-structures of well-defined topology, such as
nanoparticles, nanorods, molecular wires and ordered monolayers.
The aggregation properties in solution and the formation of nano- and mesoscopic structures on
solid substrates of a cholic acid disubstituted porphyrin (H2Ch2P) were investigated by
spectroscopy (UV-Vis absorption, steady-state fluorescence, circular dichroism), microscopy
(fluorescence, scanning electrons, atomic force) and molecular mechanics calculations. Monoand multilayer films of H2Ch2P have been obtained by Langmuir-Blodgett (LB) deposition on
quartz supports, and their features at the air/water interface were characterized by pressure-area
isotherms. Interestingly, it was found that LB deposition, carried out at a surface pressure above
the liquid-expanded to liquid-condensed phase transition, gave rise to the formation of
mesoscopic rod-like structures, the morphology of which is modulated by the interactions
established by the chiral steroid units functionalizing the porphyrin macrocycle. In Figure 1 the
micrometric fibers formed by H2Ch2P by LB deposition are clearly imaged by fluorescence
microscopy.
Fig. 1. Fluorescence microscopy imaging of H2Ch2P mesoscopic fibers formed by LangmuirBlodgett deposition.
______________
References:
1. Lorecchio, C.; Venanzi, M.; Mazzuca, C.; Lettieri, R.; Palleschi, A.; Thi, N. H. N.; Cardova, L.; Drasar, P.;
Monti, D. Org. Biomol. Chem. 2014, 12, 3956-3963.
30
OC19
PHOTO-ASSISTED CHEMICAL SENSORS BASED ON PORPHYRINS
COATED ZnO
a
a
a
a
Corrado DI NATALE , Gabriele MAGNA, Francesco MOSCIANO, Eugenio MARTINELLI, Roberto
b
PAOLESSE
a
b
University of Rome Tor Vergata, Department of Electronic Engineering, Rome, 00133, Italy. University
of Rome Tor Vergata, Department of Chemical Science and Technologies, Rome, 00133, Italy
[email protected]
Hybrid materials formed by a layer of dye molecules over a wide-band gap semiconductor, are
widely studied mainly for optoelectronics and photovoltaic applications. However, besides the
conversion of visible photons into an excess of carriers, the combination of organic-inorganic
materials offers other additional properties such as chemical sensing. ZnO and porphyrins are a
good example of the combination of a metal oxide semiconductor and a dye molecule.
We have investigated different routes for the preparation of the hybrid materials. To this regard
we found that porphyrin-ZnO materials can be obtained from a one-pot growth method where
porphryins are directly added to the precursor solution of the hydrothermal growth of ZnO.
Porphyrins interfere with the ZnO growth altering the morphology of the materials. Interestingly,
the sensing properties of the one-pot material are different from those of the material prepared
growing the porphyrin onto the yet formed ZnO nanorods1 and they offer a further degree of
freedom for the design of sensor arrays extending the properties and the capabilities of
porphyrins based sensor array in particular for medical diagnosis, the quality and control of the
foods and the detection of compounds signalling harmful or dangerous substances.
The enhanced catalytic properties of porphyrins coated ZnO were studied in the past as
electrochemical sensors for the detection of compounds in solution. Recenty we found that the
exposure to visible light enhances both the sensitivity and the selectivity with respect to the
detection of L-cysteine in water where the porphyrin coated ZnO is used as the work electrode of
a voltammetric setup.2
The sensing properties of layers of porphyrins onto ZnO nanostructures offer a further degree of
freedom for the design of sensor arrays extending the properties and the capabilities of
porphyrins based sensor array in particular for medical diagnosis, the quality and control of
foods and the detection of compounds signalling harmful or dangerous substances.
______________
References:
1. Magna, G.; Sivalingam, Y.; Martinelli, E.; Pomarico, G.; Basoli, F.; Paolesse, R.; Di Natale, C. Anal Chim Acta
2014, 810, 6-93.
2. Sivalingam, Y.; Pudi, R.; Lvova, L.; Pomarico, G.; Basoli, F.; Catini, A.; Legin A.; Paolesse, R.; Di Natale, C.
Sens Actuators B 2015, 209, 613-621.
31
OC20
EXPANDED CORROLES BY β-FUSED AROMATIC RINGS
Beatrice Berionni BERNA, Sara NARDIS, Federica MANDOJ, Roberto PAOLESSE
Department of Chemical Science and Technology, University of Rome “Tor Vergata”
[email protected]
Among the different corrole functionalizations, we focused our interest on the fusion of aromatic
substituents at the macrocyclic β-positions. It is well-known that an expansion of porphyrinoids
core aromaticity results in a remarkable modification of the optical features of the chromophore,
making them particularly interesting for potential applications in fields ranging from PDT to
chemical sensors, and especially as sensitizer in dye-sensitized solar cells (DSSC)[1].
Taking into account such a consideration, we investigated novel and straightforward synthetic
approaches for the preparation of expanded corroles using pyrazino units as linking bridges.
[2-(NH2)-3-(NO2)-triarylcorrolato]Cu has been chosen as starting material[2]: the reduction of the
nitro group to amino and the further condensation have been carried out by an one-pot
procedure, using different diones.
The condensed compounds exhibited some intriguing spectroscopic features; their application is
currently under investigation.
X-ray structure of Cu-2,3-[9',10'-phenanthrene(b)-pirazino]-5,10,15-tris(4-tert-butylphenyl)corrolato
____________
References:
1. H. Imahori, K. Kurotobi, M. G. Walter, A. B. Rudine, and C. C. Wamser, in “Handbook of Porphyrin Science”,
K. M. Kadish, K. M. Smith, and R. Guilard, eds., World Scientific, Singapore, 2012, Vol. 18, Chapter 80, pages
58-123.
2. Stefanelli, M.; Mandoj, F.; Mastroianni, M.; Nardis, S.; Mohite, P.; Fronczek, F. R.; Smith, K. M.; Kadish, K. M.;
Xiao, X.; Ou, Z.; Chen, P.; Paolesse, R. Inorg. Chem. 2011, 50, 8281–8292
32
OC21
ASSESSMENT IN ELECTRONIC INTERACTIONS IN MONO-OXIDATED
TETRAFERROCENYLPORPHYRINS
a
a
b
a
Pierluca GALLONI, Andrea VECCHI, Andrea MARRANI, Daniel O. CICERO, Valeria CONTE,
a
c
d
Barbara FLORIS, Victor NEMYKIN, Alessandro BAGNO
a
a
Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma Tor Vergata, Via della Ricerca
b
Scientifica, 00133, Roma, Italia. Dipartimento di Chimica, Università degli Studi di Roma “La Sapienza”,
c
P. Aldo Moro 5, 00185 Roma, Italia. Department of Chemistry & Biochemistry, University of Minnesotad
Duluth, Duluth, Minnesota 55812, USA. Dipartimento di Scienze Chimiche, Università degli Studi di
Padova, Via Marzolo 1, 35131 Padova, Italia.
We recently characterized metal free and metallated 5,10,15,20-tetraferrocenylporphyrin
(H2TFcP and MTFcP), which showed reversible electrochemical behavior and mixed-valence
states.1,2 Moreover interesting results were obtained using this macrocycle on gold surface.3
The easy accessibility to the monocationic porphyrin (TFcP+) is of particular interest because of
the long-range electronic communication among ferrocenyl units, which gives rise to an intense
inter-valence charge transfer (IVCT) band in the NIR region of the spectrum. This peculiar
absorption can be used in the construction of redox-driven optical sensors and switches in the
NIR.
Both mono-oxidized TFcPs free-base and zinc complex were prepared in good yields and
characterized by XPS and NMR spectroscopy. Experimental data as well as theoretical
calculations support the idea that the oxidation process involves a hydrogen atom abstraction,
and the effects are very different between metallated and free base derivatives.
______________
References:
1. Nemykin, V. N.; Rohde, G. T.; Barrett, C. D.; Hadt, R. G.; Bizzarri, C.; Galloni, P.; Floris, B.; Nowik, I.; Herber,
R. H.; Marrani, A. G.; Zanoni, R.; Loim, N. M. J. Am. Chem. Soc. 2009, 131, 14969.
2. Rhode, G. T.; Sabin, J. R.; Barret, C. D.; Nemykin, V. N. New J. Chem. 2011, 35, 1440.
3. Vecchi, A.; Gatto, E.; Floris, B.; Conte, V.; Venanzi, M.; Nemykin, V. N.; Galloni, P. Chem. Commun. 2012, 48,
5145.
33
OC22
PORPHYRINS AND ANTIMICROBIAL PEPTIDES FOR
PHOTODYNAMIC THERAPY OF CANCER
1
2
Francesca MORET , Marina GOBBO , Elena REDDI
1
1
University of Padova, Department of Biology, Via U. Bassi 58/B, 35121, Padova, 0498276335.
University of Padova, Department of Chemical Sciences, Via Marzolo 1, 35121, Padova, 0498275741
2
[email protected]
Some antimicrobial peptides (AMPs) have the ability to penetrate and kill not only pathogenic
microorganisms but also cancer cells while are less active toward normal eukaryotic cells 1. Thus,
we investigated the potential of three AMPs, namely apidaecin 1b (Api), magainin 2 (Mag) and
buforin II (Buf), as carriers of photosensitizers for cancer photodynamic therapy (PDT) by using
the hydrophobic 5-(4-carboxyphenyl)-10,15,20-triphenylporphyrin (cTPP) as model porphyrin
conjugated to the N-terminus of the peptides. The delivery efficiency and photo-toxicity of the
conjugates (T-Buf, T-Mag, T-Api) were compared to that of the un-conjugated cTPP in A549
lung cancer cells in vitro. Flow cytometry experiments showed that the kinetic of cellular uptake
of the conjugates was very rapid and, after 5 h of incubation, the uptake of T-Mag, T-Buf and TApi was respectively 32, 8.5 and 6.5-fold higher than that of cTPP. In vitro PDT experiments
showed that, after cells irradiation with 1.5 J cm-2 of blue light, comparable photo-killing was
measured with AMP-porphyrin conjugates at nanomolar concentrations instead of micromolar
concentrations required for the un-conjugated cTPP.
Investigations on the mechanisms by which the cells
die after PDT treatments showed that the exclusive
mechanism of cell death was necrosis. Confocal
microscopy revealed that the intracellular
localization of the porphyrin was changed by using
the AMPs as delivery systems, since while the unconjugated cTPP accumulated in Golgi apparatus
and in endoplasmic reticulum, all the conjugates
showed
a
predominantly punctuated
and
cytoplasmic localization, without co-localizing with
mitochondria or lysosomes. Serum proteins interacted with cTPP conjugated to Buf and Api and
slightly interfered with cellular uptake of these conjugates but not with that of Mag. The
mechanisms of cellular uptake is based on electrostatic interactions of the conjugates with sialic
acid and gangliosides rich domains, as lipid rafts of the plasma membrane followed by
internalization via non-caveolar dynamin-dependent endocytosis. Our study demonstrated that
the three AMPs investigated, Mag in particular, have the ability to carry a hydrophobic cargo
inside cancer cells and may therefore represent useful carriers of anticancer drugs especially
those with poor capacity to penetrate inside the target cells.
______________
References:
1. Gaspar, D.; Veiga, A.S.; Castanho M.A.R.B. Front. Microbiol., 2013, 4, 294-310.
34
OC23
PHOTODYNAMIC THERAPY: GOOD NEWS FROM COMPUTATIONAL
APPROACHES
Nino RUSSO, Marta E. ALBERTO, Gloria MAZZONE, Bruna C. DE SIMONE, Tiziana MARINO, Emilia
SICILIA
Dipartimento di Chimica e Tecnologie Chimiche, Università della Calabria, I-87036 Rende, Italy.
[email protected]
Recent developments in design new photosensitizers active in photodynamic therapy starting
from computed electronic and geometrical properties by using density functional theory should
be presented. In particular, we will show as the main photophysical properties that a drug active
in photodynamic therapy must possess (absorption wavelengths shifted in the Near Infrared
Region, singlet-triplet energy gaps and spin-orbit matrix elements large enough to allow an
efficient intersystem spin crossing) can be reliably predicted by modern density functional
methods. The studied systems include a series of free porphyrin-like and metallated porphyrinlike systems able to activate singlet O2 excited state (Type II reactions)1.
______________
References:
1 G. Mazzone, N. Russo, E. Sicilia, Can. J. Chem. 91(2013)902–906; M. E. Alberto, C. Iuga, A. D. Quartarolo, and
N, Russo, J. Chem. Inf. Model., 53 (2013) 2334−2340; M. E. Alberto, T. Marino, A. D. Quartarolo, N. Russo,
Phys.Chem. Chem. Phys., 15 (2013)16167; A. D. Quartarolo, D. Pérusse, F. Dumoulin, N. Russo, E. Sicilia, J.
Porphyrins Phthalocyanines, 17(2013) 980–988; Marta E. Alberto, Bruna C. De Simone, Gloria Mazzone,
Angelo D. Quartarolo, and Nino Russo, J. Chem. Theory Comput, 10 (2014) 4006−4013; M. E. Alberto, G.
Mazzone, A. D. Quartarolo, F. Fortes Ramos Sousa, E. Sicilia, N. Russo, Journal of Computational Chemistry
35 (2014) 2107–2113.
35
OC24
SYNTHESIS AND CHARACTERIZATION OF NEW FERROCENE,
PORPHYRIN AND C60 TRIADS, CONNECTED BY TRIPLE BONDS
Pietro TAGLIATESTA
Dipartimento di Scienze e Tecnologie Chimiche. Universita' di Roma-Tor Vergata
[email protected]
Electron and energy transfer are important topics in the chemistry of biological and artificial
systems and have been extensively studied over the past twenty years.1 Photosynthesis in plants
and bacteria is based on chemical reactions induced by the electron-transfer phenomena between
natural tetrapyrrolic pigments, such as chlorophyls and related molecules, and quinones, both
embedded in a protein matrix.2 The entire process is not yet well understood and more
information can be obtained by the use of synthetic models.3
During our studies on the possibility to use molecular wires to connect to the beta-pyrrole
positions of the porphyrins one C60 unit through the assembling of one or more triple bond, we
found that it was very convenient and important to have a large delocalization of the π electrons
between the donor and the acceptor moieties of the models.4 Recently we have reported the beta
functionalization of H2TPP by one or two ferrocene molecules in the 2 and 3 positions through
ethynyl or phenylethynyl groups, applying a new approach of the Sonogashira reaction, never
used before in the case of porphyrins.5 In this communication we report on the synthesis of four
new triads, useful as a model for investigating the electron-transfer processes, connecting
ferrocene and C60 to the 2,12 pyrrole positions of H2TPP through ethynyl bonds.
In Figures 1 and 2 the structures of the free bases and their zinc complexes are reported.
We will also show the fluorescence spectra of the triads compared to the related reference
compounds.
Ph
N
Ph
N
N
CH3
Fe
N
M
N
Ph
Ph
Figure 2: M=2H, M=Zn
Figure 1: M= 2H, M=Zn
______________
References:
1. (a) Marcus, R. A. J. Phys. Chem., 1968, 72, 891; (b) Gust, D; Moore, T. A.; Moore A. L., Acc. Chem. Res., 2009,
42, 1890.
2. Gregory, R. L. Biochemistry of photosynthesis, New York: Wiley-Interscience, New York, 1971.
3. (a) Wurfel, P., Physics of Solar Cells in Basic Principles to Advanced Concepts, 2nd edn, Wiley-VCH Verlag
GmbH, Weinheim, 2009; (b) Wenham, S. R.; Green, M. A.; Watt M. E.; Corkish, R. Applied Photovoltaics, 2nd
edn, Earthscan Publications Ltd., London, 2007; (c) Green, M. T. Generation Photovoltaics in Advanced Solar
Energy Conversion, Springer Series in Photonics, Springer, Heidelberg, 2005.
4. Lembo, A.; Tagliatesta, P.; Guldi, D. M. J. Phys. Chem. A, 2006, 110, 11424; (b) Lembo, A.; Tagliatesta, P.;
Guldi, D. M.; Wielopolski, M.; Nuccetelli M. J. Phys. Chem. A, 2009, 113, 1779; (c) Guldi, D. M.; Lembo, A.;
Tagliatesta, P. ECS Transactions, 2007, 2, 3.
5. Tagliatesta, P.; Lembo, A.; Leoni, A. New J. Chem., 2013, 37, 3416
36
OC25
RUTHENIUM PORPHYRIN COMPLEXES AS EFFICIENT CATALYSTS
OF BIOLOGICAL AZA-DERIVATIVES
Emma GALLO, Paolo ZARDI, Daniela Maria CARMINATI, Daniela INTRIERI
Chemistry Department of Milan University; Via Golgi 19, 20133 Milan (Italy)
[email protected]
The direct amination of hydrocarbons is a reaction of great synthetic interest because of the
biological and pharmaceutical relevance of aza-derivatives. For several years we have studied
the formation of C-N bonds using aryl azides (ArN3)1 as nitrogen sources and metal porphyrins
as catalysts. Amongst all the metal porphyrin catalysts,2 ruthenium porphyrins show a good
catalytic activity in both inter- and intramolecular transfer of a nitrene functionality “ArN” from
aryl azides into C-H bonds. The sustainability of the synthetic procedure is related to the high
atom efficiency of azides which insert the aza-fragment into the organic skeleton with the
formation of benign molecular nitrogen as the only stoichiometric side product.
Herein we report the use
Ar NH
[Ru]
of ruthenium porphyrins
CH2
CH2
COOMe
COOMe
Ph
Ph
+ArN3 to promote the synthesis
N2
-amino esters
of biologically interesting
a)
O
compounds such us: a) αAr
O
Ar NH O
[Ru]
N
COMe
CH2
and β-amino esters3 by
CH COMe
Ph
+ArN3 Ph
Ph
amination of benzylic
OMe
N2
OMe
OMe
-amino esters
-lactames
C−H
bonds.
The
methodology was also
R3
R4
R3
2
3
3
4
R
R
effective in synthesizing
R
C3-N
R2
[Ru]
2
R
4
NH
R
two derivatives of methyl
N
b)
cleavage
+ArN3 R1
R1
L-3-phenyllactate
in
1
N2
R
R
order to convert one of
2,5-dihydro-1H-benzo[b]azepines
R
them
into
the
Ar
Ar
R
R
corresponding β-lactam;
[Ru]
3
+
c)
b) benzoazepines4
by
R'
-N2
2
N
N3
R'
aza-[3,3]-Claisen
H indoles
rearrangement of N-aryl2-vinylaziridines derived from the reaction of aryl azides with diene substrates; c) C3functionalized indoles5 by an intermolecular reaction of aryl azides with alkynes. Several
derivatives were synthesized with yields up to 95%, high regioselectivity, and without requiring
the time consuming prefunctionalisation of reagents and the addition of oxidants and/or
additives.
______________
References:
1. a) S. Cenini, E. Gallo, A. Caselli, F. Ragaini, S. Fantauzzi, C. Piangiolino Coord. Chem. Rev. 2006, 250, 1234; b)
D. Intrieri, P. Zardi, A. Caselli, E. Gallo Chem. Commun., 2014, 50, 11440.
2. S. Fantauzzi, A. Caselli, E. Gallo Dalton Trans, 2009, 5434.
3. P. Zardi, A. Caselli, P. Macchi, F. Ferretti, E. Gallo Organometallics 2014, 33, 2210.
4. a) C. Piangiolino, E. Gallo, A. Caselli, S. Fantauzzi, F. Ragaini S. Cenini Eur. J. Org. Chem. 2007, 743; b) S.
Fantauzzi, E. Gallo, A. Caselli, C. Piangiolino, F. Ragaini, N. Re, S. Cenini Chem. Eur. J. 2009, 15, 1241.
5. P. Zardi, A. Savoldelli, D. M. Carminati, A. Caselli, F. Ragaini, E. Gallo ACS Catal. 2014, 4, 3820.
37
OC26
THE FASCINATING WORLD OF -PYRROLIC SUBSTITUTED
Zn(II)-TETRAARYLPORPHYRINATES FOR DYE-SENSITIZED SOLAR
CELLS
a
b
a
Gabriele DI CARLO, Alessio ORBELLI BIROLI, Giulia MAGNANO, Maddalena PIZZOTTI,
a
Francesca TESSORE
a
a
b
Dipartimento di Chimica, Università degli Studi di Milano, via C. Golgi 19, 20133 Milano; Istituto di
Scienze e Tecnologie Molecolari del CNR (CNR-ISTM), via C. Golgi 19, 20133 Milano.
[email protected]
In the last few years porphyrins attracted considerable
attention as sensitizers in DSSCs, because of their strong
electronic absorption bands up to the NIR region and their
long-lived * singlet excited states.1 In particular, mesodisubstituted push-pull Zn(II)-porphyrinates were deeply
investigated thanks to their directional electronic charge
transfer process,2 and a well engineered derivative reached
photovoltaic performances comparable to those of the
benchmark Ru(II) dye N719.3 However, meso-disubstituted
Zn(II)-porphyrinates suffer of time consuming and low yield
syntheses. -pyrrolic Zn(II)-tetraarylporphyrinates are much
more convenient because the preparation of the core
requires a one pot reaction and the functionalization of the
porphyrin ring is readily achievable by selective mono or di-bromination reaction under mild
conditions.4 The sterically hindered architecture of -pyrrolic derivatives lowers -stacking
aggregation phenomena and the enhancement of solubility in most common organic solvents
allows to obtain very pure compounds.5 Although the HOMO-LUMO energy gap of -pyrrolic
systems is higher in comparison to that of the meso analogues, the -mono or disubstituted
Zn(II)-tetraarylporphyrinates show comparable or even better photovoltaic performances as dyes
in DSSCs, because they offer a superior screening effect against detrimental charge
recombination processes.6 Moreover, the replacement in the side aryl rings of tert-butyl groups
with octyloxy chains in ortho position allows an almost 80% increase of the power conversion
efficiency, making this class of green dyes particularly attractive for technological applications.7
______________
References:
1. Urbani, M.; Grätzel, M.; Nazeeruddin, M. K.; Torres, T. Chem. Rev., 2014, 114, 12330.
2. De Angelis, F.; Fantacci, S.; Sgamellotti, A.; Pizzotti, M.; Tessore, F.; Orbelli Biroli, A. Chem. Phys. Lett., 2007,
447, 10.
3. Mathew, S.; Yella, A.; Gao, P.; Humphry-Baker, R.; Curchod, B. F. E.; Ashari-Astani, N.; Tavernelli, I.;
Rothlisberger, U.; Nazeeruddin, M. K.; Grätzel, M. Nat. Chem., 2014, 6, 242.
4. Di Carlo, G.; Orbelli Biroli, A.; Tessore, F.; Rizzato, S.; Forni, A.; Magnano, G.; Pizzotti, M. J. Org. Chem.,
2015, DOI: 10.1021/acs.joc.5b00367.
5. a) Di Carlo, G. ; Orbelli Biroli, A. ; Pizzotti, M. ; Tessore, F. ; Trifiletti, V. ; Ruffo, R. ; Abbotto, A. ; Amat, A. ;
De Angelis, F. ; Mussini, P. R. Chem. Eur. J., 2013, 19, 10723. b) Di Carlo, G. ; Orbelli Biroli, A. ; Tessore, F. ;
Pizzotti, M. ; Mussini, P. R. ; Amat, A. ; De Angelis, F. ; Abbotto, A. ; Trifiletti, V. ; Ruffo, R. J. Phys. Chem. C,
2014, 118, 7307.
6. Di Carlo, G. ; Caramori, S. ; Trifiletti, V. ; Giannuzzi, R. ; De Marco, L. ; Pizzotti, M. ; Orbelli Biroli, A. ;
Tessore, F. ; Argazzi, R. ; Bignozzi, C. A. ACS Appl. Mater. Interfaces, 2014, 18, 15841.
7. Orbelli Biroli, A. ; Tessore, F. ; Vece, V. ; Di Carlo, G. ; Mussini, P. R. ; Trifiletti, V. ; De Marco, L. ; Giannuzzi,
R. ; Manca, M. ; Pizzotti, M. J. Mater. Chem. A, 2015, 3, 2954.
38
OC27
PHOTOSYNTHETIC BACTERIA PLAY HEAVY METALS
Massimo TROTTA and Angela AGOSTIANO
Istituto per i Processi Chimico Fisici – Consiglio Nazionale delle Ricerche Università degli Studi di Bari
[email protected]
Purple photosynthetic bacteria as tool for remediation of environmental sites polluted by heavy
metals have been explored in the last 10 years. In selecting these microorganisms for
bioremediation one of the most stringent parameter, beside lack of pathogenicity, is the energy
source required for their growth and for driving their metabolism: photosynthetic
microorganisms rely on solar light, a cheap and largely available energy supplement, which
makes them very appealing.
Among photosynthetic microorganisms, purple photosynthetic bacteria represent a small group,
well characterized by the ability of using different energy sources, which allows them to switch
metabolism if the environmental condition changes. Photosynthetic metabolism, which is the
sturdiest one that the bacterium can employ to survive to the nastiest environment, is based on a
molecular machinery that relies on a careful spatial organization of bacteriochlorophylls, the
well-known photosynthetic reaction center.
A story of how such bacterium copes with heavy metals under photosynthetic conditions will be
presented, along with successful and unsuccessful attempts to employ them as bioremediators.
______________
References:
1. L. Giotta, F. Italiano, F. Milano, A. Agostiano and M. Trotta (2006) Chemosphere 62, 1490-1499.
2. A. Buccolieri, F. Italiano, A. Dell’atti, G. Buccolieri, L. Giotta, A. Agostiano, F. Milano and M. Trotta (2006)
Annali di Chimica 96, 195-203
3. M. Trotta e L. Fanizzi (2006) L’Ambiente XII(2), 14-17.
4. F. Pisani, F. Italiano, F. De Leo, R. Gallerani, S. Rinalducci, L. Zolla, A. Agostiano, L. R. Ceci and M. Trotta
Journal of Applied Microbiology (2009) 106 338–349.
5. F. Italiano, A. Buccolieri, L. Giotta, A. Agostiano, L. Valli, F. Milano and M. Trotta. International
Biodeterioration & Biodegradation, (2009) 63(7), 948-957
6. Losurdo L., Italiano F., Trotta M., Gallerani R. Ceci L. R., De Leo F. Journal of Basic Microbiology, (2010)
50, 1–4.
7. E. Asztalos, F. Italiano, F. Milano, P. Maróti, and M. Trotta (2010) Photochem. and Photobiol. Sci. 9 12181223.
8. L. Giotta, D. Mastrogiacomo, F. Italiano, F. Milano, A. Agostiano, K. Nagy, L. Valli, and M. Trotta (2011)
Langmuir 27 (7), 3762–73.
9. F. Italiano, GM D’Amici, S Rinalducci, F De Leo, L Zolla, R Gallerani, M Trotta and LR. Ceci (2011) Res.
Microbiology, 162 (5) 520-7.
10. E. Asztalos, G. Sipka, M. Kis, M. Trotta, P. Maróti (2012) Phototosynthesis Research. 112(2), 129-140.
11. F. Italiano, S. Rinalducci, A. Agostiano, Lello Zolla, F. De Leo, L.R. Ceci and M. Trotta. (2012) BioMetals
Volume 25(5), 939-949, DOI: 10.1007/s10534-012-9561-7.
12. Benny D. Belviso, Francesca Italiano, Rocco Caliandro, Benedetta Carrozzini, Alessandra Costanza, Massimo
Trotta. (2013) BioMetals 26(5): 693-703. DOI: 10.1007/s10534-013-9641-3.
13. Calvano C.D., F. Italiano, L. Catucci, A. Agostiano, Tommaso R.I. Cataldi, F. Palmisano, M. Trotta (2014)
BioMetals 27 65–73.
14. Volpicella, M.; Costanza, A.; Palumbo, O.; Claudia, L.; Italiano, F.; Placido, A.; Picardi, E.; Carella, M.; Trotta,
M.; Ceci, L. (2014) FEMS Microbiology Ecology 88(2):345-57 DOI: 10.1111/1574-6941.12303.
39
OC28
PORPHYRAZINES IN COMBINED PHOTO- AND CHEMIOANTICANCER THERAPIES: RECENT RESULTS IN WATER SOLUTION
a
a
a
b
Maria Pia DONZELLO , Elisa VIOLA , Fabiola SCISCIONE , Giuseppe TRIGIANTE , Claudio
a
ERCOLANI
a
b
Università La Sapienza, P.le A. Moro 5, 00185 Roma, Italy, Centre for Cutaneous Research, Queen
Mary University of London, 4 Newark Street London E1 2AT, U.K.
[email protected]
During the last ten years, our group has been directing some of its efforts to synthesize novel
water-soluble porphyrazine species, multicharged [1] and neutral [2], in view of their promising
potentialities as photo/chemioactive drugs for biomedical applications, and a wide general
characterization of these materials has been carried out in the solid state and in solution. Among
the studied species, the mononuclear octacationic Zn(II) (Figure 1-A) and the binuclear
hexacationic Zn(II)/Pt(II) related species, this latter carrying one exocyclic cis-platin-like
functionality (Figure 1-B), proved in DMF solution to be excellent photosensitisers for the
generation of singlet oxygen, the main citotoxic agent in photodynamic therapy (PDT). It has
been recently shown that both mentioned species when dissolved in water solution: (a) bind to a
telomeric G-quadruplex structure, favoring its parallel conformation [3a], (b) interact non
covalently with a synthetic double strand as model for B-DNA.[3c], (c) show a high
photoactivity for the generation of singlet oxygen. Tests in vitro conducted using the melanoma
C8161 tumor cells indicate a strong anticancer action of both the octacationic and the
hexacationic compounds (Figure 1), with an increased cytotoxic activity toward cancerous cells
for the hexacation presumably due to the presence of the external cis-platin-like functionality.
N
+
+N
N
+
H3C
N
N
N
N
+
N
N+
+
N
H3C
N
N
N
N
+
N
N
N
N
CH3
+
CH3
N
N
H3C
N
M
N
N
N
N
N
H3C
CH3
N
N
N
N
N
N
N
N
+
+
CH3
N
M
N
H3C
+N
H3C
N
N
N
N
+
CH3
N
N
+
N
H3C
CH3
N
+
N
CH3
N
N
Pt
Cl
Cl
A
B
Figure 1. Schematic formulations of the ZnII octacation (A) and the ZnII/PtII hexacation
(B) (both neutralized by I- ions).
_____________
References:
1. Donzello, M. P.; Viola, E.; Mannina, L.; Barteri, M.; Fu, Z.; Ercolani, C. J. Porphyrins Phthalocyanines, 2011,
15, 984 and refs.therein.
2. Donzello, M. P. et al. submitted to E. J. Inorg. Chem.
3. a) Manet, I.; Manoli, F.; Donzello, M. P.; Ercolani, C.; Vittori, D.; Cellai, L.; Masi, A.; Monti, S. Inorg. Chem.
2011, 50, 7403; b) Manet, I; Manoli, F.; Donzello, M. P.; Viola, E.; Masi, A.; Andreano, G.; Ricciardi, G.; Rosa,
A.; Cellai, L.; Ercolani, C.; Monti, S. Inorg. Chem., 2013, 52, 321.
40
OC29
FLUORESCENCE ENHANCEMENT IN AN UNSYMMETRICALLYSUBSTITUTED COPPER PHTHALOCYANINE
a
b
a
a
Nicola ANGELINI , Daniela CASCHERA ,Sara NOTARANTONIO , Anna Maria PAOLETTI , Giovanna
a
a
a
PENNESI , Gentilina ROSSI , Gloria ZANOTTI
a
b
CNR – ISM, Via Salaria km 29.500, Monterotondo Scalo (Rm), 00015 – Italy. CNR - ISMN, Via Salaria
km 29.500, Monterotondo Scalo (Rm), 00015 - Italy
[email protected]
Amongst all the properties that phthalocyanines possess, their photochemical behavior is
extremely peculiar and useful for an extremely wide range of applications such as photodynamic
therapy and photovoltaics. During the last years we have synthesized and tested a considerable
number of new macrocyclic-based dyes for Dye-Sensitized Solar Cells bearing zinc in the central
cavity. We have recently chosen to change the central ion to investigate the potentialities of other
metals and we have focused our attention on copper derivatives because of their extremely high
stability, fundamental for a long lifetime of the solar cell, and color intensity which is needed in
order to maximize the light harvesting properties of the device. Even if Cu(II) is a well known
fluorescence quencher because of its capability to induce an intersystem crossing in the
molecular systems that interact with it, a consistent number of copper chlorines, porphyrins and
corroles have been reported as photosensitizers1,2 showing interesting results in terms of
efficiencies.
Our contribution will deal with the fluorescence properties of some copper phthalocyanines with
increasing degree of substitution synthesized as potential photochemical sensitizers, analyzed
both with steady-state and time-resolved measurements. The results will be compared with those
of the corresponding free-base and, when possible, zinc derivatives and in one specific case the
evidence of a consistent fluorescence in a copper derivative has been highlighted.
N
-C(CH3 )3
N
N
N
-COOH
N
M
N
R=
N
N
COOH
COOH
R
M = Cu, Zn, H2
______________
References:
1. Kay, A.; Grätzel, M. J. Phys. Chem. 1993, 97, 6272-6277
2. Calogero, G.; Citro, I.; Crupi, C.; Di Marco, G. Spectrochim. Acta A: Molecular and Biomolecular Spectroscopy
2014, 132, 477–484
41
OC30
GENETRATING FUNCTION APPROACH TO THE CALCULATION OF
SPECTRAL BAND SHAPES
Raffaele BORRELLI, Amedeo CAPOBIANCO, Amalia VELARDO, Andrea PELUSO
di Torino, I-10095 Grugliasco (TO).
[email protected]
Figure 1. Lowest energy tautomer of free-base chlorin.
The calculation and the analysis of absorption and emission band shapes of molecules from first
principles is a fundamental problem of modern physical chemistry, with a widespread range of
applications, extending from the understanding of the basic aspects of light-matter interaction to
the development of organic dyes with tailored spectroscopic properties. Herein, we present a
generating function approach to the calculation of spectral band shapes including Duschinsky
and Herzberg−Teller effects,1,2 together with an application to the computation of the free-base
chlorin Q absorption bands, using molecular geometries and normal vibrations obtained by
density functional theory computations.3 The results clearly show that non-Condon effects can
significantly affect the relative intensities of the weakest Qy and, to a lesser extent, Qx bands. The
proposed approach is extremely powerful and can be used in the cases where the molecular size
makes the direct calculation of Franck−Condon integrals by recurrence formulas prohibitive.
______________
References:
1. Kubo, R.; Toyozawa, Y. Prog. Theor. Phys. 1955, 13, 160−182
2. Borrelli, R.; Peluso, A. Phys. Chem. Chem. Phys. 2011, 13, 442
3. Borrelli, R.; Capobianco A.; Peluso, A. J. Phys. Chem. A 2012, 116, 9934−9940.
42
OC31
THE PORPHYRIN IN THE TRIPLET STATE AS A POTENTIAL SPIN
LABEL FOR NANOMETER DISTANCE MEASUREMENTS BY EPR
SPECTROSCOPY
Marilena DI VALENTIN, Marco ALBERTINI, Enrico ZURLO, Maria Giulia DAL FARRA, Laura ORIAN,
Antonino POLIMENO, Marina GOBBO and Donatella CARBONERA
Department of Chemical Sciences, University of Padova, Italy
[email protected]
Pulsed electron-electron double resonance (PELDOR/DEER) is a pulsed EPR spectroscopy that
measures, via the dipolar electron-electron coupling between two paramagnetic species,
distances in the nanometer range (currently 15-80 Å) with high precision and reliability. This
technique is complementary to the methods of X-ray crystallography, NMR and FRET and it is
becoming a powerful method for structural determination of biomolecules.
Conventionally, PELDOR/DEER measurements are performed between two nitroxide spin
labels which have been attached to biological molecules either by site-directed spin labelling or
by chemical modification. In recent years, numerous efforts have been devoted to the
development of alternative spin labels, featuring more attractive properties than conventional
nitroxide radicals, despite the widespread employment of the latter for distance measurements.
This work demonstrates the feasibility of distance measurements between a porphyrin in the
photoexcited triplet state and a nitroxide spin label chemically incorporated in a small helical
peptide [1]. We have constructed a porphyrin-based molecular ruler where the nitroxide spin
label is attached to different positions along the peptide sequence in the range from 15 to 60 Å.
We have demonstrated that high sensitivity, and consequently high accuracy, is acquired in the
distance measurements due the spectroscopic properties of the porphyrin molecule in the
photoexcited triplet state.
The methodology has been extended from the peptide model system to paradigmatic proteins,
where the porphyrin derivative probe is endogenously bound, in order to prove that this labelling
approach has a high potential for measuring nanometer distances in more complex biological
systems.
______________
Reference:
1. Di Valentin, M.; Albertini, M.; Zurlo, E.; Gobbo,M.; Carbonera, D.; Journal of the American Chemical Society
Communication, 2014, 136, 6582.
43
OC32
METAL-OXO PORPHYRIN COMPLEXES:
CATALYTIC INTERMEDIATES IN THE GAS PHASE
Francesco LANUCARA, Maria Elisa CRESTONI, Simonetta FORNARINI
Dipartimento di Chimica e Tecnologie del Farmaco, Università di Roma “La Sapienza”, P.le A. Moro 5,
Roma, I-00185, Italy
[email protected]
High-valent transition metal-oxo complexes are active intermediates involved in many metal
catalyzed biological and industrial oxidation processes. High-valent iron porphyrin complexes,
namely the iron(IV)-oxo porphyrin cation radical oxidant or Compound I, are frequently invoked
as the competent catalysts of monooxygenase heme enzymes. Biomimetic studies in the gas
phase may allow to reveal the inherent reactivity of these active species by disclosing the
specific contributions of solvent and environmental effects. The preparation of functional models
of the Compound I, namely [(TPFPP)·+FeIV=O]+ and [(TPFPP)MnV=O]+ (TPFPP = meso-tetrakis
(pentafluorophenyl)porphyrinato dianion) is achieved by controlled oxidation of
[MeIII(TPFPP)]Cl (Me= Fe, Mn) either in solution, by using different oxidants, including H2O2
and iodosyl benzene, or in the gas-phase, using ozone.1-3 Electrospray ionization (ESI) in
combination with Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry is used
to explore (under carefully controlled experimental conditions) the underlying factors that
govern the reaction routes in the catalytic activity of these high-valent oxo-metal intermediates.
Patterns of ionic products, involving: (i) addition; (ii) oxygen atom transfer; (iii) formal hydride
transfer; (iv) electron transfer, and thermal rate constants were determined and found to depend
on the nature of the metal, the axial ligands trans to the oxo-function, and the specific substrate.
The selected substrates include (aromatic) hydrocarbons, olefins, thiols, amines, and
phosphites.4-6
[(TPFPP)MeIII]Cl + oxidant
ESI
[(TPFPP)MeIV=O]+
solution
Ft-icr
Products
gas-phase
The kinetic acidity towards selected reference bases of putative hydroxo intermediates, playing a
role in catalytic oxidations, [(TPFPP)FeIVOH]+ and [(TPFPP)MnIVOH]+, has been examined as
well.
______________
References:
1. Crestoni, M. E.; Fornarini, S. Inorg. Chem., 2005, 44, 5379.
2. Crestoni, M. E.; Fornarini, S. Inorg. Chem., 2007, 46, 9018.
3. Chiavarino, B.; Cipollini, R.; Crestoni, M. E.; Fornarini, S.; Lanucara, F. Lapi, A. J. Am. Chem. Soc., 2008, 130,
3208.
4. Crestoni, M. E.; Fornarini, S.; Lanucara, F. Chem. Eur. J. 2009, 15, 7863.(5. Lanucara, F.; Crestoni, M. E. Chem.
Eur. J., 2011, 17, 12092.
6. Sainna, M. A.; Kumar, S.; Kunar, D.; Fornarini, S.; Crestoni, M. E.; de Visser, S. P. Chem. Science, 2015, 6,
1516.
44
OC33
THE SPECIAL PAIR OF CHLOROPHYLLS IN PHOTOSYNTHESIS.
INSIGHTS BY COMPUTER SIMULATIONS
Daniele BOVI, Daniele NARZI, and Leonardo GUIDONI
Dipartimento di Scienze Fisiche e Chimiche, Università degli studi dell’Aquila
[email protected]
Chorophylls and bacterio-chlorophylls molecules are at the basis of the photosynthetic energy
conversion mechanisms in algae, green plants and many bacteria. In this respect, they serve to
different roles: as light-capturing chromophores and excitation transporters in light harvesting
antennas, and as primary electron donors in the photo-induced charge separation occurring in
reaction centres. In the oxygen-evolving reaction centre Photosystem II, the photo-produced
electrons leave a special pair of chlorophylls (named PD1 and PD2) that becomes cationic. This
oxidizing pair (PD1PD2)+ in turn, triggers a cascade of oxidative events, eventually leading to
water splitting and oxygen evolution. Two different oxidative pathways start from the special
pair: an active channel, which is gated by PD1 and leads to water oxidation, and an alternative
channel, likely starting from PD2, that is supposed to be related to photo-protective mechanisms
[1].
Ab initio Molecular Dynamics simulations using a Quantum Mechanics / Molecular Mechanics
approaches and based on the high-resolution crystal structure of Photosystem II [2] have been
recently carried out by us to describe the catalytic mechanisms of Photosystem II complex along
the water-splitting cycle [3-4]. In the present work, using these techniques we have investigated
the electronic structure and the dynamics of the special pair of chlorophylls in both its oxidised
(PD1PD2)+ and reduced (PD1PD2) states.
In agreement with previously reported static calculations [4] we have found that the symmetry
between the two chlorophylls is broken, the positive charge being preferentially located on PD1.
This is consistent with the fact that
PD1 chlorophyll is the gate for the
active channel for water oxidation.
The simulation reveals that large
charge fluctuations occur along
dynamics, temporarily inverting the
charge preference for the two
branches. A vibrational analysis of
the computational data has also
pinpointed
that
such
charge
fluctuations are strongly coupled to
specific modes of the special pair
with frequency below 500 cm-1.
Webpage: http://bio.phys.uniroma1.it
______________
References:
1. Styring S.; Sjöholm J.; Mamedov F. BBA-Bioenergetics, 2012, 1817, 16.
2. Umena, Y.; Kawakami, K.; Shen, J.-R.; Kamiya, N. Nature, 2011,473, 7345.
3. Bovi, D.; Narzi.D.; Guidoni L. Angewandte Chemie, 2013, 125, 11960.
4. Narzi, D.; Bovi, D.; Guidoni L. P.N.A.S., 2014, 111, 8723.
5. Saito, K. et al. J.A.C.S., 2011, 133, 14379.
45
46
POSTERS
47
P01
COMPOSITE NAFION AND sPEEK-PORPHYRIN MEMBRANES
1
1
1
1
Alessandra CARBONE, Ada SACCA’, Rolando PEDICINI, Irene GATTO, Massimiliano GAETA,
2,3
2,3
2
Andrea ROMEO, Luigi MONSU’ SCOLARO, Maria Angela CASTRICIANO
2
1
Istituto di Tecnologie Avanzate per l’Energia “Nicola Giordano”, via S. Lucia sopra Contesse 5, 98126
2
Messina, Italy. Istituto per lo Studio dei Materiali Nanostrutturati, c/o Dipartimento di Scienze Chimiche,
3
V.le F. Stagno D'Alcontres n.31, 98166 Messina, Italy. Dipartimento di Scienze Chimiche, University of
Messina, V.le F. Stagno D'Alcontres n.31, 98166 Messina, Italy.
[email protected]
The ability to control the spatial arrangement of porphyrins, through non covalent intermolecular
interactions, is very important for accessing advanced functional materials with peculiar
properties. Recently, we reported on the ability to easily tune porphyrin J-aggregates optical
features using inner channels of Nafion membranes as confined environment to arrange and
orient the chromophores.1 Since Nafion is usually involved as electrolyte in fuel cells
applications, also the contribution of the porphyrin aggregates on the membranes proton
conduction mechanism has been investigated. Furthermore, in order to overcome the Nafion
limitations such as high production cost and low performance at low temperature, pressure and
humidity we explored porphyrin modified sulphonated polyetheretherketone (sPEEK)
membranes. Generally, sPEEK-membranes possess good mechanical properties, reduced
hydrogen cross-over, similar unit area resistance to Nafion, improved stability to radical species
and reduced production cost. Opportunely selected porphyrins embedded in the membranes
allowed to increase the proton transmissibility of the material forming a hydrogen ion sieve
structure.2
Here, we report on composite membranes based on highly sPEEK and different weight
percentage (0 - 5wt%) of 5,10,15,20-tetra(4-pyridyl)porphyrin (TPyP)3 and meso-tetrakis(4sulfonatophenyl)porphyrin (TPPS) developed and tested for their use in portable applications.
The aim is to exploit the ability of two different porphyrins, containing polar functional groups,
to create specific interactions in a polymeric matrix, in order to stabilize the membranes
maintaining a proton path for the conduction mechanism. The membranes have been obtained by
a standardized doctor-blade method, thermally and chemically treated. UV-Vis and Fluorescence
emission were carried out to investigate the porphyrin aggregation state. Physical-chemical
characterizations in terms of ionic exchange capacity, water uptake, dimensional variations and
swelling, structural and morphological analyses have been performed. Proton conductivity
measurements at low temperatures allowed to investigate the role of the interaction between
polymer and porphyrin on the proton transport mechanism. Furthermore, the composite
membranes were tested in a PEFC 25 cm2 single cell to verify the electrochemical performance
at the selected operative conditions. We anticipate that sPEEK-TPPS membranes operating at
30°C, dry H2/ 100%RH air and 1 abs. bar showed the best fuel cell performance with a limiting
current approaching 1A/cm2.
______________
References:
1. Castriciano, M.A.; Carbone, A.; Saccà, A.;Donato M.G.; Micali, N.; Romeo, A.; De Luca, G.; Monsù Scolaro, L.
J. Mater. Chem.,, 2010, 20, 2882-2886.
2. Fei, Y.; Zhen-Tao, Z.; Ge, Z. G. Patent CN 102020781 B, 2012.
3. Carbone, A.; Saccà, A.; Pedicini, R.; Gatto, I.; Romeo, A.; Monsù Scolaro, L.; Castriciano, M.A. Int. J. Hydrogen
Energy, 2015, submitted.
48
P02
INTERACTION OF ZnTCPPSpm4 WITH DNA. IN A SINGLE
MOLECULE: PROBE, CATALYTIC & STABILIZING EFFECT
TOWARD Z-FORM.
a,b
b
a
a
Chiara M. A. GANGEMI , Nina BEROVA , Alessandro D’URSO , Gaetano A. TOMASELLI , Roberto
a
PURRELLO
a
Dipartimento di Scienze Chimiche, Università di Catania, Viale Andrea Doria 6, 95125 Catania (Italy).
b
Department of Chemistry, Columbia University, 3000 Broadway, NY, 10027 (USA).
[email protected]
DNA containing an alternation of purine and pyrimidine repeats has the potential to adopt the Z
structure, a left-handed double helix characterized by a high-energy structure.1 It has been shown
that Z-DNA can exist in vivo under physiological conditions as a transient structure, occasionally
induced by a biological process. Therefore, tracts of Z-DNA can exist within a single duplex of
segments of right-handed B-DNA if the conditions and sequences are appropriate.2 Several
research groups have studied the possible correlation between chromosomal breakpoints in
human tumours with potential Z-DNA forming sequences.3 For these reasons the possibility to
recognize, to induce or in some cases to stabilize this conformation could represent an important
goal to understand the mechanism of action of this important structure of DNA. Porphyrinoids
are ideal compounds to interact with DNA due to their peculiar characteristics.4 In this work, we
developed a new achiral zinc-spermine-porphyrin conjugate that shows a catalytic and a
stabilizer effect toward the changing of B-DNA into Z-DNA of poly(dG-dC) sequence. In
addition, it works as probe, showing an intense ICD signal.
______________
References:
1. a) Herbert, A.; Rich, A. J. Biol. Chem., 1996, 271 , 11595. b) Herbert, A.; Rich, A. Genetica, 1999, 106, 37. c)
Wang, A. H.; Quigley, G. J.; Kolpak, F. J.; Crawford, J. L.; van Boom, J. H.; van der Marel, G.; Rich, A. Nature,
1979, 282, 680.
2. a) Jovin, T. M.; Soumpasis, D. M.; McIntosh, L. P. Annu. Rev. Phys. Chem., 1987, 38, 521. b) Rich, A.;
Nordheim, A.; Wang, A. H. J. Annu. Rev. Biochem., 1984, 53, 791.
3. a) Adachi, M; Tsujimoto, Y. Oncogene, 1990, 5, 1653. b) Boehm, T.; Mengle-Gaw, L.; Kees, U. R.; Spurr, N.;
Lavenir, I.; Forster, A.; Rabbitts, T. H. EMBO Journal, 1989, 8, 2621.
4.a) Balaz, M.; De Napoli, M.; Holmes,A.E.; Mammana, A.; Nakanishi,K.; Berova, N.; Purrello, R. Angew. Chem.
Int. Ed. 2005, 44, 4006-4009; b) D’Urso, A.; Nardis, S.; Pomarico, G.; Fragala, M. E.; Paolesse, R.; Purrello, R.;
J. Am. Chem. Soc., 2013, 135, 8632-8638.
49
P03
CYCLODEXTRIN POLYMER/PORPHYRINS ASSEMBLIES AS CAPPING
AGENTS FOR METAL NOBLE NANOPARTICLES WITH POTENTIAL IN
DUAL PHOTOTHERAPY
1
1
1
2
Antonino MAZZAGLIA , Mariachiara TRAPANI , Maria Angela CASTRICIANO , Bernard MARTEL ,
1,3
1,3
Andrea ROMEO , and Luigi MONSU’ SCOLARO
1
CNR-Istituto per lo studio dei Materiali Nanostrutturati, CNR-ISMN c/o Dip. di Scienze Chimiche, dell’
2
Università di Messina, Viale Ferdinando Stagno D’Alcontres 31, 98166, Messina, Italy. Université de Lille
- Sciences et Technologies UFR de Chimie, UMET CNRS 8207 59655 Villeneuve d'Ascq – France.
3
Dip. di Scienze Chimiche, Università di Messina, Viale Ferdinando Stagno D’Alcontres 31, 98166,
Messina, Italy
[email protected]
Nowadays, researchers are interested to design and investigate multifunctional metal noble
nanoparticles (NPs) with high potential in biomedical applications. The utilize of agents which
acts simultaneously as reductants and stabilizers of metal nanoparticles is a well- established
procedure. -Cyclodextrin (CD) polymers bearing citrate and cyclodextrin functionalities have
been extensively used as coatings of a wide range of biomaterials for drug delivery.1
Nanoassemblies based on CD were used as shell entrapping photosensitisers (PSs) to cover
metal noble NPs for photothermal and photodynamic combined therapy (PTT-PDT).2 Here we
report an one-pot synthesis of gold and silver NPs, respectively, covered by water-soluble
cyclodextrins polymer entrapping photosensitisers based on porphyrins. CD polymer was
produced by condensation between hydroxypropylated CD (HPCD) and citric acid (CTR),
named polyCTR-HPCD, according to a previously reported method.2 [email protected] polyCTRHPCD have been prepared by addition of the polymer suspension to a HAuCl4 solution at
reflux and under stirring, thus the polymer acts as both reductant and stabilizing agent. The
synthesis of [email protected] polyCTR-HPCD has been carried out at room temperature by addition of
NaBH4 to a stirred solution of AgNO3 previously mixed to polyCTR-HPCD, using NaBH4 as
reductant and polyCTR-HPCD as capping agent to avoid agglomeration. Au and Ag core-shell
NPs have been characterized by UV-Vis, DLS, TEM and STEM to elucidate size and confirm
the presence of the polymeric cover. The non-covalent interaction between core-shell NPs with
water-soluble anionic porphryin (tetrakis(4-sulfonatophenyl) porphyrin (H2TPPS4) and the
positively charged meso-tetrakis(N-methylpyridinium-4-yl)porphine (H2T4), respectively, was
studied in aqueous solution by complementary techniques such as UV-Vis, fluorescence
emission and circular dichroism. Our data evidence as H2T4 interacts more strongly with
polymeric shell than H2TPPS4, pointing to the both electrostatic and hydrophobic effects which
can address the porphyrin entrapment. This approach consents a control of the PS content in
core-shell NPs with the aim to design novel nanophotherapeutics with dual action.
Webpage:http://www.ismn.cnr.it/index.php?option=com_cnrprofile&view=profile&profileid=73
5&lang=it
______________
References:
1. Sobocinski, J.; Laure, W.; Taha, M.; Courcot, E.; Chai, F.; Simon, N.; Addad, A.; Martel, B.; Haulon, S.; Woisel,
P.; Blanchemain, N.; Lyskawa, J. ACS Appl. Mater. Interface, 2014, 6, 3575-3586.
2. Trapani, M.; Romeo, A.; Parisi, T. Sciortino, M. T.; Villari, V. ; Mazzaglia, A. RSC Adv., 2013, 3, 5607–5614.
3. Martel, B.; Ruffin, D.; Morcellet, M.; Weltrowski, M.; Lechiri, Y.; J Appl Poly Sci, 2005; 97, 433–442.
50
P04
ZINC-PHTHALOCYANINE AS PRECURSOR FOR PREPARATION OF
EXTREMELY HIGH SURFACE AREA N-DOPED CARBON FOR
POTENTIAL APPLICATIONS IN ELECTROCHEMICAL DEVICES
Luigi OSMIERI, Alessandro H. A. MONTEVERDE VIDELA, Reza ALIPOUR MOGHADAM ESFAHANI,
Svetoslava VANKOVA, Marco ARMANDI, Stefania SPECCHIA
Politecnico di Torino – DISAT – Corso Duca degli Abruzzi, 24 – 10129 – Torino – Italy
[email protected]
The development of non-precious metal catalysts and/or ultra-low Pt loading catalysts with
improved performance and durability is essential in order to reduce the use of Pt as catalyst for
the oxygen reduction reaction (ORR) in PEMFCs, making their large-scale commercialization
possible in the future [1]. Different types of C-N-Me (Me = mainly Fe or Co) electrocatalysts for
ORR have been developed so far. Me(II)-phthalocyanines (Me-Pc) have been proved to be
suitable precursors to produce active ORR catalysts [2]. However, to our knowledge the use of
Zn(II)-Pc for this purpose has not been investigated so far. Moreover, the use of N-doped carbon
based materials as support for Pt catalysts should increase the stability of Pt particles preventing
sintering, and have a synergistic effect on ORR activity [3]. An important interaction between Pt
clusters and N atoms on the C support has also been found to increase the catalyst mass activity
[4], allowing to significantly reduce the Pt loading [5]. In addition, C materials with a high
amount of N doping atoms (≈10%) have been found to have interesting properties for
applications in the field of Li-ion batteries [6].
In our work, Zn(II)-Pc is dissolved in ethanol-water solution and impregnated on SBA-15
ordered mesoporous silica [7]. Afterwards, a heat treatment under inert atmosphere at 800 °C is
performed. Finally, the silica template is removed by HF washing. The resulting material was
characterized by BET-porosimetry, XPS, FTIR, XRD,
SEM-EDX and FESEM analyses. It is a highly Ndoped carbon material, with some Zn still present on
the surface. The survey surface atomic chemical
composition (by XPS) is 89% C, 8.3% N, 2.2% O,
0.5% Zn. The Zn amount is also confirmed by EDX.
In addition, this material exhibits a surprisingly high
surface area of ≈1850 m2 g–1. These properties make it
a potential candidate to be used as non-precious metal
ORR catalyst in alkaline membrane fuel cells, as well
as support for ultra-low Pt loading ORR catalysts.
Fig. 1 - Isotherm linear plots and SEM
Electrochemical tests were performed in order to
image for Zn(II)-Pc.
investigate the activity towards ORR using a Rotating Disk Electrode (RDE) under acid (0.5 M
H2SO4 electrolyte) and alkaline conditions (0.1 M KOH electrolyte). Potential applications as
electrode material for Li-ion batteries have also been tested.
___________
References:
1. Feng, Y. ; Alonso-Vante, N. ; Physica Status Solidi (b), 2008, 245, 1792-1806
2. Othman, R.; Dicks, A.L.; Zhu, Z., International Journal of Hydrogen Energy, 2012, 37, 357-372
3. Chen, Y.; Wanga, J.; Liu, H.; Li, R.; Sun, X.; et al.; Electrochemistry Communications, 2009, 11, 2071-2076.
4. Ma, J.; Habrioux, A.; Luo, Y.; et al.; J. Mater. Chem. A, 2015, DOI: 10.1039/C5TA01285F
5. Vinayan, B.P.; Nagar, R.; Rajalakshmi, N.; et al.; Advanced Functional Materials, 2012, 22, 3519-3526
6. Zheng, F.; Yang, Y.; Chen, Q.; Nature communications, 2014, 5, 5261.
7. Monteverde Videla, A.H.; Osmieri, L.; et al.; Electrochim. Acta, 2015, DOI: 10.1016/j.electacta.2015.01.165
51
P05
SUNTHESIS OF FUNCTIONALIZED
TETRAFERROCENYLPORPHYRINS
Fabio POSSANZA, Andrea VECCHI, Barbara FLORIS, Valeria CONTE, Pierluca GALLONI
Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma Tor Vergata, via ricerca scientifica
snc, 00133 Rome, Italy
[email protected]
Metallocenyl porphyrins are of great interest for their electrochemical and photophysical
properties and for possible application in different fields such as energy conversion, memory
devices and elctrochemical capacitors.1,2 In our group we studied the tetraferrocenylporphyrins
showing interesting features in terms of electrochemical processes and photoelectrochemical
catalysis.3 We recently investigated the mono-functionalized derivatives bearing an acetyl group
on one ferrocenyl moiety that showed interesting features in terms of electronic interactions. 4
With the aim to analyze the effects of 4 acetyl groups on the electronic properties of this class of
macrocyle, we synthetized a tetrasubstitutedferrocenyl porphyrins.
The compounds obtained have been characterized by electrochemical and spectroscopic
techniques, and the quite unexpected effects of the acetyl groups will be discussed in comparison
with the classical tetraferrocenylporphyrin.
______________
References:
1. Vecchi, A.; Galloni, P.; Floris, B.; Dukin, S. V.; Nemykin, V. N. Coord. Chem. Rev. 2015, 291, 95.
2. Bucher, C.; Devillers, C. H.; Moutet, J.-C.; Royal, G.; Saint-Aman, E. Coord. Chem. Rev. 2009, 253, 21.
3. Vecchi, A.; Gatto, E.; Floris, B.; Conte, V.; Venanzi, M.; Nemykin, V. N.; Galloni, P. Chem. Commun. 2012, 48,
5145.
4. Vecchi, A.; Erickson, N. R.; Sabin J. R.; Floris, B.; Conte, V.; Venanzi, M.; Galloni, P.; Nemykin, V. N. Chem.
Eur. J. 2015, 21, 269.
52
P06
SYNTHESIS OF NEW GLICOPORPHYRIN LIGANDS FOR
HOMOGENEOUS CATALYSIS
Paolo ZARDI, Giorgio TSEBERLIDIS, Daniela Maria CARMINATI, Luigi LAY, Emma GALLO
Università degli Studi di Milano, Milan, Italy.
[email protected]
Glycoporphyrins are generated by the conjugation of saccharide units with a porphyrin molecule.
These compounds have several biological applications due to the good activity of carbohydrates
in ligand-acceptor interaction and recognition, and also because the porphyrin ligand is a
biocompatible scaffold1. Since metallo-porphyrins are active in promoting nitrene and carbene
transfer reactions2, glycoporphyrin complexes can be a new class of catalysts. Taking advantage
of the chiral and hydrophilic nature of saccharide units, this class of compounds can be used
either for asymmetric synthesis or to develop new sustainable water-soluble catalysts.
We synthesised glycoporphyrin derivatives following two synthetic strategies (Scheme 1):
a) Aromatic nucleophilic substitution using F20-TPPH2 (tetra-(pentafluoro)phenyl-porphyrin) and
a sugar carrying an unprotected OH group.
b) Copper catalyzed azide-alkyne cycloaddiction (CuAAC), starting from TAPPH2 (tetra(amino)phenyl-porphyrin) and a sugar functionalised with a propargyl moiety.
We were able to synthesise the corresponding iron(III), cobalt (II) and ruthenium(II)-carbonyl
complexes of the obtained glycoporphyrins. A preliminary study concerning the photochemical
properties of the free-base compounds and the catalytic activity of the metal complexes was
performed.
____________________
References:
1) Top. Heterocycl. Chem. 2007 ,7 , 179-248.
2) S. Fantauzzi, A. Caselli, E. Gallo, Dalton Trans, 2009, 28, 5434. b) D. Intrieri, A. Caselli A, E. Gallo , Eur. J.
Inorg. Chem., 2011, 33, 5071-5081.
53
P07
OPTICAL SENSORS CROSS-SENSITIVITY AMENDMENT: THE CASE
STUDY OF HEAVY METALS CSPT DETECTION
1,2,
Larisa LVOVA
1
1
1
3
4
, Pierluca GALLONI , Barbara FLORIS , Corrado DI NATALE , Ingemar LUNDSTRÖM ,
5
5
1
Vito LIPPOLIS , Alessandra GARAU , Roberto PAOLESSE
2
Department of Chemical Science and Technologies, University “Tor Vergata”, Rome, ITALY. Faculty of
3
Biology and Soil Science, St. Petersburg State University, St. Petersburg, RUSSIA. Department of
4
Electronic Engineering, University “Tor Vergata”, Rome, ITALY. IFM, Linköping University, SWEDEN.
5
Dipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari,Monserrato, ITALY
The application of optical sensors has recently spread in many fields, such as environmental
analysis, industrial control, and routine laboratory testing1. Being non invasive, easy to handle,
and possessing the notable selectivity, optical chemical sensors have been previously utilized for
the analysis of several hazardous compounds in aquatic environments, and in particular for the
transition metal ions detection2,3. Recently we reported novel optical sensors based on the mixed
aza-thioether macrocycles bearing coumarin pendant arm, [4] and tetraferrocenylporphyrin PFc4
[5] chromophores for the selective fluorimetric detection of Hg(II) and Pb(II) respectively; the
former increases the fluorescence with the analyte concentration growth, while TFc4
fluorescence quenches under exposure to analyte, Figure 1. The possibility to substitute
fluorimetric signal detection of the developed optodes with the Computer Screen Photo-Assisted
Technique (CSPT), applying a computer monitor screen as polychromatic light source and a
webcam as optical response detector, have been also demonstrated. In this contribution we
propose the simple, fast and effective method to tune the cross-sensitivity of optical sensors for
multisensory CSPT analysis of heavy metals in complex liquid samples.
Figure 1: The chemical structures and fluorimetric response of PFc4 and L3 chromoinophores.
______________
References:
1. B.A. McKinley, Chem. Rev. ,108 (2008) 826
2.M. Shamsipur, M. Hosseini, K. Alizadeh, N. Alizadeh, A. Yari, C. Caltagirone, V. Lippolis, Anal. Chim. Acta 533
(2005) 17.
3. D. Monti, M. Venanzi, M. Russo, G. Bussetti, C. Goletti, M. Montalti, N. Zaccheroni, L. Prodi, R. Rella, M.G.
Manera, G. Mancini, C. Di Natale, R. Paolesse, New J. Chem., 28 (2004) 1123
4. Z. Cao, L. Lvova, C. Di Natale, I. Lundström, R. Paolesse, A. Garau, V. Lippolis, Fluorimetric Chemosensors
Combined with Familiar CSPT Devices for the Selective Detection of Mercury(II) Ions, Proc. Eurosensors
XXVI, September 9-12, 2012, Krakow, Poland.
5. R. Paolesse, L. Lvova, P. Galloni, B. Floris, C. D.Natale, A. D’Amico, Porphyrin-Ferrocene conjugate based
hyphenated opto-electroche-mical sensors for transition metals detection, IMCS 14, July 11-14, 2010, Perth,
Australia.
6. D. Filippini, C. Di Natale, R. Paolesse, A. D’Amico, I. Lundstrom, Sens.Act B, 121 (2007) 93
54
P08
FOUR METAL IONS FOR ONE MACROCYCLE:
FERROCENYL-CORROLE METAL COMPLEXES
Giuseppe POMARICO, Pierluca GALLONI, Federica MANDOJ, Andrea VECCHI, Sara LENTINI, Roberto
PAOLESSE
Università di Roma “Tor Vergata”, Dipartimento di Scienze e Tecnologie Chimiche, Via della Ricerca
Scientifica 1, 00133 Roma.
[email protected]
Among the different polypyrrolic macrocycles, corrole is one of the more intriguing compounds
due to its particular reactivity and to its non-innocent behaviour as ligand. Several modifications
of corrole backbone have been investigated to fit its properties with those needed for the
application in the field of material science. For example, the introduction of ferrocenyl moieties
may led to the formation of the so called mixed-valence states [1], of potential interest for optoelectronic applications. We recently reported the first example of triferrocenylcorrole as Cu
derivative [2]. Now a series of corrole bearing one or two ferrocene units, or different metal ions
in the inner core have been prepared and fully characterized by UV-vis, NMR, electrochemical
and DFT technique.
______________
References:
1. Nemykin, V. N.; Galloni, P.; Floris, B.; Barrett, C. D.; Hadt, R. G.; Subbotin, R. I.; Marrani, A. G.; Zanoni, R.;
Loim, N. M. Dalton Trans. 2008, 4233-4246.
2. Pomarico, G.; Vecchi, A.; Mandoj, F.; Bortolini, O.; Cicero, D. O.; Galloni, P.; Paolesse, R. Chem. Commun.
2014, 50, 4076-4078.
55
P09
IRON-PORPHYRIN ELECTROPOLYMERS FOR MULTITRANSDUCTION ANALYSIS APPLICATIONS
a
a
b
c
a
Rajesh PUDI , Larisa LVOVA , Corrado DI NATALE , Ingemar LUNDSTRÖM , Roberto PAOLESSE
a
b
Department of Chemical Science and Technologies, University “Tor Vergata”, Rome, Italy. Department
c
of Electronic Engineering, University “Tor Vergata”, Rome, Italy. IFM, Linköping University, Sweden
The comparative study of the optical and electrocatalytic activity of the electrochemically
generated Fe-porphyrin polymeric films I, II (semiconductive and intrinsically conductive
respectively) was performed [1,2]. Opto-electrochemical sensors were then developed,
employing the combination of two transduction principles in the same Fe-porphyrin-based
sensing layer, and they have been applied for the analysis of foodstuffs, namely for the detection
of forbidden diazo-conjugated Sudan dye additives [3]. The Computer Screen Photoassisted
Technique, CSPT, was employed as an optical method, while Differential Pulse Voltammetry,
DPV, was applied for the reduction of Sudan I and Sudan IV analytes, catalyzed by polymeric
ironporphyrin films I, II, Fig.1. The fusion of DPV and CSPT data has permitted to improve
significantly the diazo-conjugated colorants classification and aided to distinguish between
Sudan I and IV.
Figure 1. The principle of multi-transduction sensing on Fe-porphyrin electropolymers for Sudan dyes forbidden
food additives PCA discrimination; A-= ClO4-.
______________
References:
1. Y. Wu, Food Chem., 121 (2010) 580.
2. P.A. Liddell, M. Gervaldo, J.W. Bridgewater, A.E. Keirstead, S. Lin, T.A Moore, A.L Moore, D. Gust, Chem.
Mater., 20 (2008) 135.
3. Z. Cao, L. Lvova, R. Paolesse, C. Di Natale, I. Lundström, A.D’Amico, Lect.Notes Electr. Eng., 162 (2014) 49
56
P10
SYNTHESIS OF CHROMOPHORE-MODIFIED GRAPHENE
1
1
1
1
Michele RAGGIO , Sara NARDIS , Mario Luigi NAITANA , Alessandra D’EPIFANIO , Saisameera
2
2
3
3
1
MITTA , Anna SGARLATA , Santodh Kiran BALIJEPALLI , Saulius KACIULIS , Roberto PAOLESSE
1
Department of Chemical Science and Technology, University of Rome “Tor Vergata” 00133, Rome, Italy.
2
3
Department of Physics, University of Rome “Tor Vergata” 00133, Rome, Italy. CNR – ISMN, P.O. Box
10, 00015 Monterotondo Stazione, Rome, Italy
Email: [email protected]
Since the first successful exfoliation of single-layer graphene from graphite in 2004 [1], this twodimensional sp2-hybridized carbon material has been deeply investigated due to its unique
properties ranging from high surface area to high thermal and electronic conductivity. Many
efforts have been made to enable this material to be processed by solvent-assisted techniques,
like layer-by-layer assembly, spin-coating and filtration, with the aim to use graphene as a
versatile material for the fabrication of electrochemical devices such as supercapacitors, fuel
cells, drug delivery system, memory devices, transistor devices, biosensors, solar cells, etc.
Functionalization with organic functional groups can be performed by covalent and noncovalent
modification techniques on both graphene oxide (GO) and reduced graphene oxide (rGO) [2], to
prepare processable graphene, preventing agglomeration and facilitating the formation of stable
dispersions in organic solvents. This is a crucial move towards nano composite materials and
moreover represents a way to introduce new properties that can be combined with those of
graphene. For this purpose we studied the interactions of both GO and rGO with a tetrapyrrolic
chromophore: different triarylcorroles have been used to covalently functionalize GO or to
enhance the solubility of rGO in polar solvents. The acylation reaction on GO allowed to
perform the coupling with an amminoarylcorrole through the formation of an amide bond. On
the other hand the intermolecular interactions between GO and corrole derivatives bearing polar
groups have been investigated. The reduction reaction to obtain rGO was carried out in the
presence of such corroles affording an increased dispersibility of graphene in polar solvents. The
materials have been characterized through XPS technique, IR and Raman spectroscopy. Several
microscopy techniques (AFM, STM, SEM) have been used to analyze GO, rGO and modified
graphene on gold substrate.
______________
References:
1. K. S. Novoselov, A. K. Geim, S. V. Morozov, D. Jiang, Y. Zhang, S. V. Dubonos, I. V. Grigorieva, A. A. Firsov,
Science, 2004, 306, 666-669.
2. V. Georgakilas, M. Otyepka, A. B. Bourlinos, V. Chandra, N. Kim, K. C. Kemp, P. Hobza, R. Zboril, K. S. Kim,
Chem. Rev., 2012, 112, 6156−6214.
57
P11
LIGHT-INDUCED REGIOSPECIFIC BROMINATION OF
MESO-TETRA(3,5-DI-TERT-BUTYLPHENYL)PORPHYRIN ON
2,12 -PYRROLIC POSITIONS
a
b
a
b
Gabriele Di Carlo, Alessio ORBELLI BIROLI, Silvia RIZZATO, Alessandra FORNI, Giulia MAGNANO,
a
a
Maddalena PIZZOTTI, Francesca TESSORE
a
a
b
Dipartimento di Chimica, Università degli Studi di Milano, via C. Golgi 19, 20133 Milano; Istituto di
Scienze e Tecnologie Molecolari del CNR (CNR-ISTM), via C. Golgi 19, 20133 Milano.
[email protected]
The antipodal introduction of two
bromine atoms on 2,12 -pyrrolic
position of 5,10,15,20-tetra(3,5-di-tertbutylphenyl)porphyrin was successfully
achieved by a light-induced reaction of
the substrate with excess NBS.
Complexation with NiII of the major
regioisomer led to good quality crystals,
suitable for X-ray structure determination
with unprecedented probability levels.
The regiospecific character of the
synthetic procedure and the exactness of
the bromine atom position assignment
were thus confirmed, suggesting also an
unexpected electrophilic aromatic
substitution pathway rather than a freeradical halogenation process. A QTAIM
topological analysis on the DFT
optimized wavefunction of the monosubstituted free-base porphyrin
intermediate carrying a bromine atom in C2 -pyrrolic position confirmed the largest negative
charge for the C12 carbon atom in antipodal position, in agreement with the proposed
electrophilic aromatic substitution mechanism.
______________
Reference:
Di Carlo, G.; Orbelli Biroli, A.; Tessore, F.; Rizzato, S.; Forni, A.; Magnano, G.; Pizzotti, M. J. Org. Chem., 2015,
80, 4973
58
P12
Effetto di polimeri cationici sulla foto-inattivazione antimicrobica
indotta da BODIPY
1
1
1
1
1
Stefano BANFI , Enrico CARUSO , Viviana ORLANDI , Paola BARBIERI , Barbara LEVA , Stefano
1
2
FERRARA , Amedea MANFREDI
1
Dipartimento di Scienze Teoriche ed Applicate (DiSTA), Università degli Studi dell’Insubria, via JH
2
Dunant, 3 – Varese. Dipartimento di Chimica, Università Statale di Milano, Via Golgi 19 – Milano
I metodi antimicrobici tradizionali risultano spesso inefficaci in ambito ambientale e clinico, di
conseguenza, negli ultimi anni, sono stati sviluppati nuovi sistemi per rimuovere la
contaminazione microbica. La Terapia Fotodinamica Antimicrobica (APDT) sembra essere
promettente per debellare contaminazioni batteriche localizzate su superfici biologiche o inerti.
Nella APDT il fotosensibilizzante (PS) e una sorgente di luce a bassa energia, inducono uno
stress ossidativo nei batteri.
Recentemente, il nostro gruppo di ricerca si è interessato dell’uso di boro-dipirrometeni,
generalmente denominati BODIPY, come PS in ambito antimicrobico. Questa classe di composti
presenta una proprietà chimico-fisica (alta resa quantica di fluorescenza, Φfl) che li rende adatti
per un’applicazione come sonde diagnostiche in campo oncologico. E’ noto che l’elevata Φfl dei
BODIPY pregiudica il loro impiego come fotosensibilizzanti, per cui si rende necessaria
un’opportuna modifica strutturale per inibire la perdita di energia attraverso la fluorescenza,
favorendo il processo di “intersystem crossing” che, in ultima analisi, incrementa la produzione
dell’ossigeno singoletto essenziale per l’efficacia fotodinamica.
Sulla base di queste premesse abbiamo sintetizzato alcuni BODIPY iodurati e che presentano
anche una carica cationica necessaria per l’interazione con la parete batterica.
In questo lavoro abbiamo analizziamo l’influenza di alcuni polimeri cationici sullo stress
fotodinamico antibatterico indotto da un BODIPY cationico. I polimeri appartengono alla
famiglia delle poli-amidoamine (PAA), macromolecole biocompatibili caratterizzate da un
elevato numero di cariche cationiche in funzione della struttura, del peso molecolare e del pH.
Per questo tipo di studio abbiamo scelto due microorganismi modello rappresentativi di batteri
Gram-negativi e Gram-positivi (Escherichia coli e Staphylococcus aureus) per i quali si è
valutato l’efficacia della foto-inattivazione ottenuta per l’azione del solo BODIPY, a bassa
concentrazione, e per effetto del sistema composto da BODIPY e PAA, quest’ultima a
concentrazione non tossica per i microorganismi.
I risultati indicano che, in generale, i polimeri incrementano l’azione fotodinamica del BODIPY
di circa 2 unità logaritmiche, e, in particolare, i polimeri più corti hanno evidenziato incrementi
superiori.
59
P13
METALLOPORPHYRINS AS PHOTOSENSITIZER FOR MULTICOMPONENT PHOTOACTIVE SYSTEMS
a
b
Paolo CAVIGLI, Maria Teresa INDELLI, Elisabetta IENGO
a
a
Dep. Chemical and Pharmaceutical Sciences, University of Trieste, Via L. Giorgieri 1, 34127 Trieste (IT);
b
Dep. Chemical and Pharmaceutical Sciences, University of Ferrara, Via Fossato di Mortara 17, 44121
Ferrara.
[email protected]
Artificial systems mimicking the natural photoinduced processes are an important topic for the
research activity. In many of these artificial systems, metalloporphyrins play an important role as
photosensitizers. Indeed, besides their well-known chemical resemblance to the chlorophylls of
the natural systems, porphyrins can be considered as ideal components for the construction of
antennas for photoinduced processes [1, 2], and/or photocatalytic purposes triggered by visible
light, such as photoreduction of CO2 to CO when the chromophore is coupled with a
Re(CO)3(bipy) catalyst [3].
Recently, we have exploited a metal-mediated approach that led us to the obtainment of multicomponent photoactive systems based on metalloporphyrins that behaves as photosensitizers.
Two examples are reported in the Figure: on the left a Zn(II)-porphyrin is and a C60 are
connected to a central Re(CO)3(bipy) unit [4]; on the right an Al(III)-porphyrin play the pivotal
role for the self-assembling of photoactive units.
For both systems, the formation of charge separated states initiated by visible light was proven.
An outlook on the synthetic strategy, characterization, and kinetic study of the electron transfer
processes occurring upon selective visible excitation of the porphyrin unit, will be presented.
______________
References:
1. Gatti, T.; Cavigli, P.; Zangrando, E.; Iengo, E.; Chiorboli, C.; Indelli, M. T. Inorg. Chem., 2014, 52, 3190.
2. Iengo, E.; Pantoş, G. D.; Sanders, J. K. M.; Orlandi, M.; Chiorboli, C.; Fracasso, S.; Scandola, F. Chem. Sci.,
2011, 2, 676.
3. Windle, C. D.; Câmpian, M. V.; Duhme-Klair, A.-K.; Gibson, E. A.; Perutz, R. N.; Schneider J. Chem. Commun.,
2012, 48, 8189.
4. Cavigli, P.; Da Ros, T.; Kahnt, A.; Gamberoni, M.; Indelli, M. T.; Iengo, E. Inorg. Chem,. 2015, 54, 280.
60
P14
PORPHYRIN NANO-ASSEMBLIES ONTO GOLD NANORODS
1
2
Mariachiara TRAPANI, Giovanna DE LUCA, Andrea ROMEO,
1,3
MONSU’ SCOLARO
1,3
1
Maria Angela CASTRICIANO, Luigi
1
Istituto per lo Studio dei Materiali Nanostrutturati, c/o Dipartimento di Scienze Chimiche, V.le F. Stagno
2
D'Alcontres n.31, 98166 Messina, Italy. Dipartimento di Scienze del Farmaco e Prodotti per la Salute,
3
Viale SS. Annunziata, 98168, Messina, Italy. Dipartimento di Scienze Chimiche, University of Messina,
V.le F. Stagno D'Alcontres n.31, 98166 Messina, Italy.
Gold nanoparticles (AuNPs) have attracted large interest due to their relatively easy syntheses
and their peculiar shape and size dependent optical properties, which make them interesting
nanomaterials for a variety of applications. In particular, gold nanorods (AuNRs) have been
extensively explored in several fields, such as in catalysis, sensing, optoelectronics and
biomedicine. Ordered assemblies in which electronic, magnetic and optical properties could be
tailored through coupling among neighboring nanorods have been investigated in order to
improve the properties of these nanomaterials.1 Self-assembling can be accomplished via
supramolecular approach by functionalization with organic or inorganic components as well as
biomolecules.2,3 The facile fabrication of linear chains of AuNRs and bifurcated junctions of
nanorods/nanospheres has been achieved through crosslinking of AuNPs with a water soluble
anionic porphyrin.3 Here, we report the interaction between tetrakis-(4-sulphonatophenyl)
porphyrin (TPPS) and AuNRs in aqueous solution. This porphyrin shows the peculiar ability to
self-aggregate forming extended J-type nano-assemblies which exhibit interesting nonlinear
optical and optoelectronic properties mainly related to their structure.4,5,6 At rather mild acidic
conditions nanohybrid assemblies composed of TPPS porphyrin J-aggregates and AuNRs has
been obtained. Kinetics for the growth of AuNRs assemblies evidence dependence on porphyrin
concentration. In particular, at high porphyrin load a fast process, i.e. a more pronounced shift of
the longitudinal plasmonic absorption band of AuNRs, have been observed. A detailed
spectroscopic investigation has been carried out using a combination of UV/Vis absorption,
resonance light scattering and fluorescence emission techniques.
______________
References:
1. Fan, H.; Yang, K.; Boye, D.M.; Sigmon, T.; Malloy, K.J.; Xu, H.; López, G.P.; Brinker, C. J. Science, 2004, 304,
567.
2. Fava, D.; Nie, Z.; Winnik, M. A.; Kumacheva, E. Adv. Mater., 2008, 20, 4318.
3. Zhang, L.; Chen, H.; Wang, J.; Li, Y. F.; Wang, J.; Sang, Y.; Xiao, S. J.; Zhan, L.; Huang, C. Z. Small, 2009, 18,
2001-2009.
4. Collini, E.; Ferrante, C.; Bozio, R. J. Phys. Chem. B, 2005, 109, 2.
5. Micali, N.; Villari, V.; Castriciano, M.; Romeo, A.; Monsù Scolaro, L. J. Phys. Chem. B, 2006, 110, 8289.
6. Villari,V.; Mazzaglia, A.; Trapani, M.; Castriciano, M. A.; De Luca, G.; Romeo, A.; Monsù Scolaro, L.; Micali,
N. J. Phys. Chem. C, 2011, 115, 5435.
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62
List of Participants
Banfi
Stefano
[email protected]
Dipartimento di Scienze Teoriche ed
Applicate (DiSTA), Università degli
Studi dell’Insubria
Belviso
Sandra
[email protected]
Dipartimento di Scienze, Università
della Basilicata
Berionni Berna
Beatrice
[email protected]
Dipartimento di Scienze e Tecnologie
Chimiche, Università di Roma “Tor
Vergata”
[email protected]
Dipartimento di Scienze e Tecnologie
Chimiche, Università di Roma “Tor
Vergata”
Calvano
Cosima
Damiana
[email protected]
Dipartimento di Chimica e Centro
Interdipartiment. di Ricerca
S.M.A.R.T., Università degli Studi di
Bari
Carminati
Daniela Maria
[email protected]
Dipartimento di Chimica, Università
degli Studi di Milano
Carofiglio
Tommaso
[email protected]
Dipartimento di Scienze Chimiche,
Università di Padova
[email protected]
I.S.M.N. – C.N.R. Dipartimento di
Scienze Chimiche, Università di
Messina
Crestoni
Maria Elisa
[email protected]
Dipartimento di Chimica e Tecnologie
del Farmaco, Università di Roma “La
Sapienza”
Di Valentin
Marilena
[email protected]
Dipartimento di Scienze Chimiche,
Università di Padova
Di Natale
Corrado
[email protected]
Dipartimento di Ingegneria
Elettronica, Università di Roma “Tor
Vergata”
Donzello
Maria Pia
[email protected]
Dipartimento di Chimica, Università di
Roma “La Sapienza”
D'Urso
Alessandro
[email protected]
INSTM UdR - Dipartimento di Scienze
Chimiche, Università di Catania
Bischetti
Martina
Castriciano
Maria Angela
63
Floris
Barbara
[email protected]
Dipartimento di Scienze e Tecnologie
Chimiche, Università di Roma Tor
Vergata
Fragalà
Maria Elena
[email protected]
INSTM UdR - Dipartimento di Scienze
Chimiche, Università di Catania
Gallo
Emma
[email protected]
Dipartimento di Chimica, Università
degli Studi di Milano
Galloni
Pierluca
[email protected]
Dipartimento di Scienze e Tecnologie
Chimiche, Università di Roma “Tor
Vergata”
Gangemi
Chiara M. A.
[email protected]
Dipartimento di Scienze Chimiche,
Università di Catania
Gobbo
Marina
[email protected]
Dipartimento di Scienze Chimiche,
Università di Padova
Guidoni
Leonardo
[email protected]
Dipartimento di Scienze Fisiche e
Chimiche, Università degli Studi
dell’Aquila
Iengo
Elisabetta
[email protected]
Dipartimento di Scienze Chimiche e
Farmaceutiche, Università di Trieste
Intrieri
Daniela
[email protected]
Dipartimento di Chimica, Università
degli Studi di Milano
[email protected]
Department of Chemical Science and
Technologies, University “Tor
Vergata”, Rome and Faculty of
Biology and Soil Science, St.
Petersburg State University, St.
Petersburg
[email protected]
Istituto di Chimica dei Composti
OrganoMetallici, ICCOM-CNR,
Firenze
Mandoj
Federica
[email protected]
Department of Chemical Science and
Technology, University of Rome “Tor
Vergata”
Mazzaglia
Antonino
[email protected]
I.S.M.N. – C.N.R. Dipartimento di
Scienze Chimiche, Università di
Messina
Mineo
Placido
[email protected]
Dipartimento di Scienze Chimiche,
Università di Catania
Lvova
Larisa
Manca
Gabriele
64
[email protected]
I.S.M.N. – C.N.R. Dipartimento di
Scienze Chimiche, Università di
Messina
Monti
Donato
[email protected]
Dipartimento di Scienze e Tecnologie
Chimiche, Università di Roma “Tor
Vergata”
Naitana
Mario
[email protected]uniroma2.it
Dipartimento di Scienze e Tecnologie
Chimiche, Università di Roma “Tor
Vergata”
Nardis
Sara
[email protected]
Department of Chemical Science and
Technologies, University of Rome Tor
Vergata
Notarantonio
Sara
[email protected]
CNR – ISM, Monterotondo Scalo,
Rome
Osmieri
Luigi
[email protected]
Politecnico di Torino – DISAT, Torino
Paolesse
Roberto
[email protected]
University of Rome Tor Vergata,
Department of Chemical Science and
Technologies
Paoletti
Anna Maria
[email protected]
CNR – ISM, Monterotondo Scalo,
Rome
Peluso
Andrea
[email protected]
Dipartimento di Chimica e Biologia,
Università di Salerno
Pennesi
Giovanna
[email protected]
CNR – ISM, Monterotondo Scalo,
Rome
Pomarico
Giuseppe
[email protected]
Dipartimento di Scienze e Tecnologie
Chimiche, Università di Roma “Tor
Vergata”
Possanza
Fabio
[email protected]
Dipartimento di Scienze e Tecnologie
Chimiche, Università di Roma Tor
Vergata
Pudi
R. Rajesh
[email protected]
Department of Chemical Science and
Technologies, University “Tor
Vergata”, Rome
Purrello
Roberto
[email protected]
Department of Chemical Science,
University of Catania
Monsù Scolaro
Luigi
65
Raggio
Michele
[email protected]
Department of Chemical Science and
Technologies, University “Tor
Vergata”, Rome
Reddi
Elena
[email protected]
Dipartimento di Biologia, Università di
Padova
Romeo
Andrea
[email protected]
Istituto per lo Studio dei Materiali
Nanostrutturati, c/o Dip. di Scienze
Chimiche, University of Messina
Russo
Nino
[email protected]
Dipartimento di Chimica e Tecnologie
Chimiche, Università della Calabria
Smulevich
Giulietta
[email protected])
Dipartimento di Chimica “Ugo Schiff”,
Università di Firenze
[email protected]
Dipartimento di Scienze e Tecnologie
Chimiche, Università di Roma “Tor
Vergata”
Tagliatesta
Pietro
[email protected]
Dipartimento di Scienze e Tecnologie
Chimiche, Università di Roma “Tor
Vergata”
Tessore
Francesca
[email protected]
Dipartimento di Chimica, Università
degli Studi di Milano
Trotta
Massimo
[email protected]
IPCF-CNR, Università degli Studi di
Bari
[email protected]
Dipartimento di Ingegneria
dell'Innovazione, Università del
Salento
Venanzi
Mariano
[email protected]
Dept. of Chemical Sciences and
Technologies, and CNR-ISM, Dept. of
Physics, University of Rome ‘Tor
Vergata’
Viola
Elisa
[email protected]
Dipartimento di Chimica, Università di
Roma “La Sapienza”
Zanotti
Gloria
[email protected]
CNR – ISM, Roma
Stefanelli
Manuela
Valli
Ludovico
66
ISBN 978–88–7959–879–8
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