17 results on '"Electron-Transfer"'
Search Results
2. Solar H₂ evolution in water with modified diketopyrrolopyrrole dyes immobilised on molecular Co and Ni catalyst-TiO₂ hybrids
- Author
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Warnan, J, Willkomm, J, Ng, J, Godin, RP, Prantl, S, Durrant, J, Reisner, E, and Commission of the European Communities
- Subjects
Science & Technology ,CARBON-DIOXIDE REDUCTION ,HYDROGEN-PRODUCTION ,SENSITIZED TIO2 ,VISIBLE-LIGHT IRRADIATION ,Chemistry, Multidisciplinary ,Chemistry ,PHOTOSYSTEM-II ,Physical Sciences ,CELLS ,ORGANIC-DYES ,ELECTRON-TRANSFER ,CHARGE RECOMBINATION ,NANOCRYSTALLINE TIO2 - Abstract
A series of diketopyrrolopyrrole (DPP) dyes with a terminal phosphonic acid group for attachment to metal oxide surfaces were synthesised and the effect of side chain modification on their properties investigated. The organic photosensitisers feature strong visible light absorption (λ = 400 to 575 nm) and electrochemical and fluorescence studies revealed that the excited state of all dyes provides sufficient driving force for electron injection into the TiO2 conduction band. The performance of the DPP chromophores attached to TiO2 nanoparticles for photocatalytic H2 evolution with co-immobilised molecular Co and Ni catalysts was subsequently studied, resulting in solar fuel generation with a dye-sensitised semiconductor nanoparticle system suspended in water without precious metal components. The performance of the DPP dyes in photocatalysis did not only depend on electronic parameters, but also on properties of the side chain such as polarity, steric hinderance and hydrophobicity as well as the specific experimental conditions and the nature of the sacrificial electron donor. In an aqueous pH 4.5 ascorbic acid solution with a phosphonated DuBois-type Ni catalyst, a DPP-based turnover number (TONDPP) of up to 205 was obtained during UV-free simulated solar light irradiation (100 mW cm−2, AM 1.5G, λ > 420 nm) after 1 day. DPP-sensitised TiO2 nanoparticles were also successfully used in combination with a hydrogenase or platinum instead of the synthetic H2 evolution catalysts and the platinum-based system achieved a TONDPP of up to 2660, which significantly outperforms an analogous system using a phosphonated Ru tris(bipyridine) dye (TONRu = 431). Finally, transient absorption spectroscopy was performed to study interfacial recombination and dye regeneration kinetics revealing that the different performances of the DPP dyes are most likely dictated by the different regeneration efficiencies of the oxidised chromophores.
- Published
- 2017
3. Impact of chirality on the photoinduced charge transfer in linked systems containing naproxen enantiomers
- Author
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Universitat Politècnica de València. Escuela Técnica Superior de Ingenieros Industriales - Escola Tècnica Superior d'Enginyers Industrials, Russian Foundation for Basic Research, Khramtsova, E.A., Sosnovsky, D.V., Ageeva, A.A., Nuin Plá, Neus Edurne, Marín García, Mª Luisa, Purtov, P.A., Borisevich, S.S., Khursan, S.L., Roth, H.D., Miranda Alonso, Miguel Ángel, Plyusnin, V.F., Leshina, T.V., Universitat Politècnica de València. Escuela Técnica Superior de Ingenieros Industriales - Escola Tècnica Superior d'Enginyers Industrials, Russian Foundation for Basic Research, Khramtsova, E.A., Sosnovsky, D.V., Ageeva, A.A., Nuin Plá, Neus Edurne, Marín García, Mª Luisa, Purtov, P.A., Borisevich, S.S., Khursan, S.L., Roth, H.D., Miranda Alonso, Miguel Ángel, Plyusnin, V.F., and Leshina, T.V.
- Abstract
[EN] The model reaction of photoinduced donor-acceptor interaction in linked systems (dyads) has been used to study the comparative reactivity of a well-known anti-inflammatory drug, (S)-naproxen (NPX) and its (R)-isomer. (R)- or (S)-NPX in these dyads is linked to (S)-N-methylpyrrolidine (Pyr) using a linear or cyclic amino acid bridge (AA or CyAA), to give (R)-/(S)-NPX-AA-(S)-Pyr flexible and (R)-/(S)-NPX-CyAA-(S)-Pyr rigid dyads. The donor-acceptor interaction is reminiscent of the binding (partial charge transfer, CT) and electron transfer (ET) processes involved in the extensively studied inhibition of the cyclooxygenase enzymes (COXs) by the NPX enantiomers. Besides that, both optical isomers undergo oxidative metabolism by enzymes from the P450 family, which also includes ET. The scheme proposed for the excitation quenching of the (R)- and (S)-NPX excited state in these dyads is based on the joint analysis of the chemically induced dynamic nuclear polarization (CIDNP) and fluorescence data. The H-1 CIDNP effects in this system appear in the back electron transfer in the biradical-zwitterion (BZ), which is formed via dyad photoirradiation. The rate constants of individual steps in the proposed scheme and the fluorescence quantum yields of the local excited (LE) states and exciplexes show stereoselectivity. It depends on the bridge's length, structure and solvent polarity. The CIDNP effects (experimental and calculated) also demonstrate stereodifferentiation. The exciplex quantum yields and the rates of formation are larger for the dyads containing (R)-NPX, which let us suggest a higher contribution from the CT processes with the (R)-optical isomer.
- Published
- 2016
4. Photoinduced structural modifications in multicomponent architectures containing azobenzene moieties as photoswitchable core
- Author
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Massimo Bonini, Abdelhalim Belbakra, Carlos-Andres Palma, Andrea Listorti, Paolo Samorì, Davide Bonifazi, Silvano Geremia, Joceline Zeitouny, Claudia Aurisicchio, Nicola Armaroli, Rita De Zorzi, Zeitouny, J., Aurisicchio, C., Bonifazi, Davide, DE ZORZI, Rita, Geremia, Silvano, Bonini, M., Palma, C. A., Samori, P., Listorti, A., Belbakra, A., and Armaroli, N.
- Subjects
Photoisomerization ,Absorption spectroscopy ,MODEL COMPOUNDS ,CIS-TRANS ISOMERIZATION ,Photochemistry ,SCANNING-TUNNELING-MICROSCOPY ,INDUCED MOLECULAR-MOVEMENTS ,DENDRITIC IRON PORPHYRINS ,SELF-ASSEMBLED MONOLAYERS ,TETHERED AXIAL LIGANDS ,ELECTRON-TRANSFER ,CHARGE-TRANSFER ,SPECTRAL REGION ,ORGANIC CHEMISTRY ,SUPRAMOLECULAR CHEMISTRY ,chemistry.chemical_compound ,Highly oriented pyrolytic graphite ,Photostationary state ,Materials Chemistry ,Chemistry ,General Chemistry ,Chromophore ,Cis trans isomerization ,Azobenzene ,Absorption (chemistry) - Abstract
Four novel π-conjugated chromophores with an azobenzene core (1-4) have been synthesized exploiting Pd-catalysed cross-coupling reactions between ethynyl-bearing azobenzene cores and suitably-designed peripheral groups. While in molecules 2 and 3 the azobenzene core is equipped, respectively, with ethynyl and 1,3-butadiyne spacers terminated with a substituted aniline, molecule 4 is an homologue of derivative 2 in which the terminal moieties are replaced by meso-substituted Zn-porphyrins. X-Ray crystallographic studies of substituted azobenzene 2 reveal a nearly planar arrangement of the four phenyl rings and the trans configuration of the NN central unit. The UV-Vis absorption spectrum of molecule 1 in cyclohexane (CHX) is very similar to that of unsubstituted azobenzenes; upon irradiation at the maximum of the intense π-π absorption feature (360 nm), 1 undergoes trans → cis photoisomerization reaching a photostationary state. The process is fully reversible both photochemically and thermally (ca. 120 min in the dark). The UV-Vis electronic absorption features of 2-4 are dramatically different compared to those of 1, but the photochemical process can still be traced and exhibits full reversibility in CHX. Also in the case of compound 4, where the photoreactive azobenzene excited states might be quenched by the low-lying porphyrin electronic levels, the photoreaction does occur. Extensive STM investigations of self-assembled monolayers (SAMs) of 2 and 3 at the solid/liquid interface were performed by means of scanning tunneling microscopy (STM) on highly oriented pyrolytic graphite (HOPG). It is evidenced that only the trans isomer can be physisorbed on the surface whereas the cis form, either produced under illumination in situ or prepared by irradiation of the solution prior to deposition (ex-situ), is never observed on the surface. The smallest azobenzene 1 and the bisporphyrin system 4 did not physisorb onto the surface because of the very small size and the bulky 3,5-di(tert-butyl) phenyl groups hindering flat adsorption on HOPG, respectively. © 2009 The Royal Society of Chemistry.
- Published
- 2009
5. Influence of a nearby substrate on the reorganization energy of hole exchange between dye molecules
- Author
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Jenny Nelson, Jarvist M. Frost, Piers R. F. Barnes, Valérie Vaissier, Fabian Manke, and Engineering & Physical Science Research Council (EPSRC)
- Subjects
Electron density ,Lithium-ion batteries ,Electron-transfer ,General Physics and Astronomy ,Solvation ,Physics, Atomic, Molecular & Chemical ,Polarizable continuum model ,Sensitized solar-cells ,Oxide-films ,Physics::Chemical Physics ,Physical and Theoretical Chemistry ,HOMO/LUMO ,Physics ,Science & Technology ,Chemical Physics ,Continuum model ,Chemistry, Physical ,Intermolecular force ,Charge density ,Molecular configuration ,Surfaces ,Chemistry ,Physical Sciences ,Chemical Sciences ,Outer sphere electron transfer ,TIO2 ,Atomic physics - Abstract
A numerical method is presented to estimate the influence of a nearby substrate on the polarization energy and outer sphere reorganization energy (λo) for intermolecular hole transfer for a series of dye molecules. The calculation considers the net charge distribution of the oxidised molecule (determined from quantum chemical calculation of the highest occupied molecular orbital of the neutral molecule within the frozen orbital approximation) encapsulated within a conformal cavity, by the molecules total electron density. An analytical point charge approximation was used at longer range. The molecular cavity was either surrounded by a single polarizable continuum, or, to simulate a nearby substrate, embedded at different positions relative to the interface between two semi-infinite slabs with different dielectric constants. The calculated λo values in the single dielectric medium were linearly related to the outer-sphere reorganisation energy calculated from DFT with a polarizable continuum model, validating the approach. In the two phase system, variations in λo was sensitive to the position of the substrate relative to the molecule and differences in the Pekar factor (1/εo - 1/εr) for the media. For dye molecules in ACN positioned touching a TiO2 substrate λo was typically about 20% lower than in pure ACN depending on the molecular configuration. Our approach can be adapted to systems of more than two media.
- Published
- 2015
6. Photooxidation mechanism of levomepromazine in different solvents
- Author
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Karen Torres, Luis E. Piñero-Santiago, Carmelo Garcia, Jaysika Leguillú, Miguel A. Miranda, Jérôme Trzcionka, Virginie Lhiaubet-Vallet, and Rolando Oyola
- Subjects
FREE-RADICALS ,Photochemistry ,EXCITED-STATE ,Biochemistry ,Levomepromazine ,chemistry.chemical_compound ,HYDROGEN-PEROXIDE ,QUIMICA ORGANICA ,Methotrimeprazine ,medicine ,IN-VITRO PHOTOTOXICITY ,ELECTRON-TRANSFER ,Physical and Theoretical Chemistry ,Acetonitrile ,Hydrogen peroxide ,Promazine ,Aqueous solution ,SINGLET OXYGEN ,Singlet oxygen ,CHLORPROMAZINE ,Sulfoxide ,TRIPLET-STATES ,General Medicine ,PHENOTHIAZINE-DERIVATIVES ,chemistry ,QUANTUM YIELDS ,Solvents ,Methanol ,Oxidation-Reduction ,Antipsychotic Agents ,medicine.drug - Abstract
Unwanted photoinduced responses are well-known adverse effects of most promazine drugs, including levomepromazine (LPZ, Levoprome((R)) or Nozinan((R))). This drug is indicated in psychiatry primarily for the treatment of schizophrenia and other schizoaffective disorders. Levomepromazine's particular sedative properties make it especially fit for use in psychiatric intensive care. Nevertheless, it is photolabile under UV-A and UV-B light in aerobic conditions resulting in the formation of its sulfoxide. The LPZ photochemistry in acetonitrile (MeCN) is completely different from that in methanol (MeOH) and phosphate buffer solutions (PBS, pH = 7.4). The major photoproduct in PBS and MeOH under aerobic conditions is levomepromazine sulfoxide (LPZSO), although the amount is considerably higher in the aqueous environment. The corresponding main photoproduct in MeCN could not be characterized. The destruction quantum yields of LPZ in PBS, MeOH and MeCN are 0.13, 0.02 and, This work has been supported in part by NIH-MBRS grant SO6GM08216 to UPR-Humacao and the UPRH-FOPI Program (CGR). Financial support by the Spanish Government (Ramon y Cajal contract to VLV) is gratefully acknowledged. We especially thank the High Performance Computing Facility at UPR Rio Piedras for assistance with the theoretical calculations and Elizabeth Hodges for the revision of the manuscript.
- Published
- 2013
7. Specific ion effects on the electrochemical properties of cytochrome c
- Author
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INSPIRE, Regione Autonoma della Sardegna, Medda, Luca, Salis, Andrea, Magner, Edmond, INSPIRE, Regione Autonoma della Sardegna, Medda, Luca, Salis, Andrea, and Magner, Edmond
- Abstract
peer-reviewed, The range of salts used as supporting electrolytes in electrochemical studies of redox proteins and enzymes varies widely, with the choice of an electrolyte relying on the assumption that the electrolyte used does not affect the electrochemical properties of the proteins and enzymes under investigation. Examination of the electrochemical properties of the redox protein cytochrome c (cyt c) at a 4,4'-bipyridyl modified gold electrode demonstrates that both the redox potential (E-o') and the faradaic current are influenced by the nature of the electrolyte used, in a manner explained primarily by Hofmeister effects. The faradaic peak currents display an atypical trend on switching from kosmotropic to chaotropic anions, with a maximum current observed in the presence of Cl-. For a series of cations, the peak current increased in the sequence: Li+ (0.34 mu A) Br- (0.35 mu A) > ClO4- (0.35 mu A) > SCN- (0.31 mu A) > F- (0.30 mu A). E-o' decreased by a total of 24 mV across the series F- > Cl- > Br- > ClO4- > SCN- whereas no specific ion effect on E-o' was observed for cations. Factorisation of E-o' into its enthalpic and entropic components showed that while no specific trends were observed, large changes in Delta H-o' and Delta S-o' occurred with individual ions. The effect of anions on the faradaic peak current can be qualitatively explained by considering Collins' empirical rule of 'matching water affinities'. The effect of cations cannot be explained by this rule. However, both anion and cation effects can be understood by taking into account the cooperative action of electrostatic and ion dispersion forces. The results demonstrate that the choice of a supporting electrolyte in electrochemical investigations of redox proteins is important and emphasize that care needs to be taken in the determination and comparison of E-o', Delta H-o' and Delta S-o' in different solutions., ACCEPTED, peer-reviewed
- Published
- 2014
8. One-pot thermally chemocontrolled double Diels-Alder strategies. A route to [4+2] functionalisation/[4+2] derivatization of C-60
- Author
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Markoulides, M. S., Ioannou, G. I., Manos, M. J., and Chronakis, N.
- Subjects
expansion ,pi-donors ,derivatives ,anthracene ,rongalite ,electron-transfer ,chemistry ,fullerene c-60 ,efficient preparation ,adducts - Abstract
The one-pot double Diels-Alder reactions of 3,4-di(methylene)tetrahydrothiophene-1,1-dioxide using temperature as the only chemocontrol element are described. Zn-dust promoted the 1,4-debromination of 3,4-bis(bromomethyl)-2,5-dihydrothiophene-1,1-dioxide in 5-nonanone, under MW conditions, followed by a Diels-Alder reaction, an SO2 extrusion step and a second Diels-Alder reaction. This approach was applied successfully in double [4 + 2] cycloadditions using the same or two different dienophiles to afford the corresponding Diels-Alder products in excellent yields. An elegant and practical method for [4 + 2] functionalisation/[4 + 2] derivatization of C-60 was achieved in a one-pot manner via the formation of a new reactive C-66 dienic intermediate. Rsc Advances
- Published
- 2013
9. Singlet oxygen production by pyrano and furano 1,4-naphthoquinones in non-aqueous medium
- Author
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Reinaldo Rodrigues, Sabrina Baptista Ferreira, M. Luisa Marin, Rodrigo J. Corrêa, Vitor F. Ferreira, Guilherme Santos, Miguel A. Miranda, José Carlos Netto-Ferreira, Carlos Eduardo M. Carvalho, Paula Miro, Nanci C. de Lucas, and Simon J. Garden
- Subjects
Triplet 2-Methyl-1,4-Naphthoquinone ,Acetonitriles ,Absorption spectroscopy ,Beta-Lapachone Derivatives ,Trypanosoma-Cruzi ,Laser Flash-Photolysis ,Electron-Transfer ,Photochemistry ,Molecular electronic transition ,chemistry.chemical_compound ,QUIMICA ORGANICA ,QUIMICA ANALITICA ,Molecular orbital ,Physical and Theoretical Chemistry ,HOMO/LUMO ,Photolysis ,Singlet Oxygen ,Aqueous-Solution ,Chemistry ,Singlet oxygen ,Diradical ,Lasers ,Solvatochromism ,Alpha-Lapachone ,Antitumor-Activity ,In-Vitro ,Solvents ,Flash photolysis ,Quantum Theory ,Biological Evaluation ,Naphthoquinones - Abstract
[EN] The influence of ring size on the photobehaviour of condensed 1,4-naphthoquinone systems, such as pyrano-and furano-derivatives (1 and 2, respectively) has been investigated. The absorption spectra for both families of naphthoquinones reveal clear differences; in the case of 2 they extend to longer wavelengths. A solvatochromic red shift in polar solvents is consistent with the pi,pi* character of the S-0 -> S-1 electronic transition in all cases. Theoretical (B3LYP) analysis of the HOMO and LUMO Kohn-Sham molecular orbitals of the S-0 state indicates that they are pi and pi* in nature, consistent with the experimental observation. A systematic study on the efficiency of singlet oxygen generation by these 1,4-naphthoquinones is presented, and values larger than 0.7 were found in every case. In accordance with these results, laser flash photolysis of deoxygenated acetonitrile solutions led to the formation of detectable triplet transient species with absorptions at 390 and 450 nm (1) and at 370 nm (2), with phi(ISC) close to 1. Additionally, the calculated energies for the T-1 states relative to the S-0 states at UB3LYP/6-311++G** are ca. 47 kcal mol(-1) for 1 and 43 kcal mol(-1) for 2. A comparison of the geometrical parameters for the S-0 and T-1 states reveals a marked difference with respect to the arrangement of the exocyclic phenyl ring whilst a comparison of electronic parameters revealed the change from a quinone structure to a di-dehydroquinone diradical structure., This research was supported by Spanish Government MICINN (CTQ2009-13699 and PHB2008-0104-PC) and by the Brazilian agencies: CAPES (Coordenacao de Aperfeicoamento de Pessoal de Nivel Superior), CNPq (Conselho Nacional de Desenvolvimento Cientifico e Tecnologico), FAPERJ (Fundacao de Amparo a pesquisa do Estado do Rio de Janeiro) and FAPERJ-PRONEX grant number 110.574/2010.
- Published
- 2012
10. Specific ion effects on the electrochemical properties of cytochrome c
- Author
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Medda, Lucca, Salis, Andrea, Magner, Edmond, INSPIRE, and Regione Autonoma della Sardegna
- Subjects
voltammetry ,complexes ,adsorption ,osmolytes ,water ,enzymatic-activity ,electron-transfer ,lysozyme - Abstract
peer-reviewed The range of salts used as supporting electrolytes in electrochemical studies of redox proteins and enzymes varies widely, with the choice of an electrolyte relying on the assumption that the electrolyte used does not affect the electrochemical properties of the proteins and enzymes under investigation. Examination of the electrochemical properties of the redox protein cytochrome c (cyt c) at a 4,4'-bipyridyl modified gold electrode demonstrates that both the redox potential (E-o') and the faradaic current are influenced by the nature of the electrolyte used, in a manner explained primarily by Hofmeister effects. The faradaic peak currents display an atypical trend on switching from kosmotropic to chaotropic anions, with a maximum current observed in the presence of Cl-. For a series of cations, the peak current increased in the sequence: Li+ (0.34 mu A) Br- (0.35 mu A) > ClO4- (0.35 mu A) > SCN- (0.31 mu A) > F- (0.30 mu A). E-o' decreased by a total of 24 mV across the series F- > Cl- > Br- > ClO4- > SCN- whereas no specific ion effect on E-o' was observed for cations. Factorisation of E-o' into its enthalpic and entropic components showed that while no specific trends were observed, large changes in Delta H-o' and Delta S-o' occurred with individual ions. The effect of anions on the faradaic peak current can be qualitatively explained by considering Collins' empirical rule of 'matching water affinities'. The effect of cations cannot be explained by this rule. However, both anion and cation effects can be understood by taking into account the cooperative action of electrostatic and ion dispersion forces. The results demonstrate that the choice of a supporting electrolyte in electrochemical investigations of redox proteins is important and emphasize that care needs to be taken in the determination and comparison of E-o', Delta H-o' and Delta S-o' in different solutions. ACCEPTED peer-reviewed
- Published
- 2012
11. Photosensitised pyrimidine dimerisation in DNA
- Author
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M. Consuelo Cuquerella, Virginie Lhiaubet-Vallet, Miguel A. Miranda, and Francisco Bosca
- Subjects
TRIPLET ENERGY-TRANSFER ,Pyrimidine ,Chemistry ,NUCLEIC-ACID BASES ,Quantum yield ,Pyrimidine dimer ,UV-IRRADIATED DNA ,EXCITED-STATE ,General Chemistry ,Photochemistry ,chemistry.chemical_compound ,Electron transfer ,Intersystem crossing ,ROOM-TEMPERATURE ,QUIMICA ORGANICA ,Excited state ,THYMINE DIMER FORMATION ,BIPYRIMIDINE PHOTOPRODUCTS ,ELECTRON-TRANSFER ,SPORE PHOTOPRODUCT ,DNA ,FROZEN AQUEOUS-SOLUTIONS - Abstract
Triplet-mediated pyrimidine (Pyr) dimerisation is a key process in photochemical damage to DNA. It may occur in the presence of a photosensitiser, provided that a number of requirements are fulfilled, such as favourable intersystem crossing quantum yield and high triplet energy. The attention has been mainly focused on cyclobutane pyrimidine dimers, as they are by far the most relevant Pyr photoproducts obtained by sensitisation. The present perspective deals with the involved chemistry, not only in DNA but also in its simple building blocks. It also includes the photophysical characterisation of the Pyr triplet excited states, as well as a brief discussion of the theoretical aspects., Financial support from the Spanish Government (CTQ2009-13699, CTQ2009-14196, JAE Doc fellowship for M. C. C. and Ramon y Cajal contract for V. L.-V.) and EU (CM0603) is gratefully acknowledged.
- Published
- 2011
12. Stereodifferentiation in the intramolecular singlet excited state quenching of hydroxybiphenyl-tryptophan dyads
- Author
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Universitat Politècnica de València. Instituto Universitario Mixto de Tecnología Química - Institut Universitari Mixt de Tecnologia Química, Universitat Politècnica de València. Departamento de Química - Departament de Química, Generalitat Valenciana, Universitat Politècnica de València, Bonancía Roca, Paula, Vayá Pérez, Ignacio, Markovitsi, Dimitra, Gustavsson, Thomas, Jiménez Molero, María Consuelo, Miranda Alonso, Miguel Ángel, Universitat Politècnica de València. Instituto Universitario Mixto de Tecnología Química - Institut Universitari Mixt de Tecnologia Química, Universitat Politècnica de València. Departamento de Química - Departament de Química, Generalitat Valenciana, Universitat Politècnica de València, Bonancía Roca, Paula, Vayá Pérez, Ignacio, Markovitsi, Dimitra, Gustavsson, Thomas, Jiménez Molero, María Consuelo, and Miranda Alonso, Miguel Ángel
- Abstract
The photochemical processes occurring in diastereomeric dyads (S, S)-1 and (S, R)-1, prepared by conjugation of (S)-2-(2-hydroxy-1,1'-biphenyl-4-yl) propanoic acid ((S)-BPOH) with (S)- and (R)-Trp, have been investigated. In acetonitrile, the fluorescence spectra of (S, S)-1 and (S, R)-1 were coincident in shape and position with that of (S)-BPOH, although they revealed a markedly stereoselective quenching. Since singlet energy transfer from BPOH to Trp is forbidden (5 kcal mol(-1) uphill), the quenching was attributed to thermodynamically favoured (according to Rehm-Weller) electron transfer or exciplex formation. Upon addition of 20% water, the fluorescence quantum yield of (S)-BPOH decreased, while only minor changes were observed for the dyads. This can be explained by an enhancement of the excited state acidity of (S)-BPOH, associated with bridging of the carboxy and hydroxy groups by water, in agreement with the presence of water molecules in the X-ray structure of (S)-BPOH. When the carboxy group was not available for coordination with water, as in the methyl ester (S)-BPOHMe or in the dyads, this effect was prevented; accordingly, the fluorescence quantum yields did not depend on the presence or absence of water. The fluorescence lifetimes in dry acetonitrile were 1.67, 0.95 and 0.46 ns for (S)-BPOH, (S, S)-1 and (S, R)-1, respectively, indicating that the observed quenching is indeed dynamic. In line with the steady-state and time-resolved observations, molecular modelling pointed to a more favourable geometric arrangement of the two interacting chromophores in (S, R)-1. Interestingly, this dyad exhibited a folded conformation in the solid state.
- Published
- 2013
13. Photooxidation mechanism of levomepromazine in different solvents
- Author
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Universitat Politècnica de València. Instituto Universitario Mixto de Tecnología Química - Institut Universitari Mixt de Tecnologia Química, Universitat Politècnica de València. Departamento de Química - Departament de Química, Universidad de Puerto Rico, National Institutes of Health, EEUU, Pinero Santiago, Luis, Garcia, Carmelo, Lhiaubet, Virginie Lyria, Trzcionka, Jéròme, Oyola, Rolando, Torres, Karen, Leguillu, Jaysika, Miranda Alonso, Miguel Ángel, Universitat Politècnica de València. Instituto Universitario Mixto de Tecnología Química - Institut Universitari Mixt de Tecnologia Química, Universitat Politècnica de València. Departamento de Química - Departament de Química, Universidad de Puerto Rico, National Institutes of Health, EEUU, Pinero Santiago, Luis, Garcia, Carmelo, Lhiaubet, Virginie Lyria, Trzcionka, Jéròme, Oyola, Rolando, Torres, Karen, Leguillu, Jaysika, and Miranda Alonso, Miguel Ángel
- Abstract
Unwanted photoinduced responses are well-known adverse effects of most promazine drugs, including levomepromazine (LPZ, Levoprome((R)) or Nozinan((R))). This drug is indicated in psychiatry primarily for the treatment of schizophrenia and other schizoaffective disorders. Levomepromazine's particular sedative properties make it especially fit for use in psychiatric intensive care. Nevertheless, it is photolabile under UV-A and UV-B light in aerobic conditions resulting in the formation of its sulfoxide. The LPZ photochemistry in acetonitrile (MeCN) is completely different from that in methanol (MeOH) and phosphate buffer solutions (PBS, pH = 7.4). The major photoproduct in PBS and MeOH under aerobic conditions is levomepromazine sulfoxide (LPZSO), although the amount is considerably higher in the aqueous environment. The corresponding main photoproduct in MeCN could not be characterized. The destruction quantum yields of LPZ in PBS, MeOH and MeCN are 0.13, 0.02 and <10(-3), respectively. It is further demonstrated that LPZSO does not form by the reaction of singlet oxygen with ground-state LPZ. This oxidation product is actually produced by the reaction of the cation radical of LPZ (LPZ.(+)) with molecular oxygen. This cation radical in turn, is produced by an electron transfer process between the (3)LPZ* and ground-state molecular oxygen.
- Published
- 2013
14. Ruthenium polyoxometalate water splitting catalyst: very fast hole scavenging from photogenerated oxidants
- Author
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Roberto Argazzi, Andrea Sartorel, Gianfranco Scorrano, Michele Orlandi, Mauro Carraro, Marcella Bonchio, and Franco Scandola
- Subjects
Inorganic chemistry ,Metals and Alloys ,chemistry.chemical_element ,General Chemistry ,OXYGEN-EVOLVING CATALYST ,ELECTRON-TRANSFER ,PHOTOSYSTEM-II ,OXIDATION ,COMPLEXES ,DIMER ,OXIDE ,EFFICIENT ,EVOLUTION ,FAMILY ,Photochemistry ,water splitting ,Catalysis ,Nanocrystalline material ,Surfaces, Coatings and Films ,Electronic, Optical and Magnetic Materials ,Ruthenium ,hole scavenging ,Catalytic oxidation ,chemistry ,Homogeneous ,artificial photosynthesis ,Polyoxometalate ,Materials Chemistry ,Ceramics and Composites ,Water splitting ,water splitting, hole scavenging, ruthenium polyoxometalate, artificial photosynthesis ,Scavenging ,ruthenium polyoxometalate - Abstract
The tetraruthenium polyoxometalate water oxidation catalyst 1 performs very fast hole scavenging from photogenerated Ru(III) polypyridine complexes, both in homogeneous solution and at a sensitized nanocrystalline TiO(2) surface.
- Published
- 2010
15. Singlet oxygen production by pyrano and furano 1,4-naphthoquinones in non-aqueous medium
- Author
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Universitat Politècnica de València. Departamento de Química - Departament de Química, Ministerio de Ciencia e Innovación, Coordenaçao de Aperfeiçoamento de Pessoal de Nível Superior, Brasil, Conselho Nacional de Desenvolvimento Científico e Tecnológico, Brasil, Fundação Carlos Chagas Filho de Amparo à Pesquisa do Estado do Rio de Janeiro, de Lucas, N.C., Correa, R.J., Garden, S, Santos, G., Rodrigues, R., Carvalho, C.E.M., Ferreira, S.B., Netto Ferreira, Jose Carlos, Ferreira, V.F., Miró Richart, Paula, Marín García, Mª Luisa, Miranda Alonso, Miguel Ángel, Universitat Politècnica de València. Departamento de Química - Departament de Química, Ministerio de Ciencia e Innovación, Coordenaçao de Aperfeiçoamento de Pessoal de Nível Superior, Brasil, Conselho Nacional de Desenvolvimento Científico e Tecnológico, Brasil, Fundação Carlos Chagas Filho de Amparo à Pesquisa do Estado do Rio de Janeiro, de Lucas, N.C., Correa, R.J., Garden, S, Santos, G., Rodrigues, R., Carvalho, C.E.M., Ferreira, S.B., Netto Ferreira, Jose Carlos, Ferreira, V.F., Miró Richart, Paula, Marín García, Mª Luisa, and Miranda Alonso, Miguel Ángel
- Abstract
[EN] The influence of ring size on the photobehaviour of condensed 1,4-naphthoquinone systems, such as pyrano-and furano-derivatives (1 and 2, respectively) has been investigated. The absorption spectra for both families of naphthoquinones reveal clear differences; in the case of 2 they extend to longer wavelengths. A solvatochromic red shift in polar solvents is consistent with the pi,pi* character of the S-0 -> S-1 electronic transition in all cases. Theoretical (B3LYP) analysis of the HOMO and LUMO Kohn-Sham molecular orbitals of the S-0 state indicates that they are pi and pi* in nature, consistent with the experimental observation. A systematic study on the efficiency of singlet oxygen generation by these 1,4-naphthoquinones is presented, and values larger than 0.7 were found in every case. In accordance with these results, laser flash photolysis of deoxygenated acetonitrile solutions led to the formation of detectable triplet transient species with absorptions at 390 and 450 nm (1) and at 370 nm (2), with phi(ISC) close to 1. Additionally, the calculated energies for the T-1 states relative to the S-0 states at UB3LYP/6-311++G** are ca. 47 kcal mol(-1) for 1 and 43 kcal mol(-1) for 2. A comparison of the geometrical parameters for the S-0 and T-1 states reveals a marked difference with respect to the arrangement of the exocyclic phenyl ring whilst a comparison of electronic parameters revealed the change from a quinone structure to a di-dehydroquinone diradical structure.
- Published
- 2012
16. Photosensitised pyrimidine dimerisation in DNA
- Author
-
Universitat Politècnica de València. Departamento de Química - Departament de Química, Universitat Politècnica de València. Instituto Universitario Mixto de Tecnología Química - Institut Universitari Mixt de Tecnologia Química, Ministerio de Ciencia e Innovación, European Cooperation in Science and Technology, Bosca Mayans, Francisco, Lhiaubet, Virginie Lyria, Cuquerella Alabort, Maria Consuelo, Miranda Alonso, Miguel Ángel, Universitat Politècnica de València. Departamento de Química - Departament de Química, Universitat Politècnica de València. Instituto Universitario Mixto de Tecnología Química - Institut Universitari Mixt de Tecnologia Química, Ministerio de Ciencia e Innovación, European Cooperation in Science and Technology, Bosca Mayans, Francisco, Lhiaubet, Virginie Lyria, Cuquerella Alabort, Maria Consuelo, and Miranda Alonso, Miguel Ángel
- Abstract
Triplet-mediated pyrimidine (Pyr) dimerisation is a key process in photochemical damage to DNA. It may occur in the presence of a photosensitiser, provided that a number of requirements are fulfilled, such as favourable intersystem crossing quantum yield and high triplet energy. The attention has been mainly focused on cyclobutane pyrimidine dimers, as they are by far the most relevant Pyr photoproducts obtained by sensitisation. The present perspective deals with the involved chemistry, not only in DNA but also in its simple building blocks. It also includes the photophysical characterisation of the Pyr triplet excited states, as well as a brief discussion of the theoretical aspects.
- Published
- 2011
17. Fine tuning of the catalytic effect of a metal-free porphyrin on the homogeneous oxygen reduction
- Author
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Trojanek, Antonin, Langmaier, Jan, Sebera, Jakub, Zalis, Stanislav, Barbe, Jean-Michel, Girault, Hubert, and Samec, Zdenek
- Subjects
Liquid/Liquid Interfaces ,Perchloric-Acid ,Behavior ,Tetraphenylporphyrin Monoacids ,Dioxygen ,Cobalt Porphyrins ,Ferrocene Derivatives ,Activation ,Electron-Transfer ,O-2 - Abstract
The catalytic effect of tetraphenylporphyrin on the oxygen reduction with ferrocene in 1,2-dichloroethane can be finely tuned by varying the molar ratio of the acid to the catalyst present in the solution. The mechanism involves binding of molecular oxygen to the protonated free porphyrin base, in competition with ion pairing between the protonated base and the acid anion present.
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