Photochemical Events Research Articles

Photoinduced electron accumulation in colloidally dispersed wide band-gap semiconductor nanosheets

We investigated photoinduced electron accumulation in a colloidal system of layered hexaniobate that is known as a photocatalytically active wide band-gap semiconductor, and attempted to control the photoresponse by introducing additives into the colloid. The inorganic nanosheets were obtained by exfoliation of the layered oxide. UV-irradiation of the colloids led to electron accumulation in the nanosheets to generate reduced niobate species. Propylammonium ions introduced as the exfoliating reagent and present as the counter ions of niobate nanosheets were indicated as the electron donor that stabilized the electron-accumulating state. Yield and half-life of the reduced niobate species greatly increased by adding an appropriate amount of photochemically inert clay nanosheets, while they increased only a little by the addition of molecular electron donors such as EDTA and triethanolamine. Moreover, the molecular species diminished the enhancement effect of the clay nanosheets. The results suggested that the photochemical event was not explained by direct interactions between the semiconductor nanosheets and the additives at molecular level but governed by indirect interactions between the colloid components regulated by the colloid structure.

The role of ascorbic acid transporter in the lens of streptozotocin-induced diabetic rat

Ascorbic acid (AA) is found in high concentrations in the lens and protects the lens from photochemical events such as photo-oxidation. Diabetes reduces the concentration of AA in the lens, and it has been suggested that AA supplementation may rescue lens AA in diabetic patients. In the present study, the effects of dietary supplementation with AA were studied to assess changes in AA concentration and AA transporter expression in the lenses of streptozotocin (STZ)-induced diabetic rats. AA was lower in the aqueous humors and lenses of diabetic rats than in control rats, and low AA levels could be normalized with dietary AA supplementation. The sodium-dependent ascorbic acid transporter2, SVCT2, is transporter of AA, and glucose transporter 1 and 3 (GLUT1 and GLUT3) are transporters of dehydroascobic acid. Transcription of GLUT1 and GLUT3 was not changed as a result of diabetes or AA treatment, and the SVCT2 was increased in diabetic rats and normalized by AA supplementation in diabetic rats. Aquaporin 0 (AQP0) expression was increased in diabetic rats and by AA treatment. The rate of AA transport of vesicle originally from diabetic lens and that with AA treatment were greater than that from control rats with or without AA treatment. These results suggest that ascorbates are transported by AQP0 as well as by SVCT2, GLUT1 and GLUT3, and that supplementation with AA may help prevent diabetic cataracts.

Conical intersection dynamics of the primary photoisomerization event in vision

Ever since the conversion of the 11-cis retinal chromophore to its all-trans form in rhodopsin was identified as the primary photochemical event in vision, experimentalists and theoreticians have tried to unravel the molecular details of this process. The high quantum yield of 0.65 (ref. 2), the production of the primary ground-state rhodopsin photoproduct within a mere 200 fs (refs 3-7), and the storage of considerable energy in the first stable bathorhodopsin intermediate all suggest an unusually fast and efficient photoactivated one-way reaction. Rhodopsin's unique reactivity is generally attributed to a conical intersection between the potential energy surfaces of the ground and excited electronic states enabling the efficient and ultrafast conversion of photon energy into chemical energy. But obtaining direct experimental evidence for the involvement of a conical intersection is challenging: the energy gap between the electronic states of the reacting molecule changes significantly over an ultrashort timescale, which calls for observational methods that combine high temporal resolution with a broad spectral observation window. Here we show that ultrafast optical spectroscopy with sub-20-fs time resolution and spectral coverage from the visible to the near-infrared allows us to follow the dynamics leading to the conical intersection in rhodopsin isomerization. We track coherent wave-packet motion from the photoexcited Franck-Condon region to the photoproduct by monitoring the loss of reactant emission and the subsequent appearance of photoproduct absorption, and find excellent agreement between the experimental observations and molecular dynamics calculations that involve a true electronic state crossing. Taken together, these findings constitute the most compelling evidence to date for the existence and importance of conical intersections in visual photochemistry.

Seaming is believing

Do excited molecules relaxing to their ground state pass through a 'seam' connecting the potential energy profiles of the states? Experimental data suggest the answer to this long-standing question is 'yes'. See Letter p. 440 The primary photochemical event in vision, isomerization of the 11-cis chromophore in rhodopsin to the all-trans form, is one of the fastest natural photochemical processes known, taking less than a millionth of a millionth of a second. The molecular details of reactions of such rapidity are a stiff challenge to experimenters, but Polli et al. now report the characterization of the reaction using ultrafast optical spectroscopy with sub-20-femtosecond time resolution and spectral coverage from the visible to the near infrared. The data confirm that rhodopsin's extreme reactivity results from a molecular funnel mechanism that involves a 'conical intersection' between the potential energy surfaces of the starting and product molecules.

Drought tolerance in Zn-deficient red cabbage (Brassica oleracea L. var. capitata f. rubra) plants

Effects of Zn deficiency were studied in red cabbage plants under well-watered or drought conditions. Impairment of growth due to Zn deficiency was higher under drought compared with well-watered conditions. Drought stress caused a drastic decline in Zn content and led to a damage of photosynthetic apparatus in Zn-deficient but not Zn-sufficient leaves. Net assimilation and transpiration rate were strongly reduced under Zn deficiency and drought conditions following reduction of stomatal conductance. Activity of antioxidant enzymes, with the exception of superoxide dismutase, increased under Zn deficiency conditions, while drought enhanced activity of all studied enzymes concomitant with accumulation of malondialdehyde and H<sub>2</sub>O<sub>2</sub>. The intensifying effect of drought on Zn-deficient leaves could be explained by impaired leaf photochemical events, reduction of whole plant photosynthesis and imbalance between production and scavenging of reactive oxygen species. Water use efficiency, water and osmotic potential of drought-stressed plants were higher under low compared with adequate Zn supply, however, these parameters were not critical for plant growth response under combinative effect of drought and Zn deficiency.

Efficient Electron Transfer Processes of the Covalently Linked Perylenediimide−Ferrocene Systems: Femtosecond and Nanosecond Transient Absorption Studies

Photoinduced electron-transfer processes of the newly synthesized rodlike covalent donor−acceptor molecules consisting of electron-donating ferrocenes (Fc) with electron-accepting perylenediimides (PDIs) with core-substituted cyano and pyrrolidine groups, forming Fc-PDI(CN)2 dyad, Fc2-PDI(CN)2 triad, and Fc-PDI(Py)2 dyad, have been investigated in benzonitrile. The geometric and electronic structures of the dyads and triad were probed by ab initio B3LYP/6-311G methods. The distribution of the highest occupied molecular orbitals (HOMOs) was on the ferrocene entities, while the distribution of the lowest unoccupied molecular orbitals (LUMOs) was on the PDI entities. Free-energy calculations verify that the light-induced processes from excited states of PDIs are exothermic. The excited state photochemical events are monitored by femtosecond and nanosecond transient absorption techniques. In benzonitrile, the quenching pathway involves fast and efficient charge separation from the ferrocenes to the excited PD...

Molecular Factors Controlling Photosynthetic Light Harvesting by Carotenoids

Carotenoids are naturally occurring pigments that absorb light in the spectral region in which the sun irradiates maximally. These molecules transfer this energy to chlorophylls, initiating the primary photochemical events of photosynthesis. Carotenoids also regulate the flow of energy within the photosynthetic apparatus and protect it from photoinduced damage caused by excess light absorption. To carry out these functions in nature, carotenoids are bound in discrete pigment-protein complexes in the proximity of chlorophylls. A few three-dimensional structures of these carotenoid complexes have been determined by X-ray crystallography. Thus, the stage is set for attempting to correlate the structural information with the spectroscopic properties of carotenoids to understand the molecular mechanism(s) of their function in photosynthetic systems. In this Account, we summarize current spectroscopic data describing the excited state energies and ultrafast dynamics of purified carotenoids in solution and bound in light-harvesting complexes from purple bacteria, marine algae, and green plants. Many of these complexes can be modified using mutagenesis or pigment exchange which facilitates the elucidation of correlations between structure and function. We describe the structural and electronic factors controlling the function of carotenoids as energy donors. We also discuss unresolved issues related to the nature of spectroscopically dark excited states, which could play a role in light harvesting. To illustrate the interplay between structural determinations and spectroscopic investigations that exemplifies work in the field, we describe the spectroscopic properties of four light-harvesting complexes whose structures have been determined to atomic resolution. The first, the LH2 complex from the purple bacterium Rhodopseudomonas acidophila, contains the carotenoid rhodopin glucoside. The second is the LHCII trimeric complex from higher plants which uses the carotenoids lutein, neoxanthin, and violaxanthin to transfer energy to chlorophyll. The third, the peridinin-chlorophyll-protein (PCP) from the dinoflagellate Amphidinium carterae, is the only known complex in which the bound carotenoid (peridinin) pigments outnumber the chlorophylls. The last is xanthorhodopsin from the eubacterium Salinibacter ruber. This complex contains the carotenoid salinixanthin, which transfers energy to a retinal chromophore. The carotenoids in these pigment-protein complexes transfer energy with high efficiency by optimizing both the distance and orientation of the carotenoid donor and chlorophyll acceptor molecules. Importantly, the versatility and robustness of carotenoids in these light-harvesting pigment-protein complexes have led to their incorporation in the design and synthesis of nanoscale antenna systems. In these bioinspired systems, researchers are seeking to improve the light capture and use of energy from the solar emission spectrum.

Photoelectrochemical control of the balance between cyclic- and linear electron transport in photosystem I. Algorithm for P700 + induction kinetics

Redox transients of chlorophyll P700, monitored as absorbance changes Δ A 810, were measured during and after exclusive PSI excitation with far-red (FR) light in pea ( Pisum sativum, cv. Premium) leaves under various pre-excitation conditions. Prolonged adaptation in the dark terminated by a short PSII + PSI− exciting light pulse guarantees pre-conditions in which the initial photochemical events in PSI RCs are carried out by cyclic electron transfer (CET). Pre-excitation with one or more 10 s FR pulses creates conditions for induction of linear electron transport (LET). These converse conditions give rise to totally different, but reproducible responses of P700 − oxidation. System analyses of these responses were made based on quantitative solutions of the rate equations dictated by the associated reaction scheme for each of the relevant conditions. These provide the mathematical elements of the P700 induction algorithm (PIA) with which the distinguishable components of the P700 + response can be resolved and interpreted. It enables amongst others the interpretation and understanding of the characteristic kinetic profile of the P700 + response in intact leaves upon 10 s illumination with far-red light under the promotive condition for CET. The system analysis provides evidence that this unique kinetic pattern with a non-responsive delay followed by a steep S-shaped signal increase is caused by a photoelectrochemically controlled suppression of the electron transport from Fd to the PQ-reducing Q r site of the cytb 6f complex in the cyclic pathway. The photoelectrochemical control is exerted by the PSI-powered proton pump associated with CET. It shows strong similarities with the photoelectrochemical control of LET at the acceptor side of PSII which is reflected by release of photoelectrochemical quenching of chlorophyll a fluorescence.

Morphological and Elemental Classification of Freshly Emitted Soot Particles and Atmospheric Ultrafine Particles using the TEM/EDS

The Transmission Electron Microscopy (TEM) and Energy Dispersive Spectroscopy (EDS) were used to determine morphology and elemental composition of a variety of freshly emitted soot particles (acetylene flame, candle flame, kerosene flame, diesel exhaust, electric arc, plastic burning, styrofoam burning, wood burning [white oak and pine bark], and rice straw burning), which can be possible candidate soot in the ambient atmosphere, and ultrafine particles sampled in urban, industrial, and coastal sites during ultrafine particle formation events (combustion and photochemical events). By using mobility-classified non-refractory ((NH 4 ) 2 SO 4 ) and refractory (Polystyrene latex (PSL) and salt (NaCl)) particles, limitation of the TEM was tested. Data showed that the TEM method can be used to examine shapes of both volatile particles such as (NH 4 ) 2 SO 4 (100 nm) at low, but not high magnification (refer to low and high beam intensity, respectively), and non-volatile particles like NaCl (100 nm) and PSL (84 nm) at either low or high magnification. Distinct differences in morphological properties such as primary particle diameter, fractal dimension, and microstructure were observed among the different types of fresh soot particles. The atmospheric ultrafine particles were classified as agglomerates, sulfate mixtures (spherical), metallic oxides (spherical and polygonal), C-rich refractory (not agglomerated), C-rich non-refractory (not agglomerated), Si-rich (spherical), Na-rich (porous), or P-containing (non-spherical) particles. At the urban Gwangju site, a higher fraction of fresh and aged agglomerates was observed than at other sites. The C-rich non-refractory and sulfate mixtures were often observed in the photochemical event. The C-rich refractory particles were abundant at the Gwangju and Yeosu sites. The coastal Taean site had few agglomerates due to limited anthropogenic combustion source.

LOVely enzymes – towards engineering light‐controllable biocatalysts

SummaryLight control over enzyme function represents a novel and exciting field of biocatalysis research. Blue‐light photoreceptors of the Light, Oxygen, Voltage (LOV) family have recently been investigated for their applicability as photoactive switches. We discuss here the primary photochemical events leading to light activation of LOV domains as well as the proposed signal propagation mechanism to the respective effector domain. Furthermore, we describe the construction of LOV fusions to different effector domains, namely a dihydrofolate reductase from Escherichia coli and a lipase from Bacillus subtilis. Both fusion partners retained functionality, and alteration of enzyme activity by light was also demonstrated. Hence, it appears that fusion of LOV photoreceptors to functional enzyme target sites via appropriate linker structures may represent a straightforward strategy to design light controllable biocatalysts.

Photoinduced energy and electron transfer in porphyrin-anthraquinone dyads bridged with a triazine group

Porphyrin-anthraquinone dyads containing a triazine group as linker were synthesized and characterized by 1H NMR, UV–visible, fluorescence and transient spectra and ESI-MS. Absorption spectra revealed that there was no appreciable interaction between the ground-state porphyrin moiety and the ground-state anthraquinone moiety. Fluorescence spectra illustrated that energy transfer takes place from the excited anthraquinone moiety to the porphyrin moiety when excited at 250 nm, whilst efficient electron transfer occurs from the singlet excited porphyrin moiety to the anthraquinone moiety in the case of excitation at 420 nm. A long-lived, charge-separated state H 2P + –EQ − was observed by transient absorption spectra with a lifetime of 1.42 μs and 1.33 μs. These photochemical events were explained from electrochemical studies and suggest that the compounds have the ability to simulate electron transfer from chlorophylls to electron acceptors.

AIR POLLUTION BY OZONE IN THE URBAN AREA OF BELGRADE (SERBIA): SURFACE OZONE PHENOMENOLOGY AND THE RELATION BETWEEN OZONE AND SOME METEOROLOGICAL PARAMETERS

<p>Meteorological conditions favorable for the build up of ozone (O ) are frequent in Belgrade and the 3<br />surrounding area. Measurements, for the seasons 1993 to 2004 performed at three different sites inside the city, revealed two main patterns of photochemical smog events in the Belgrade area: a progressive increase and accumulation of photochemical oxidants during period of warm and stable weather with frequent high daytime ozone concentrations, and transport of local oxidants with sporadically occurring high ozone concentrations during the night. In most cases diurnal ozone concentrations generally showed the typical pattern of photo-smog formation; a steep rise of ozone in the morning, a maximum in the early afternoon (sometimes with 1-h ozone levels greater than 110 ppb) and a rapid decrease in the evening. During such events nocturnal ozone concentrations were usually as low as 10 to 20 ppb (below the background level), but in some cases they were as high as 80 ppb. These variations of ozone concentrations were ascribed to transport of pollutant, ozone depletion chemistry (mainly with nitric oxide NO during the night) and enhanced deposition of ozone on wet surfaces at high humidity. A strong anticorrelation was found between elevation of nocturnal ozone concentration and relative humidity probably affected by small, local rise of temperature.</p>

Assessment of toxic effects of pesticide extracts on different green algal species by using chlorophyll a fluorescence

In this study, the toxicity of pesticides extracted from the Yamaska River watershed surface waters were tested on three species of green algae (Chlorella vulgaris, Scenedesmus obliquus and Pseudokirchneriella subcapitata) by using slow and fast fluorescence kinetics (Maxi-Imaging-Pulse-Amplitude-Modulated and Plant Efficiency Analysis). Two types of extractions for a variety of herbicides and insecticides (organosphosphorous-type (OP) and phenoxyacid-type (PA)) were conducted on the water samples of three sites having different pesticide concentrations (‘Deborah Stairs’, ‘Rivière Noire’ and ‘Rivière à la Barbue’). Our results showed that of the three species of green algae studied, S. obliquus was the most sensitive to both pesticide extracts. Moreover, PA pesticide extracts from ‘Rivière à la Barbue’ were the most toxic since the algae exposed to those extracts had the lowest photosynthetic activity when evaluated by the PSII quantum yields (ΦM and ), the photochemical quenching (qP(REL)) and the electron transport rate per reaction center (ET0/RC). The fast fluorescence kinetic data also indicate that the site of action of the different extracts was at the level of the primary photochemical events, probably electron flow blockage at the Q B binding site. This study demonstrated the advantages of using chlorophyll fluorometry in assessing toxic effect of pesticide mixtures.

An Azido-Biotin Reagent for Use in the Isolation of Protein Adducts of Lipid-derived Electrophiles by Streptavidin Catch and Photorelease

HNE (4-hydroxynonenal), a byproduct of lipid peroxidation, reacts with nucleophilic centers on proteins. A terminal alkynyl analog of HNE (alkynyl HNE, aHNE) serves as a surrogate for HNE itself, both compounds reacting with protein amine and thiol functional groups by similar chemistry. Proteins modified with aHNE undergo reaction with a click reagent that bears azido and biotin groups separated by a photocleavable linker. Peptides and proteins modified in this way are affinity purified on streptavidin beads. Photolysis of the beads with a low intensity UV light releases bound biotinylated proteins or peptides, i.e. proteins or peptides modified by aHNE. Two strategies, (a) protein catch and photorelease and (b) peptide catch and photorelease, are employed to enrich adducted proteins or peptide mixtures highly enriched in adducts. Proteomics analysis of the streptavidin-purified peptides by LC-MS/MS permits identification of the adduction site. Identification of 30 separate peptides from human serum albumin by peptide catch and photorelease reveals 18 different aHNE adduction sites on the protein. Protein catch and photorelease shows that both HSA and ApoA1 in human plasma undergo significant modification by aHNE.

Measurements of Hygroscopicity and Volatility of Atmospheric Ultrafine Particles during Ultrafine Particle Formation Events at Urban, Industrial, and Coastal Sites

The tandem differential mobility analyzer (TDMA) technique was applied to determine the hygroscopicity and volatility of atmospheric ultrafine particles in three sites of urban Gwangju, industrial Yeosu, and coastal Taean in South Korea. A database for the hygroscopicity and volatility of the known compositions and sizes of the laboratory-generated particles wasfirst constructed for comparison with the measured properties of atmospheric ultrafine particles. Distinct differences in hygroscopicity and volatility of atmospheric ultrafine particles werefound between a "photochemical event" and a "combustion event" as well as among different sites. At the Gwangju site, ultrafine particles in the "photochemical event" were determined to be more hygroscopic (growth factor (GF) = 1.05-1.33) than those in the "combustion event" (GF = 1.02-1.12), but their hygroscopicity was not as high as pure ammonium sulfate or sulfuric acid particles in the laboratory-generated database, suggesting they were internally mixed with less soluble species. Ultrafine particles in the "photochemical event" at the Yeosu site, having a variety of SO2, CO, and VOC emission sources, were more hygroscopic (GF = 1.34-1.60) and had a higher amount of volatile species (47-75%)than those observed at the Gwangju site. Ultrafine particle concentration at the Taean site increased during daylight hours with low tide, having a higher GF (1.34-1.80) than the Gwangju site and a lower amount of volatile species (17-34%) than the Yeosu site. Occasionally ultrafine particles were externally mixed according to their hygroscopicity and volatility, and TEM/EDS data showed that each type of particle had a distinct morphology and elemental composition.

Deciphering Intrinsic Deactivation/Isomerization Routes in a Phytochrome Chromophore Model

High level ab initio correlated (CASPT2) computations have been used to elucidate the details of the photoinduced molecular motion and decay mechanisms of a realistic phytochrome chromophore model in vacuo and to explore the reasons underneath its photophysical/photochemical properties. Competitive deactivation routes emerge that unveil the primary photochemical event and the intrinsic photoisomerization ability of this system. The emerged in vacuo based static (i.e., nondynamical) reactivity model accounts for the formation of different excited state intermediates and suggests a qualitative rationale for the short (picosecond) excited state lifetime and ultrafast decay of the emission, its small quantum yield, and the multiexponential decay observed in both solvent and phytochromes. It is thus tentatively suggested that this is a more general deactivation scheme for photoexcited phytochrome chromophores that is independent of the surrounding environment. Spectroscopic properties have also been simulated in both isolated conditions and the protein that satisfactorily match experimental data. For this purpose, preliminary hybrid QM/MM computations at the correlated (CASPT2) level have been used in the protein and are reported here for the first time.

Photosynthetic Antenna−Reaction Center Mimicry: Sequential Energy- and Electron Transfer in a Self-assembled Supramolecular Triad Composed of Boron Dipyrrin, Zinc Porphyrin and Fullerene

A self-assembled supramolecular triad, a model to mimic the photochemical events of photosynthetic antenna-reaction center, viz., sequential energy and electron transfer, has been newly constructed and studied. Boron dipyrrin, zinc porphyrin, and fullerene respectively constitute the energy donor, electron donor, and electron acceptor segments of the antenna-reaction center mimicry. For the construction, first, boron dipyrrin was covalently attached to a zinc porphyrin entity bearing a benzo-18-crown-6 host segment at the opposite end of the porphyrin ring. Next, an alkyl ammonium functionalized fullerene was used to self-assemble the crown ether entity via ion-dipole interactions. The newly formed supramolecular triad was fully characterized by spectroscopic, computational, and electrochemical methods. Selective excitation of the boron dipyrrin moiety in the dyad resulted in energy transfer over 97% efficiency creating singlet excited zinc porphyrin. The rate of energy transfer from the decay measurements of time-correlated singlet photon counting (TCSPC) and up-conversion techniques agreed well with that obtained by the pump-probe technique and revealed efficient photoinduced energy transfer in the dyad (time constant in the order of 10-60 ps depending upon the conformer). Upon forming the supramolecular triad by self-assembling fullerene, the excited zinc porphyrin resulted in electron transfer to the coordinated fullerene yielding a charge-separated state, thus mimicking the antenna-reaction center functionalities of photosynthesis. Nanosecond transient absorption studies yielded a lifetime of the charge-separated state to be 23 micros indicating charge stabilization in the supramolecular triad. The present supramolecular system represents a successful model to mimic the rather complex "combined antenna-reaction center" events of photosynthesis.

Structure of the intermediate species of the photoreaction cycle of rhodopsin

Bacteriorhodopsin, a chromoprotein having retinal as chromophore is linked to protein opsin through a protonated Schiff base, and undergoes a cyclic photoreaction on light absorption involving a number of intermediate species. The conformational preferences of the protonated and deprotonated Schiff bases of all-trans and 13-cis retinal withn-pentylamine as model for lysine have been investigated using molecular orbital PCILO (Perturbative Configuration Interaction of Localised Orbitals) method. The theoretical calculations reveal that there is an intrinsic differential flexibility between the protonated and deprotonated Schiff bases irrespective of the retinal isomers. The deprotonation of the Schiff base enhances the flexibility of the chromophore in the molecule. Based upon this information and that there are no major changes in the conformation of the protein opsin, two models for the photoreaction cycle involving intermediates of different structures have been proposed. Of these, experimental evidences seem to favour model 1 in which deprotonation and notrans-cis isomerisation accompanies the primary photochemical event. In other words, the intermediate species of the photoreaction cycle of bacteriorhodopsin have all-trans retinal as the chromophore with varying degree of non-covalent interaction with the protein opsin.

Electrostatic Control of the Photoisomerization Efficiency and Optical Properties in Visual Pigments: On the Role of Counterion Quenching

Hybrid QM(CASPT2//CASSCF/6-31G*)/MM(Amber) computations have been used to map the photoisomerization path of the retinal chromophore in Rhodopsin and explore the reasons behind the photoactivity efficiency and spectral control in the visual pigments. It is shown that while the electrostatic environment plays a central role in properly tuning the optical properties of the chromophore, it is also critical in biasing the ultrafast photochemical event: it controls the slope of the photoisomerization channel as well as the accessibility of the S(1)/S(0) crossing space triggering the ultrafast decay. The roles of the E113 counterion, the E181 residue, and the other amino acids of the protein pocket are explicitly analyzed: it appears that counterion quenching by the protein environment plays a key role in setting up the chromophore's optical properties and its photochemical efficiency. A unified scenario is presented that discloses the relationship between spectroscopic and mechanistic properties in rhodopsins and allows us to draw a solid mechanism for spectral tuning in color vision pigments: a tunable counterion shielding appears as the elective mechanism for L<-->M spectral modulation, while a retinal conformational control must dictate S absorption. Finally, it is suggested that this model may contribute to shed new light into mutations-related vision deficiencies that opens innovative perspectives for experimental biomolecular investigations in this field.

Metal Quinolinolate−Fullerene(s) Donor−Acceptor Complexes: Evidence for Organic LED Molecules Acting as Electron Donors in Photoinduced Electron-Transfer Reactions

Tris(quinolinolate)aluminum(III) (AlQ3) is the most widely used molecule in organic light-emitting devices. There exists a strong demand for understanding the photochemical and photophysical events originating from this class of molecules. This paper provides the first report on the electron donor ability of MQ(n) (M = Al or Zn for n = 3 or 2) complexes covalently connected to a well-known electron acceptor, fullerene. To accomplish this, fullerene was functionalized with 8-hydroxyquinoline at different ligand positions and their corresponding zinc(II) and aluminum(III) complexes were formed in situ. The weakly fluorescent metal quinolinolate-fullerene complexes formed a new class of donor-acceptor conjugates. The stoichiometry and structure of the newly formed metal quinolinolate-fullerene complexes were established from various spectroscopic methods including matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and computational density functional theory studies. Electrochemical studies involving free-energy calculations suggested the possibility of photoinduced electron transfer from excited metal-quinolinolate complex to the appended fullerene entity. Femtosecond transient absorption studies confirmed such a claim and analysis of the kinetic data allowed us to establish the different photophysical events in sufficient detail. The novel features of this class of donor-acceptor conjugates include faster charge recombination compared to charge separation and decay of the charge-separated state to populate the low-lying fullerene triplet state in competition with direct charge recombination to the ground state.