Yield Of Photoproducts Research Articles

Ultrafast photochemistry and electron diffraction for cyclobutanone in the S2 state: Surface hopping with time-dependent density functional theory.

We simulate the photodynamics of gas-phase cyclobutanone excited to the S2 state using fewest switches surface hopping (FSSH) dynamics powered by time-dependent density functional theory (TDDFT). We predict a total photoproduct yield of 8%, with a C3:C2 product ratio of 0 trajectories to 8 trajectories. One primary S2 → S1 conical intersection is identified involving the compression of an α-carbon-carbon-hydrogen bond angle. Excited state lifetimes computed with respect to electronic state populations were found to be 3.96ps (S2 → S1) and 498fs (S1 → S0). We also generate time-resolved difference pair distribution functions (ΔPDFs) from our TDDFT-FSSH dynamics results in order to generate direct comparisons with ultrafast electron diffraction experiment observables. Global and target analysis of time-resolved ΔPDFs produced a distinct set of lifetimes: (i) a 0.548ps decay and (ii) a 1.69ps decay, both resembling the S2 minimum, as well as (iii) a long decay that resembles the S1 minimum geometry and the fully separated C2 products. Finally, we contextualize our results by considering the impact of the most likely sources of significant errors.

Intrinsic tryptophan fluorescence quenching by iodine in non-canonical amino acid reveals alteration of the hydrogen bond network in the photoactive orange carotenoid protein

The Orange Carotenoid Protein (OCP) regulates cyanobacterial photosynthetic activity through photoactivation in intense light. A hydrogen bonding network involving the keto-carotenoid oxygen and Y201 and W288 residues prevents the spontaneous activation of dark-adapted OCP. To investigate the role of the hydrogen bonds in OCP photocycling, we introduced non-canonical amino acids near the keto-carotenoid, particularly iodine at the meta-position of Y201. This modification significantly increased the yield of red OCP photoproducts, albeit with a shorter lifetime. Changes in tryptophan fluorescence during photocycling influenced by the presence of iodine near W288 revealed interactions between Y201 and W288 in the absence of the carotenoid in the C-domain. We propose that upon the relaxation of red states, a ternary complex with the carotenoid is formed. Analysis of spectral signatures and interaction energies indicates that the specific iodo-tyrosine configuration enhances interactions between the carotenoid and W288.

Photodegradation of Triclosan on the Kaolinite Surface: Kinetic, Mechanistic, and Molecular Modeling Approach.

The photodegradation of triclosan (TCS) was investigated on the kaolinite surface. The quantum yield was evaluated, and the photoproducts were identified by HPLC/MS (LC/Q-TOF), showing that the phototransformation is completely different from that reported in aqueous solutions. In particular, the formation of dioxin derivatives was fostered and occurred with a higher efficiency when compared to aqueous solutions. This suggests that TCS has specific interactions with the clay that clearly modifies its photochemical behavior. Moreover, it has also been shown that higher concentrations of TCS, namely, higher than 1.0 μmol g-1 of kaolinite, lead to a significant decrease of the photodegradation rate constant and enhance the formation yield of dimer-type photoproducts. This suggests that the distribution of TCS is clearly not homogeneous at the clay surface and the formation of aggregates is more likely occurring. To get a better insight into this specific interaction, a molecular dynamic modeling of TCS adsorption at the surface of kaolinite was carried out. This clearly shows that when equilibrium is reached, TCS binds to the kaolinite surface by hydrogen bonds involving the phenol function of TCS and the hydroxyl groups of the kaolinite surface. Such behavior confers a particular conformation to the adsorbed TCS that is different from that obtained in water and which could be a key step to partially explain the specific photochemical reactivity in both media. In addition, several TCS molecules appear to interact with each other through the π-stacking (aromatic stacking) process while retaining this hydrogen bond with the kaolinite surface. This is clearly in favor of cluster formation on the clay surface and promotes dimer-type photoproducts.

Photocatalytic Transformations of the Resveratrol Derivative in Microflow Reactor

A simple and efficient protocol is utilized for the transformation studies of a thiophene analog of E-resveratrol by photocatalytic oxygenation using an anionic and a cationic free-base porphyrin, as well as their manganese(III) complexes. The starting substrate was chosen as a representative of heterostilbenes with proven good antioxidant activity. The experiments were carried out in two photoreactor types (batch and microflow reactor) to investigate the impact of the reactor type and design on conversion and photoproduct composition. NMR spectroscopy and UHPLC/MS analyses were applied for the identification and quantification of four photoproducts (Z-1, 2, 3, and 4), results of isomerization, dimerization, cyclization, and oxygenation. Different yields of photoproducts were obtained in a batch reactor and microflow reactor. In the experiments performed in a microflow reactor, Z-1 was most dominant because it was constantly removed from the reaction mixture. Therefore, the formation of other products (2, 3, 4, and undefined) whose precursor is Z-1 was avoided. This was not the case in the experiments performed in a batch reactor. Additionally, all the reactions tested were significantly accelerated in a microflow reactor, making it the preferred reactor type and design for the photocatalytic transformation of resveratrol derivative.

Vacuum-UV Photodesorption from Compact Amorphous Solid Water: Photon Energy Dependence, Isotopic and Temperature Effects

Photodesorption from water-rich interstellar ice mantles is known to play an important role on the gas-to-ice ratio in stars and planet formation regions. Quantitative determination of the photodesorption yields in the laboratory is crucial to astrochemical models. This study presents for the first time, the photon-energy dependence of the photodesorption yields from water ice samples in the vacuum-UV (VUV) range. Experiments have been performed with the Surface Processes and ICES (SPICES) setup coupled to the DESIRS beamline at the SOLEIL synchrotron facility (St. Aubin, France). Thick (20–100 ML) compact amorphous solid water ices (H2O and D2O) grown onto a cold Au substrate have been irradiated at sample temperatures ranging from 15 to 110 K. Photodesorption yields of water and photoproducts have been obtained by mass-spectrometry from 7 to 13.5 eV. In interstellar conditions, average H2O photodesorption yields are (5 ± 2) × 10–4 molecule/photon at low temperature (15 K) whereas, lower yields, by a factor of ∼6–9 on average, were found for D2O. This strong isotopic effect can be explained by a differential chemical recombination between OH (OD) and H (D) photofragments at the surface of the samples. In addition, an enhancement of the yields above (70 ± 10) K suggests a thermally induced ice restructuration at this threshold temperature.

Wavelength-dependent photochemistry of a salicylimine derivative studied with cryogenic and ultrafast spectroscopy approaches.

Salicylimines are versatile compounds in which an excited-state intramolecular proton transfer and torsional motions may set in upon photoexcitation. Here, we study N-(α-phenylethyl)salicylimine (PESA) to elucidate how the photochemical reaction pathways depend on the excitation wavelength and to what extent the relative photoproduct distribution can be steered towards a desired species. DFT structure and potential energy calculations disclose that the most stable ground-state conformer is an enol species and that the photodynamics may proceed differently depending on the excited state that is reached. With matrix isolation infrared spectroscopy, the predominance of the enol conformer of PESA is confirmed. Illumination of the cryogenic sample with different wavelengths shifts the ratio of enol and keto products, and by sequential irradiation a selective re- and depopulation is possible. Femtosecond transient absorption spectroscopy further reveals that also at room temperature, the outcome of the photoreaction depends on excitation wavelength, and in combination with the calculations, it can be rationalized that the decisive step occurs within the first hundred femtoseconds. Since the ultrafast dynamics mostly match those of similar salicylimines, our findings might also apply to those systems and provide additional insight into their reported sensitivity on excitation energy.

Photocatalyst assemblies with two halide ions

A series of ruthenium polypyridyl photocatalysts bearing amide functional groups were designed that successfully promoted halide assembly in CH2Cl2 and CH3CN solution. In CH2Cl2, halide assembly was accompanied by a visible color change, and the spectral changes presented clear evidence for two halide binding events, yielding a 1:2 ruthenium:halide assembly. In the more polar solvent CH3CN, 1:2 assembly structures were also observed with chloride, bromide, and iodide, and large equilibrium constants were measured for association of the first and second halide (K11 = 0.04 – 2 × 106 M−1, K12 = 0.01 – 3 × 105 M−1). Varying the functional groups on the ancillary ligands tuned the excited-state reduction potentials (Ru2+⁎/+), resulting in a photocatalyst capable of performing iodide oxidation. Quenching of the photocatalyst excited state resulted in static and dynamic quenching, and a Stern-Volmer analysis yielded two linear regions at low and high iodide concentrations. The dynamic quenching rate constants (kq = 6.8 and 4.0 × 1010 M−1 s−1) and static quenching constants (KS = 2.4 and 0.13 × 104 M−1) at low and high iodide concentrations, respectively, were consistent with dynamic quenching of Ru2+ and [Ru2+,I−]+, and static quenching of [Ru2+,I−]+and [Ru2+,2I−]. Transient absorption spectroscopy revealed that the quenching reaction yielded a reduced ruthenium (Ru+) as the primary photoproduct and diiodide (I2•−) as a secondary photoproduct. The second-order rate constant for I2•− formation was measured to be 2.5 × 1010 M−1 s−1, a value consistent with the diffusion limited reaction. The transient absorption data indicates that oxidized halide photoproducts only result from the diffusional quenching reactions, and not from static quenching with an associated iodide ion. Fast back-electron transfer rates and low cage-escape yields in the ruthenium:iodide assemblies are invoked to explain why the static quenching pathway does not lead to measurable photoproduct yields.

Role of hydrogen bond alternation and charge transfer states in photoactivation of the Orange Carotenoid Protein

Here, we propose a possible photoactivation mechanism of a 35-kDa blue light-triggered photoreceptor, the Orange Carotenoid Protein (OCP), suggesting that the reaction involves the transient formation of a protonated ketocarotenoid (oxocarbenium cation) state. Taking advantage of engineering an OCP variant carrying the Y201W mutation, which shows superior spectroscopic and structural properties, it is shown that the presence of Trp201 augments the impact of one critical H-bond between the ketocarotenoid and the protein. This confers an unprecedented homogeneity of the dark-adapted OCP state and substantially increases the yield of the excited photoproduct S*, which is important for the productive photocycle to proceed. A 1.37 Å crystal structure of OCP Y201W combined with femtosecond time-resolved absorption spectroscopy, kinetic analysis, and deconvolution of the spectral intermediates, as well as extensive quantum chemical calculations incorporating the effect of the local electric field, highlighted the role of charge-transfer states during OCP photoconversion.

Next-generation derivatization reagents optimized for enhanced product ion formation in photodissociation-mass spectrometry of fatty acids.

Ultraviolet-photodissociation (UVPD) mass spectrometry is an emerging analytical tool for structural elucidation of biomolecules including lipids. Gas phase UVPD of ionised fatty acids (FAs) can promote fragmentation that is diagnostic for molecular structure including the regiochemistry of carbon-carbon double bonds and methyl branching position(s). Typically, however, lipids exhibit poor conversion to photoproducts under UVPD and thus require longer integration times to achieve the signal-to-noise required for structural assignments. Consequently, the integration of UVPD into liquid-chromatography mass spectrometry (LC-MS) workflows for FAs has been limited. To enhance photofragmentation efficiency, an alternative strategy has been devised using wet-chemical derivatization of FAs to explicitly incorporate photolabile groups. FA derivatives that include an aryl-iodide motif have photodissociation conversions of up to 28% when activated by a single 266 nm photon. The radical-directed dissociation product ions resulting from UVPD of these derivatives provide key details of molecular structure and discriminate between lipid isomers. Herein, we describe the structure-activity guided development of new FA derivatives capable of photoproduct yields of up to 97%. UVPD-action spectroscopy demonstrates that photodissociation for FAs derivatized with N-(2-aminoethyl)-4-iodobenzamide (NIBA) is maximised near 266 nm and highlights the key role of the 4-iodobenzamide motif in the efficient formation of [M - I]˙+ radical cations (and diagnostic secondary product ions). The high photodissociation yield of NIBA-derivatized lipids is maintained across 37 commonly observed FAs with the resulting UVPD mass spectra shown to be effective in the discrimination of isomeric FAs that differ in the position(s) of carbon-carbon double bonds. Integration of this strategy with reversed-phase LC-MS workflows is confirmed with high-quality UVPD mass spectra acquired across each chromatographic peak.

Tracing the Full Bimolecular Photocycle of Iron(III)-Carbene Light Harvesters in Electron-Donating Solvents.

Photoinduced bimolecular charge transfer processes involving the iron(III) N-heterocyclic carbene (FeNHC) photosensitizer [Fe(phtmeimb)2]+ (phtmeimb = phenyltris(3-methyl-imidazolin-2-ylidene)borate) and triethylamine as well as N,N-dimethylaniline donors have been studied using optical spectroscopy. The full photocycle of charge separation and recombination down to ultrashort time scales was studied by investigating the excited-state dynamics up to high quencher concentrations. The unconventional doublet ligand-to-metal charge transfer (2LMCT) photoactive excited state exhibits donor-dependent charge separation rates of up to 1.25 ps–1 that exceed the rates found for typical ruthenium-based systems and are instead more similar to results reported for organic sensitizers. The ultrafast charge transfer probed at high electron donor concentrations outpaces the solvent dynamics and goes beyond the classical Marcus electron transfer regime. Poor photoproduct yields are explained by donor-independent, fast charge recombination with rates of ∼0.2 ps–1, thus inhibiting cage escape and photoproduct formation. This study thus shows that the ultimate bottlenecks for bimolecular photoredox processes involving these FeNHC photosensitizers can only be determined from the ultrafast dynamics of the full photocycle, which is of particular importance when the bimolecular charge transfer processes are not limited by the intrinsic excited-state lifetime of the photosensitizer.

Triplet photosensitizer-nanotube conjugates: synthesis, characterization and photochemistry of charge stabilizing, palladium porphyrin/carbon nanotube conjugates.

The ability of a triplet photosensitizer to generate long-lived charge separated states, in contrast to traditionally used singlet photosensitizers, in covalently functionalized single-walled carbon nanotube hybrids has been investigated. Enriched single-walled carbon nanotubes with two diameters, namely (6,5) and (7,6), were covalently modified to carry a charge-stabilizing triplet photosensitizer derived from a palladium porphyrin. The nanohybrids were fully characterized and the presence of intramolecular interactions between the porphyrin and nanotubes was established from various spectroscopic, imaging, electrochemical and thermochemical studies. Photoluminescence of palladium porphyrin was found to be quantitatively quenched in the presence of covalently appended SWCNTs and this quenching is due to excited state charge separation and has been established by femtosecond transient absorption studies. Owing to the presence of the triplet photosensitizer, the charge separated states lasted over 3 ns, i.e., much longer than those reported earlier for singlet photosensitizer-derived nanotube hybrids. The nanohybrids also exhibited efficient photocatalytic behavior in experiments involving electron pooling of one-electron reduced methyl viologen in the presence of a sacrificial electron donor. Higher yields of photoproducts were achieved from the present donor-acceptor nanohybrids when compared with those of singlet photosensitizer-derived nanohybrids, more so for (6,5) nanotube derived hybrids compared to (7,6) nanotube derived hybrids. The present findings highlight the importance of triplet photosensitizer derived nanohybrids in artificial photosynthesis of charge separation and photocatalytic applicatons.

Engineering opposite electronic polarization of singlet and triplet states increases the yield of high-energy photoproducts

Efficient photosynthetic energy conversion requires quantitative, light-driven formation of high-energy, charge-separated states. However, energies of high-lying excited states are rarely extracted, in part because the congested density of states in the excited-state manifold leads to rapid deactivation. Conventional photosystem designs promote electron transfer (ET) by polarizing excited donor electron density toward the acceptor ("one-way" ET), a form of positive design. Curiously, negative design strategies that explicitly avoid unwanted side reactions have been underexplored. We report here that electronic polarization of a molecular chromophore can be used as both a positive and negative design element in a light-driven reaction. Intriguingly, prudent engineering of polarized excited states can steer a "U-turn" ET-where the excited electron density of the donor is initially pushed away from the acceptor-to outcompete a conventional one-way ET scheme. We directly compare one-way vs. U-turn ET strategies via a linked donor-acceptor (DA) assembly in which selective optical excitation produces donor excited states polarized either toward or away from the acceptor. Ultrafast spectroscopy of DA pinpoints the importance of realizing donor singlet and triplet excited states that have opposite electronic polarizations to shut down intersystem crossing. These results demonstrate that oppositely polarized electronically excited states can be employed to steer photoexcited states toward useful, high-energy products by routing these excited states away from states that are photosynthetic dead ends.

Photolytic Properties of Antivitamins B12.

Antivitamins B12 represent an important class of vitamin B12 analogues that have gained recent interest in several research areas. In particular, 4-ethylphenylcobalamin (EtPhCbl) and phenylethynylcobalamin (PhEtyCbl) exemplify two such antivitamins B12 which have been characterized structurally and chemically. From a spectroscopic point of view, EtPhCbl is photolabile with a very low quantum yield of photoproducts, while PhEtyCbl is incredibly photostable. Herein, DFT and TD-DFT computations are provided to explore the photolytic properties of these compounds to shed light on the electronic properties that are indicative of these differences. Potential energy surfaces (PESs) were constructed to investigate the mechanisms of photodissociation leading to radical pair (RP) formation and the mechanisms of deactivation to the ground state. The S1 PESs for each antimetabolite contain two energy minima, one being the metal-to-ligand charge transfer (MLCT) and another the ligand-field (LF) state. There are two possible pathways for photodissociation that can be identified for EtPhCbl but only one (path B) is energetically feasible and involves the lengthening of the Co-NIm bond through the MLCT region followed by the lengthening of the Co-C bond through the LF region. For PhEtyCbl, there is not an energetically favorable path for photolysis; rather, internal conversion (IC) is the significantly preferred photophysical event.

Effects of wavelength, fluence, and dose on fragmentation pathways and photoproduct ion yield in 213 nm and 266 nm ultraviolet photodissociation experiments.

Ultraviolet photodissociation tandem mass spectrometry is a powerful tool to investigate the structure of biomolecules, due to its ability to generate rich fragmentation patterns or bond selective cleavage, as a function of used laser wavelength, laser fluence, dose (number of accumulated laser pulses), and available chromophores. Herein, we report first results obtained with a newly developed two-wavelength (266 nm and 213 nm) ultraviolet photodissociation setup coupled to a Fourier-transform ion cyclotron resonance mass spectrometer. Photoproduct yields for protonated 3-iodo-l-tyrosine were up to ∼75%. Dose and fluence dependent measurements for protonated 3-iodo-l-tyrosine, doubly charged protonated bradykinin and Fe(II) attached to 1,2-dioleoyl-sn-glycero-3-phosphocholine reveal that the ultraviolet photodissociation mechanism for photoproduct formation qualitatively differs between these model systems. Three derived photodissociation models were used to interpret the experimental results and show that while protonated 3-iodo-l-tyrosine and Fe(II) attached to 1,2-dioleoyl-sn-glycero-3-phosphocholine most likely dissociates via a single-photon process, fragmentation of doubly charged bradykinin ions was found to be most consistent with sequential two-photon dissociation (213 nm). The introduced dissociation models present an easy means to study the mechanism of ultraviolet photodissociation processes for a variety of analytes without prior knowledge of their photochemistry or to optimize experimental conditions by adjusting laser fluence or number of laser pulses.

Photooxidation of cyclohexanone in simulated atmosphere: A potential source of atmospheric formic acid

Gas phase photooxidation of cyclohexanone (CH) has been studied in the laboratory in a simulated atmospheric environment (synthetic air, 1 bar pressure) under the exposure of 311 nm UV light. Formic acid along with formaldehyde and ethylene are identified as the major photooxidation products. Quantum yield for the production of these species is measured and the values are compared with previous studies on the photo dissociation of CH. For 6 h of light irradiation with initial CH concentration of 9.19 ± 0.1 × 1016 molecules cm−3, the measured quantum yield values of ethylene and formaldehyde, the two primary photooxidation products, are 0.0395 ± 0.001 and 0.0028 ± 0.002, respectively. These values are comparable with CH dissociation quantum yield, 0.24 ± 0.02, and also the quantum yield of CO production, 0.0940 ± 0.001. The energetic parameters of different steps of the proposed reaction mechanism are calculated by electronic structure theory method at DFT/B3LYP/6–311++G** level. A reaction modeling has been performed, and similarity in simulated quantum yield values with that of the experimentally measured ones validates the suggested reaction mechanism. Experimentally measured values of rate constants of most of the elementary reaction steps incorporated in the modeling are not known, and the calculated values, obtained by use of CVT and RRKM theoretical methods are used. The total yield of formic acid, which has been assigned as a secondary oxidation product, is 3.46 ± 0.25 × 1015 molecules cm−3 as obtained from experiment and this data matches well with the value of 2.67 × 1015 molecules cm−3 obtained from reaction modeling for 6 h of UV irradiation. The yield of formic acid is comparable with the yield of primary photo products. The results imply that photooxidation of CH and analogous compounds might have significant contributions to production of formic acid in the earth's troposphere. According to the prediction of the modeling results presented here, the contribution of cyclohexanone photooxidation to the atmospheric concentration of formic acid is ∼1 pptv.

Probing the Biexponential Dynamics of Ring-Opening in 7-Dehydrocholesterol.

Our prior discovery of a novel biexponential photochemical ring-opening in 7-dehydrocholesterol (DHC) to previtamin D3 [ Tang J. Chem. Phys. 2011 , 134 , 104503 ] is further explored with ultrafast transient absorption spectroscopy, and the results are compared with recently reported high-level theoretical calculations. Three types of experiments are reported. First, variation of the excitation wavelength from 297 to 266 nm leaves the excited state dynamics unaffected. The biexponential decay of the excited state absorption is independent of excitation wavelength with time constants of 0.57 ± 0.06 and 1.88 ± 0.09 ps, in excellent agreement with the results reported earlier (0.56 ± 0.06 and 1.81 ± 0.15 ps) following excitation at 266 nm. Second, variation of the chirp of the excitation pulse influences the relative amplitude of the fast and slow decay components but has no influence on the photoproduct yield. Third, a 545 nm pulse delayed by 0.64 ps with respect to the initial 266 nm pulse was used to perturb the "slow" population and probe the influence of additional electronic or vibrational energy on the reaction process. The results show ultrafast internal conversion Sn → S1 on a ca. 150 fs time scale but no subsequent effect on the reaction dynamics. The experiments reported here are consistent with the recent state averaged complete active space self-consistent field ab initio multiple spawning (SA-CASSCF-AIMS) calculations of Snyder et al. [ J. Phys. Chem. Lett. 2016 , 7 , 2444 ] that assign the biexponential decay to nonequilibrium dynamics related to the opening and closing motion of the cyclohexadiene ring moiety on the excited state surface. These new experiments support the model prediction that the biexponential dynamics does not involve multiple minima and demonstrate the direction for new experimental designs to manipulate the product yields and pathways.

On the wavelength dependence of UV induced thymine photolesions: a synchrotron radiation circular dichroism study.

Solar mutagenesis via the formation of thymine dimer photoproducts is a primary cause of skin cancer. The aim of this study is to provide a direct method for following the development of photolesions in thymine single strands and to determine how the formation of these photoproducts depends on the excitation wavelength in the ultraviolet (UV) between 210 nm and 325 nm. Experiments were performed both with a 20 Hz pulsed, intense, tunable laser as well as UV lamps (at 254 nm and 302 nm), but we find that only the dose matters at these wavelengths for the yield of photoproducts. Hence in both cases the lesion process is due to one-photon absorption. The formation and yields of the photoproducts as the irradiation dose is increased is followed through measurement of synchrotron radiation circular dichroism (SRCD) spectra. A principal component analysis (PCA) of the SRCD data yields CD signatures for each of the resulting photoproducts and reveals a strong irradiation wavelength dependence upon which products are formed; cyclobutane pyrimidine dimers (CPDs) are formed primarily at higher irradiation wavelengths (from 250 to 300 nm); the 6,4 pyrimidine-pyrimidone photoadduct (64PP) is formed in the range 210 to 285 nm, with a higher rate of formation in the lower part of that range, while in the very lowest irradiation wavelength range (210 to 240 nm) we find thymidine monophosphate (dTMP), which indicates cleavage of the DNA backbone. Our work demonstrates the strength of SRCD spectroscopy compared to ordinary absorption spectroscopy, as the latter is not sufficient to obtain fingerprints of the thymine photoproducts.

A new hair follicle-derived human epidermal model for the evaluation of sunscreen genoprotection

Induction of skin cancer is the most deleterious effect of excessive exposure to sunlight. Accurate evaluation of sunscreens to protect the genome is thus of major importance. In particular, the ability of suncare products to prevent the formation of DNA damage should be evaluated more directly since the Sun Protection Factor is only related to erythema induction. For this purpose, we developed an in vitro approach using a recently characterized reconstituted human epidermis (RHE) model engineered from hair follicle. The relevance of this skin substitute in terms of UV-induced genotoxicity was compared to ex vivo explants exposed to solar-simulated radiation (SSR). The yield of bipyrimidine photoproducts, their rate of repair, and the induction of apoptosis were very similar in both types of skin samples. In order to evaluate the protection afforded by sunscreen against DNA damage, bipyrimidine photoproducts were quantified in tissue models following SSR exposure in the presence or absence of a SPF50+ formula. A rather high DNA protection factor of approximately 20 was found in RHE, very similar to that determined for explants. Thus, RHE is a good surrogate to human skin, and also a convenient and useful tool for investigation of the genoprotection of sunscreens.

Probing and Exploiting the Interplay between Nuclear and Electronic Motion in Charge Transfer Processes.

The Born-Oppenheimer approximation refers to the assumption that the nuclear and electronic wave functions describing a molecular system evolve and can be determined independently. It is now well-known that this approximation often breaks down and that nuclear-electronic (vibronic) coupling contributes greatly to the ultrafast photophysics and photochemistry observed in many systems ranging from simple molecules to biological organisms. In order to probe vibronic coupling in a time-dependent manner, one must use spectroscopic tools capable of correlating the motions of electrons and nuclei on an ultrafast time scale. Recent developments in nonlinear multidimensional electronic and vibrational spectroscopies allow monitoring both electronic and structural factors with unprecedented time and spatial resolution. In this Account, we present recent studies from our group that make use of different variants of frequency-domain transient two-dimensional infrared (T-2DIR) spectroscopy, a pulse sequence combining electronic and vibrational excitations in the form of a UV-visible pump, a narrowband (12 cm(-1)) IR pump, and a broadband (400 cm(-1)) IR probe. In the first example, T-2DIR is used to directly compare vibrational dynamics in the ground and relaxed electronic excited states of Re(Cl)(CO)3(4,4'-diethylester-2,2'-bipyridine) and Ru(4,4'-diethylester-2,2'-bipyridine)2(NCS)2, prototypical charge transfer complexes used in photocatalytic CO2 reduction and electron injection in dye-sensitized solar cells. The experiments show that intramolecular vibrational redistribution (IVR) and vibrational energy transfer (VET) are up to an order of magnitude faster in the triplet charge transfer excited state than in the ground state. These results show the influence of electronic arrangement on vibrational coupling patterns, with direct implications for vibronic coupling mechanisms in charge transfer excited states. In the second example, we show unambiguously that electronic and vibrational movement are coupled in a donor-bridge-acceptor complex based on a Pt(II) trans-acetylide design motif. Time-resolved IR (TRIR) spectroscopy reveals that the rate of electron transfer (ET) is highly dependent on the amount of excess energy localized on the bridge following electronic excitation. Using an adaptation of T-2DIR, we are able to selectively perturb bridge-localized vibrational modes during charge separation, resulting in the donor-acceptor charge separation pathway being completely switched off, with all excess energy redirected toward the formation of a long-lived intraligand triplet state. A series of control experiments reveal that this effect is mode specific: it is only when the high-frequency bridging C≡C stretching mode is pumped that radical changes in photoproduct yields are observed. These experiments therefore suggest that one may perturb electronic movement by stimulating structural motion along the reaction coordinate using IR light. These studies add to a growing body of evidence suggesting that controlling the pathways and efficiency of charge transfer may be achieved through synthetic and perturbative approaches aiming to modulate vibronic coupling. Achieving such control would represent a breakthrough for charge transfer-based applications such as solar energy conversion and molecular electronics.

Theoretical study of the photo-isomerisation reactions of 1,2-dihydro-1,2-phosphaborine and 1,2-dihydro-1,2-alumazaine

The mechanisms of the photochemical isomerisation reactions are investigated theoretically using the model systems, 1,2-dihydro-1,2-phosphaborine (5) and 1,2-dihydro-1,2-alumazaine (6), using the CAS(6,6)/6-311G(d,p) and MP2-CAS-(6,6)/6-311++G(3df,3pd)//CAS(6,6)/6-311G(d,p) methods. For each model reactant, three reaction pathways, which lead to three kinds of photo-isomers, are examined. The structures of the conical intersections, which play a key role in such photo-rearrangements, are determined. The thermal (or dark) reactions of the reactant species are also examined, using the same level of theory, to provide a qualitative explanation of the reaction pathways. These model investigations demonstrate that the preferred reaction route for these two aromatic heterocyclics is as follows: reactant → Franck–Condon region → conical intersection → photoproduct. The theoretical evidences anticipate that after irradiation of 5, the photoproduct yield of the Dewar BP-isomer, 8, should be larger than that of the Dewar BP-isomer, 7, whereas no Dewar BP-isomer 9 can be observed. Moreover, the present theoretical data predict after irradiation of 6, all three Dewar AlN-isomers (10, 11, and 12) and the starting molecule, 6, are produced.