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2'-Deoxy-5-formylcytidine (5fdCyd), a naturally occurring nucleoside found in mammalian DNA and mitochondrial RNA, exhibits important epigenetic functionality in biological processes. Because it efficiently generates triplet excited states, it is an endogenous photosensitizer capable of damaging DNA, but the intersystem crossing (ISC) mechanism responsible for ultrafast triplet state generation is poorly understood. In this study, time-resolved mid-IR spectroscopy and quantum mechanical calculations reveal the distinct ultrafast ISC mechanisms of 5fdCyd in water versus acetonitrile. Our experiment indicates that in water, ISC to triplet states occurs within 1 ps after 285 nm excitation. PCM-TD-DFT computations suggest that this ultrafast ISC is mediated by a singlet state with significant cytosine-to-formyl charge-transfer (CT) character. In contrast, ISC in acetonitrile proceeds via a dark 1 nπ* state with a lifetime of ∼3 ps. CT-induced ISC is not favored in acetonitrile because reaching the minimum of the gateway CT state is hampered by intramolecular hydrogen bonding, which enforces planarity between the aldehyde group and the aromatic group. Our study provides a comprehensive picture of the non-radiative decay of 5fdCyd in solution and new insights into the factors governing ISC in biomolecules. We propose that the intramolecular CT state observed here is a key to the excited-state dynamics of epigenetic nucleosides with modified exocyclic functional groups, paving the way to study their effects in DNA strands.

DNA-templated silver clusters are chromophores in which the nucleobases encode the cluster spectra and brightness. We describe the coordination environments of two nearly identical Ag106+ clusters that form with 18-nucleotide strands CCCCA CCCCT CCCX TTTT, with X = guanosine and inosine. For the first time, femtosecond time-resolved infrared (TRIR) spectroscopy with visible excitation and mid-infrared probing is used to correlate the response of nucleobase vibrational modes to electronic excitation of the metal cluster. A rich pattern of transient TRIR peaks in the 1400-1720 cm-1 range decays synchronously with the visible emission. Specific infrared signatures associated with the single guanosine/inosine along with a subset of cytidines, but not the thymidines, are observed. These fingerprints suggest that the network of bonds between a silver cluster adduct and its polydentate DNA ligands can be deciphered to rationally tune the coordination and thus spectra of molecular silver chromophores.

To balance the requirements of transparency, mechanical strength, stable conductivity and biocompatibility of traditional electronic conductive hydrogels in intelligent devices is still a formidabl...

Liquid phase charge-transfer-to-solvent (CTTS) transitions are important, as they serve as photochemical routes to solvated electrons. In this work, broadband deep-ultraviolet electronic sum frequency generation (DUV-ESFG) and two-photon absorption (2PA) spectroscopic techniques were used to assign and compare the nature of the aqueous iodide CTTS excitations at the air/water interface and in bulk solution. In the one-photon absorption (1PA) spectrum, excitation to the 6s Rydberg-like orbital (5p → 6s) gives rise to a pair of spin-orbit split iodine states, 2P3/2 and 2P1/2. In the 2PA spectra, the lower-energy 2P3/2 peak is absent and the observed 2PA peak, which is ∼0.14 eV blue-shifted relative to the upper 2P1/2 CTTS peak seen in 1PA, arises from 5p → 6p electronic promotion. The band observed in the ESFG spectrum is attributed to mixing of excited states involving 5p → 6p and 5p → 6s promotions caused by both vibronic coupling and the external electric field generated by asymmetric interfacial solvation.

Supramolecular assemblies form when silver nitrate is added to an aqueous solution of adenine (Ade) or 2-aminopurine (2AP) in a 2:1 mole ratio. Atomic force microscopy images reveal nanofibers that are ∼30 nm in diameter and micrometers in length in the dried film formed from a room-temperature solution. Femtosecond broadband transient absorption spectroscopy was used to investigate the dynamics of excited states formed by UV excitation of the nanofibers in room-temperature aqueous solutions in an effort to learn how nonradiative decay pathways of the uncomplexed nucleobases are altered in the silver-ion-mediated assemblies. The changes in the spectroscopy and dynamics of Ade and 2AP upon forming nanofibers with silver ions closely parallel the ones seen when these bases are organized into DNA strands. The similarities strongly suggest that these structures feature extensive π-π stacking interactions between nucleobases. The results show that time-resolved spectroscopy combined with growing understanding of the photophysics of DNA strands can deliver new insights into the properties of metal-nucleobase nanoassemblies.

The catechol functional group plays a major role in the chemistry of a wide variety of molecules important in biology and technology. In eumelanin, intermolecular hydrogen bonding between these functional groups is thought to contribute to UV photoprotective and radical buffering properties, but the mechanisms are poorly understood. Here, aggregates of 4-t-butylcatechol are used as model systems to study how intermolecular hydrogen bonding influences photochemical pathways that may occur in eumelanin. Ultrafast UV-visible and mid-IR transient absorption measurements are used to identify the photochemical processes of 4-t-butylcatechol monomers and their hydrogen-bonded aggregates in cyclohexane solution. Monomer photoexcitation results in hydrogen atom ejection to the solvent via homolytic O-H bond dissociation with a time constant of 12 ps, producing a neutral semiquinone radical with a lifetime greater than 1 ns. In contrast, intermolecular hydrogen bonding interactions within aggregates retard O-H bond photodissociation by over an order of magnitude in time. Excited state structural relaxation is proposed to slow O-H dissociation, allowing internal conversion to the ground state to occur in hundreds of picoseconds in competition with this channel. The semiquinone radicals formed in the aggregates exhibit spectral broadening of both their electronic and vibrational transitions. LB acknowledges financial support from the Spanish Ministerio de Economía y Competitividad (CTQ2015-69363-P) and computational time from Consorci de Serveis Universitarisde Catalunya

The electrochemical conversion of the greenhouse gas, carbon dioxide (CO2), to energy fuels and value-added chemicals presents one of the most valuable approaches to harvest pollutants and produce renewable energy. However, the stable molecular structure of CO2 and the sluggish reaction kinetics make CO2 reduction reaction (CO2RR) formidably challenging to achieve reaction rate and selectivity practical in industry. Graphene and its derivatives have been considered a group of intriguing materials to develop advanced CO2RR electrocatalysts due to their large specific surface area, remarkable electron transfer ability, superior stability, and easy tunability of the structure and surface properties. Herein, we comprehensively discuss the state-of-the-art electrocatalysts constructed with graphene and derivatives for active and selective CO2RR within the recent five years, mainly including the electrocatalysts with both metal-based (e.g., noble, non-noble, or combined thereof) and non-metal (e.g., doped, modified, defected, or composited) catalytic sites. To present the versatile, high-performance metal-based CO2RR electrocatalysts constructed with graphene, we further subdivide them according to the sizes, oxidation states, metal species synergies, dimensionalities, and versatility. Finally, we provide the challenges and perspectives in this emerging area of utilising CO2 to produce various carbon-based fuels and chemicals via graphene chemistry.

Three novel polydiacetylenes (PDAs) are synthesized through the self-assembly followed by the topochemical polymerization via controllable electrophoretic deposition. All the samples could undergo a multi-step thermochromic process, turning purple and red successively over a wide range from room temperature to above 250 °C. Resulting PDAs are studied by UV–vis, IR, Raman spectroscopies, and chromoisomerism by naked eye visualization; their stabilities by thermogravimetric method, and emission behavior by fluorescence spectroscopy. To study the mechanism of the thermochromic response, temperature-dependent UV–vis spectra, the results of which successfully highlighted the close relationship between chromatic transitions and the conformational changes.

With the energy crisis and resource depletion nowadays, novel, highly performing, and cost-effective semiconductors are in urgent demand for efficiently harvesting solar energy for photoelectrochemical applications. Herein, this study presents low-cost anatase TiO2 hollow nanoparticles as prepared by a critical liquid-phase deposition (LPD) processing combined with a hydrothermal reaction and calcination processing, without involving any templates. The additional LPD processing not only makes the resulting samples more visible light responsive, but also results in hollowing the TiO2 nanoparticles (nanosheets vs. hollow nanoparticles). Importantly, commercial TiO2 powder is employed as the starting material to achieve the final synthesis of TiO2 hollow nanoparticles, making it scalable and cost-effective for production and applications. As a by-product, the fluoride, formed during the preparation process, is assumed to play a significant role in hollowing through chemically induced self-transformation and Ostwald ripening, in addition to enhancing the crystallinity. The beneficial structural evolution to the hollow nanoparticles enables the improvement of the photoelectrochemical performance through impressive inhibition of the recombination of the photoelectrons and holes, which is well evidenced by I ph and EIS (Nyquist plot), as well as by I–V curve and electron lifetime evaluations as for the assembled DSSCs with the prepared TiO2 hollow nanoparticles under simulated sunlight illumination (50 mW/cm2).

Heteroatom-doped lamellar-structured carbon with a high surface area synthesized from alfalfa leaves is utilized as a cathode catalyst in this study to improve the power output of microbial fuel cells (MFCs). Different chemical activation agents are used to treat alfalfa leaf-derived carbon (ALC). It is found that chemical activation agents substantially affect the catalytic activities of the alfalfa leaf-derived carbon materials in the power output of MFCs and the oxygen reduction reaction (ORR). ALC materials activated by KOH (ALC-K) exhibit the best electrochemical activity compared with those of materials activated by FeCl3 (ALC-Fe) or ZnCl2 (ALC-Zn). A high limiting current density and excellent long-term stability can be seen with ALC-K as the cathode catalyst, which gives superior results to those of Pt/C. Moreover, a maximum power density of approximately 1328.9 mW/m2 is obtained from an MFC equipped with an ALC-K cathode, offering performance characteristics comparable to those of a Pt/C cathode ...

Uniform doping is usually recognized as an efficient method for enhancing photocatalysis of TiO 2 , while non-uniform doping is generally supposed to be inefficient because of the inhomogeneous dispersion of dopants. However, in this study, we present the first example of non-uniform doping (with Au)-better enhanced photocatalysis of TiO 2 nanotubes, as compared to uniform doping, in terms of the photocatalytic organic dye degradation. The extent to which the non-uniform doping (achieved by liquid phase deposition (LPD)) can enhance photocatalysis is evaluated, along with a comparison with uniform doping. There exists an additional positive effect in the non-uniform doping system, that is, as generated interfaces between pure phase TiO 2 and Au-doped TiO 2 , in contrast to the uniform doping system leading to a positive “platinum island” effect. Such double beneficial effects contribute to the highest performance in the photocatalytic organic dye degradation for the Au-non-uniformly doped TiO 2 nanotubes as compared to other samples involved in this study. Both the “platinum island” and interfacial separation effects are helpful to isolate the photo-generated electrons and holes, resulting in enhanced photocatalytic activities.

A new strategy to fabricate CoNx single cluster supported nanocarbon catalysts (C/P/2Co600) with enhanced atomic utilization towards the oxygen reduction reaction (ORR) is reported. N-Coordination protection and low-temperature pyrolysis are the two key factors for the formation of CoNx single clusters on nanocarbon supports. Morphological and structural identification confirmed the simultaneous anchoring of homo-dispersed CoNx single clusters and N-doping on the nanocarbon under relatively mild thermal treatment conditions. Expectedly, the obtained single cluster catalyst with a trace amount of metal atoms exhibited excellent ORR performance including a positive half-wave potential (0.846 V), a high mass activity (0.98 A mgCo−1, ampere per milligram of cobalt) and outstanding chemical durability after 8000 potential cycles. We believe that our findings provide a new route for the rational design of low-cost and highly active ORR catalytic materials.

Two-photon absorption (2PA) spectra of liquid methanol and ethanol are reported for the energy range 7-10 eV from the first electronic excitation to close to the liquid-phase ionization potential. The spectra give detailed information on the electronic structures of these alcohols in the bulk liquid. The focus of this Article is to examine the electronic structure change compared with water on substitution of a hydrogen by an alkyl group. Continuous 2PA spectra are recorded in the broadband pump-probe fashion, with a fixed pump pulse in the UV region and a white-light continuum as a probe. Pump pulses of two different energies, 4.6 and 6.2 eV, are used to cover the spectral range up to 10 eV. In addition, theoretical 2PA cross sections for both molecules isolated in the gas phase are computed by the equation-of-motion coupled-cluster method with single and double substitutions (EOM-CCSD). These computational results are used to assign both the experimental 2PA and literature one-photon linear absorption spectra. The most intense spectral features are due to transitions to the Rydberg states, and the 2PA spectra are dominated by the totally symmetric 3pz ← 2pz transition in both alcohols. The experimental 2PA spectra are compared with the simulated 2PA spectra based on ab initio calculations that reveal a general blue shift of the excited transitions upon solvation. The effective 2PA thresholds in methanol and ethanol decrease to 6.9 eV compared with 7.8 eV for water. The analysis of the 2PA polarization ratio leads us to conclude that the excited states of ethanol deviate more markedly from water in the lower energy region compared with methanol. The polarization dependence of the 2PA spectra reveal the symmetries of the excited states within the measured energy range. Natural transition orbital calculations are performed to visualize the nature of the transitions and the orbitals participating during electronic excitation.

Changing the solvent from H2O to D2O dramatically affects the branching of the initial excited electronic states in an alternating G·C DNA duplex into two distinct decay channels. The slower, multisite PCET channel that deactivates more than half of all excited states in D2O becomes six times weaker in H2O.

With three distinct layers, multicolor, hierarchical nanocomposite films based on anodized aluminum oxide (AAO) were fabricated on the 6063 aluminum alloy surface by anodizing and alternating current electrodeposition. The impact of the electrolysis time on the nanostructures and optical properties of the as-grown film was investigated. It was found that with the extension of electrolysis time, the sample color could be varied from gray, yellow, red, blue, to green, realizing almost full-spectrum colors of the AAO-based films in the visible light range. The nanostructure characterizations and the UV–Vis reflectance spectroscopy of the AAO-based films showed that the thickness of the bottom one (i.e., layer 3) of the three layers was dictated by the electrolysis time over the range of 55–145 s, corresponding to the thickness from 135 to 264 nm. Additionally, the optical pathway of the AAO-based film with hierarchical composite nanostructures was analyzed. An increase in the layer 3 thickness would cause a shift in the peak wavelength in the corresponding reflectance spectra, conforming to the Bragg-Snell formula. The colors of AAO films were speculated to originate from constructive interference between the light reflected from the layer 1-layer 2 interface and the light reflected from the layer 3-aluminum alloy substrate interface.

With quite limited use, biomass tar has been a long-standing issue that strongly impaired the cost-efficiency of biomass gasification. Here, a facile activation-annealing route for upcycling biomass tar into graphene nanohybrids with developed porosity and enriched pyridinic nitrogen was reported, whilst the metal-free product revealed with superior catalytic activities to the benchmark Pt/C and RuO2 catalysts toward oxygen reduction reaction (ORR) and evolution reaction (OER). By associating the dual functionalities with products’ physiochemical properties, it was unveiled that those pyridinic-N and defects were accounted for the promoted oxygen reduction and evolution, respectively. Together with reinforced electric conductivity and hierarchical porosity and enlarged interface via ammonia annealing, the heterogeneously structured carbon catalyst finally endowed an assembled primary Zn-air battery with maximum energy density of 121 mW/cm−2, in addition to robust stability against long-term running. This work highlights the great potential of biomass tar for advanced carbon materials, and therefore a novel strategy to address the tar-related challenges faced by gasification technologies.

UV radiation creates excited electronic states in DNA that can decay to mutagenic photoproducts. When excited states return to the electronic ground state, photochemical injury is avoided. Understanding of the available relaxation pathways has advanced rapidly during the past decade, but there has been persistent uncertainty, and even controversy, over how to compare results from transient absorption and time-resolved emission experiments. Here, emission from single- and double-stranded AT DNA compounds excited at 265 nm was studied in aqueous solution using the time-correlated single photon counting technique. There is quantitative agreement between the emission lifetimes ranging from 50 to 200 ps and ones measured in transient absorption experiments, demonstrating that both techniques probe the same excited states. The results indicate that excitations with lifetimes of more than a few picoseconds are weakly emissive excimer and charge transfer states. Only a minute fraction of excitations persist beyond 1 ns in AT DNA strands at room temperature.

The excited-state dynamics of two cyclic DNA miniduplexes, each containing just two base pairs, are investigated using time-resolved infrared spectroscopy. As in longer DNA duplexes, intrastrand electron transfer induced by UV excitation triggers interstrand proton transfer in the alternating miniduplex containing two out-of-phase G·C base pairs. The resulting excited state decays on a time scale of several tens of picoseconds. This state is absent when one of the two G residues is substituted by 8-oxo-7,8-dihydroguanine, a modification that is suggested to disrupt base stacking, while maintaining base pairing. These findings demonstrate that a nucleobase tetramer arranged as two stacked base pairs accurately captures the interplay between intrastrand and interstrand decay channels. The similar signals seen in the miniduplexes and longer sequences suggest that excited states in the latter rapidly localize on two adjacent base pairs.

The excited-state dynamics of three distinct forms of the d(GC)9·d(GC)9 DNA duplex were studied by combined time-resolved infrared experiments and quantum mechanical calculations. In the B- and Z-forms, bases on opposite strands form Watson-Crick (WC) base pairs but stack differently because of salt-induced changes in backbone conformation. At low pH, the two strands associate by Hoogsteen (HG) base pairing. Ultraviolet-induced intrastrand electron transfer (ET) triggers interstrand proton transfer (PT) in the B- and Z-forms, but the PT pathway is blocked in the HG duplex. Despite the different decay mechanisms, a common excited-state lifetime of ∼ 30 ps is observed in all three duplex forms. The ET-PT pathway in the WC duplexes and the solely intrastrand ET pathway in the HG duplex yield the same pair of π-stacked radicals on one strand. Back ET between these radicals is proposed to be the rate-limiting step behind excited-state deactivation in all three duplexes.

The IR spectrum of a charge transfer (CT) excited electronic state in DNA has been computed for the first time, enabling assignment of the long-lived component of the transient IR spectrum of a d(AT)9 single strand to an A → T CT state. Experimentally, the CT state lifetime is much shorter than in the double strand, and our calculations explain this result using Marcus Theory.

Photophysical investigations of the canonical nucleobases that make up DNA and RNA during the past 15 years have revealed that excited states formed by the absorption of UV radiation decay with subpicosecond lifetimes (i.e.,10(-12) s). Ultrashort lifetimes are a general property of absorbing sunscreen molecules, suggesting that the nucleobases are molecular survivors of a harsh UV environment. Encoding the genome using photostable building blocks is an elegant solution to the threat of photochemical damage. Ultrafast excited-state deactivation strongly supports the hypothesis that UV radiation played a major role in shaping molecular inventories on the early Earth before the emergence of life and the subsequent development of a protective ozone shield. Here, we review the general physical and chemical principles that underlie the photostability, or "UV hardiness", of modern nucleic acids and discuss the possible implications of these findings for prebiotic chemical evolution. In RNA and DNA strands, much longer-lived excited states are observed, which at first glance appear to increase the risk of photochemistry. It is proposed that the dramatically different photoproperties that emerge from assemblies of photostable building blocks may explain the transition from a world of molecular survival to a world in which energy-rich excited electronic states were eventually tamed for biological purposes such as energy transduction, signaling, and repair of the genetic machinery.

To better understand the nexus between structure and photophysics in metallo-DNA assemblies, the parallel-stranded duplex formed by the all-cytosine oligonucleotide, dC20, and silver nitrate was studied by circular dichroism (CD), femtosecond transient absorption spectroscopy, and time-dependent-density functional theory calculations. Silver(I) ions mediate Cytosine–Cytosine (CC) base pairs by coordinating to the N3 atoms of two cytosines. Although these silver(I) mediated CC base pairs resemble the proton-mediated CC base pairs found in i-motif DNA at first glance, a comparison of experimental and calculated CD spectra reveals that silver ion-mediated i-motif structures do not form. Instead, the parallel-stranded duplex formed between dC20 and silver ions is proposed to contain consecutive silver-mediated base pairs with high propeller twist-like ones seen in a recent crystal structure of an emissive, DNA-templated silver cluster. Femtosecond transient absorption measurements with broadband probing from the near UV to the near IR reveal an unusually long-lived (>10 ns) excited state in the dC20 silver ion complex that is not seen in dC20 in single-stranded or i-motif forms. This state is also absent in a concentrated solution of cytosine–silver ion complexes that are thought to assemble into planar ribbons or sheets that lack stacked silver(I) mediated CC base pairs. The large propeller twist angle present in metal-mediated base pairs may promote the formation of long-lived charged separated or triplet states in this metallo-DNA.

The increasing environmental pollution calls for the development of stable functional materials for efficiently binding contaminants, while they can be synthesized and recycled easily. Herein, a three-dimensional (3D) aerogel is constructed by bio-inspired adhesion of graphene and MoS2 sheets with polydopamine (PDA) through a one-step hydrothermal route for the adsorption of the water-soluble organic contaminants. The impact of the bio-inspired interfacial adhesion on the resulting composite aerogel is thoroughly investigated, e.g., the interfacial PDA layer renders the composite aerogel considerably more porous, together with the much higher specific surface area and pore volume, as well as strikingly smaller average pore size and superior stability upon exposure to air, relative to the counterpart without the bio-inspired adhesion. The 3.2 wt% PDA composition is adequate to yield a composite structure with small MoS2 nanocrystallites uniformly dispersed over the modified graphene surface without aggregation. The adsorption of methylene green onto such a 3D composite architecture is spontaneous and endothermic and obeys the Langmuir isotherm model and pseudo-second-order kinetics, with the maximum adsorption capacities over 200 mg/g at all the operating temperatures and the satisfactory recycling properties without significant degradation after 5 cycles.

To better understand how the solvent influences excited-state deactivation in DNA strands, femtosecond time-resolved IR (fs-TRIR) pump–probe measurements were performed on a d(AT)9·d(AT)9 duplex dissolved in a deep eutectic solvent (DES) made from choline chloride and ethylene glycol in a 1:2 mol ratio. This solvent, known as ethaline, is a member of a class of ionic liquids capable of solubilizing DNA with minimal disruption to its secondary structure. UV melting analysis reveals that the duplex studied here melts at 18 °C in ethaline compared to 50 °C in aqueous solution. Ethaline has an excellent transparency window that facilitates TRIR measurements in the double-bond stretching region. Transient spectra recorded in deuterated ethaline at room temperature indicate that photoinduced intrastrand charge transfer occurs from A to T, yielding the same exciplex state previously detected in aqueous solution. This state decays via charge recombination with a lifetime of 380 ± 10 ps compared to the 300 ± 10 ps...

The photophysical properties of the natural pigment violacein extracted from an Antarctic organism adapted to high exposure levels of UV radiation were measured in a combined steady-state and time-resolved spectroscopic study for the first time. In the low-viscosity solvents methanol and acetone, violacein exhibits low fluorescence quantum yields on the order of 10-4, and femtosecond transient absorption measurements reveal excited-state lifetimes of 3.2 ± 0.2 and 4.5 ± 0.2 picoseconds in methanol and acetone, respectively. As solvent viscosity is increased, both the fluorescence quantum yield and excited-state lifetime of this intensely colored pigment increase dramatically and stimulated emission decays 30-fold more slowly in glycerol than in methanol at room temperature. Excited-state deactivation is suggested to occur via a molecular-rotor mechanism in which torsion about an interring bond leads to a conical intersection with the ground state.

This study presents a novel visible light-active TiO2 nanotube anode film by sensitization with Bi2O3 nanoparticles. The uniform incorporation of Bi2O3 contributes to largely enhancing the solar light absorption and photoelectric conversion efficiency of TiO2 nanotubes. Due to the energy level difference between Bi2O3 and TiO2, the built-in electric field is suggested to be formed in the Bi2O3 sensitized TiO2 hybrid, which effectively separates the photo-generated electron-hole pairs and hence improves the photocatalytic activity. It is also found that the photoelectric conversion efficiency of Bi2O3 sensitized TiO2 nanotubes is not in direct proportion with the content of the sensitizer, Bi2O3, which should be carefully controlled to realize excellent photoelectrical properties. With a narrower energy band gap relative to TiO2, the sensitizer Bi2O3 can efficiently harvest the solar energy to generate electrons and holes, while TiO2 collects and transports the charge carriers. The new-type visible light-sensitive photocatalyst presented in this paper will shed light on sensitizing many other wide-band-gap semiconductors for improving solar photocatalysis, and on understanding the visible light-driven photocatalysis through narrow-band-gap semiconductor coupling.

Melamine may have been an important prebiotic information carrier, but its excited-state dynamics, which determine its stability under UV radiation, have never been characterized. The ability of melamine to withstand the strong UV radiation present on the surface of the early Earth is likely to have affected its abundance in the primordial soup. Here, we studied the excited-state dynamics of melamine (a proto-nucleobase) and its lysine derivative (a proto-nucleoside) using the transient absorption technique with a UV pump, and UV and infrared probe pulses. For melamine, the excited-state population decays by internal conversion with a lifetime of 13 ps without coupling significantly to any photochemical channels. The excited-state lifetime of the lysine derivative is slightly longer (18 ps), but the dominant deactivation pathway is otherwise the same as for melamine. In both cases, the vast majority of excited molecules return to the electronic ground state on the aforementioned time scales, but a minor population is trapped in a long-lived triplet state.

This article explores the extent to which insights gleaned from detailed studies of molecular photodissociations in the gas phase (i.e. under isolated molecule conditions) can inform our understanding of the corresponding photofragmentation processes in solution. Systems selected for comparison include a thiophenol (p-methylthiophenol), a thioanisole (p-methylthioanisole) and phenol, in vacuum and in cyclohexane solution. UV excitation in the gas phase results in RX-Y (X = O, S; Y = H, CH3) bond fission in all cases, but over timescales that vary by similar to 4 orders of magnitude - all of which behaviours can be rationalised on the basis of the relevant bound and dissociative excited state potential energy surfaces (PESs) accessed by UV photoexcitation, and of the conical intersections that facilitate radiationless transfer between these PESs. Time-resolved UV pump-broadband UV/visible probe and/or UV pump-broadband IR probe studies of the corresponding systems in cyclohexane solution reveal additional processes that are unique to the condensed phase. Thus, for example, the data clearly reveal evidence of (i) vibrational relaxation of the photoexcited molecules prior to their dissociation and of the radical fragments formed upon X-Y bond fission, and (ii) geminate recombination of the RX and Y products (leading to reformation of the ground state parent and/or isomeric adducts). Nonetheless, the data also show that, in each case, the characteristics (and the timescale) of the initial bond fission process that occurs under isolated molecule conditions are barely changed by the presence of a weakly interacting solvent like cyclohexane. These condensed phase studies are then extended to an ether analogue of phenol (allyl phenyl ether), wherein UV photo-induced RO-allyl bond fission constitutes the first step of a photo-Claisen rearrangement.