Transient Electronic Absorption Spectroscopy Research Articles

Characteristic Photoprotective Molecules from the Sphagnum World: A Solution-Phase Ultrafast Study of Sphagnic Acid.

A natural UV-absorbing chromophore extracted from sphagnum mosses, sphagnic acid, is proposed as a new natural support to chemical UV filters for use in cosmetic applications. Sphagnic acid is structurally related to the cinnamate family of molecules, known for their strong UV absorption, efficient non-radiative decay, and antioxidant properties. In this study, transient electronic absorption spectroscopy is used, in conjunction with steady-state techniques, to model the photodynamics following photoexcitation of sphagnic acid in different solvent systems. Sphagnic acid was found in each system to relax with lifetimes of ~200 fs and ~1.5 ps before generating a cis-isomer photoproduct. This study helps to elucidate the photoprotective mechanism of a new potential natural support to sunscreens, from a unique plant source.

Ring buckling and C=N isomerization pathways for efficient photoprotection in two nature-inspired UVA sunscreens revealed through ultrafast dynamics and high-level calculations.

Sunscreens provide a frontline defense for our DNA against the damage caused by ultraviolet (UV) radiation. The active ingredients in topically applied sunscreens that provide this defense are UV filters, which preferentially absorb or reflect UV radiation before it penetrates the skin and interacts with photosensitive nucleic acids. However, there are concerns related to human and environmental toxicity of current UV filters, and consequently a shift toward nature-inspired, particularly microbial, UV filters. In this paper, new physical insight is provided into the fundamental mechanisms of photoprotection in two synthetic analogs of mycosporine-like amino acid-type UV filters, demonstrating new methods of protection that are distinct from those of current commercial sunscreens, extending previous work in this area. Transient absorption measurements (both transient electronic absorption spectroscopy and transient vibrational absorption spectroscopy) are combined with steady-state studies and high-level computational results to aid our mapping of the experimentally derived lifetimes to real-time photodynamic processes. The conclusions reached here pave the way toward developing new and more efficient biomimetic DNA photoprotectant materials.

Direct structural observation of ultrafast photoisomerization dynamics in sinapate esters

Sinapate esters have been extensively studied for their potential application in ‘nature-inspired’ photoprotection. There is general consensus that the relaxation mechanism of sinapate esters following photoexcitation with ultraviolet radiation is mediated by geometric isomerization. This has been largely inferred through indirect studies involving transient electronic absorption spectroscopy in conjunction with steady-state spectroscopies. However, to-date, there is no direct experimental evidence tracking the formation of the photoisomer in real-time. Using transient vibrational absorption spectroscopy, we report on the direct structural changes that occur upon photoexcitation, resulting in the photoisomer formation. Our mechanistic analysis predicts that, from the photoprepared ππ* state, internal conversion takes place through a conical intersection (CI) near the geometry of the initial isomer. Our calculations suggest that different CI topographies at relevant points on the seam of intersection may influence the isomerization yield. Altogether, we provide compelling evidence suggesting that a sinapate ester’s geometric isomerization can be a more complex dynamical process than originally thought.

Unravelling the Photoprotection Properties of Garden Cress Sprout Extract.

Plants, as with humans, require photoprotection against the potentially damaging effects of overexposure to ultraviolet (UV) radiation. Previously, sinapoyl malate (SM) was identified as the photoprotective agent in thale cress. Here, we seek to identify the photoprotective agent in a similar plant, garden cress, which is currently used in the skincare product Detoxophane nc. To achieve this, we explore the photodynamics of both the garden cress sprout extract and Detoxophane nc with femtosecond transient electronic absorption spectroscopy. With the assistance of liquid chromatography-mass spectrometry, we determine that the main UV-absorbing compound in garden cress sprout extract is SM. Importantly, our studies reveal that the photoprotection properties of the SM in the garden cress sprout extract present in Detoxophane nc are not compromised by the formulation environment. The result suggests that Detoxophane nc containing the garden cress sprout extract may offer additional photoprotection to the end user in the form of a UV filter booster.

Ultrafast dynamics of heme distortion in the O2-sensor of a thermophilic anaerobe bacterium

Heme-Nitric oxide and Oxygen binding protein domains (H-NOX) are found in signaling pathways of both prokaryotes and eukaryotes and share sequence homology with soluble guanylate cyclase, the mammalian NO receptor. In bacteria, H-NOX is associated with kinase or methyl accepting chemotaxis domains. In the O2-sensor of the strict anaerobe Caldanaerobacter tengcongensis (Ct H-NOX) the heme appears highly distorted after O2 binding, but the role of heme distortion in allosteric transitions was not yet evidenced. Here, we measure the dynamics of the heme distortion triggered by the dissociation of diatomics from Ct H-NOX using transient electronic absorption spectroscopy in the picosecond to millisecond time range. We obtained a spectroscopic signature of the heme flattening upon O2 dissociation. The heme distortion is immediately (<1 ps) released after O2 dissociation to produce a relaxed state. This heme conformational change occurs with different proportions depending on diatomics as follows: CO < NO < O2. Our time-resolved data demonstrate that the primary structural event of allostery is the heme distortion in the Ct H-NOX sensor, contrastingly with hemoglobin and the human NO receptor, in which the primary structural events are respectively the motion of the proximal histidine and the rupture of the iron-histidine bond.

Influence of the Solvent Environment on the Ultrafast Relaxation Pathways of a Sunscreen Molecule Diethylamino Hydroxybenzoyl Hexyl Benzoate.

The excited-state dynamics of photoexcited diethylamino hydroxybenzoyl hexyl benzoate (DHHB), a UVA absorber widely used in sunscreen formulations, are studied with transient electronic and vibrational absorption spectroscopy methods in four different solvents. In the polar solvents methanol, dimethyl sulfoxide (DMSO), and acetonitrile, strong stimulated emission (SE) is observed at early time delays after photoexcitation at a near-UV wavelength of λex = 360 nm, and decays with time constants of 420 fs in methanol and 770 fs in DMSO. The majority (∼95%) of photoexcited DHHB returns to the ground state with time constants of 15 ps in methanol and 25 ps in DMSO. In the nonpolar solvent cyclohexane, ∼ 98% of DHHB photoexcited at λex = 345 nm relaxes to the ground state with a ∼ 10 ps time constant, and the SE is weak. DHHB preferentially adopts an enol form in its ground S0 state, but excited state absorption (ESA) bands seen in TEAS are assigned to both the S1-keto and S1-enol forms, indicating a role for ultrafast intramolecular excited state hydrogen transfer (ESHT). This ESHT is inhibited by polar solvents. The two S1 tautomers decay with similar time scales to the observed recovery of ground state population. For molecules that avoid ESHT, torsion around a central C-C bond minimizes the S1-enol energy, quenches the SE, and is proposed to lead to a conical intersection with the S0 state that mediates the ground state recovery. A competing trans-enol isomeric photoproduct is observed as a minor competitor to parent recovery in polar solvents. Evidence is presented for triplet (T1) enol production in polar solvents, and for T1 quenching by octocrylene, a common UVB absorber sunscreen additive. The T1 keto form is observed in cyclohexane solution.

Determining the photostability of avobenzone in sunscreen formulation models using ultrafast spectroscopy.

Avobenzone is an ultraviolet (UV) filter that is often included in sunscreen formulations despite its lack of photostability. Its inclusion is necessary due to few existing alternatives for photoprotection in the UVA region (320-400 nm). To better understand and predict the photostability of avobenzone, ultrafast transient electronic absorption spectroscopy (TEAS) has been used to study the effects of solvent (including emollients), concentration and skin surface temperature on its excited-state relaxation mechanism, following photoexcitation with UVA radiation (∼350 nm). Subtle differences between the excited-state lifetimes were found between the systems, but the TEAS spectral features were qualitatively the same for all solution and temperature combinations. Alongside TEAS measurements, UV filter/emollient blends containing avobenzone were irradiated using simulated solar light and their degradation tracked using steady-state UV-visible spectroscopy. Sun protection factor (SPF) and UVA protection factor (UVA-PF) assessments were also carried out on representative oil phases (higher concentration blends), which could be used to formulate oil-in-water sunscreens. It was found that there was an apparent concentration dependence on the long-term photoprotective efficacy of these mixtures, which could be linked to the ultrafast photodynamics by the presence of a ground-state bleach offset. This combination of techniques shows potential for correlating long-term behaviours (minutes to hours) of avobenzone with its ultrafast photophysics (femtoseconds to nanoseconds), bridging the gap between fundamental photophysics/photochemistry and commercial sunscreen design.

Reinvestigating the Photoprotection Properties of a Mycosporine Amino Acid Motif.

With the growing concern regarding commercially available ultraviolet (UV) filters damaging the environment, there is an urgent need to discover new UV filters. A family of molecules called mycosporines and mycosporine-like amino acids (referred to as MAAs collectively) are synthesized by cyanobacteria, fungi and algae and act as the natural UV filters for these organisms. Mycosporines are formed of a cyclohexenone core structure while mycosporine-like amino acids are formed of a cyclohexenimine core structure. To better understand the photoprotection properties of MAAs, we implement a bottom-up approach by first studying a simple analog of an MAA, 3-aminocyclohex-2-en-1-one (ACyO). Previous experimental studies on ACyO using transient electronic absorption spectroscopy (TEAS) suggest that upon photoexcitation, ACyO becomes trapped in the minimum of an S1 state, which persists for extended time delays (>2.5 ns). However, these studies were unable to establish the extent of electronic ground state recovery of ACyO within 2.5 ns due to experimental constraints. In the present studies, we have implemented transient vibrational absorption spectroscopy (as well as complementary TEAS) with Fourier transform infrared spectroscopy and density functional theory to establish the extent of electronic ground state recovery of ACyO within this time window. We show that by 1.8 ns, there is >75% electronic ground state recovery of ACyO, with the remaining percentage likely persisting in the electronic excited state. Long-term irradiation studies on ACyO have shown that a small percentage degrades after 2 h of irradiation, plausibly due to some of the aforementioned trapped ACyO going on to form a photoproduct. Collectively, these studies imply that a base building block of MAAs already displays characteristics of an effective UV filter.

A systematic approach to methyl cinnamate photodynamics

ABSTRACT Methyl cinnamate (MC) is an ester within the cinnamate family. Recent time-resolved gas-phase studies have suggested that upon excitation to its first singlet ππ* (11ππ*) state, there is initial decay to the lowest lying singlet 1nπ* (11nπ*) state within 10 ps, en route to trans–cis isomerisation. In the present study, we have implemented time-resolved ion yield (TR-IY) and time-resolved photoelectron spectroscopy (TR-PES) experiments in the gas-phase to precisely determine the lifetime of the 11ππ* state. We found this lifetime to be ∼ 4.5 ps using both TR-IY and TR-PES. MC was also studied in a more complex cyclohexane solution environment, using transient electronic absorption spectroscopy. Along with complementary steady-state irradiation and 1H NMR studies, these studies demonstrate that trans–cis isomerisation is preserved in the more complex, cyclohexane solution environment.

Conservation of ultrafast photoprotective mechanisms with increasing molecular complexity in sinapoyl malate derivatives.

Sinapoyl malate is a natural plant sunscreen molecule which protects leaves from harmful ultraviolet radiation. Here, the ultrafast dynamics of three sinapoyl malate derivatives, sinapoyl L‐dimethyl malate, sinapoyl L‐diethyl malate and sinapoyl L‐di‐t‐butyl malate, have been studied using transient electronic absorption spectroscopy, in a dioxane and methanol solvent environment to investigate how well preserved these dynamics remain with increasing molecular complexity. In all cases it was found that, upon photoexcitation, deactivation occurs via a trans‐cis isomerisation pathway within ∼20–30 ps. This cis‐photoproduct, formed during photodeactivation, is stable and longed‐lived for all molecules in both solvents. The incredible levels of conservation of the isomerisation pathway with increased molecular complexity demonstrate the efficacy of these molecules as ultraviolet photoprotectors, even in strongly perturbing solvents. As such, we suggest these molecules might be well‐suited for augmentations to further improve their photoprotective efficacy or chemical compatibility with other components of sunscreen mixtures, whilst conserving their underlying photodynamic properties.

Bimolecular photoinduced electron transfer in non-polar solvents beyond the diffusion limit.

Electron transfer (ET) quenching dynamics in non-polar solvents are investigated using ultrafast spectroscopy with a series of six fluorophore/quencher pairs, covering a driving force range of more than 1.3 eV. The intrinsic ET rate constants, k0, deduced from the quenching dynamics in the static regime, are of the order of 1012-1013 M-1 s-1, i.e., at least as large as in acetonitrile, and do not exhibit any marked dependence on the driving force. A combination of transient electronic and vibrational absorption spectroscopy measurements reveals that the primary product of static quenching is a strongly coupled exciplex that decays within a few picoseconds. More weakly coupled exciplexes with a longer lifetime are generated subsequently, during the dynamic, diffusion-controlled, stage of the quenching. The results suggest that static ET quenching in non-polar solvents should be viewed as an internal conversion from a locally excited state to a charge-transfer state of a supermolecule rather than as a non-adiabatic ET process.

Computational and experimental characterization of novel ultraviolet filters.

Many current ultraviolet filters present potential hazards both to humans and to the natural environment. As such there is a new impetus to develop, through intimate characterisation, ultraviolet filters for use in cosmeceuticals. Here we report a new class of organic molecules which have a strong absorption band across the ultraviolet-A and -B regions of the electromagnetic spectrum and high photostability. We have performed ultrafast transient electronic absorption spectroscopy and steady-state spectroscopies, alongside computational studies to track and manipulate photoprotection mechanisms. Our results present a potentially new generation of ultraviolet filters for use in commercial formulations.

UV irradiation of Cu-based complexes with aliphatic amine ligands as used in living radical polymerization

The effect UV irradiation on Cu(II)-based complexes with aliphatic amine ligands is investigated. Four aliphatic amines are used as ligands and Cu(II)Br2 as the metal source for the formation of catalyst complexes that can be used for the photoinduced Cu-RDRP of methyl acrylate. Different characterization techniques such as transient electronic absorption spectroscopy (TEAS), ultraviolet–visible (UV–Vis) spectroscopy, electrospray ionization time of flight mass spectrometry (ESI-ToF-MS) and cyclic voltammetry (CV) are applied in order to provide insights into the catalyst behaviour upon photo-irradiation. The excited-state dynamics, the electrochemical behaviour of the Cu(II)/Cu(I) redox couples and the detection of different species upon complexation of the ligand to the metal center (before and after UV irradiation) are further depicted in the quality of the obtained polymers.

Ultrafast Photodynamics of an Azopyridine-Functionalized Iron(II) Complex: Implications for the Concept of Ligand-Driven Light-Induced Spin Change.

We report on the ultrafast photodynamics of an iron(II) complex with a photoisomerizable pentadentate azo-tetrapyridylamino ligand after irradiation with ultraviolet light. The results of femtosecond transient electronic absorption spectroscopy performed on the low-spin (LS) form of the title complex show that initial excitation of the ππ* state of the azopyridine unit in the ligand at λpump = 312 nm is followed by an ultrafast intersystem crossing (ISC) that leads to the formation of a metal-centered (MC) 5T state, in competition with the intended photoswitching of the azopyridine unit. Additional measurements carried out upon excitation of the singlet metal-to-ligand charge-transfer (1MLCT) transition at λpump = 455 nm suggest that this energy transfer occurs via an MLCT state. The resulting high-spin (HS) 5T state of the complex is metastable and recovers to the LS ground state with a time constant of ∼3 ns. The implications of these observations on the ligand-driven light-induced spin change concept are discussed.

Determination of Secondary Species in Solution through Pump-Selective Transient Absorption Spectroscopy and Explicit-Solvent TDDFT.

The measured electronic excitations of a given species in solution are often a composite of the electronic excitations of various equilibrium species of that molecule. It is common for a proportion of a species to deprotonate in solution, or form a tautomeric equilibrium, producing new peaks corresponding to the electronic excitations of the new species. One prominent example is alizarin in methanol, which at different temperatures, and in solutions with differing pH, has an isosbestic point between the two dominant excitations at 435 and 540 nm. The peak at 435 nm has been attributed to alizarin; the peak at 540 nm, however, more likely results from a species in equilibrium with alizarin. In this work, we were able to use both experimental and computational techniques to selectively examine electronic properties of both alizarin and its secondary species in equilibrium. This was achieved through use of transient electronic absorption spectroscopy, following selective photoexcitation of a specific species in equilibrium. The resulting transient electronic absorption spectra were compared to the known transient absorption spectra of potential secondary equilibrium species. The ground state absorption spectra associated with each species in equilibrium were predicted using linear-scaling time-dependent density functional theory with an explicitly modeled solvent and compared to the experimental result. This evidence from both techniques combines to suggest that the excitation at 540 nm arises from a specific monoanionic form of alizarin.

Ultrafast electronic deactivation of UV-excited adenine and its ribo- and deoxyribonucleosides and -nucleotides: A comparative study

The high stability of the DNA bases after UV photoexcitation is generally ascribed to their intrinsic ability to dissipate the supplied electronic energy on ultrafast time scales. The sugar-phosphate backbone of the related nucleosides and nucleotides may modulate the efficiency of these relaxation processes by hydrogen bonding and/or intramolecular energy transfer. To elucidate these effects, we performed a comparative study of the excited-state lifetimes of 9H-adenine, its nucleosides adenosine and deoxyadenosine, and its nucleotides adenosine monophosphate and deoxyadenosine monophosphate by transient electronic absorption spectroscopy under otherwise constant experimental conditions. All five adenine derivatives were found to exhibit virtually identical spectro-temporal behavior with uniform excited-state lifetimes of τ1=0.19±0.03 ps and τ2=0.45±0.05 ps. The results support a common deactivation mechanism within the adenine unit that leaves the DNA sugar-phosphate backbone groups idle.

Unravelling the Photoprotection Properties of Mycosporine Amino Acid Motifs.

Photoprotection from harmful ultraviolet (UV) radiation exposure is a key problem in modern society. Mycosporine-like amino acids found in fungi, cyanobacteria, macroalgae, phytoplankton, and animals are already presenting a promising form of natural photoprotection in sunscreen formulations. Using time-resolved transient electronic absorption spectroscopy and guided by complementary ab initio calculations, we help to unravel how the core structures of these molecules perform under UV irradiation. Through such detailed insight into the relaxation mechanisms of these ubiquitous molecules, we hope to inspire new thinking in developing next-generation photoprotective molecules.

Ultrafast Observation of a Photoredox Reaction Mechanism: Photoinitiation in Organocatalyzed Atom-Transfer Radical Polymerization.

Photoredox catalysis has driven a revolution in the field of organic chemistry, but direct mechanistic insights into reactions of genuine synthetic utility remain relatively scarce. Herein we report ultrafast time-resolved spectroscopic observation of a bimolecular organocatalyzed photoredox reaction, from catalyst photoexcitation through to photoinduced electron transfer (PET) and intermediate formation, using transient vibrational and electronic absorption spectroscopy with sub-picosecond time resolution. Specifically, the photochemical dynamics of initiation in organocatalyzed atom-transfer radical polymerization (O-ATRP) are elucidated for two complementary photoredox organocatalysts (N,N-diaryl-5,10-dihydrophenazines). Following photoexcitation, a dissociative bimolecular electron transfer is observed from the first excited singlet state of both photocatalysts to methyl 2-bromopropionate in dichloromethane, toluene, and dimethylformamide. The photocatalyst excited donor state, ground state, and radical cation are tracked in real time alongside the debrominated radical fragment. Our work challenges previously proposed mechanisms of initiation in O-ATRP and indicates that PET from short-lived excited singlet states can exert control of polymer molecular weight and dispersity by suppressing the steady-state concentration of the reactive debrominated radical. More broadly, we aim to demonstrate the potential of ultrafast absorption spectroscopy to observe directly transient, open-shell intermediates in mechanistic studies of photoredox catalysis.

Photophysics of the sunscreen ingredient menthyl anthranilate and its precursor methyl anthranilate: A bottom-up approach to photoprotection

The ultrafast excited state dynamics of the sunscreen ingredient menthyl anthranilate (MenA) and its precursor methyl anthranilate (MA) were studied in vacuum (using time-resolved ion yield spectroscopy) and in solution (using transient electronic absorption spectroscopy). MenA and MA both show long-lived dynamics, with the observation of a kinetic isotope effect suggesting that hydrogen motion acts as the rate determining process in the overall decay. Complementary computational studies exploring the intuitive decay pathways of MA revealed a bound S1 state with a shallow ‘up-hill’ gradient with respect to proton transfer. From these results, it is suggested that photoexcited population is trapped in this excited state from which luminescence occurs as a prominent decay pathway. This work has shown that the photophysics of MA and MenA – and hence their photoprotection capabilities – are not drastically influenced by aliphatic structure or solvent environment alone. A bottom-up approach, such as the one described herein, is essential to understand the combination of factors that afford optimum photoprotection and to develop a new generation of tailor made, efficacious sunscreens.

Charge Localization after Ultrafast Photoexcitation of a Rigid Perylene Perylenediimide Dyad Visualized by Transient Stark Effect.

The intramolecular charge-transfer (CT) dynamics of a rigid and strongly conjugated perylenediimide-bridge-perylene dyad (PDIPe) has been investigated in dichloromethane using ultrafast transient electronic absorption spectroscopy and quantum chemical calculations. The strong electronic coupling between the dyad units gives rise to a CT band. Its photoexcitation forms a delocalized CT state with well-preserved ion bands despite the strong coupling. In the dyad, the electronic transition dipole moment of the electron donor perylene is aligned along the axis of the electric field vector with respect to the CT species. This alignment makes the donor sensitive to the Stark effect and thus charge density fluctuations in the CT state. Charge localization on the picosecond time scale manifests as a time-dependent Stark shift in the visible region. Quantum chemical calculations reveal a twist around the acetylene bridging unit to be the responsible mechanism generating a partial to an almost complete CT state. An estimate of the electric field strength in the CT state yields approximately 25 MV/cm, which increases to around 31 MV/cm during charge localization. Furthermore, the calculations illustrate the complexity of electronic structure in this strongly delocalized superchromophore and reflect the complications in the interpretation of transient absorption results when compared to steady-state approaches such as spectroelectrochemistry and model chromophore experiments such as photoinduced bimolecular charge transfer.