Urocanic acid as a novel scaffold for next-gen nature-inspired sunscreens: I. electronic laser spectroscopy under isolated conditions.

Urocanic acid is a naturally occurring UV-A and UV-B absorbing compound found in the skin. Its use in artificial sunscreens has been abandoned because of health risks associated with the cis isomer. Here we report laser spectroscopic studies on urocanic acid and various substituted derivatives under supersonically cooled conditions. We find that the spectroscopy and excited-state dynamics of urocanic acid are dominantly determined by the nearly degenerate 1nπ* and 1ππ* electronically excited states. These properties are only affected to a minor extent by esterification of the carboxylic acid group or NH alkylation of the N3H tautomer. Tautomerization, on the other hand, has a much more profound influence and leads-from a photoprotective point of view-to more favorable excited-state dynamics. The approach presented here paves the way to tailoring the photoactive properties of urocanic acid for specific applications amongst which their use as safe UV filters.

Urocanic acid as a novel scaffold for next-gen nature-inspired sunscreens: II. Time-resolved spectroscopy under solution conditions.

In recent years the use of synthetic UV filters in commercial skincare formulations has come under considerable scrutiny. Urocanic acid is a naturally occurring UV filter that could serve as a scaffold for developing next-generation biomimetic UV filters. We have carried out time-resolved electronic and vibrational absorption studies on urocanic acid and modified variants in various solvents on timescales spanning eighteen orders of magnitude; from femtoseconds to hours. In combination with quantum chemical calculations these provide vital insight into the photochemical and photophysical properties of urocanic acid and how these are tuned by substitutions and solvents. Moreover, they solve the hitherto conundrum of the wavelength dependence of the photochemistry of trans-urocanic acid in an aqueous environment. Crucially, these studies - together with the accompanying article that reports high-resolution laser spectroscopic studies performed under isolated gas-phase conditions (https://doi.org/10.1039/D4CP02087A) open novel avenues for a rational design of urocanic acid-based UV filters.

Molecular beam laser spectroscopic studies of the photoactive properties of resveratrol.

Resonance Enhanced MultiPhoton Ionization spectroscopic techniques coupled with laser desorption and supersonic cooling have been employed to elucidate the photoactive properties of resveratrol. The observed excitation spectra give evidence for an internal-energy dependent trans-cis isomerisation pathway in the electronically excited state, while pump-probe studies show dynamics that are in line with what is known for the parent compound, trans-stilbene. Similar studies have been performed on a derivative of resveratrol with methoxy instead of hydroxy groups, a compound aimed to reduce previously observed photodegradation pathways of resveratrol. Time-resolved studies of the latter compound under solution conditions have given further insight into its excited-state dynamics and support the isolated-molecule conclusions on the topology of the potential energy surface of the electronically excited state. Spectroscopic studies under prolonged irradiation conditions show that both compounds suffer from photodegradation, although in the alkylated compound other pathways appear to be involved than in resveratrol.

Resonance-Enhanced Multiphoton Ionization Studies of the Lower Electronically Excited States of Flavone.

The spectroscopic and dynamics properties of flavone─the core chromophore of a wide variety of naturally occurring ultraviolet protecting filters─have been studied under supersonic beam conditions using (1 + 1') resonance-enhanced two-photon ionization spectroscopic techniques. Excitation spectra recorded under such conditions are found to differ significantly from previously reported spectra. Pump-probe studies find that intersystem crossing is the dominant decay pathway of the excited singlet manifold, in agreement with previous solution phase studies and quantum chemical predictions for the isolated molecule. Microsolvation studies on flavone-water clusters reveal that the addition of one and two water molecules leads to considerable shifts in excitation energies but that further complexation does not result in further noticeable shifts. The relaxation pathways of the electronically excited states, on the other hand, do not appear to be influenced by interactions with the solvent molecules. Finally, photoionization spectra have enabled the accurate determination of the adiabatic ionization energy to the ground state of the molecular ion─key to the antioxidant properties of flavone─as 65,415 cm-1 (8.110 eV).

Elucidating the photoprotective properties of natural UV screening agents: ZEKE-PFI spectroscopy of methyl sinapate.

As a prominent derivative of a natural sunscreen, methyl sinapate is an ideal candidate to provide fundamental insight into strategies on how to come to a rational design of artificial sunscreen filters with improved photoprotective properties. Here, static and time-resolved Zero Kinetic Energy-Pulsed Field Ionization (ZEKE-PFI) photoelectron spectroscopy has been used to study the spectroscopy and decay pathways of its electronically excited states. We find that different conformers are subject to distinct structural changes upon electronic excitation, and trace the structural changes that occur upon excitation back to the character of the LUMO. Ionization efficiency spectra in combination with pump-probe ZEKE-PFI spectra are consistent with the conclusion that the long-lived electronically excited state observed in the decay of the lowest excited singlet state is the lowest excited triplet state. Concurrently with providing information on the electronically excited states, the studies allow for a detailed characterization of the spectroscopic properties of the ground state of the radical ion, which is important in the context of the use of cinnamates in nature as antioxidants. Our studies determine the adiabatic ionization energies of the syn/cis, anti/cis and anti/trans conformers as 60 291.1 ± 0.5, 60 366.9 ± 0.5 and 60 503.9 ± 1.0 cm-1, respectively, and provide accurate vibrational fequencies of low-frequency modes of the molecular ion in its electronic ground state. Finally, the studies emphasize the important role of vibrational and electronic autoionization processes that start to dominate the ionization dynamics in non-rigid molecules of the present size.

Tailoring the optical and dynamic properties of iminothioindoxyl photoswitches through acidochromism.

Multi-responsive functional molecules are key for obtaining user-defined control of the properties and functions of chemical and biological systems. In this respect, pH-responsive photochromes, whose switching can be directed with light and acid-base equilibria, have emerged as highly attractive molecular units. The challenge in their design comes from the need to accommodate application-defined boundary conditions for both light- and protonation-responsivity. Here we combine time-resolved spectroscopic studies, on time scales ranging from femtoseconds to seconds, with density functional theory (DFT) calculations to elucidate and apply the acidochromism of a recently designed iminothioindoxyl (ITI) photoswitch. We show that protonation of the thermally stable Z isomer leads to a strong batochromically-shifted absorption band, allowing for fast isomerization to the metastable E isomer with light in the 500-600 nm region. Theoretical studies of the reaction mechanism reveal the crucial role of the acid-base equilibrium which controls the populations of the protonated and neutral forms of the E isomer. Since the former is thermally stable, while the latter re-isomerizes on a millisecond time scale, we are able to modulate the half-life of ITIs over three orders of magnitude by shifting this equilibrium. Finally, stable bidirectional switching of protonated ITI with green and red light is demonstrated with a half-life in the range of tens of seconds. Altogether, we designed a new type of multi-responsive molecular switch in which protonation red-shifts the activation wavelength by over 100 nm and enables efficient tuning of the half-life in the millisecond-second range.

Dynamic Covalent Chemistry-based Sensing: Pyrenyl Derivatives of Phenylboronic Acid for Saccharide and Formaldehyde.

We synthesized two specially designed pyrenyl (Py) derivatives of phenylboronic acid, PSNB1 and PSNB2, of which PSNB2 self-assemble to form dynamic aggregate in methanol-water mixture (1:99, v/v) via intermolecular H-bonding and pi-pi stacking. Interestingly, the dynamic aggregate shows smart response to presence of fructose (F) as evidenced by fluorescence color change from green to blue. More interestingly, the fluorescence emission of the resulted PSNB2-F changes from blue to green with the addition of formaldehyde (FA). The reason behind is formation of a PSNB2-F dimer via FA cross-linking. Based upon the reactions as found, sensitive and fast sensing of F and FA in water was realized, of which the experimental DLs could be significantly lower than 10 µM for both analytes, and the response times are less than 1 min. It is believed that not only the materials as created may have the potential to find real-life applications but also the strategy as developed can be adopted to develop other dynamic materials.

Functionality-Oriented Derivatization of Naphthalene Diimide: A Molecular Gel Strategy-Based Fluorescent Film for Aniline Vapor Detection.

Modification of naphthalene diimide (NDI) resulted in a photochemically stable, fluorescent 3,4,5-tris(dodecyloxy)benzamide derivative of NDI (TDBNDI), and introduction of the long alkyl chains endowed the compound with good compatibility with commonly found organic solvents and in particular superior self-assembly in the solution state. Further studies revealed that TDBNDI forms gels with nine of the 18 solvents tested at a concentration of 2.0% (w/v), and the critical gelation concentrations of five of the eight gels are lower than 1.0% (w/v), indicating the high efficiency of the compound as a low-molecular mass gelator (LMMG). Transmission electron microscopy, scanning electron microscopy, and confocal laser scanning microscopy studies revealed the networked fibrillar structure of the TDBNDI/methylcyclohexane (MCH) gel. On the basis of these findings, a fluorescent film was developed via simple spin-coating of the TDBNDI/MCH gel on a glass substrate surface. Fluorescence behavior and sensing performance studies demonstrated that this film is photochemically stable, and sensitive and selective to the presence of aniline vapor. Notably, the response is instantaneous, and the sensing process is fully and quickly reversible. This case study demonstrates that derivatization of photochemically stable fluorophores into LMMGs is a good strategy for developing high-performance fluorescent sensing films.

Constitutional Dynamic Chemistry-based New Concept of Molecular Beacons for High Efficient Development of Fluorescent Probes.

Inspired by the concept of constitutional dynamic chemistry, we propose a new and well-adaptable strategy for developing molecular beacon (MB)-like fluorescent probes. To demonstrate the strategy, we synthesized and used an amino group containing pyrenyl derivative of cholesterol (CP) for the construction of new fluorescent probes with EDTA and sulfuric acid. The probes as created were successfully used for n-hexane purity checking and Ba(2+)and Pb(2+)sensing, respectively.