Nanofibrous active layers offer hierarchical control over molecular structure, and the size and distribution of electron donor:acceptor domains, beyond conventional organic photovoltaic architectures. This structure is created by forming donor pathways via electrospinning nanofibers of semiconducting polymer, then infiltrating with an electron acceptor. Electrospinning induces chain and crystallite alignment, resulting in enhanced light-harvesting and charge transport.
View Article and Find Full Text PDFSinapoyl malate, naturally present in plants, has proved to be an exceptional UV filter and molecular heater for plants. Although there are nowadays industrially relevant sustainable synthetic routes to sinapoyl malate, its incorporation into certain cosmetic formulations, as well as its adsorption on plant leaves, is limited by its hydrophilicity. To overcome these obstacles, it is important to find a way to effectively control the hydrophilic-lipophilic balance of sinapoyl malate to make it readily compatible with the cosmetic formulations and stick on the waxy cuticle of leaves.
View Article and Find Full Text PDFExcess energy redistribution dynamics operating in nitrobenzene under hexane and isopropanol solvation were investigated using ultrafast transient absorption spectroscopy (TAS) with a 267 nm pump and a 340-750 nm white light continuum probe. The use of a nonpolar hexane solvent provides a proxy to the gas-phase environment, and the findings are directly compared with a recent time-resolved photoelectron imaging (TRPEI) study on nitrobenzene using the same excitation wavelength [L. Saalbach et al.
View Article and Find Full Text PDFBiomimicry has become a key player in researching new materials for a whole range of applications. In this study, we have taken a crude extract from the red algae containing mycosporine-like amino acids - a photoprotective family of molecules. We have applied the crude extract onto a surface to assess if photoprotection, and more broadly, light-to-heat conversion, is retained; we found it is.
View Article and Find Full Text PDFCoumaric acids and flavonoids play pivotal roles in protecting plants against ultraviolet radiation (UVR) exposure. In this work, we focus our photoprotection studies on -coumaric acid and the flavonoid naringenin chalcone. Photoprotection is well-understood in -coumaric acid; in contrast, information surrounding photoprotection in naringenin chalcone is lacking.
View Article and Find Full Text PDFHypoxia represents a remarkably exploitable target for cancer therapy, is encountered only in solid human tumors, and is highly associated with cancer resistance and recurrence. Here, a hypoxia-activated mitochondria-accumulated Ru(II) polypyridyl prodrug functionalized with conjugated azo (Az) and nitrogen mustard (NM) functionalities, RuAzNM, is reported. This prodrug has multimodal theranostic properties toward hypoxic cancer cells.
View Article and Find Full Text PDFSinapate 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.
View Article and Find Full Text PDFSolar exposure of avobenzone, one of the most widely used commercial UVA filters on the market, is known to cause significant degradation. This finding has fueled research into developing photostabilizer molecules. In an effort to provide insight into their stand-alone photoprotection properties, the excited state dynamics of the photostabilizer, 3-(3,4,5-trimethoxybenzylidene) pentane-2,4-dione (TMBP), and its phenolic derivative, 3-(4-hydroxy-3,5-dimethoxybenzylidene) pentane-2,4-dione (DMBP), were studied with ultrafast transient absorption spectroscopy.
View Article and Find Full Text PDFAlthough organic UV-filters are extensively used in cosmetics to protect consumers from the deleterious effects of solar UV radiation-exposure, they suffer from some major drawbacks such as their fossil origin and their toxicity to both humans and the environment. Thus, finding sustainable and non-toxic UV-filters is becoming a topic of great interest for the cosmetic industry. A few years ago, sinapoyl malate was shown to be a powerful naturally occurring UV-filter.
View Article and Find Full Text PDFMycosporine-like amino acids are a prevalent form of photoprotection in micro- and macro-organisms. Using a combination of natural product extraction/purification and femtosecond transient absorption spectroscopy, we studied the relaxation pathway for a common mycosporine-like amino acid pair, usujirene and its geometric isomer palythene, in the first few nanoseconds following photoexcitation. Our studies show that the electronic excited state lifetimes of these molecules persist for only a few hundred femtoseconds before the excited state population is funneled through an energetically accessible conical intersection with subsequent vibrational energy transfer to the solvent.
View Article and Find Full Text PDFThiomaleimides undergo efficient intermolecular [2 + 2] photocycloaddition reactions and offer applications from photochemical peptide stapling to polymer crosslinking; however, the reactions are limited to the formation of the head-to-head isomers. Herein, we present an intramolecular variation which completely reverses the stereochemical outcome of this photoreaction, quantitatively generating adducts which minimise the structural disturbance of the disulfide staple and afford a 10-fold increase in quantum yield. We demonstrate the application of this reaction on a protein scaffold, using light to confer thiol stability to an antibody fragment conjugate.
View Article and Find Full Text PDFMany photoactivated processes involve a change in oxidation state during the reaction pathway and formation of highly reactive photoactivated species. Isolating these reactive species and studying their early-stage femtosecond to nanosecond (fs-ns) photodynamics can be challenging. Here we introduce a combined ultrafast transient absorption-spectroelectrochemistry (TA-SEC) approach using freestanding boron doped diamond (BDD) mesh electrodes, which also extends the time domain of conventional spectrochemical measurements.
View Article and Find Full Text PDFLight-to-heat conversion materials generate great interest due to their widespread applications, notable exemplars being solar energy harvesting and photoprotection. Another more recently identified potential application for such materials is in molecular heaters for agriculture, whose function is to protect crops from extreme cold weather and extend both the growing season and the geographic areas capable of supporting growth, all of which could help reduce food security challenges. To address this demand, a new series of phenolic-based barbituric absorbers of ultraviolet (UV) radiation has been designed and synthesised in a sustainable manner.
View Article and Find Full Text PDFPlants, 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.
View Article and Find Full Text PDF-hydroxy methylcinnamate is part of the cinnamate family of molecules. Experimental and computational studies have suggested conflicting non-radiative decay routes after photoexcitation to its S(ππ*) state. One non-radiative decay route involves intersystem crossing mediated by an optically dark singlet state, whilst the other involves direct intersystem crossing to a triplet state.
View Article and Find Full Text PDFThe negative effects of ultraviolet radiation (UVR) on human skin have led to the widespread use of sunscreens, skincare products containing UV filters to absorb, reflect or otherwise block UVR. The mechanisms by which UV filters dissipate energy following photoexcitation, their photodynamics, can crucially determine a molecule's performance as a sunscreen UV filter. In this work, we evaluate the effects of substituent position on the in-solution relaxation pathways of two derivates of methyl anthranilate (an compound that is a precursor to the UV filter meradimate), - and -methyl anthranilate, -MA and -MA, respectively.
View Article and Find Full Text PDFMicroorganisms require protection against the potentially damaging effects of ultraviolet radiation exposure. Photoprotection is, in part, provided by mycosporine-like amino acids (MAAs). Previous reports have proposed that nonradiative decay mediates the impressive photoprotection abilities of MAAs.
View Article and Find Full Text PDFPhys Chem Chem Phys
November 2020
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.
View Article and Find Full Text PDFWith 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.
View Article and Find Full Text PDFHeterostructures built from 2D, atomically thin crystals are bound by the van der Waals force and exhibit unique optoelectronic properties. Here, we report the structure, composition and optoelectronic properties of 1D van der Waals heterostructures comprising carbon nanotubes wrapped by atomically thin nanotubes of boron nitride and molybdenum disulfide (MoS). The high quality of the composite was directly made evident on the atomic scale by transmission electron microscopy, and on the macroscopic scale by a study of the heterostructure's equilibrium and ultrafast optoelectronics.
View Article and Find Full Text PDFMycosporine-like amino acids have long been known as a natural form of photoprotection for fungi and cyanobacteria. This review will highlight the key time-resolved experimental and theoretical techniques unravelling their photochemistry and photophysics, and directly link this to their use in commercial skin-care products, namely as sunscreen filters. Three case studies have been selected, each having aided advancement in this burgeoning field of research.
View Article and Find Full Text PDFPhotoisomerisation has been shown to be an efficient excited-state relaxation mechanism for a variety of nature-based and artificial-based molecular systems. Here we report on the excited-state relaxation dynamics and consequent photostability of a symmetrically functionalised cinnamate by transient electronic absorption spectroscopy, along with complementary computational and steady-state spectroscopy methods. The findings are then discussed in comparison to 2-ethylhexyl-E-4-methoxycinnamate, a structurally related 'off the shelf' chemical filter present in commercial sunscreens with a similar absorption profile.
View Article and Find Full Text PDFPhotoprotection 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.
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