Illuminating the Effect of the Local Environment on the Performance of Organic Sunscreens: Insights From Laser Spectroscopy of Isolated Molecules and Complexes

Sunscreens are essential for protecting the skin from UV radiation, but significant questions remain about the fundamental molecular-level processes by which they operate. In this mini review, we provide an overview of recent advanced laser spectroscopic studies that have probed how the local, chemical environment of an organic sunscreen affects its performance. We highlight experiments where UV laser spectroscopy has been performed on isolated gas-phase sunscreen molecules and complexes. These experiments reveal how pH, alkali metal cation binding, and solvation perturb the geometric and hence electronic structures of sunscreen molecules, and hence their non-radiative decay pathways. A better understanding of how these interactions impact on the performance of individual sunscreens will inform the rational design of future sunscreens and their optimum formulations.

The Role of Triazole and Glucose Moieties in Alkali Metal Cation Complexation by Lower-Rim Tertiary-Amide Calix[4]arene Derivatives

The binding of alkali metal cations with two tertiary-amide lower-rim calix[4]arenes was studied in methanol, N,N-dimethylformamide, and acetonitrile in order to explore the role of triazole and glucose functionalities in the coordination reactions. The standard thermodynamic complexation parameters were determined microcalorimetrically and spectrophotometrically. On the basis of receptor dissolution enthalpies and the literature data, the enthalpies for transfer of reactants and products between the solvents were calculated. The solvent inclusion within a calixarene hydrophobic basket was explored by means of 1H NMR spectroscopy. Classical molecular dynamics of the calixarene ligands and their complexes were carried out as well. The affinity of receptors for cations in methanol and N,N-dimethylformamide was quite similar, irrespective of whether they contained glucose subunits or not. This indicated that sugar moieties did not participate or influence the cation binding. All studied reactions were enthalpically controlled. The peak affinity of receptors for sodium cation was noticed in all complexation media. The complex stabilities were the highest in acetonitrile, followed by methanol and N,N-dimethylformamide. The solubilities of receptors were greatly affected by the presence of sugar subunits. The medium effect on the affinities of calixarene derivatives towards cations was thoroughly discussed regarding the structural properties and solvation abilities of the investigated solvents.

Alkali Metal Cation Incorporated Ag3BiI6 Absorbers for Efficient and Stable Rudorffite Solar Cells

Objectives Toxic lead and poor stability are the main obstacles of perovskite solar cells. Lead-free silver bismuth iodide (SBI) was first attempted as solar cells photovoltaic materials in 2016. However, the short-circuit current of the SBI rudorffite materials is commonly below 10 mA/cm2, limiting the overall photovoltaic performance. Here, we present a chemical composition engineering to enhance the photovoltaic performance. Methods In this study, we incorporated a series of alkali metal cations (Li+, Na+, K+, Rb+, and Cs+) into Ag3BiI6 absorbers to investigate the effects on the photovoltaic performance of rudorffite solar cells. Results Cs+ doping improved VOC and Na+ doping showed an obvious enhancement in JSC. Therefore, we co-doped Na+ and Cs+ into SBI (Na/Cs-SBI) as the absorber and investigated the crystal structure, surface morphology, and optical properties. The photo-assisted Kelvin probe force microscopy (photo-KPFM) was used to measure surface potential and verified that Na/Cs doping could reduce the electron trapping at the grain boundary and facilitate electron transportation. Conclusion Na/Cs-SBI reduced the electron-holes pairs recombination and promoted the carrier transport of rudorffite solar cells. Finally, the Na/Cs-SBI rudorffite solar cell exhibited a PCE of 2.50%, a 46.0% increase to the SBI device (PCE = 1.71%), and was stable in ambient conditions for over 6 months.

Surface Characteristics of TiO2 and Their Effect on Specific Capacity in Lithium and Sodium Systems

The paper presents the results of studies of nanosized titanium dioxide (TiO2) samples synthesized by alkaline hydrolysis. The surface properties of the samples were modified using high-temperature annealing. As a result, samples with a specific surface area of 31-203 m2/g were obtained. The specific capacity of TiO2 in lithium and sodium cells was determined. It is noted that the nature of the curves obtained, the specific capacity and its stability during cycling depend on the nature of the alkali metal cation and the surface properties of TiO2.

Crystal structures and X-ray powder diffraction data for Cs2NiSi5O12, RbGaSi2O6, and CsGaSi2O6 synthetic leucite analogues

Leucites are tetrahedrally coordinated silicate framework structures with some of the silicon framework cations partially replaced by divalent or trivalent cations. These structures have general formulae A2BSi5O12 and ACSi2O6; where A is a monovalent alkali metal cation, B is a divalent cation, and C is a trivalent cation. In this paper, we report the Rietveld refinements of three more synthetic leucite analogues with stoichiometries of Cs2NiSi5O12, RbGaSi2O6, and CsGaSi2O6. Cs2NiSi5O12 is Ia $\bar{3}$ d cubic and is isostructural with Cs2CuSi5O12. RbGaSi2O6 is I41/a tetragonal and is isostructural with KGaSi2O6. CsGaSi2O6 is $I\bar{4}3d$ cubic and is isostructural with RbBSi2O6.

Concerted Cation–Electron Transfer Mechanism for CO2 Electroreduction

Converting carbon dioxide (CO2) into valuable products is one of the most important processes for a sustainable society. Especially, the electrochemical CO2 reduction reaction (CO2RR) offers an effective means, but its reaction mechanism is not yet fully understood. Here, we demonstrate that concerted cation–electron transfer (CCET) is a key catalytic step in the CO2RR to carbon monoxide. The first-principles-based multiscale simulation identifies a single cation that coordinates a CO2− intermediate adsorbed on Ag electrode. The CCET is experimentally verified by a collapse of the CO2RR polarization curves upon correcting for the thermodynamic activity of the cation. As further confirmation, a kinetic study shows that the CO2RR obeys first-order kinetics on the local cation concentration at the electric double layer (estimated by measuring the electrode surface charge). Finally, this work unveils the fundamental origin of different CO2RR activity depending on the species of alkali metal cation, and further highlights the importance of ion-pairing tendency of the cations for electrochemical interface design to achieve high-performance CO2 electrolysis.

Iron Complexes of a Proton-Responsive SCS Pincer Ligand with Sensitive Electronic Structure

SCS pincer ligands have an interesting combination of strong-field and weak-field donors that is also present in the nitrogenase active site. Here, we explore the electronic structures of iron(II) and iron(III) complexes with such a pincer ligand, bearing a monodentate phosphine, thiolate S donor, amide N donor, ammonia, or CO. The ligand scaffold features a protonresponsive thioamide site, and the protonation state of the ligand greatly influences the reduction potential of iron in the phosphine complex. The N–H bond dissociation free energy can be quantitated as 56 ± 2 kcal/mol. EPR spectroscopy and SQUID magnetometry measurements show that the iron(III) complexes with S and N as the fourth donors have an intermediate spin (S = 3/2) ground state with large zero field splitting, and X-ray absorption spectra show high Fe–S covalency. The Mössbauer spectrum changes drastically with the position of a nearby alkali metal cation in the iron(III) amido complex, and DFT calculations explain this phenomenon through a change between having the doubly-occupied orbital as dz2 or dyz, as the former is more influenced by the nearby positive charge.

Direct Etherification Reaction of Glycerol Using Alkali Metal Cation (Li+, Na+ and K+) Containing X-Type Zeolites as Heterogeneous Catalysts: Optimization of the Reaction Conditions

X-type zeolite (XZ-Na) containing Na+ as a cation was synthesized, and XZ-Li and XZ-K were prepared by exchanging the cations of XZ-Na with Li+ and K+, respectively. The specific surface areas, structures, and chemical compositions of the prepared zeolites were analyzed by BET, XRD, and SEM-EDX. The activity of the direct and selective etherifications of glycerol to diglycerol (DG) and triglycerol (TG) were investigated using each zeolite XZ-M (M = Li, Na or K) as a basic heterogeneous catalyst. The etherification reactions of glycerol were carried out at atmospheric pressure while controlling the reaction temperature, reaction time, and the amount of each zeolite. As the amount of each zeolite, reaction time, and reaction temperature increased, the conversion of glycerol also increased, but the selectivities of DG and TG decreased due to the increase in the production of oligomers. When each zeolite was used as a catalyst, the catalytic activity for the conversion of glycerol was observed as XZ-K > XZ-Li > XZ-Na, but the selectivities of DG and TG were observed as XZ-Li > XZ-Na > XZ-K. Especially, 3 wt.% of XZ-Li exhibited the excellent catalytic performance when the etherification of glycerol was optimized and carried out at 280 °C for 2 h: the conversion of glycerol was 89.6% and the yields of DG and TG were 61.2 and 21.2%, respectively.