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.

Search for the radiative $$ {\Xi}_b^{-} $$ → Ξ−γ decay

The first search for the rare radiative decay $$ {\Xi}_b^{-} $$ Ξ b − → Ξ−γ is performed using data collected by the LHCb experiment in proton-proton collisions at a center-of-mass energy of 13 TeV, corresponding to an integrated luminosity of 5.4 fb−1. The $$ {\Xi}_b^{-} $$ Ξ b − → Ξ−J/ψ channel is used as normalization. No $$ {\Xi}_b^{-} $$ Ξ b − → Ξ−γ signal is found and an upper limit of $$ \mathcal{B} $$ B ($$ {\Xi}_b^{-} $$ Ξ b − → Ξ−γ) < 1.3 × 10−4 at 95% confidence level is obtained.

Tuning Non-Radiative Decay Channels via Symmetric/Asymmetric Substituent Effects on Phenazine Derivative and Their Phototherapy Switch Between Dynamic and Thermal Process

Recently, some discovery based on non-radiative decay process leading to photodynamic therapy or photothermal therapy has become an attaching hotspot, and how to achieve better performance is becoming important in...

Radiative and Non-Radiative Decay Pathways in Carbon Nanodots toward Bioimaging and Photodynamic Therapy

The origin and classification of energy states, as well as the electronic transitions and energy transfers associated with them, have been recognized as critical factors for understanding the optical properties of carbon nanodots (CNDs). Herein, we report the synthesis of CNDs in an optimized process that allows low-temperature carbonization using ethanolamine as the major precursor and citric acid as an additive. The results obtained herein suggest that the energy states in our CNDs can be classified into four different types based on their chemical origin: carbogenic core states, surface defective states, molecular emissive states, and non-radiative trap states. Each energy state is associated with the occurrence of different types of emissions in the visible to near-infrared (NIR) range and the generation of reactive oxygen species (ROS). The potential pathways of radiative/non-radiative transitions in CNDs have been systematically studied using visible-to-NIR emission spectroscopy and fluorescence decay measurements. Furthermore, the bright photoluminescence and ROS generation of these CNDs render them suitable for in vitro imaging and photodynamic therapy applications. We believe that these new insights into the energy states of CNDs will result in significant improvements in other applications, such as photocatalysis and optoelectronics.

Local strain and tunneling current modulated excitonic luminescence in MoS2 monolayers

The excitonic luminescence of monolayer molybdenum disulfide (MoS2) on a gold substrate is studied by scanning tunneling microscopy (STM). STM-induced light emission (STM-LE) from MoS2 is assigned to the radiative decay of A and B excitons. The intensity ratio of A and B exciton emission can be modulated by the tunneling current, since the A exciton emission intensity saturates at high tunneling currents. Moreover, the corrugated gold substrate introduces local strain to the monolayer MoS2, resulting in significant changes of electronic bandgap and valence band splitting. The modulation rates of strain on A and B exciton energies are estimated as -72 meV/% and -57 meV/%, respectively. STM-LE provides a direct link between exciton energy and local strain in monolayer MoS2 with a spatial resolution <10 nm.

Three-dimensional tomographically reconstructed optical emission profiles of Hall thruster plasmas

A diagnostic system was developed for spectrally resolved, three-dimensional tomographic reconstruction of Hall thruster plasmas, and local intensity profiles of Xe I and Xe II emissions were reconstructed. In this diagnostic system, 28 virtual cameras were generated using a single, fixed charge-coupled device (CCD) camera by rotating the Hall thruster to form a sufficient number of lines of sight. The Phillips-Tikhonov regularization algorithm was used to reconstruct local emission profiles from the line-integrated emission signals. The reconstruction performance was evaluated using both azimuthally symmetric and asymmetric synthetic phantom images including 5% Gaussian white noise, which resulted in a root-mean-square error of the reconstruction within an order of 10-3 even for a 1% difference in the azimuthal intensity distribution. Using the developed system, three-dimensional local profiles of Xe II emission (541.9 nm) from radiative decay of the excited state 5p4(3P2)6p2[3]˚5/2 and Xe I emission (881.9 nm) from 5p5(2P˚3/2)6p2[5/2]3 were obtained, and two different shapes were found depending on the wavelength and the distance from the thruster exit plane. In particular, a stretched central jet structure was distinctively observed in the Xe II emission profile beyond 10 mm from the thruster exit, while gradual broadening was found in the Xe I emission. Approximately 10% azimuthal nonuniformities were observed in the local Xe I and Xe II intensity profiles in the near-plume region (< 10 mm), which could not be quantitatively distinguished by analysis of the frontal photographic image. Three-dimensional Xe I and Xe II intensity profiles were also obtained in the plume region, and the differences in the structures of both emissions were visually confirmed.

Probing the Purcell effect without radiative decay: Lessons in the frequency and time domains

The effect of cavities or plates upon the electromagnetic quantum vacuum are considered in the context of electro-optic sampling, revealing how they can be directly studied. These modifications are at the heart of e.g. the Casimir force or the Purcell effect such that a link between electro-optic sampling of the quantum vacuum and environment-induced vacuum effects is forged. Furthermore, we discuss the microscopic processes underlying electro-optic sampling of quantum-vacuum fluctuations, leading to an interpretation of these experiments in terms of exchange of virtual photons. With this in mind it is shown how one can reveal the dynamics of vacuum fluctuations by resolving them in the frequency and time domains using electro-optic sampling experiments.

Experimental and Computational Analysis of Para-Hydroxy Methylcinnamate Following Photoexcitation

Para-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 S1(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. Furthermore, irrespective of the decay mechanism, the lifetime of the initially populated S1(ππ*) state is yet to be accurately measured. In this study, we use time-resolved ion-yield and photoelectron spectroscopies to precisely determine the S1(ππ*) lifetime for the s-cis conformer of para-hydroxy methylcinnamate, combined with time-dependent density functional theory to determine the major non-radiative decay route. We find the S1(ππ*) state lifetime of s-cis para-hydroxy methylcinnamate to be ∼2.5 picoseconds, and the major non-radiative decay route to follow the [1ππ*→1nπ*→3ππ*→S0] pathway. These results also concur with previous photodynamical studies on structurally similar molecules, such as para-coumaric acid and methylcinnamate.