Molecular photoswitches based on the norbornadiene--quadricylane (NBD--QC) couple have been proposed as key elements of molecular solar-thermal energy storage schemes. To characterise the intrinsic properties of such systems, reversible isomerization of a charge-tagged NBD-QC carboxylate couple is investigated in a tandem ion mobility mass spectrometer, using light to induce intramolecular [2+2] cycloaddition of NBD carboxylate to form the QC carboxylate and driving the back reaction with molecular collisions. The NBD carboxylate photoisomerization action spectrum recorded by monitoring the QC carboxylate photoisomer extends from 290 nm to 360 nm with a maximum at 315 nm, and in the longer wavelength region resembles the NBD carboxylate absorption spectrum recorded in solution. Key structural and photochemical properties of the NBD--QC carboxylate system, including the gas-phase absorption spectrum and the energy storage capacity, are determined through computational studies using density functional theory.Physical vapor deposition can produce remarkably stable glassy materials. However, a mechanistic understanding of the interplay between control parameters during such nonequilibrium processing (e.g., deposition rate, substrate temperature, incident velocity, etc.) remains an unresolved challenge to date. In this study, we report on the discovery of a dual role of incident molecules' mass-center velocity in controlling the stability of vapor-deposited glasses through atomistic modeling. On one hand, larger velocities would impose the surface atoms into a higher effective temperature environment and facilitate the relaxation as the sample approaches the glass transition temperature. On the other hand, larger velocities would meanwhile cause faster cooling rates for the deposited molecules and destabilize the sample. The competition between the two factors results in a remarkable nonmonotonic variation of the sample's stability where an optimal velocity can be quantitatively resolved. Implications of our findings for better controlling molecular-level mechanisms in glassy materials are discussed.Transition metal (TM)-based layered oxides NaTMO2 (TM = Fe, Ni, Co, Mn, etc.) have been intensively pursued as high-capacity cathode materials for Na-ion batteries. Nevertheless, they still suffer from fast capacity loss and voltage decay, as a result of the layered structure instability upon extended electrochemical cycling. The mechanism underlying such instability remains poorly understood. Here we unravel the TM migrations and structural evolution of a quaternary NaNi0.3Co0.12Mn0.18Fe0.4O2 compound during electrochemical cycling using atomic-resolution electron microscopy and associated spectroscopies. We discover successive migrations of TM ions to Na layers that account for structure and performance degradations. The Fe ions migrate into the interstices of both tetrahedra and octahedra of the layers; on the contrary, the Ni ions migrate predominantly in the octahedral ones, and the Mn and Co ions mostly remain in the TM layers. Direct atomic-level observations of the TM migration process upon cycling offer deep insight into designing high-capacity and long-life span cathode materials for sodium-ion batteries.Exposure to phthalates is pervasive and is of concern due to associations with adverse health effects. https://www.selleckchem.com/products/z-ietd-fmk.html Exposures and exposure pathways of six phthalates were investigated for 51 women aged 18-44 years in Ontario, Canada, based on measured phthalate concentrations in hand wipes and indoor media in their residences. All six phthalates had detection frequencies of 100% in air (∑6670 ng m-3 geomean) and floor dust (∑6630 μg g-1), nearly 100% detection frequencies for hand palms and backs that were significantly correlated and concentrations were repeatable over a 3 week interval. Phthalates on hands were significantly correlated with levels in air and dust, as expected according to partitioning theory. Total exposure was estimated as 4860 ng kg bw-1 day-1 (5th and 95th percentiles 1980-16 950 ng kg bw-1 day-1), with dust ingestion, followed by hand-to-mouth transfer, as the dominant pathways. With the exception of diethyl phthalate (DEP), phthalates had over 50% detection frequencies in surface wipes of most electronic devices sampled, including devices in which the use of phthalates was not expected. Phthalate concentrations on surfaces of hand-held devices were ∼10 times higher than on non-hand-held devices and were correlated with levels on hands. The data are consistent with phthalate emissions from sources such as laminate flooring and personal care products (e.g., scented candles), followed by partitioning among air, dust, and surface films that accumulate on electronic devices and skin, including hands. We hypothesize that hands transfer phthalates from emission sources and dust to hand-held electronic devices, which accumulate phthalates due to infrequent washing and which act as a sink and then a secondary source of exposure. The findings support those of others that exposure can be mitigated by increasing ventilation, damp cloth cleaning, and minimizing the use of phthalate-containing products and materials.The ent-kaurenes represent a class of naturally occurring diterpenes of biological importance. Several members of the ent-kaurenes contain a common, tricyclic spirolactone core as a key structural motif. This study details a concise approach toward the development of a Mizoroki-Heck reaction to access this spirolactone core. The strategy described herein was enabled in microscale high-throughput experiments to allow for the rapid identification and optimization of superior reaction conditions.Cavity ring-down spectroscopy (CRDS) was employed to investigate the kinetics of the reaction between phenyl radicals (C6H5•) and ethyl acetate (EtOAc) in the gas phase. Nitrosobenzene (C6H5NO) was used as the radical precursor to generate C6H5• at 248 nm, and the generated radicals were subsequently probed at 504.8 nm. The rate coefficients were investigated experimentally in the temperature range of 258-358 K with an interval of 20 K and at a total pressure of 55 Torr in the nitrogen atmosphere. The obtained Arrhenius expression for the title reaction (C6H5• + EtOAc) in the temperature range of 258-358 K was kphenyl + EtOAcExpt - (258 - 358 K) = (9.33 ± 0.11) × 10-16 exp[(883.7 ± 181.0)/T] cm3 molecule-1 s-1, and the rate coefficient at room temperature (298 K) was kphenyl + EtOAcExpt - 298 K = (2.20 ± 0.12) × 10-14 cm3 molecule-1 s-1. Negligible effects of pressure and photolysis laser fluence were found on the experimentally measured rate coefficients. To complement our experimental findings, rate coefficients of the title reaction were computationally investigated employing the canonical variational transition-state theory with small curvature tunnelling (CVT/SCT) at the CCSD(T)/cc-pVDZ//B3LYP/6-31+G(d,p) level of theory in the temperature range of 200-400 K.