Substituted Li-layered transition-metal oxide (LTMO) electrodes such as LixNiyMnzCo1-y-zO2 (NMC) and LixNiyCo1-y-zAlzO2 (NCA) show reduced first cycle Coulombic efficiency (90-87% under standard cycling conditions) in comparison with the archetypal LixCoO2 (LCO; ∼98% efficiency). Focusing on LixNi0.8Co0.15Al0.05O2 as a model compound, we use operando synchrotron X-ray diffraction (XRD) and nuclear magnetic resonance (NMR) spectroscopy to demonstrate that the apparent first-cycle capacity loss is a kinetic effect linked to limited Li mobility at x > 0.88, with near full capacity recovered during a potentiostatic hold following the galvanostatic charge-discharge cycle. This kinetic capacity loss, unlike many capacity losses in LTMOs, is independent of the cutoff voltage during delithiation and it is a reversible process. The kinetic limitation manifests not only as the kinetic capacity loss during discharge but as a subtle bimodal compositional distribution early in charge and, also, a dramatic increase of the charge-discharge voltage hysteresis at x > 0.88. https://www.selleckchem.com/products/acy-738.html 7Li NMR measurements indicate that the kinetic limitation reflects limited Li transport at x > 0.86. Electrochemical measurements on a wider range of LTMOs including Lix(Ni,Fe)yCo1-yO2 suggest that 5% substitution is sufficient to induce the kinetic limitation and that the effect is not limited to Ni substitution. We outline how, in addition to a reduction in the number of Li vacancies and shrinkage of the Li-layer size, the intrinsic charge storage mechanism (two-phase vs solid-solution) and localization of charge give rise to additional kinetic barriers in NCA and nonmetallic LTMOs in general.Structures composed of SiOxF6-x (x = 1, 2, 3, 4, 5) or SiOxF4-x (x = 1, 2, 3) species have thus far been observed in only a few compounds, and their functional properties are completely unknown in silicate chemistry. By introducing the least electronegative element, cesium, and the most electronegative element, fluorine, into the silicophosphate system, we successfully designed the first noncentrosymmetric fluorooxosilicophosphate with Si-F bonds, CsSiP2O7F, whose structure consists of an unprecedented SiP2O10F moiety containing hexacoordinate SiO5F species. The experimental results highlight CsSiP2O7F as the first fluorooxosilicophosphate deep-UV nonlinear optical (NLO) material. The first-principles calculations reveal that the SiP2O10F moiety is a new type of NLO-active unit and that both cesium and fluorine increase the deep-UV transparency of CsSiP2O7F. This work provides a new source of deep-UV NLO materials and insights into obtaining noncentrosymmetric structures that are indispensable to functional materials in nonlinear optics, piezoelectricity, ferroelectric, pyroelectricity, etc.Plastic production has outgrown most other man-made materials, with more than 90% being petroleum-based and nonbiodegradable. Packaging, primarily food packaging, consumes the most plastic and is the largest contributor to municipal solid waste. In addition, its dependence on crude oil feedstock makes the plastic industry unsustainable and renders plastic markets vulnerable to oil price volatility. Therefore, the development of bioalternatives to conventional plastics is now a priority of the food packaging industry. Bioplastics are polymers that are either biobased (fully or partially), or biodegradable, or both. This review aims to provide an insightful overview of the most recent research and development successes in bioplastic materials, focusing on food packaging applications. Bioplastics are compared to their conventional counterparts with respect to their mechanical, thermal, barrier, and processability properties. The gaps between bio- and conventional plastics in food packaging are elucidated. Potential avenues for improving bioplastic properties to broaden their food packaging applications are critically examined. Furthermore, two of the most controversial topics on bioplastic alternatives, sustainability assessment and their impact on the plastic waste management system, are discussed.Electrophilic halofunctionalization reactions have undergone a resurgence sparked by recent discoveries in the field of catalytic asymmetric halocyclizations. To build mechanistic understanding of these asymmetric transformations, a toolbox of analytical methods has been deployed, addressing the roles of catalyst, electrophile (halenium donor), and nucleophile in determining rates and stereopreferences. The test reaction, (DHQD)2PHAL-catalyzed chlorocyclization of 4-arylpent-4-enoic acid with 1,3-dichloro-5,5-dimethylhydantoin (DCDMH), is revealed to be first order in catalyst and chlorenium ion donor and zero order in alkenoic acid substrate under synthetically relevant conditions. The simplest interpretation is that rapid substrate-catalyst binding precedes rate-limiting chlorenium attack, controlling the face selectivity of both chlorine attack and lactone closure. ROESY and DFT studies, aided by crystal structures of carboxylic acids bound by the catalyst, point to a plausible resting state of the catalyst-substrate complex predisposed for asymmetric chlorolactonization. As revealed by our earlier labeling studies, these findings suggest modes of binding in the (DHQD)2PHAL chiral pocket that explain the system's remarkable control over rate- and enantioselection-determining events. Though a comprehensive modeling analysis is beyond the scope of the present work, quantum chemical analysis of the fragments' interactions and candidate reaction paths point to a one-step concerted process, with the nucleophile playing a critical role in activating the olefin for concomitant electrophilic attack.Coherent anti-Stokes Raman scattering (CARS) imaging is widely used for imaging molecular vibrations inside cells and tissues. Lipid bilayers are potential analytes for CARS imaging due to their abundant CH2 vibrational bonds. However, identifying the plasma membrane is challenging since it possesses a thin structure and is closely apposed to lipid structures inside the cells. Since the plasma membrane provides the most prominent asymmetric location within cells, orientation sensitive sum-frequency generation (SFG) imaging is a promising technique for selective visualization of the plasma membrane labeled by a nonfluorescent and SFG-specific dye, Ap3, when using a CARS microscope system. In this study, we closely compare the characteristics of lipid bilayer imaging by dye-based SFG and CARS using giant vesicles (GVs) and N27 rat dopaminergic neural cells. As a result, we show that CARS imaging can be exploited for the visualization of whole lipid structures inside GVs and cells but is insufficient for identification of the plasma membrane, which instead can be achieved using dye-based SFG imaging.