蓝宝石冲击消光晶向效应的第一性原理

蓝宝石的冲击消光现象是高压领域中的研究热点.低压段(86 GPa范围内)的实验研究表明蓝宝石的冲击消光与晶向相关,但在高压段(压力范围:131255 GPa)是否也具有晶向相关性目前尚不清楚.为此,利用第一性原理方法,分别计算了八个不同晶向的蓝宝石理想晶体和含氧离子空位缺陷晶体在高压段的光吸收性质,结果发现:1)蓝宝石在高压段的冲击消光表现出明显的晶向效应,且该效应还随压力增大而增强;一步的数据分析可以看出,在冲击实验采用的波段内,a晶向的消光最弱(透明性最好),c晶向的消光最强与c晶向的消光接近,g晶向的消光要弱于s晶向的消光.鉴于此,如果在高压段开展加窗冲击波实验,建议选择a晶向或m晶向的蓝宝石作为其光学窗口.本文结果不仅有助于深入地认识蓝宝石在极端条件下的光学性质,而且对未来的实验研究有重要的参考作用.     

Astrocyte and ions metabolism during epileptogenesis:A review for modeling studies

As a large group of cells in a central nervous system, astrocytes have a great influence on ion and energy metabolism in a nervous system. Disorders of neuronal ion and energy metabolism caused by impaired astrocytes play a key role in the pathogenesis of epilepsy. This paper reviews the existing computational models of epileptogenesis resulting from impaired astrocytes and presents several open perspectives with regard to ion and energy metabolism-induced epileptogenesis in a neuron-astrocyte-capillary coupled model.     

A new method to test the cosmic distance duality relation using the strongly lensed gravitational waves

We propose a new method to test the cosmic distance duality relation using the strongly lensed gravitational waves. The simultaneous observation of the image positions, relative time delay between different images, redshift measurements of the lens and the source, together with the mass modelling of the lens galaxy, provide the angular diameter distance to the gravitational wave source. On the other hand, the luminosity distance to the source can be obtained from the observation of the gravitational wave signals. To our knowledge this is the first time a method is proposed to simultaneously measure the angular diameter distance and the luminosity distance from the same source. Hence, the strongly lensed gravitational waves provide a unique method to test the cosmic distance duality relation. With the construction of the third generation gravitational detectors such as the Einstein Telescope, it will be possible to test the cosmic distance duality relation with an accuracy of a few percent.     

Photoinduced dynamics of a cyanine dye: parallel pathways of non-radiative deactivation involving multiple excited-state twisted transients

Cyanine dyes are broadly used for fluorescence imaging and other photonic applications. 3,3′-Diethylthiacyanine (THIA) is a cyanine dye composed of two identical aromatic heterocyclic moieties linked with a single methine, –CH. The torsional degrees of freedom around the methine bonds provide routes for non-radiative decay, responsible for the inherently low fluorescence quantum yields. Using transient absorption spectroscopy, we determined that upon photoexcitation, the excited state relaxes along two parallel pathways producing three excited-state transients that undergo internal conversion to the ground state. The media viscosity impedes the molecular modes of ring rotation and preferentially affects one of the pathways of non-radiative decay, exerting a dominant effect on the emission properties of THIA. Concurrently, the polarity affects the energy of the transients involved in the decay pathways and further modulates the kinetics of non-radiative deactivation.     

Rational Design of an Ultrasensitive and Highly Selective Chemodosimeter by a Dual Quenching Mechanism for Cysteine Based on a Facile Michael‐Transcyclization Cascade Reaction

Differentiation of biologically important thiols, such as cysteine (Cys), homocysteine (Hcy), and glutathione (GSH) is still a challenging task. Herein, we present a novel fluorescent chemodosimeter capable of selectively detecting Cys over other biothiols including Hcy and GSH and other amino acids by a facile thiol‐Michael addition/transcyclization rearrangement cascade click process. The unique transcyclization step is critical for the selectivity as a result of the kinetically favorable formation of a six‐membered ring with the Cys Michael adduct. Moreover, the probe adopts a distinctive dual quenching mechanism—photoinduced electron transfer (PET) and photoinduced intramolecular charge transfer (ICT) to deliver a drastic turn‐on fluorescence response only at the Cys‐selective transcylization step. The judicious selection of strong electron‐withdrawing naphthalimide fluorophore with maleimide group enhances the electrophilicity and thus reactivity for the cascade process leading to fast detection and ultrasensitivity with a detection limit of 2.0 nm (S/N=3). The probe has demonstrated its practical utility potential in Cys imaging in live cells.     

Domino Radical Addition/Oxidation Sequence with Photocatalysis: One‐Pot Synthesis of Polysubstituted Furans from α‐Chloro‐Alkyl Ketones and Styrenes

A new domino reaction has been developed that allows the combination of styrenes and α‐alkyl ketone radicals to afford a wide array of polysubstituted furans in good to excellent yields under mild and simple reaction conditions. The key to success of this novel protocol is the use of photocatalyst fac‐Ir(ppy)₃ and oxidant K₂S₂O₈. Mechanistic studies by a radical scavenger and photoluminescence quenching suggest that a radical addition/oxidation pathway is operable.     

Salt effect on molecular orientation at air/liquid methanol interface

The salt effects on molecular orientation at air/liquid methanol interface were investigated by the polarization-dependent sum frequency generation vibrational spectroscopy(SFG-VS). We clarified that the average tilting angle of the methyl group to be u = 308 58 at the air/pure methanol surface assuming a d-function orientational distribution. Upon the addition of 3 mol/L Na I, the methyl group tilts further away from the surface normal with a new u = 418 38. This orientational change does not explain the enhancement of the SFG-VS intensities when adding Na I, implying the number density of the methanol molecules with a net polar ordering in the surface region also changed with the Na I concentrations. These spectroscopic findings shed new light on the salt effects on the surfaces structures of the polar organic solutions. It was also shown that the accurate determination of the bulk refractive indices and Raman depolarization ratios for different salt concentrations is crucial to quantitatively interpret the SFG-VS data.     

Lipase‐Supported Metal–Organic Framework Bioreactor Catalyzes Warfarin Synthesis

A green and sustainable strategy synthesizes clinical medicine warfarin anticoagulant by using lipase‐supported metal–organic framework (MOF) bioreactors (see scheme). These findings may be beneficial for future studies in the industrial production of chemical, pharmaceutical, and agrochemical precursors.