Experimental and theoretical study on the photoionization of styrene

This study employed a vacuum ultraviolet synchrotron radiation source and reflectron time-of-flight mass spectrometry (TOF-MS) to investigate the photoionization and dissociation of styrene. By analyzing the photoionization mass spectrum and efficiency curve alongside G3B3 theoretical calculations, we determined the ionization energy of the molecular ion, appearance energy of fragment ions, and relevant dissociation pathways. The major ion peaks observed in the photoionization mass spectra of styrene correspond to C₈H₈⁺, C₈H₇⁺ and C₆H₆⁺. The ionization energy of styrene is measured as 8.46 ± 0.03 eV, whereas the appearance energies of C₈H₇⁺ and C₆H₆⁺ are found to be 12.42 ± 0.03 and 12.22 ± 0.03 eV, respectively, in agreement with theoretical values. The main channel for the photodissociation of styrene molecular ions is the formation of benzene ions, whereas the dissociation channel that loses hydrogen atoms is the secondary channel. Based on the experimental results and empirical formulas, the required dissociation energies (E_d) of C₈H₇⁺, C₈H₆⁺ and C₆H₆⁺ are calculated to be (3.96 ± 0.06), (4.00 ± 0.06) and (3.76 ± 0.06) eV, respectively. Combined with related thermochemical parameters, the standard enthalpies of formations of C₈H₈⁺, C₈H₇⁺, C₈H₆⁺ and C₆H₆⁺ are determined to be 964.2, 1346.3, 1350.2 and 1327.0 kJ/mol, respectively. Based on the theoretical study, the kinetic factors controlling the styrene dissociation reaction process are determined by using the Rice–Ramsperger–Kassel–Marcus (RRKM) theory. This provides a reference for further research on the atmospheric photooxidation reaction mechanism of styrene in atmospheric and interstellar environments.     

中空碳材料用于钠离子电池负极的研究进展

实现钠离子电池等储能设备的大规模应用对于能源的可持续发展以及完成“碳达峰碳中和”目标具有重要意义.开发高性能的负极材料可提升钠离子电池的能量密度和循环稳定性,是实现钠离子电池大规模应用的关键性因素.中空碳材料因其独特的结构而具有优异的倍率性能与循环稳定性,作为钠离子负极材料具有广阔的应用前景.本文从多角度出发,综合评述了中空碳材料的合成方法,以及其形貌、杂原子修饰策略与储钠性能之间的关系,并对其未来发展方向进行了展望.     

A Highly Stable Copper‐Based Catalyst for Clarifying the Catalytic Roles of Cu0 and Cu+ Species in Methanol Dehydrogenation

Identification of the active copper species, and further illustration of the catalytic mechanism of Cu‐based catalysts is still a challenge because of the mobility and evolution of Cu⁰ and Cu⁺ species in the reaction process. Thus, an unprecedentedly stable Cu‐based catalyst was prepared by uniformly embedding Cu nanoparticles in a mesoporous silica shell allowing clarification of the catalytic roles of Cu⁰ and Cu⁺ in the dehydrogenation of methanol to methyl formate by combining isotope‐labeling experiment, in situ spectroscopy, and DFT calculations. It is shown that Cu⁰ sites promote the cleavage of the O?H bond in methanol and of the C?H bond in the reaction intermediates CH₃O and H₂COOCH₃ which is formed from CH₃O and HCHO, whereas Cu⁺ sites cause rapid decomposition of formaldehyde generated on the Cu⁰ sites into CO and H₂.     

MoS_2@Co_9S_8蛋黄壳复合材料的制备及其电化学性能

近年来,过渡金属硫化物已成为锂离子电池理想的负极材料之一。其中,MoS_2具有的独特二维层状结构使得其能够让Li+在电化学反应中可逆地嵌入和脱出,且拥有较高的理论储锂容量(670 m A·h/g)而受到广泛关注。但MoS_2作为典型的半导体材料,电导率低下且在锂离子嵌入-脱出的过程中会发生较大程度的体积收缩膨胀,所以具有较差的倍率性能和循环性能,限制了其商业化的使用。很多研究通过优化MoS_2结构或与其它导电材料复合来克服上述缺陷。Co_9S_8具有较高的电导率,但由于其迟缓的离子传输动力学表现出低的首次库仑效率及较差的循环稳定性,基于此,将MoS_2与Co_9S_8结合利用二者协同效应来提高复合材料的电化学性能。本文采用溶剂热与气相沉积法制备得MoS_2@Co_9S_8蛋黄结构复合材料电极。MoS_2与Co_9S_8均匀分布于整个蛋黄壳结构,这有利于电子和锂离子的快速传输,从而有效地提升了电极的循环性能和倍率性能。其次,蛋黄壳的空穴有效缓解了在充放电过程中的体积膨胀,及其活性位点有效缩短了离子和电子的传输距离,提高了电极反应动力学并获得高比容量。MoS_2@Co_9S_8蛋黄壳复合物的循环性能与倍率性能在同等条件下均高于Co_9S_8和MoS_2,在电流密度为0.2 A/g下循环500圈后,放电容量仍能维持在631.5 m A·h/g。     

A dynamic visco-hyperelastic model of dielectric elastomers and their energy dissipation characteristics

In this paper, we present a model describing the nonlinear dynamic visco-hyperelastic behaviors of dielectric elastomers (DE), with the purpose to explain the material’s dynamic energy dissipation mechanism, and provide convenience for actual design of DE devices. On the basic mechanical properties of the material, a visco-hyperelastic constitutive relationship, derived from Kelvin–Voigt rheological model and expressed as complex modulus, is created at first. Then, from the approximate relationship between harmonic motion frequency and the stretch rate (as well as the amplitude of stretch ratio) of the film, a new model-fitting approach is put forward to obtain the three intrinsic parameters, based on the uniaxial tensile tests for VHB 4910 DE film at different stretch rates (from 0.029 to 0.71 s^?1). Applying the proposed parameters, the hysteresis and energy dissipation behaviors of the DE film are subsequently predicted, showing good agreement with the experimental results. Finally, the influences of the kinematic variable pair on energy dissipation properties are quantitatively investigated.     

Analysis of five active ingredients of Er-Zhi-Wan,a traditional Chinese medicine water-honeyed pill,using the biopharmaceutics classification system

Er-Zhi-Wan (EZW) is a traditional Chinese medicine with many clinical applications and used as a health product in East Asia. Five active ingredients (salidroside, specnuezhenide, nuezhenoside, luteolin, and oleanolic acid) were screened out from EZW to develop an in vitro rapid evaluation method for the classification of in vivo drug absorption behavior by biopharmaceutics classification system (BCS). Ultra-performance liquid chromatography was used for quantitative analysis. Solubility and permeability were assayed by equilibrium solubility and multiple models: everted rat intestinal sac model, cultured Caco-2 cells, octanol–water partition coefficient (LogP) method. The BCS properties of drugs were predicted using software applications, and the correlations of measured and predicted values of factors affecting oral drug absorption were calculated. The results were verified by measuring the absolute bioavailability of the active ingredients. Salidroside, specnuezhenide, and nuezhenoside were classified as BCS class III drugs, and luteolin was classified as a BCS class III/I drug because of the difference in LogP and intestinal permeability. Oleanolic acid was classified as a BCS class II/IV drug in acidic media and BCS class I/III drug in other media. Overall, EZW may be classified as a BCS class III drug, and permeability was identified as the primary factor limiting absorption. The results provide a novel method for the evaluation of the in vivo absorption of oral traditional Chinese medicines.     

Highly Efficient Cyclic Dinucleotide Based Artificial Metalloribozymes for Enantioselective Friedel–Crafts Reactions in Water

The diverse secondary structures of nucleic acids are emerging as attractive chiral scaffolds to construct artificial metalloenzymes (ArMs) for enantioselective catalysis. DNA-based ArMs containing duplex and G-quadruplex scaffolds have been widely investigated, yet RNA-based ArMs are scarce. Here we report that a cyclic dinucleotide of c-di-AMP and Cu²⁺ ions assemble into an artificial metalloribozyme (c-di-AMP⋅Cu²⁺) that enables catalysis of enantioselective Friedel–Crafts reactions in aqueous media with high reactivity and excellent enantioselectivity of up to 97 % ee. The assembly of c-di-AMP⋅Cu²⁺ gives rise to a 20-fold rate acceleration compared to Cu²⁺ ions. Based on various biophysical techniques and density function theory (DFT) calculations, a fine coordination structure of c-di-AMP⋅Cu²⁺ metalloribozyme is suggested in which two c-di-AMP form a dimer scaffold and the Cu²⁺ ion is located in the center of an adenine-adenine plane through binding to two N7 nitrogen atoms and one phosphate oxygen atom.     

带有多点边条件的高阶微分算子的自共轭性

研究带有多点边条件的Sturm-Liouville问题,在新的Hilbert空间中,定义与多点边条件中连接特性相关的最大算子和最小算子,建立了带有多点边条件的高阶微分算子自共轭性的解析判别准则.