Fast Cysteine Bioconjugation Chemistry

Cysteine bioconjugation serves as a powerful tool in biological research and has been widely used for chemical modification of proteins, constructing antibody-drug conjugates, and enabling cell imaging studies. Cysteine conjugation reactions with fast kinetics and exquisite selectivity have been under heavy pursuit as they would allow clean protein modification with just stoichiometric amounts of reagents, which minimizes side reactions, simplifies purification and broadens functional group tolerance. In this concept, we summarize the recent advances in fast cysteine bioconjugation, and discuss the mechanism and chemical principles that underlie the high efficiencies of the newly developed cysteine reactive reagents.     

气体摩尔热容的拓展性教学

物质的摩尔热容是热量传递、熵增、焓变等计算中的重要参数之一。为让学生全面掌握摩尔热容的概念及其计算方法，以气体为例，基于文献调研，对理想气体、范德瓦尔斯气体、昂尼斯气体、雷德利克-邝气体的摩尔热容进行了系统化地归纳分析。利用热力学第一定律及热力学相关公式导出了改进型雷德利克-邝气体的摩尔热容。并对气体摩尔热容与物态方程的内在联系、摩尔定压热容与摩尔定体热容的差别进行了讨论与分析。这些研究结果对气体摩尔热容的拓展性教学及学生的创新性自学具有较好的参考价值。     

Mechanism and rate constants of the CH2 + CH2CO reactions in triplet and singlet states: A theoretical study

Ab initio and density functional CCSD(T)-F12/cc-pVQZ-f12//B2PLYPD3/6-311G** calculations have been performed to unravel the reaction mechanism of triplet and singlet methylene CH₂ with ketene CH₂CO. The computed potential energy diagrams and molecular properties have been then utilized in Rice–Ramsperger–Kassel–Marcus-Master Equation (RRKM-ME) calculations of the reaction rate constants and product branching ratios combined with the use of nonadiabatic transition state theory for spin-forbidden triplet-singlet isomerization. The results indicate that the most important channels of the reaction of ketene with triplet methylene lead to the formation of the HCCO + CH₃ and C₂H₄ + CO products, where the former channel is preferable at higher temperatures from 1000 K and above. In the C₂H₄ + CO product pair, the ethylene molecule can be formed either adiabatically in the triplet electronic state or via triplet-singlet intersystem crossing in the singlet electronic state occurring in the vicinity of the CH₂COCH₂ intermediate or along the pathway of CO elimination from the initial CH₂CH₂CO complex. The predominant products of the reaction of ketene with singlet methylene have been shown to be C₂H₄ + CO. The formation of these products mostly proceeds via a well-skipping mechanism but at high pressures may to some extent involve collisional stabilization of the CH₃CHCO and cyclic CH₂COCH₂ intermediates followed by their thermal unimolecular decomposition. The calculated rate constants at different pressures from 0.01 to 100 atm have been fitted by the modified Arrhenius expressions in the temperature range of 300–3000 K, which are proposed for kinetic modeling of ketene reactions in combustion. © 2018 Wiley Periodicals, Inc.     

A Weighted Trudinger–Moser Inequality on R^N and Its Application to Grushin Operator

Let x=(x',x')with x'∈Rk and x'∈R^N-k andΩbe a x'-symmetric and bounded domain in R^N(N≥2).We show that if 0≤a≤k-2,then there exists a positive constant C>0 such that for all x'-symmetric function u∈C0^∞(Ω)with∫Ω|■u(x)|^N-a|x'|^-adx≤1,the following uniform inequality holds1/∫Ω|x|^-adx∫Ωe^βa|u|N-a/N-a-1|x'|^-adx≤C,whereβa=(N-a)(2πN/2Γ(k-a/2)Γ(k/2)/Γ(k/2)r(N-a/2))1/N-a-1.Furthermore,βa can not be replaced by any greater number.As the application,we obtain some weighted Trudinger–Moser inequalities for x-symmetric function on Grushin space.     

Atmospheric oxidation chemistry of 1–methoxy 2–propyl acetate initiated by OH radicals: kinetics and mechanisms

Kinetics and mechanism of the gas-phase reaction of CH₃C(O)OCH(CH₃)CH₂OCH₃ (MPA) with OH radicals in the presence of O₂ and NO have been investigated theoretically by performing a high and reliable level of theory, viz., CCSD(T)/6-311?+?G(d,p)//BH&HLYP/6-311++G(d,p)?+?0.9335×ZPE. The calculations predict that the H-abstraction from the ?CH₂?O? position of MPA is the most facile channel, which leads to the formation of the corresponding alkoxy radicals CH₃C(O)OCH(CH₃)C(O ?)HOCH₃ under atmospheric conditions. This activated radicals CH₃C(O)OCH(CH₃)C(O ?)HOCH₃ will undergo further rearrangement, fragmentation and oxidative reactions and predominantly leads to the formation of various products (methyl formate HC(O)OCH₃ and acetic anhydride CH₃C(O)OC(O)CH₃). In the presence of water, acetic anhydride can convert into acetic acid CH₃C(O)OH via the hydrolysis reaction. The calculated total rate constants over the temperature range 263–372?K are used to derive a negative activation energy (E_a= ?5.88 kJ/mol) and an pre-exponential factor (A?=?1.78×10^?12 cm³ molecule^?1 s^?1). The obtained Arrhenius parameters presented here are in strong agreement with the experimental values. Moreover, the temperature dependence of the total rate constant over a temperature range of 263?1000?K can be described by k?=?5.60 × 10^?14×(T/298?K)^3.4×exp(1725.7?K/T) cm³ molecule^?1 s^?1.     

The opaque nature of generic examples: The structure of student teachers’ arguments in multiplicative reasoning

The study aims to explore the structural aspects of generic examples, to get better insight into what makes them potentially opaque for learners. We have analyzed 27 written arguments, for which student teachers (grades 1–10) were asked to use a generic example to prove a given statement in multiplication. Using Toulmin’s framework, we developed five categories of arguments based on their structure: examples, empirical arguments, leap arguments, embedded arguments, and other arguments. Also, we conclude that none of the student teachers provided arguments that we recognize as complete generic examples. The results bring us to a discussion about features of generic examples making them difficult to come to grips with, having implications for how teacher educators can support student teachers’ learning to prove. From this, we propose a definition of generic examples that attends to the criteria suggested in previous research, yet, emphasizing their structural nature.     

对《关于〈一维圆环上双原子链的马德隆常数〉的解析解》的讨论

本文绘制了一维等距离子晶体的累加法、埃夫琴法和平均值法的各级马德隆常数的曲线.本文推导了二聚化直线离子晶体马德隆常数的求和式,比较了两种解析式的优劣.本文详细地推导了圆环上等距和二聚化离子晶体的马德隆常数的解析式,使读者更易于理解.本文修正了《关于〈一维圆环上双原子链的马德隆常数〉的解析解》的两个笔误,还建议修正二聚化马德隆常数的定义式,使其物理意义更明显.     

一种改进的轨道动力学模型

航天器的矢径可以分解为矢径模和单位矢量的乘积,利用该性质将传统轨道动力学方程分解为矢径模和矢径方向的动力学方程组,实现了航天器位置信息的分离;针对两个方程分别采用常数变易法和四元数描述方法,将轨道动力学模型转化为线性无奇异的方程组,同时得到了7 个新轨道变量,且建立了新轨道变量与惯性系下航天器位置速度信息以及轨道六要素之间的相互转换关系. 该轨道模型适用于任意形式的推力和摄动,避免了奇异性,且在虚拟时间的意义下,航天器的旋转角速度只取决于法向力;在常值推力和变推力的情况下,对该模型进行了数值验证,验证了新模型的可适用性、数值稳定性以及计算精度高的优势.     

Novel low-dielectric constant and soluble polyimides from diamines containing fluorene and pyridine unit

Polyimides (PI's) with low-dielectric constant and excellent organic solubility have broad application prospects in the electronic field. Herein, this study designed a series of novel, low dielectric, organic soluble PI films by creatively introducing fluorene and pyridine ring into diamine monomers. Because of the noncoplanar structure of fluorenyl and the polarization of pyridine ring, PI films achieved a low-dielectric constant (2.22–3.09 at 10 MHz) and excellent organic solubility. Even in some organic solvents with low-boiling points, these PI films still exhibited outstanding solubility. In addition, all the films possessed high-tensile strength (≈120 MPa) and excellent optical transparency (>70%, 450 nm). It was worth noting that the glass transition temperature of films was all above 280°C and 5% weight loss temperature (T_5%) was at 486–553°C. In general, the novel high-performance low-dielectric PI films are expected to be used in the field of microelectronics.