Thermodynamic studies on protonation constant of adenosine and guanosine at different temperatures and ionic strengths

Stepwise protonation constants of two purine nucleosides (adenosine and guanosine) were determined at different temperatures (293.15 to 308.15) and various ionic strengths (0.101 to 3.503 mol · kg⁻¹ NaClO₄) using a combination of potentiometric and spectrophotometric method. The thermodynamic parameters (i.e. enthalpy change, ΔH, and entropy change, ΔS) of the protonations were calculated at different temperatures using van’t Hoff and virial equations. The dependence of the protonation constant on ionic strength is modeled by a Debye–Hückel type equation and discussed. Finally, the protonation constants of the nucleosides and the enthalpy change of protonations were determined at zero ionic strength.     

Dividing a complex reaction involving a hypervalent iodine reagent into three limiting mechanisms by ab initio molecular dynamics

The electrophilic N‐trifluoromethylation of MeCN with a hypervalent iodine reagent to form a nitrilium ion, that is rapidly trapped by an azole nucleophile, is thought to occur via reductive elimination (RE). A recent study showed that, depending on the solvent representation, the S_N2 is favoured to a different extent over the RE. However, there is a discriminative solvent effect present, which calls for a statistical mechanics approach to fully account for the entropic contributions. In this study, we perform metadynamic simulations for two trifluoromethylation reactions (with N‐ and S‐nucleophiles), showing that the RE mechanism is always favoured in MeCN solution. These computations also indicate that a radical mechanism (single electron transfer) may play an important role. The computational protocol based on accelerated molecular dynamics for the exploration of the free energy surface is transferable and will be applied to similar reactions to investigate other electrophiles on the reagent. Based on the activation parameters determined, this approach also gives insight into the mechanistic details of the trifluoromethylation and shows that these commonly known mechanisms mark the limits within which the reaction proceeds. © 2015 Wiley Periodicals, Inc.     

Quantum properties of nonclassical states generated by an optomechanical system with catalytic quantum scissors

A scheme is proposed to investigate the non-classical states generated by a quantum scissors device (QSD) operating on the the cavity mode of an optomechanical system. When the catalytic QSD acts on the cavity mode of the optomechanical system, the resulting state contains only the vacuum, single-photon and two-photon states depending upon the coupling parameter of the optomechanical system as well as the transmission coefficients of beam splitters (BSs). Especially, the output state is just a class of multicomponent cat state truncations at time t=2π by choosing the appropriate value of coupling parameter. We discuss the success probability of such a state and the fidelity between the output state and input state via QSD. Then the linear entropy is used to investigate the entanglement between the two subsystems, finding that QSD operation can enhance their entanglement degree. Furthermore, we also derive the analytical expression of the Wigner function (WF) for the cavity mode via QSD and numerically analyze the WF distribution in phase space at time t=2π. These results show that the high non-classicality of output state can always be achieved by modulating the coupling parameter of the optomechanical system as well as the transmittance of BSs.     

Sodiation Of Hard Carbon: How Separating Enthalpy And Entropy Contributions Can Find Transitions Hidden In The Voltage Profile

Sodium-ion batteries (NIBs) utilize cheaper materials than lithium-ion batteries (LIBs) and can thus be used in larger scale applications. The preferred anode material is hard carbon, because sodium cannot be inserted into graphite. We apply experimental entropy profiling (EP), where the cell temperature is changed under open circuit conditions. EP has been used to characterize LIBs; here, we demonstrate the first application of EP to any NIB material. The voltage versus sodiation fraction curves (voltage profiles) of hard carbon lack clear features, consisting only of a slope and a plateau, making it difficult to clarify the structural features of hard carbon that could optimize cell performance. We find additional features through EP that are masked in the voltage profiles. We fit lattice gas models of hard carbon sodiation to experimental EP and system enthalpy, obtaining: 1. a theoretical maximum capacity, 2. interlayer versus pore filled sodium with state of charge.     

High-entropy transition metal chalcogenides as electrocatalysts for renewable energy conversion

High-entropy transition metal chalcogenides (HE-TMCs) are advantageous in electrocatalytic applications compared to other entropy-stabilized systems owing to the greater orbital extension and energetic match of p-orbitals in chalcogenides with d-orbitals of the transition metals providing additional space to tailor their electronic structure. The high-configurational entropy of HE-TMCs leads to stabilization of cubic rock salt, wurtzite-type and hexagonally packed 2D structures. Due to the multi-element nature of HE-TMCs, the synergy among different elements results in tunable d- and p-band positions. As a consequence, the adsorption energies of electrocatalytic reaction intermediates can be tailored to enhance catalytic performance in water splitting and CO₂ reduction. Furthermore, the entropy-stabilized disordered microstructural state of the material endows HE-TMCs with improved corrosion resistance. Despite recent advances in HE-TMC electrocatalysis, challenges such as identification and synthesis of efficient HE-TMCs as well as the identification of catalytically active sites and reaction mechanisms on HE-TMCs remain to be investigated.     

Free volume,molecular grains,self-organisation,and anisotropic entropy: machining materials

ABSTRACT

In this article, the relationship between molecular architecture and the formation of twist-bend phases is reviewed under the context of shape dependency. We conclude that the twist-bend phase is a universal phenomenon, which occurs in a wide variety of materials, for dimers through to main chain polymers. In the process, the chemical information on molecular design is effectively lost or irrelevant, and molecular topology takes precedence over electrostatic interactions in mesophase formation. As a consequence of this macro-scale material, engineering by shape alone becomes a possibility, potentially more phases may be realised, and entropy is anisotropic.     

Abel群的一些分解定理的推广(I)

这项研究的目的是要把Abel群（有限或无限）的诸多分解定理尽可能地推广到主理想整环的模上,得到这类模上的分解定理,随后再把所得定理应用到向量空间（有限维或无限维）及其线性变换,得到向量空间的分解定理.本文是系列文章的第一篇,主要目的是建立起支撑整个研究的最基本概念,例如纯子模、有界模、局部循环模、具有minimax条件的模等.本文主要内容有： （1）确定了主理想整环上可除模、有界模、局部循环模的结构; （2）给出了主理想整环上拟循环模的生成性质,这类模在以后的研究里起着非常重要的作用; （3）描述了主理想整环上满足极小条件,minimax条件的模的结构; （4）给出了两个不同构的Z[i]-模,它们作为Abel群是同构的.     

所有极大子群都为SMSN-群的有限群

若有限群G的每个2-极大子群在G中次正规,则称G为SMSN-群.本文研究了有限群G的每个真子群是SMSN-群但G本身不是SMSN-群的结构,利用局部分析的方法,获得了这类群的完整分类,推广了有限群结构理论的一些成果.     

Continuous spin models on annealed generalized random graphs

We study Gibbs distributions of spins taking values in a general compact Polish space, interacting via a pair potential along the edges of a generalized random graph with a given asymptotic weight distribution $P$, obtained by annealing over the random graph distribution.First we prove a variational formula for the corresponding annealed pressure and provide criteria for absence of phase transitions in the general case.We furthermore study classes of models with second order phase transitions which include rotation-invariant models on spheres and models on intervals, and classify their critical exponents. We find critical exponents which are modified relative to the corresponding mean-field values when $P$ becomes too heavy-tailed, in which case they move continuously with the tail-exponent of $P$. For large classes of models they are the same as for the Ising model treated in Dommers et al. (2016). On the other hand, we provide conditions under which the model is in a different universality class, and construct an explicit example of such a model on the interval.     

广义Khasminskii条件下自变量分段连续型带Poisson随机测度随机微分方程Euler方法的依概率收敛性

针对满足广义Khasminskii条件的由维纳过程和泊松随机测度驱动的自变量分段连续型随机微分方程(EPCASDEs),给出了Euler方法,广义Khasminskii条件比经典条件包容了更多的EPC.ASDEs.现有文献对该类方程的研究成果较少.针对EPCASDEs在广义Khasminskii条件下证明了全局解的存在唯一性,并研究了Euler方法的依概率收敛性.给出了数值算例支持主要结论.