非定常输运问题适应于消息传递并行编程环境的香农熵计算方法

在多计算步的非定常输运问题的蒙特卡罗模拟中,为自动调整每一步的样本数以获得较高的计算效率,可以有多种准则.一种可选的方法是在每一步每隔若干样本监测一次系统中未死亡粒子属性分布对应的香农熵的收敛情况以决定何时停止追加样本,此种方法需要在每一步频繁计算香农熵值.由于在MPI消息传递并行编程环境下香农熵的经典计算方法必须广播大量的数据,导致每一步的计算时间随香农熵计算频率的提高而快速增大,这显然是不能满足实际需求的.本文提出了一种适应于消息传递并行编程环境的香农熵计算新方法,该方法计算得到的香农熵值并不等价于经典方法,但二者之间的差别会随着样本数的增加而趋于零.新方法的最大优势是高频计算香农熵值的时间代价大为降低,为最终实现基于香农熵收敛判断的每步样本数的自动调整奠定了必要的基础.     

The total synthesis of roquefortine C and a rationale for the thermodynamic stability of isoroquefortine C over roquefortine C

The first total synthesis of roquefortine C is achieved by implementation of a novel elimination strategy to construct the thermodynamically unstable E-dehydrohistidine moiety. Molecular modeling studies are presented which explain the instability of the roquefortine C structure compared to that of isoroquefortine C.     

Expression and Characterization of a Novel Enantioselective Lipase from Aspergillus fumigatus

A 1,080-bp cDNA (CGMCC 2873) encoding of a cold-active lipase of Aspergillus fumigatus (AFL67) was cloned and expressed in Escherichia coli for the first time. The new lipase, AFL67, was one-step purified by 8.30 folds through Ni?CNTA affinity chromatography with a recovery of 86.8?%. The specific activity of purified AFL67 was 449?U?mg^?1 on p-NP hexanoate. AFL67 preferentially hydrolyzed p-nitrophenyl esters of short- and medium-chain fatty acids, with p-nitrophenyl hexanoate the maximum. The optimum temperature and pH was 15?°C and 7.5, respectively. The purified AFL67 was stable at 10?C25?°C for 30?min, and in the pH range of 6.0?C9.0 for 16?h (at 4?°C). Its activity was increased by 47 and 50?%, in the presence of 10?% (v/v) ethanol and isopropanol, respectively. The new lipase AFL67 highly enantioselectively deacylated (S)-??-acetoxyphenylacetic acid (APA) and o-Cl-APA, m-Cl-APA, and p-Cl-APA to (S)-mandelic acid and its derivates. These features render this cold-active novel lipase AFL67 attractive for biotechnological applications in the field of enantioselective synthesis of chiral mandelic acids, o-acylated mandelic acids, and their derivates and detergent additives.     

Effect of disorder with long-range correlation on transport in graphene nanoribbon

Transport in disordered armchair graphene nanoribbons (AGR) with long-range correlation between quantum wire contacts is investigated by a transfer matrix combined with Landauer's formula. The metal-insulator transition is induced by disorder in neutral AGR. Therein, the conductance is one conductance quantum for the metallic phase and exponentially decays otherwise, when the length of AGR approaches infinity and far longer than its width. Similar to the case of long-range disorder, the conductance of neutral AGR first increases and then decreases while the conductance of doped AGR monotonically decreases, as the disorder strength increases. In the presence of strong disorder, the conductivity depends monotonically and non-monotonically on the aspect ratio for heavily doped and slightly doped AGR, respectively. For edge disordered graphene nanoribbon, the conductance increases with the disorder strength of long-range correlated disordered while no delocalization exists, since the edge disorder induces localization.     

Synthesis and Biological Evaluation of 3-Aryl-quinoxaline-2-carbonitrile 1,4-Di-<em>N</em>-oxide Derivatives as Hypoxic Selective Anti-tumor Agents

A series of 3-aryl-2-quinoxaline-carbonitrile 1,4-di-N-oxide derivatives were designed, synthesized and evaluated for hypoxic and normoxic cytotoxic activity against human SMMC-7721, K562, KB, A549 and PC-3 cell lines. Many of these new compounds displayed more potent hypoxic cytotoxic activity compared with TX-402 and TPZ in the tumor cells based evaluation, which confirmed our hypothesis that the replacement of the 3-amine with the substituted aryl ring of TX-402 increases the hypoxic anti-tumor activity. The preliminary SAR revealed that 3-chloro was a favorable substituent in the phenyl ring for hypoxic cytotoxicity and 7-methyl or 7-methoxy substituted derivatives exhibited better hypoxic selectivity against most of the tested cell lines. The most potent compound, 7-methyl-3-(3-chlorophenyl)-quinoxaline-2-carbonitrile 1,4-dioxide (9h) was selected for further anti-tumor evaluation and mechanistic study. It also exhibited significant cytotoxic activity against BEL-7402, HepG2, HL-60, NCI-H460, HCT-116 and CHP126 cell lines in hypoxia with IC₅₀ values ranging from 0.31 to 3.16 μM, and preliminary mechanism study revealed that 9h induced apoptosis in a caspase-dependent pathway.     

Mechanism of thio acid/azide amidation

A combined experimental and computational mechanistic study of amide formation from thio acids and azides is described. The data support two distinct mechanistic pathways dependent on the electronic character of the azide component. Relatively electron-rich azides undergo bimolecular coupling with thiocarboxylates via an anion-accelerated [3+2] cycloaddition to give a thiatriazoline. Highly electron-poor azides couple via bimolecular union of the terminal nitrogen of the azide with sulfur of the thiocarboxylate to give a linear adduct. Cyclization of this intermediate gives a thiatriazoline. Decomposition to amide is found to proceed via retro-[3+2] cycloaddition of the neutral thiatriazoline intermediates. Computational analysis (DFT, 6-31+G(d)) identified pathways by which both classes of azide undergo [3+2] cycloaddition with thio acid to give thiatriazoline intermediates, although these paths are higher in energy than the thiocarboxylate amidations. These studies also establish that the reaction profile of electron-poor azides is attributable to a prior capture mechanism followed by intramolecular acylation.     

A query on crystallization temperature‐dependent cooling function under nonisothermal condition

The cooling function (κ) in Ozawa model was investigated through theoretic analysis and experimental method. Different from the fact accepted by researchers over past decades that κ(T) depends only on the crystallization temperature (T) and consequently the parameters for nonisothermal crystallization kinetics could be obtained by plotting ln[? ln(1 ? X(T))] versus ln λ at a given T, we found that κ at a given T was also dependent on onset temperature (T₀) of crystallization process. Because T₀ varies with cooling rate (λ) in nonisothermal crystallization, we conclude that κ is a binary function of T and λ, which was validated by our kinetic data from differential scanning calorimetry measurement in a wide λ range from 1 to 80 °C/min. It is suggested that the conventional method for calculating kinetic parameters based on Ozawa model, by plotting ln[? ln(1 ? X(T))] versus ln λ, might not be exact for nonisothermal crystallization. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44:795–800, 2006     

Some intriguing upper bounds for separating hash families

An N ×n matrix on q symbols is called {w_1,...,w_t}-separating if for arbitrary t pairwise disjoint column sets C_1,..., C_t with |C_i|=w_i for 1 ≤i≤t, there exists a row f such that f(C_1),...,f(C_t) are also pairwise disjoint, where f(C_i) denotes the collection of componentn of C_i restricted to row f. Given integers N, q and w_1,...,w_t, denote by C(N,q,{w_1,...,w_t}) the maximal a such that a corresponding matrix does exist.The determination of C(N,q,{w_1,...,w_t}) has received remarkable attention during the recent years. The main purpose of this paper is to introduce two novel methodologies to attack the upper bound of C(N, q, {w_1,...,w_t}).The first one is a combination of the famous graph removal lemma in extremal graph theory and a Johnson-type recursive inequality in coding theory, and the second onc is the probabilistic method. As a consequence, we obtain several intriguing upper bounds for some parameters of C(N,q,{w_1,...,w_t}), which significantly improve the previously known results.     

In situ One-Pot Fabrication of MoO3-x Clusters Modified Polymer Carbon Nitride for Enhanced Photocatalytic Hydrogen Evolution

Developing low-cost and high-efficient noble-metal-free cocatalysts has been a challenge to achieve economic hydrogen production. In this work, molybdenum oxides (MoO\begin{document}$_{3-x}$\end{document}) were in situ loaded on polymer carbon nitride (PCN) via a simple one-pot impregnation-calcination approach. Different from post-impregnation method, intimate coupling interface between high-dispersed ultra-small MoO\begin{document}$_{3-x}$\end{document} nanocrystal and PCN was successfully formed during the in situ growth process. The MoO\begin{document}$_{3-x}$\end{document}-PCN-\begin{document}$X$\end{document} (\begin{document}$X$\end{document}=1, 2, 3, 4) photocatalyst without noble platinum (Pt) finally exhibited enhanced photocatalytic hydrogen performance under visible light irradiation (\begin{document}$\lambda$\end{document}\begin{document}$>$\end{document}420 nm), with the highest hydrogen evolution rate of 15.6 μmol/h, which was more than 3 times that of bulk PCN. Detailed structure-performance revealed that such improvement in visible-light hydrogen production activity originated from the intimate interfacial interaction between high-dispersed ultra-small MoO\begin{document}$_{3-x}$\end{document} nanocrystal and polymer carbon nitride as well as efficient charge carriers transfer brought by Schottky junction formed.