Hemin-histamine-montmorillonite clay conjugate as a model biocatalyst to mimic natural peroxidase

We successfully synthesized the first hemin-montmorillonite bio-conjugate with an amino acid residue to mimic natural peroxidase enzyme. Histamine was intercalated in montmorillonite by cation exchange, then a hemin molecule was loaded onto the histamine-montmorillonite with an adsorption capacity of 7.0 mg g-1. The hemin-histamine-montmorillonite conjugate shows high peroxidase activity as indicated by the oxidation of guaiacol, which is attributed to the activation of hemin by Fe–N complex formation between the imidazole group in histamine and the iron ion in the hemin molecule. Temperature- dependent peroxidase activity for this synthesized biomimetic material indicates that raising the reaction temperature could significantly enhance the activity of the conjugate. The biomimetic catalyst has good reusability; nearly 100% activity can be retained after three cycles. Because montmorillonite clay is widely distributed in the environment, this material offers great potential for in situ and ex situ remediation of many organic contaminants in surface/subsurface soils.     

Ferrocenylethynyl‐Terminated Azobenzenes: Synthesis,Electrochemical, and Photoisomerization Studies

Ferrocenylethynyl‐terminated derivatives 8 – 12 have been synthesized and characterized by electrochemistry and UV/Vis spectroscopy. The electrochemical and photophysical studies indicate that the electronic communication in ferrocenylethynyl‐substituted derivatives is strongly influenced by the substituted position of the ferrocenylethynyl moiety. In situ electrochemical oxidation or chemical oxidation caused a characteristically weak ligand‐to‐metal charge‐transfer (LMCT) band to appear at 700–1000 nm. Subsequent electrochemical reduction or chemical reduction recovered the most of the original curve and the color of the solution as well. Among the derivatives, compound 8 exhibits the highest cis/trans molar ratio (64:36) in the photostationary state (PSS) upon light irradiation at 365 nm. Compound 8 exhibits excellent fatigue resistance and reversibility under several repeated reversible isomerization cycles.     

Operando X-ray absorption and EPR evidence for a single electron redox process in copper catalysis

An unprecedented single electron redox process in copper catalysis is confirmed using operando X-ray absorption and EPR spectroscopies. The oxidation state of the copper species in the interaction between Cu(ii) and a sulfinic acid at room temperature, and the accurate characterization of the formed Cu(i) are clearly shown using operando X-ray absorption and EPR evidence. Further investigation of anion effects on Cu(ii) discloses that bromine ions can dramatically increase the rate of the redox process. Moreover, it is proven that the sulfinic acids are converted into sulfonyl radicals, which can be trapped by 2-arylacrylic acids and various valuable β-keto sulfones are synthesized with good to excellent yields under mild conditions.     

A three‐dimensional cadmium(II) coordination polymer with unequal homochiral double‐stranded concentric helical chains

A homochiral helical three‐dimensional coordination polymer, poly[[(μ₂‐acetato‐κ³O,O′:O)(hydroxido‐κO)(μ₄‐5‐nicotinamido‐1H‐1,2,3,4‐tetrazol‐1‐ido‐κ⁵N¹,O:N²:N⁴:N⁵)(μ₃‐5‐nicotinamido‐1H‐1,2,3,4‐tetrazol‐1‐ido‐κ⁴N¹,O:N²:N⁴:N⁵)dicadmium(II)] 0.75‐hydrate], {[Cd₂(C₇H₅N₆O)₂(CH₃COO)(OH)]·0.75H₂O}_n, was synthesized by the reaction of cadmium acetate, N‐(1H‐tetrazol‐5‐yl)isonicotinamide (H‐NTIA), ethanol and H₂O under hydrothermal conditions. The asymmetric unit contains two crystallographically independent Cd^II cations, two deprotonated 5‐nicotinamido‐1H‐1,2,3,4‐tetrazol‐1‐ide (NTIA⁻) ligands, one acetate anion, one hydroxide anion and three independent partially occupied water sites. The two Cd^II cations, with six‐coordinated octahedral and seven‐coordinated pentagonal bipyramidal geometries are located on general sites. The tetrazole group of one symmetry‐independent NTIA⁻ ligand links one of the independent Cd^II cations into 6₁ helical chains, while the other NTIA⁻ ligand links the other independent Cd^II cations into similar but unequal 6₁ helical chains. These chains, with a pitch of 24.937 (5) Å, intertwine into a double‐stranded helix. Each of the double‐stranded 6₁ helices is further connected to six adjacent helical chains through an acetate μ₂‐O atom and the tetrazole group of the NTIA⁻ ligand into a three‐dimensional framework. The helical channel is occupied by the isonicotinamide groups of NTIA⁻ ligands and two helices are connected to each other through the pyridine N and carbonyl O atoms of isonicotinamide groups. In addition, N—H...O and O—H...N hydrogen bonds exist in the complex.     

A free boundary problem arising from DCIS mathematical model

Ductal carcinoma in situ – a special cancer – is confined within the breast ductal only. We derive the mathematical ductal carcinoma in situ model in a form of a nonlinear parabolic equation with initial, boundary, and free boundary conditions. Existence, uniqueness, and stability of problem are proved. Algorithm and illustrative examples are included to demonstrate the validity and applicability of the technique in this paper. Copyright © 2016 John Wiley & Sons, Ltd.     

Understanding Molecular Dynamics with Stochastic Processes via Real or Virtual Dynamics

Molecular dynamics with the stochastic process provides a convenient way to compute structural and thermodynamic properties of chemical, biological, and materials systems. It is demonstrated that the virtual dynamics case that we proposed for the Langevin equation[J. Chem. Phys. 147 , 184104 (2017)] in principle exists in other types of stochastic thermostats as well. The recommended "middle" scheme[J. Chem. Phys. 147 , 034109 (2017)] of the Andersen thermostat is investigated as an example. As shown by both analytic and numerical results, while the real and virtual dynamics cases approach the same plateau of the characteristic correlation time in the high collision frequency limit, the accuracy and efficiency of sampling are relatively insensitive to the value of the collision frequency in a broad range. After we compare the behaviors of the Andersen thermostat to those of Langevin dynamics, a heuristic schematic representation is proposed for understanding efficient stochastic thermostatting processes with molecular dynamics.     

基于黄酮的ESIPT型荧光探针检测三苯基膦

三苯基膦(PPh3)是一种重要的有机化合物,具有亲核性和还原性,已被广泛用于有机合成和有机金属化合物配位中。然而PPh3的过量使用不可避免地会引起环境的污染,并且对人体的健康也具有潜在威胁。因此我们迫切需要一种方便而高效的检测PPh3的方法。已有检测方法在便捷性和灵敏性等方面不如人意,而小分子荧光探针因其灵敏度高、选择性好、检测简单等优点受到广泛关注。受生物标记领域常用的无痕Staudinger连接反应的启发,本文设计合成了一个类似Staudinger连接反应,以能够具有固态发光性质的激发态分子内质子转移(ESIPT)特性的3-羟基黄酮荧光染料为母核,以邻叠氮苯乙酸酯为识别基团,用于检测PPh3的荧光增强型的探针分子。通过叠氮与PPh3反应,经过氮杂叶立德中间体,进行快速的分子内酰胺化,释放3-羟基黄酮染料并恢复荧光发射,从而实现在溶液中及滤纸上快速检测PPh3的目的。该探针在定量和定性检测PPh3方面具有潜在应用价值。     

高效大面积有机白光照明研究及其展望

白光有机发光二极管(OLED)是新一代健康节能照明光源,光效性能已超过荧光灯水平。自从OLED技术问世以来,研究人员陆续开展了关于OLED照明的研究工作。本文介绍了OLED照明的特点,以及国内外OLED照明发展现状,讨论了发展OLED照明技术和装备国产化所亟待解决的重大难题和面临的挑战,重点论述了发展高效大面积OLED照明器件制备技术及推动OLED照明产业化的重要意义。     

广义算子半群的PERRON问题

借助于广义算子半群和广义积分算子半群的关系,讨论广义算子半群的Perron型指数稳定性,研究了广义积分算子半群的渐近行为.     

李color三系的Frattini子系的性质

给出了李color三系的Frattini子系的定义,得到了李color三系的Frattini子系的一些性质·特别的,证明了李color三系T有分解T=T_1⊕T_2⊕…⊕T_m,则φ(T)有分解φ(T)=φ(T_1)⊕φ(T_2)⊕…⊕φ(T_m).