Fluorobenziodoxole−BF3 Reagent for Iodo(III)etherification of Alkynes in Ethereal Solvent

A combination of fluorobenziodoxole (FBX) and BF₃ ? OEt₂ in cyclopentyl methyl ether promotes regio‐ and stereoselective addition of benziodoxole and methoxy groups to alkynes. This difunctionalization reaction tolerates a variety of functionalized internal and terminal alkynes to afford trans‐β‐alkoxyvinylbenziodoxoles, which represent versatile precursors to stereochemically well‐defined multisubstituted vinyl ethers. The reaction is proposed to involve cleavage of the I?F bond of FBX by BF₃, followed by electrophilic activation of the alkyne by the resulting cationic I^III species that triggers the nucleophilic addition of the ethereal oxygen.     

Hybrid Copolymerization via the Combination of Proton Transfer and Ring-opening Polymerization

Phosphazene base,t-BuP2,was employed to catalyze the proton transfer polymerization(PTP)of 2-hydroxyethyl acrylate(HEA),and PTP was further combined with ring-opening polymerization(ROP)to exploit a new type of hybrid copolymerization.The studies on homopolymerization showed that t-BuP2 was a particularly efficient catalyst for the polymerization of HEA at room temperature,giving an excellent monomer conversion.Throughout the polymerization,transesterification reactions were unavoidable,which increased the randomness in the structures of the resulting polymers.The studies on copolymerization showed that t-BuP2 could simultaneously catalyze the hybrid copolymerization via the combination of PTP and ROP at 25°C.During copolymerization,HEA not only provided hydroxyl groups to initiate the ROP ofε-caprolactone(CL)but also participated in the polymerization as a monomer for PTP.The copolymer composition was approximately equal to the feed ratio,demonstrating the possibility to adjust the polymeric structure by simply changing the monomer feed ratio.This copolymerization reaction provides a simple method for synthesizing degradable functional copolymers from commercially available materials.Hence,it is important not only in polymer chemistry but also in environmental and biomedical engineering.     

金属有机框架材料UTSA-74高效去除水溶液中的砷

利用水热法合成金属有机框架材料UTSA-74,并用它同时去除水中的As(Ⅴ)和As(Ⅲ)。 批次实验结果表明,在低质量浓度情况下(~1 mg/L),UTSA-74对As(Ⅴ)的去除率高达95%。 对As(Ⅲ)的去除率达85%。 经拟合,本实验符合拟二级动力学及Freundlich等温吸附模型。 本文还探究了共存离子(如Cl^-、NO₃^-、PO₄^3-)干扰影响,结果表明PO₄^3-的存在会抑制吸附的进行,可能是由于竞争吸附位点所致。 此外,本文对吸附后的材料进行洗脱(0.1 mol/L NaOH),将洗脱后的UTSA-74材料再次进行吸附探究,反复3次,其去除率仍可达70%左右。 为探究其中机理,本文通过X射线衍射(XRD)、扫描电子显微镜(SEM)、红外光谱(IR)对吸附前后材料进行表征,结果表明吸附过程中可能形成了Zn—O—As,以此促进吸附反应的进行。 综上所述,UTSA-74可以作为一种处理砷的新型吸附剂,具有一定的实用价值。     

Highly Selective CO2 Electroreduction to CH4 by In Situ Generated Cu2O Single-Type Sites on a Conductive MOF: Stabilizing Key Intermediates with Hydrogen Bonding

It is still a great challenge to achieve high selectivity of CH₄ in CO₂ electroreduction reactions (CO₂RR) because of the similar reduction potentials of possible products and the sluggish kinetics for CO₂ activation. Stabilizing key reaction intermediates by single type of active sites supported on porous conductive material is crucial to achieve high selectivity for single product such as CH₄. Here, Cu₂O(111) quantum dots with an average size of 3.5 nm are in situ synthesized on a porous conductive copper-based metal–organic framework (CuHHTP), exhibiting high selectivity of 73 % towards CH₄ with partial current density of 10.8 mA cm⁻² at −1.4 V vs. RHE (reversible hydrogen electrode) in CO₂RR. Operando infrared spectroscopy and DFT calculations reveal that the key intermediates (such as *CH₂O and *OCH₃) involved in the pathway of CH₄ formation are stabilized by the single active Cu₂O(111) and hydrogen bonding, thus generating CH₄ instead of CO.     

An alternative approach to Privault's discrete-time chaotic calculus

In this paper, we present an alternative approach to Privault's discrete-time chaotic calculus. Let Z be an appropriate stochastic process indexed by N (the set of nonnegative integers) and l²(Γ) the space of square summable functions defined on Γ (the finite power set of N). First we introduce a stochastic integral operator J with respect to Z, which, unlike discrete multiple Wiener integral operators, acts on l²(Γ). And then we show how to define the gradient and divergence by means of the operator J and the combinatorial properties of l²(Γ). We also prove in our setting the main results of the discrete-time chaotic calculus like the Clark formula, the integration by parts formula, etc. Finally we show an application of the gradient and divergence operators to quantum probability.     

Influence of substrate temperature on surface textured ZnO:Al films etched with NaOH solution

Transparent conducting Al-doped ZnO (ZnO:Al, AZO) thin films with good optical and electrical characteristics were prepared by direct current pulse magnetron sputtering. Textured surfaces of AZO films were obtained by etching with NaOH solution successfully and the effect of substrate temperature on the surface texture was investigated. The surface is covered with craters after etching with 5% NaOH solution, and the crater diameter decreases gradually as substrate temperature increases. For AZO film deposited at 270, the crater diameters is 0.5-1 μm, which is an effective surface texture for light trapping.     

O2流量对磁控溅射N掺杂TiO2薄膜成分及晶体结构的影响

利用直流脉冲磁控溅射方法在室温下通过改变O₂流量制备具有不同晶体结构的N掺杂TiO₂薄膜,利用台阶仪、X射线光电子能谱仪、X射线衍射仪、紫外-可见分光光度计等设备对薄膜沉积速率、化学成分、晶体结构、禁带宽度等进行分析.结果表明:所制备的薄膜元素配比约为TiO_1.68±0.06N_0.11±0.01,N为替位掺杂,所有样品退火前后均未形成Ti—N相结构,N掺杂TiO₂薄膜的沉积速率、晶体结构等主要依赖于O₂流量.在O₂流量为2 sccm时,N掺杂TiO₂薄膜沉积速率相对较高,薄膜为非晶态结构,但薄膜内含有锐钛矿(anatase)和金红石(rutile)相晶核,退火后薄膜呈anatase和rutile相混合结构,禁带宽度仅为2.86 eV.随着O₂流量的增加,薄膜沉积速率单调下降,退火后样品禁带宽度逐渐增加.当O₂流量为12 sccm时,薄膜为anatase相择优生长,退火后呈anatase相结构,禁带宽度为3.2 eV.综合本实验的分析结果,要在室温条件下制备晶态N掺杂TiO₂薄膜,需在高O₂流量(＞10 sccn)条件下制备. 关键词： 2薄膜')" href="#">N掺杂TiO₂薄膜 磁控溅射 化学配比 晶体结构     

混沌量子克隆算法求解认知无线网络频谱分配问题

对认知无线网络中的频谱进行有效分配是实现动态频谱接入的关键技术.考虑3次用户对频谱的需求和分配的公平性,给出了频谱分配的数学模型,并将其转换为以最大化网络收益为目标的带约束优化问题,进而提出一种采用混沌量子克隆优化求解的认知无线网络频谱分配算法, 并证明了该算法以概率1收敛.最后,通过仿真实验比较了本文算法与颜色敏感图着色算法、基于遗传算法的频谱分配、基于量子遗传算法的频谱分配的性能.结果表明:本文算法性能较优, 能更好地实现网络收益最大化. 关键词： 混沌量子克隆算法 认知无线网络 频谱分配     

Electrochemical behavior of uranyl in ionic liquid 1-butyl-3-methylimidazolium chloride mixture with water

Electrochemical behaviors of U(VI) in 1-butyl-3-methylimidazolium chloride (C₄MimCl) with various water contents investigated by chronopotentiometry and cyclic voltammetry. The electrochemical reduction of U(VI) was identified to follow two processes: a lower valence intermediate U(V) was initially formed at the potential of ca. ?0.2 V(vs. Ag wire). Then, further deposition of UO₂ was followed at around ?0.8 V. Little amount of water (1–4 wt%) in C₄MimCl, however, has an effect on the U(VI) reduction by changing the current density of the redox reaction and the diffusion coefficient of U(VI) in C₄MimCl. The deposited product by potentiostatic electrolysis on the surface of stainless steel electrode was characterized by the scanning electron microscopy (SEM), energy dispersive X-ray (EDX) and X-ray diffraction (XRD) methods. Although the electrodeposited black film was amorphous, the electrochemical reduced product of U(VI) can be still confirmed to be UO₂ by XRD after the crystallization of the amorphous deposits at 1,073 K in nitrogen atmosphere.     

Synthesis and acaricidal activity of strobilurin-pyrimidine derivatives简

Pyriminostrobin, a new acaricide, was discovered in our previous studies. Because introducing fluorine into organic compounds can increase bioactivity, pyriminostrobin was modified as a series of strobilurin-pyrimidine derivatives for biological screening. The compounds were characterized by 1H NMR, MS and elemental analysis. Preliminary bioassays demonstrated that compounds 7e and 7i exhibited significant control against Tetranychus cinnabarinus （Boisd.） at 0.625 mg L^-1, and their acaricidal potencies were higher than pyriminostrobin in a greenhouse. The relationship between structure and acaricidal activity was also studied.