2'''',3''''-双脱氢-2'''',3''''双脱氧胸苷5''''-亚磷酸苄酯的ESI-MS~n中的一种新颖的重排反应

爱滋病(AIDS)是一种严重威胁人类健康的传染性疾病。研究和开发新的、高疗效的抗AIDS的药物已成了生物学家、化学家和药物学家的主要的研究方向之一。2',3'-双脱氢.2',3'-双脱氧胸苷(d4T)是HIV逆转录酶抑制剂,它们是美国FDA通过的可用于治疗AIDS的一类药物。由于d4T等本身对HIV无活性,只有经细胞代谢成5'-磷酸化产物后才对HIV产生抑制作用,因此很有必要对d4T进行结构改造,而对上述药物的结构进行改造是研制新的抗AIDS的化学药物最简捷的途径。因此,我们合成了一系列的d41、5'-亚磷酸酯的衍生物,并对它们的电喷雾质谱进行了详细的研究。研究发现了2',3'-双脱氢,2',3'双脱氧胸苷(d4T)-5'-氢亚磷酸苄酯的一种新颖的重排反应,并对其机理进行了进一步的研究。有关结果不仅有助于对这类化合物的结构分析,而且对它们的合成、药物性质以及药物代谢等方面的研究都具有重要意义。     

Multistage Electrochemical Reactions with the Transfer of Intermediates between the Near-Electrode Layer and the Bulk Solution: The Accumulation of the Intermediates and the Current Redistribution between the Stages during Electrolysis

Dependences of reactant concentrations and current densities of individual stages on the electrolysis time for a multistage electrode process complicated by the transfer of intermediates between the near-electrode layer and the bulk electrolyte are obtained by numerical computer-aided modeling. Effect of various factors on the dynamics of variations in the concentration of the initial reactant and intermediate in the bulk electrolyte is analyzed. The possibility of a substantial increase in the current efficiency of the second stage of discharge during electrolysis is shown.     

液相OH•, NO3•和SO4•-与二甲基硫反应机理

利用激光闪光光解技术研究了液相二甲基硫(DMS)与OH^•, NO₃^•和SO₄^•-自由基的微观反应机理. 实验结果表明: 在pH 5～9时, OH^•氧化DMS生成DMSOH^•, DMSOH^•会与DMS反应生成(DMS)₂⁺; 而NO₃^•和SO₄^•-;会直接氧化DMS生成DMS^＋, 生成的DMS^＋会与DMS反应生成(DMS)₂⁺.(DMS)₂⁺与氧气的反应很慢, 它的衰减受pH影响较大.     

Group testing procedures with incomplete identification and unreliable testing results

We consider multistage group testing with incomplete identification and unreliability features. The objective is to find a cost‐efficient group testing policy to select a prespecified number of non‐defective items from some population in the presence of false‐positive and false‐negative test results, subject to reliability and other constraints. To confirm the status of tested groups, various sequential retesting procedures are suggested. We also extend the model to include the possibility of inconclusive test results. We derive all relevant cost functionals in analytically closed form. Numerical examples are also given. Copyright © 2006 John Wiley & Sons, Ltd.     

Scalable Formation of Concentrated Monodisperse Lignin Nanoparticles by Recirculation-Enhanced Flash Nanoprecipitation

A highly controllable and scalable process for fabrication of large amounts of concentrated lignin nanoparticles (LNPs) is reported. These lignin core nanoparticles are formed through flash nanoprecipitation, however, scaling up of the fabrication process requires fundamental understanding of their operational formation mechanism and surface properties. It is shown how a semicontinuous synthesis system with a recirculation loop makes it possible to produce flash precipitated lignin nanoparticles in large amounts for practical applications. The roles of the process parameters, including flow rates and lignin concentration, are investigated and analyzed. The results indicate that the LNPs are formed by a process of continuous burst nucleation at the point of mixing without diffusive growth, which yields nanoparticles of highly uniform size following a modified LaMer nucleation and growth mechanism. This mechanism makes possible facile process control and scale-up. Effective control of the resulting nanoparticle size is achieved through the initial concentration of lignin in the injected solution. The impressive capability to produce suspensions of any predesigned multimodal distribution is demonstrated. The resulting nanofabrication technique can produce large volumes of concentrated LNP suspensions of high stability and tightly controlled size distributions for biological or agricultural applications.     

Dynamic modeling of copper flash smelting process at a Smelter in China

Due to the highly dynamic characteristic in copper smelting process at a Copper Smelter in China, it is difficult to maintain high performance level control. As a key process indicator to evaluate smelting performance, matte grade is in urgent need of being monitored online. Thus, a real-time dynamic model of predicting matte grade was developed and validated with data collected at an actual plant. Based on desulfurization ratio of copper concentrate, the model couples dynamic mass balances on each species with equilibrium relationships for major component (Cu, Fe, S, SiO₂, et al.) to form a system of differential and algebraic equations. The simulation results illustrate that the maximum relative error and average relative error of matte grade between measured values and predicted value of the model proposed is 3.3%, and the average relative error is 0.54%, which verify the effectiveness of the model developed in providing the guidance for controlling the copper flash smelting process.     

Cooling rate controlled microstructure evolution through flash DSC and enhanced energy density in P(VDF–CTFE) for capacitor application

Poly(vinylidene fluoride) (PVDF) based polymers are attracting tremendous interest because of their potential applications in advanced energy storage devices. Fundamental understanding of their crystal structure evolution has been proved elusive due to the nature of rapid crystallization rate. Fortunately, flash differential scanning calorimeter (Flash DSC) with a precise control of cooling rate helps to investigate an understanding of structure–property relationships. For the first time, a bimodal distribution of the crystallization rate of P(VDF‐chlorotrifluoroethylene) (CTFE) in the whole temperature range, and a 3D profile of melting point and enthalpy dependence of annealing temperature and time, which is the corresponding crystal structure evolution and the mechanism of crystal nucleation and growth, are revealed by flash DSC. Based on the above conclusions, fast cooling or annealing at low temperature regulates the crystallization behavior, favors a tiny ferroelectric β‐phases, drastically reduces paraelectric spherulite sizes, and leads to greatly enhanced energy storage capacity, but reduction in discharged efficiency. For instance, compared with other processing methods, P(VDF‐CTFE) quenched by liquid nitrogen achieves the highest discharged energy of 10.6 J cm^?3 at the maximum electric field of 270 MV m^?1. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55 , 1245–1253     

闭杯闪点法测定氢化三丁基锡的闪点

使用MINIFLASH FLA全自动中温八杯闪点仪(闭杯闪点法)测定了氢化三丁基锡的闪点。探讨了诸多因素如样品的储存状态、点火次数、升温速率、大气压的校正、仪器保养方法等对闪点测定的影响。     

基于STM32的NAND flash的块分配框架设计

STM32对大容量数据文件存储与管理问题可通过NAND flash来解决;而NAND flash的高效管理需要文件系统参与;NAND flash有特殊的块读写及擦除机制,一般的嵌入式文件系统组织结构并不完全兼容NAND flash;针对NAND flash的特点兼顾STM32的资源承受力要提出新的NAND flash块分配框架,框架通过块分配槽这种数据结构,在不使用块分配表与垃圾表的情况下,实现了NAND flash均衡负载与垃圾块的回收;同时通过节点分配栈与文件节点表的结合来提高STM32对文件的读写速度,空间利用率和系统性能;仿真实验和计算结果表明该块分配框架可有效提高NAND flash块的均衡负载与节省RAM空间。     

Phototransformation mechanism of monuron induced by the triplet benzophenone in aqueous solution

Phototransformation mechanism of monuron induced by the triplet benzophenone in aqueous solution was investigated by laser flash photolysis technique, while quenching of the triplet benzophenone by monuron was studied by nanosecond transient absorption spectroscopy. The transient species in the transient absorption spectra have been identified by quantum chemistry calculations. The results show that under 355‐nm irradiation proton transfer between the triplet benzophenone and monuron happens, and monuron radical is formed and followed by dechlorination degradation reactions. This work indicated that in aqueous solution some dissolved natural organic matters are helpful to degradation of the organic pollutants under the sunlight. Copyright © 2015 John Wiley & Sons, Ltd.