2'-chloro-2',3'-dideoxy-3'-fluoro-d-ribonucleosides: synthesis,stereospecificity, some chemical transformations,and conformational analysis

The synthesis of methyl 5-O-benzoyl-2-chloro-2,3-dideoxy-3-fluoro-beta-d-ribofuranoside (5) and its use as a glycosylating agent for persilylated thymine, N(6)-benzoyladenine, and N(4)-benzoylcytosine are described (Scheme 1). The 2'-chloro-2',3'-dideoxy-3'-fluoro-d-ribonucleosides 10-12 synthesized were transformed to 2',3'-dideoxy-3'-fluoro-alpha- and -beta-d-erythro-pentofuranoside nucleosides of thymine (13a,b), adenine (14a,b), and cytidine (15a,b) by treatment with tributyltin hydride in the presence of alpha,alpha'-azobisisobutyronitrile (Scheme 2). Treatment of 2'-chloro-2',3'-dideoxy-3'-fluoro-d-ribonucleosides with 1 M MeONa/MeOH under reflux for 1-5 h afforded 2',3'-didehydro-2',3'-dideoxy-2'-chloro-d-pentofuranosyl nucleosides as the principal products (47-81%) of the reaction, along with recovered starting nucleoside (11-33%) (Scheme 3). Easy HF elimination was also observed in the case of the 2'-azido-2',3'-dideoxy-3'-fluoro-beta-d-ribofuranosides of thymine (17) and adenine (20) (Scheme 3). The role of conformational peculiarities of 2'-chloro-2',3'-dideoxy-3'-fluoro-d-ribonucleosides as well as of 17 and 20 in the observed exclusive elimination of HF is discussed. The conformational analysis of a rather broad palette of 2,3-dideoxy-3-fluoro-2-(X-substituted)-d-ribofuranosides was performed with the aid of the PSEUROT (version 6.3) program, using (i) the recently reparametrized Karplus-type relation (Chattopadhyaya and co-workers. J. Org. Chem. 1998, 63, 4967) and (ii) empirical bond angle correction terms suggested by us. The predictive power of the Brunck and Weinhold model (J. Am. Chem. Soc. 1979, 101, 1700) of the gauche effect between atoms and groups as a conformational driving force acting upon the pentofuranose ring is explored. Their model invokes maximum antiperiplanar sigma <--> sigma stabilization when the donating bond is the least polar one and the acceptor orbital is at the most polarized bond and is found at least as satisfactory, and in various specific cases more so than, as rationalizations on the basis of the preference of the gauche vs the trans conformation of two vicinal electronegative substituents (Wolfe. Acc. Chem. Res. 1972, 5, 102).     

HYDROGEN GENERATION FROM ARTIFICIAL SEA HATER IN A SEMICONDUCTOR SEPTUM ELECTROCHEMICAL PHOTOVOLTAIC CELL

Visible light of the solar spectrum is directly converted to stored chemical energy of hydrogen from artificial sea water in a novel electrochemical photovoltaic cell. The principal element of the cell, modeled after the photosynthetic thylakoid membrane, is a semiconductor septum made of polycrystalline n-CdSe thin film deposited on nickel foil, which separates two aqueous solutions. Under short-circuit conditions, vigorous hydrogen evolution was seen at the Ni surface and continued as long as the cell was operated. The novel cell, the concept of which was derived from pigmented bilayer lipid membrane studies, is easy to construct, simple to operate, and appears to be a practical approach to the photochemical conversion and storage of solar energy.     

PHOTOELECTRIC EFFECTS IN DYE-SENSITIZED ARTIFICIAL LIPID MEMBRANES

Using dyes of known redox potentials the specific mechanisms of dark and light potential generation is analyzed in pigmented lipid membranes. The role of the ionic and electronic conductance, as well as the redox potential gradient is specifically related to the observed open circuit voltage developed across the membrane. The results can be most easily explained by the redox electrode model.     

充液弹性毛细管低温相变的力学分析

充液弹性毛细管广泛存在于生物体（如毛细血管、植物导管等）和工程领域（如微流控冰阀门、制冷系统热管、MEMS微通道谐振器等）.低温工作环境中,充液弹性毛细管内部的液柱会发生相变并引发冻胀效应,从而导致管壁的变形、损伤乃至断裂.该文建立并求解了考虑温度梯度、界面张力及液体冻胀作用的弹性毛细管平衡方程,分析了液柱低温相变过程中毛细管壁的径向和环向应力,发现管壁应力分布受热毛细弹性数和冻毛细弹性数的影响,且影响大小跟壁厚相关.该研究不仅有助于理解生物体内充液弹性毛细管冻胀失效机制,还可为MEMS微流控芯片的抗冻胀失效设计提供理论指导.     

区间毕达哥拉斯模糊幂几何-几何Heronian平均算子及其在多属性群决策中的应用

本文在区间毕达哥拉斯模糊环境下,将幂几何(PG)算子和几何Heronian平均(GHM)算子相结合,提出区间毕达哥拉斯模糊幂几何-几何Heronian平均(IVPFPG-GHM)算子和区间毕达哥拉斯模糊加权幂几何-几何Heronian平均(IVPFWPG-GHM)算子。在模糊信息聚合过程中,新算子不仅能体现属性间的关联性,而且能最大限度地避免专家“奇异值”(过大或过小)带来的干扰。此外,还研究了它们的基本性质。最后,给出基于IVPFWPG-GHM算子的多属性群决策(MAGDM)方法,并以实例说明其可行性与合理性。     

Slater绝缘体的磁性和能带计算研究

Slater相变是一种由于反铁磁序形成而导致的金属—绝缘体相变.本文采用第一性原理密度泛函计算方法研究了两种Slater绝缘体材料NaOsO_3和Cd_2Os_2O_7的电子结构,进而研究了反铁磁序排列、自旋轨道耦合和电子关联对其电子结构以及相变性质的影响.研究结果表明,非磁相的NaOsO_3具有金属性;而G型线性反铁磁结构是驱动NaOsO_3发生Slater相变的磁基态.此外,研究结果表明,非磁相的焦绿石Cd_2Os_2O_7的能带结构在费米能级处是连续的,表现为金属性;并且带有磁阻挫的Cd_2Os_2O_7发生Slater相变的条件十分苛刻,只有在自旋轨道耦合和1.8 eV电子关联的共同作用下一种全进—全出非线性反铁磁结构才能使其发生Slater相变.说明全进—全出非线性反铁磁结构是使Cd_2Os_2O_7发生Slater相变的磁基态,而自旋轨道耦合和1.8 eV的电子关联在消除磁阻挫上起到了关键作用.     

基于UPLC-Q-TOF MS鉴定复方香薷水化学成分

采用超高效液相色谱-四极杆串联飞行时间质谱(UPLC-Q-TOF MS)技术对中药复方香薷水的化学成分进行快速分析鉴定.通过色谱峰响应程度和分离效果优化复方香薷水的前处理方法和仪器条件;采用Agi-lent Phe Hex(150 mm×2.1 mm,1.9 μm)色谱柱进行分离,以0.1%甲酸水溶液-乙腈为流动相进行梯度洗脱,柱温35℃,流速0.3 mL/min;通过正、负两种离子模式采集复方香薷水的质谱数据,得到精确质量数和二级碎片,结合对照品、Pubchem、安捷伦中药化合物质谱数据库和文献报道等信息对其化合物进行分析鉴定.鉴定出复方香薷水的112个成分,其中黄酮类22个,苯丙素类20个、有机酸18个、萜类14个、生物碱11个、氨基酸5个以及其他类型化合物22个.该研究全面阐述了复方香薷水的化学物质基础,为其质量控制和药效物质研究提供了理论依据.     

Runaway Electron Beam Instability in Slide-Away Discharges in the HT-7 Tokamak

Slide-away discharges are achieved by decreasing the plasma density or ramping down the plasma current in runaway discharges in the HT-7 tokamak. In the case of plasma current ramp down, the ratio of the electron plasma frequency to the electron cyclotron frequency is higher than in the stationary pulses when the discharge goes into a slide-away regime. The instability regime is characterized by relaxations in the electron cyclotron emission due to relativistic anomalous Doppler effect which transfers energy from parallel to perpendicular motion. The triggering of relativistic anomalous Doppler effect at higher density by ramping down of plasma current may provide a alternative runaway energy control scenario.     

HT-7装置电子回旋辐射系统接收天线改进

为了提高HT-7装置上等离子体电子回旋辐射(ECE)超外差诊断系统的极向分辨率,根据高斯光学原理,分析了诊断系统天线的改进方案。优化了天线的圆形角锥喇叭尺寸和凸透镜参数以及在装置上的相对位置,使天线接收到的等离子体ECE异常模二次谐波辐射的高斯光束束半径只有30mm左右,能量的高斯光学性质损失不大于13%。