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.     

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.     

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.     

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.     

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%。     

ENERGY TRANSFER FROM CAROTENOIDS TO CHLOROPHYLL a IN BLACK LIPID MEMBRANES

Abstract— Black lipid membranes (BLM) were prepared from extracts of Chlorella and spinach chloroplasts. Excitation spectra of the 730 nm fluorescence of chlorophyll a in the BLM contained peaks identified as due to carotenoids and which therefore indicate sensitization of the chlorophyll fluorescence by them. The efficiency of this energy transfer was evaluated by comparison of the actual excitation spectra with those corresponding to 0 and 100 per cent transfer efficiency. Efficiencies were of the order of 40–50 per cent in BLM, but only 10 per cent in pigment solutions, when the mean distance between pigment molecules was 23 Å in both systems. The fluorescence quantum yield of chlorophyll a in such solutions was only 2 per cent of that found in BLM. Enhancement of energy transfer in BLM is considered to be mainly due to suppression of competing deactivation processes of excited carotenoid states, such as diffusional quenching by ground-state molecules and internal conversion. Favorable orientation of pigment molecules in the BLM constitutes a further enhancement factor.     

WHOLE-CELL CLAMP STUDY OF XENOPUS EMBRYONIC CHOLINERGIC NEURONS

Whole-cell clamped myoballs are placed into direct visible contact with the growth cones of isolated neurons in embryonic Xenopus culture to serve as probe of acetylchollne (AcCHo) release in order to determine whether these neurons are cholinergic or not. Using a GQ-seal, whole-cell recording method, the electrophysiological properties of these identified cholinergic neurons are studied. It is found that these embryonic neurons, like adult frog motor neurons, exhibit repetitive firings in a certain embryonic developing stage. A development of repetitive firings is observed simultaneously. Tracing the development of one neuron, we find that the development of repetitive firing is completed at the 48th h after fertilization. Tetrodotoxin (TTX) which blocks Na~+ channels can abolish all firings; and tetraethyl ammonium chloride (TEA), the blocker of K~+ channels, reverses this development, i. e. it makes the repetitive firings disappear again. These data show that the nature of the development of repetiti     

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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%。