Electrochemical and in situ spectroelectrochemical behavior of 2,3,7,8,12,13,17,18-octakis(hexyl-thio) tetraazaporphyrin (H(2)OHTTAP) and (Zn(II)OHTTAP)

The characterization of free base porphyrin 2,3,7,8,12,13,17,18-octakis(hexyl-thio) tetraazaporphyrin (H(2)OHTTAP) and its zinc(II) complexes [Zn(II)OHTTAP] containing eight thioether groups at the beta -pyrrole positions of the macrocycle was reported. Results obtained by cyclic voltammetry and differential pulse voltammetry indicated a five-electron reduction in five steps for each complex. They were oxidized in two single-electron-transfer steps to yield pi -cation radicals and dications and reduced in three single-electron-transfer steps to yield pi -anion radicals, dianions and trianions, respectively. The redox property of H(2)OHTTAP was unusual as compared to porphyrins (PPs) and phthalocyanines (Pcs). Each process was monitored by in situ thin-layer spectroelectrochemistry, which indicated that only the Ligand was electroactive. The existence of the eight hexylthio groups was responsible for the intrastack interactions and enhanced intracolumnar and intercolumnar electron motions, resulting in improved conductivity. Copyright (C) 2001 John Wiley & Sons, Ltd.

Energy conversion in shape memory alloy heat engine - Part II: Simulation

In this paper, a theoretical model proposed in Part I (Zhu et al., 2001a) is used to simulate the behavior of a twin crank NiTi SMA spring based heat engine, which has been experimentally studied by Iwanaga et al. (1988). The simulation results are compared favorably with the measurements. It is found that (1) output torque and heat efficiency decrease as rotation speed increase; (2) both output torque and output power increase with the increase of hot water temperature; (3) at high rotation speed, higher water temperature improves the heat efficiency. On the contrary, at low rotation speed, lower water temperature is more efficient; (4) the effects of initial spring length may not be monotonic as reported. According to the simulation, output torque, output power and heat efficiency increase with the decrease of spring length only in the low rotation speed case. At high rotation speed, the result might be on the contrary.

Influence of dew on biomass and photosystem II activity of cyanobacterial crusts in the Hopq Desert, northwest China

Dew is an important water source for desert organisms in semiarid and arid regions. Both field and laboratory experiments were conducted to investigate the possible roles of dew in growth of biomass and photosynthetic activity within cyanobacterial crust. The cyanobacteria, Microcoleus vaginatus Gom. and Scytonema javanicum (Kutz.) Born et Flah., were begun with stock cultures and sequential mass cultivations, and then the field experiment was performed by inoculating the inocula onto shifting sand for forming cyanobacterial crust during late summer and autumn of 2007 in Hopq Desert, northwest China. Measurements of dew amount and Chlorophyll a content were carried out in order to evaluate the changes in crust biomass following dew. Also, we determined the activity of photosystem II(PSII) within the crust in the laboratory by simulating the desiccation/rehydration process due to dew. Results showed that the average daily dew amount as measured by the cloth-plate method (CPM) was 0.154 mm during fifty-three days and that the crust biomass fluctuated from initial inoculation of 4.3 mu g Chlorophyll a cm(-2) sand to 5.8-7.3 mu g Chlorophyll a cm(-2) crust when dew acted as the sole water source, and reached a peak value of approximately 8.2 mu g Chlorophyll a cm(-2) crust owing to rainfalls. It indicated that there was a highly significant correlation between dew amounts and crust moistures (r = 0.897 or r = 0.882, all P < 0.0001), but not a significant correlation between dew and the biomass (r = 0.246 or r = 0.257, all P > 0.05), and thus concluded that dew might only play a relatively limited role in regulating the crust biomass. Correspondingly, we found that rains significantly facilitated biomass increase of the cyanobacterial crust. Results from the simulative experiment upon rehydration showed that approximately 80% of PSII activity could be achieved within about 50 min after rehydration in the dark and at 5 degrees C, and only about 20% of the activity was light-temperature dependent. This might mean that dew was crucial for cyanobacterial crust to rapidly activate photosynthetic activity during desiccation and rehydration despite low temperatures and weak light before dawn. It also showed in this study that the cyanobacterial crusts could receive and retain more dew than sand, which depended on microclimatic characteristics and soil properties of the crusts. It may be necessary for us to fully understanding the influence of dew on regulating the growth and activity of cyanobacterial crust, and to soundly evaluate the crust's potential application in fighting desertification because of the available water due to dew. (C) 2009 Published by Elsevier Ltd.

氟化物晶体中铕（II）及其共掺体系的光谱化学

利用坩埚下降法生长了KMgF_3:Eu~(2+)和KMgF_3:Eu~(2+)-X(X=Gd~(3+)、Ce~(3+)、Cr~(3+)、Cu~(+))等12种单晶体。测试了所有单晶体的UV-Vis吸收光谱、近红外吸收光谱、低分辨荧光光谱以及在300 K和77 K的高分辨发射光谱。测试了所有晶体研成粉末后的漫反射光谱。光谱研究表明，晶体中含有氧中心和色心，发现了氧中心和色心与掺杂离子之间的能量传递。不同掺杂离子之间的光谱相互影响，并存在能量传递现象。首次研究了Eu~(2+)振动光谱与其它掺杂离子格位取代的关系，发现从振动光谱的研究可以获得许多有用的信息。利用时间分辨技术测量了4种晶体中Eu~(2+) ~6P_(7/2)激发态的四能级衰减模型和双指数拟合方程，并从光谱上证实了该模型的正确性。对双指数拟合方程中每一项参数的物理意义给出了明确的解释。根据这些拟合常数，建立了一种研究能量传递现象和机理的新方法。首次发现了Eu~(2+)和Ce~(3+)通过d-d相互作用发生的能量传递现象。根据我们建立的模型和可获得的文献数据，从理论和实验上证明了KMgF_3:Eu~(2+)晶体存在净光学增益。

I.茚基和环戊二烯基钕二氯化物-烷基铝二元体系催化丁二烯聚合反应动力学II.萘基钕及二环戊二烯基钕化合物的合成

本文研究所了四种钕化合物（茚基钕有机金属化合物C_9H_7NdCl_2·HCl·C_4H_8O，环戊二烯基钕有机金属化合物-C_5H_5NdCl_2·C_4H_8O，无水氯化钕络合物-NdCl_3·2C_4H_8O及NdCl_3·C_6H_5OH·C_4H_8O）与三异丁基铝（i-Ba_3Al）或一氢二异丁基铝（i-Bu_2AlH）所组成的二元催化体系中丁二烯聚合动力学。这些体系的动力学特点尚未被人们研究，通过实验揭示出一些新的规律，丰富了我们对稀土体系催化丁二烯聚合动力学的认识。研究中着重考察了聚合物活性链的变化条件，从而能较深刻地认识各体系的动力学特点，结果表明：C_9H_7NdCl_2·HCl·C_4H_8O，C_5H_5NdCl_2·C_4H_8O，NdCl_3·2C_4H_8O，NdCl_3·C_6H_5OH·C_4H_8O与i-Bu_2AlH所组成的二元催化体系中，当[Mo]=1.11克分子/升、[Nd]=1.12*10~(-4)克分子/升、[i-Bu_2AlH]\3.36*10~(-3)克分子/升、50 ℃聚合时为缓慢引发非稳态聚合反应。而当增加铝用量至[i-Bu_2AlH] = 6.72*10~(-3)克分子/升，C_9H_7NdCl_2·HCl·C_4H_8O体系转变为迅速引发稳态聚合反应，其余体系反应动力学行为无变化。各稀土钕催化体系动力学的差异主要是由配位体供电性不同产生的。当配位体供电性强时有利于降低稀土离子的正电荷，从而有利于烷基化反应和活性中心的形成和稳定，因此决定了各催化体系的不同动力学行为。C_9H_7NdCl_2·HCl·C_4H_8O体系当聚合温度、烷基铝浓度变化时以及Nd(naph)_3体系当温度变化时聚合物活性链状况会发生变化，从而改变了动力学行为。缓慢引发和迅速引发，稳态和非稳态间会发生转化而不是一成不变的。凝胶渗透色谱法应用于反应机理的研究不仅在理论上是可能的，在实践上是成功的。缓慢引发非稳态聚合（C_5H_5NdCl_2·C_4H_8O，NdCl_3·C_6H_5OH·C_4H_8O,NdCl_3·ZC_4H_8O），迅速引发非稳态聚合（Nd(naph)_3），迅速引发稳态聚合（C_9H_7NdCl_2·HCl·C_4H_8O）不同的动力学类型都具有不同的分子量分布特点。C_9H_7NdCl_2·HCl·C_4H_8O体系中丁二烯聚合速率方程为：K_p=K_p[C~*][M]. 50 ℃,[Nd]=1.12*10~(-4),[i-Bu_2AlH]=6.72*10~(-3)克分子/升条件下，丁二烯为快引发稳态聚合反应。此体系中活性中以浓度为2.43*10~(-6)克分子/升，催化剂有效利用率2%，链增长速率常数为81.42升/克分子，秒，聚合反应表观活化能为8.5±0.5千卡/克分子。聚合物顺-1，4结构均为98%左右。活性链平均寿命为7.22分钟。活性链对烷基铝的转移为主要链转移方式而对单体无明显转移。链转移速率常数为2.99升/克分子秒。

12路40Gb/s甚短距离并行光传输信号转换器研究

基于OIF-VSR5-01.0规范,分析了12路并行40Gb/s甚短距离(VSR)光传输转换器模块的实现原理.采用top-down分析方法,使用硬件描述语言verilog,在可编程逻辑器件上完成了时钟数据恢复、基于字节对齐方案的帧同步、信道去斜移、比特间差奇偶校验(BIP)等功能模块的程序设计,实现了SFI-5与OIF-VSR5-01.0电信号格式的相互转换,并在Altera的Stratix II GX 系列的高速现场可编程门阵列(FPGA)上对功能模块进行了功能验证和联合仿真.结果表明所设计的各个功能模块满足系统应用要求,为下一步将系统设计转换为专用集成电路(ASIC)奠定了基础.

在多工位炉上CeO_2:Bi_12SiO_20单晶生长的研究（II）——空间生长实验部分

掺Ce：Bi_(12)SiO_(20)单晶在神舟3号(SZ-3)飞船上成功地进行了空间生长，得到晶体尺寸为φ10mmx40mm．将空间生长的晶体和地面生长晶体对比发现：空间生长晶体的外观同地面生长晶体有明显差异．分析测试空间和地面晶体的x射线摇摆曲线、吸收曲线和喇曼光谱，结果表明：空间生长掺Ce：BSO晶体的结构完整性优于地面生长的晶体，掺Ce对BSO晶体光学性能的影响空间制备晶体要大于地面制备的晶体