芳基汞化合物的性质研究——Ⅶ.邻位取代苯基氯化汞的质子分解反应

本文研究了邻位取代苯基氯化汞o-XC_6H_4HgCl(X=CH_3、H、Cl、Br、COOC_2H_5、NO_2)与HCl(NaI)在85％对氧陆圜水溶液中的质子分解反应,证明反应按S_El历程进行。视取代基不同,反应速度次序如下:CH_3>H>Cl>COOC_2H_5～Br>NO_2。从化学反应与紫外光谱的研究以及理论计算结果表明,p或π电子的邻位取代基对水原子有分子内配位,它对反应速度有重要影响。测定了15种p-、m-、o-取代苯基氯化汞在80％对氧陆圜水溶液中在40.0℃的质子分解反应的速度常数k_1,表明给电性取代基加速反应,吸电性取代基使反应减慢,这可以看作是反应中心在芳环上的芳基汞化合物的S_E1反应所具有的一个特点。     

制备方法对WO_3/ZrO_2结构的影响

用XRD、比表面测定、LRS定性和定量的方法对用Zr（OH）4和已晶化的ZrO2作载体制得的两类WO3／ZrO2催化剂进行了表征．揭示了样品比表面、载体物相、活性组分的存在状态与制备方法、WO3含量、焙烧温度之间的关系．结果表明，WO3能单层分散在ZrO2上；单层覆盖在Zr（OH）4上的WO3使载体在焙烧时晶粒生长受阻，形成介稳的四方ZrO2，并阻止载体微粒间的烧结，使从Zr（OH）4出发制得的WO3／ZrO2比表面明显增大，在WO3含量达到单层分散容量时以上作用表现得最充分；WO3与Zr（OH）4（或四方ZrO2）在高温（～800℃）可能发生了某种化学结合，开创出超强酸位．用以上观点可对文献中已报导的主要实验事实作出较满意的解释.     

Visible-NIR Photodetectors Based on Low-Dimensional GeSe Micro-Crystals: Designed Morphology and Improved Photoresponsivity

GeSe micro-sheets and micro-belts have been synthesized by a facile one-pot wet chemical method in 1-octadecene solvent and oleic acid solvent, respectively. The adsorption of more oleic acid molecules on the (002) plane promoted growth along [010] direction of the GeSe micro-belts and limited carrier transport in this direction, resulting in higher carrier concentration and mobility of the GeSe micro-belts. The performance of the photodetectors based on the single GeSe micro-sheet and the single GeSe micro-belt was investigated under illumination at 532 nm, 980 nm and 1319 nm. Both, photodetectors based on a single GeSe micro-sheet and a single GeSe micro-belt, exhibit a high photoresponse, short response/recovery times, and long-term durability. Moreover, the photodetector based on a single GeSe micro-belt displays a broadband response with a high responsivity (5562 A/W at 532 nm, 1546 A/W at 980 nm) and detectivity (3.01×10¹² Jones at 532 nm, 8.38×10¹¹ Jones at 980 nm). These excellent characteristics render single GeSe micro-belts very interesting for use as highly efficient photodetectors, especially in the NIR region.     

乙酰胆碱酯酶/Nafion/普鲁士蓝修饰玻碳电极的制备及其在有机农药检测中的应用

制备了乙酰胆碱酯酶/Nafion/普鲁士蓝修饰的玻碳电极,测试了该修饰电极检测有机农药西维因(carbaryl)和敌百虫(trichlorfon)的性能指标。 利用原子力显微镜和电化学技术研究了电极的构造及其对于有机农药检测性能指标的影响。 结果表明,乙酰胆碱酯酶均匀地分散到Nafion/普鲁士蓝修饰的玻碳电极上。 在最优的实验条件下,构筑的修饰电极检测西维因和敌百虫的线性范围分别为0.01~0.5 μmol/L及2.0~10.0 μmol/L和0.02~1.0 μmol/L及2.0~8.0 μmol/L,检出限分别为5.0和10.0 nmol/L。 并对模拟的实际样品进行了检测,发现该方法有较高的检测灵敏度、较好的重复性和抗干扰性。     

利用光泵磁共振曲线测量氢原子密度

本文给出利用光泵磁共振曲线测量氢原子密度的实验.在我们的实验中,当射频源放电功率一定时,在25~61℃的泡温范围内测量到9.2×10¹¹~1.6×10¹¹(原子/厘米³)的氢原子密度.实验结果表明,当放电功率一定时,氢原子密度随泡温升高而下降.     

Continuous-Time Controlled Markov Chains with Discounted Rewards

This paper studies denumerable state continuous-time controlled Markov chains with the discounted reward criterion and a Borel action space. The reward and transition rates are unbounded, and the reward rates are allowed to take positive or negative values. First, we present new conditions for a nonhomogeneous Q(t)-process to be regular. Then, using these conditions, we give a new set of mild hypotheses that ensure the existence of -optimal (0) stationary policies. We also present a martingale characterization of an optimal stationary policy. Our results are illustrated with controlled birth and death processes.     

In-situ Synthesis of Copper Phthalocyanine in Silica Xerogel Matrix

Using a newly developed in-situ syntheses technique during sol-gel process, copper phthalocyanine (CuPc) is synthesized in-situ in silica xerogel matrix homogeneously. It has been confirmed by UV-Vis and IR spectroscopies that the copper ions which existed in the form of complex-ions [Cu(H₂O)₄]²⁺ and [CuCl₄]^2– in the stages of sol and wet gel were destroyed in the heat treatment process, meanwhile the copper phthalocyanine molecules were synthesized in-situ gradually during the wet gel to xerogel transition. The dimerization phenomenon of CuPc in the composite is suppressed greatly because the in-situ synthesized CuPc molecules were well isolated in the micro-pores of the xerogel matrix. The doping concentration of Copper phthalocyanine in sol-gel derived matrix can be enhanced also by this in-situ synthesis method.     

Synthesis of phenothiazine-functionalized porphyrins with high fluorescent quantum yields

Two porphyrins with oligo-phenothiazine arms have been synthesized by a combination of Heck and Adler reaction, and their photophysical properties have been investigated by absorption and steady-state fluorescence spectroscopy. It is found that the excitation energy transfer occurs from the phenothiazine units to the porphyrin core, and that the porphyrins can emit intense red light with high fluorescent quantum yields.     

NMR Study of Laser-polarized 129Xe in Low Pressure Natural Xenon Gas

The NMR signal from the laser-polarized t29 Xe in low-pressure natural xenon gas has been observed with a Bruker WP-80SY NMR spectrometer. The laser-polarized 129 Xe was produced by the method of laser pumping and spin exchange in a magnetic field of 1.87 Tesla. It is obtained experimentally that the nuclear spin relaxation rate 1/T1 of laser-polarized 129Xe are (4.03±1.97)×10-3/see～(2.21±0.78)×10-3/see in the range of the 3.33×103 Pa～8.29×104 Pa Xe gas pressures, the apparent wall relaxation rate 1/Tw* =(1.98±0.18)×10-3/see, and the relaxation rate coefficient C of 133Cs-129Xe spin exchange is (2.81±0.74)×10-16 em3/sec.