伯胺N_(1923)萃取过渡金属离子机理的研究

伯胺由于其特殊的结构（R-NH_2），使它具有和仲、数胺不相同的一些性质。有较强的和矿物酸HX结合形成RNH_3X的能力，从而以离子交换机理萃取金属离子；也可以-NH_2上的氮、氢原子同以高价存在的过渡金属含氧酸以氢键方式相结合；另外，RNH_2也可通过氮原子以配位键形式与一些属于软酸类的过度金属离子形成配合物。通过伯胺萃取金属离子行为的研究，可发现新的萃取体系，扩大我国自行设计的伯胺N_(1923)萃取剂的应用领域，为金属离子的分离提纯工艺提供基本参数。我们实验室过去曾对伯胺N_(1923)萃取稀土（III）、Fe（III）、Zn （II）、Cd（II）、Ag（I）、Sc（III）等的机理进行了比较系统的研究。本工作是在此基础上，进一步完善及扩大N_(1923)对周期表中各族元素的萃取及应用。为此，我们选择了文献尚未报道的Ti（IV）、HgCl_2、Hg(CH_3COO)_2、Cu(CH_3COO)_2为研究对象，对它们的萃取机理进行了较详细的研究。结果表明，自由的N_(1923)或其盐对上述体系具有良好的萃取性能，并初步讨论了N_(1923)在金属离子萃取分离中的应用。一、伯胺N_(1923)萃取HgCl_2的机理 微量汞的萃取及分离对环境保护具有重要的实际意义。我们的研究结果表明，在pH值为3-4.5范围内，即使Cl~-浓度很低时，伯胺N_(1923)也能几乎定量地萃取HgCl_2，其盐酸盐亦能有效地萃取Hg（II），但两者的萃取机理不同。自由伯胺RNH_2可与HgCl_2形成配合物，其萃取机理为：RHN_(2(0)) + HgCl_2 <-> Hg(RNH_2)Cl_(2(0))对伯胺盐，实验证明其机理主要为加合反应，但当Cl~-浓度较高时，则为阴离子交换反应：加合反应：2RNH_3Cl_((0)) + HgCl_2 <-> (RNH_3Cl)_2HgCl_(2(0))交换反应：2RNH_3Cl_((0)) + HgCl_4~(2-) <-> (RNH_3)_2HgCl_(4(0)) + 2Cl~-通过考察温度对配位萃取反应的影响，求得反应的热效应ΔH = -48.82 KJ/mol，并分析了萃合物的IR、NMR谱。二、伯胺N_(1923)萃取Hg(CH_3COO)_2的机理 与HgCl_2体系相似，自由伯胺或其盐均能萃取Hg(CH_3COO)_2，萃取机理分别为：RNH_(2(0)) + Hg(CH_3CCO)_2 <-> Hg(RNH_2)(CH_3COO)_(2(0)) (CH_3COONH_3R)_(2(0)) + Hg(CH_3COO)_2 <-> (CH_3COONH_3R)_2Hg(CH_3COO)_(2(0))。在不同的萃取剂浓度下，上述反应的表观平衡常数基本不随萃取剂浓度的变化而改变，其对数值分别为：11.85、8.11。三、伯胺N_(1923)萃取Cu(CH_3COO)_2的机理 水相酸度对萃取反应的影响表明，RNH_2在近中性体系中具有很好的萃取性能，而在乙酸浓度较高的条件下，Cu（II）几乎不被RNH_2所萃取。说明自由伯胺能以配位机理的形式萃取Cu(Oh_3coo)_2，经确定，萃取反应式为：2RNH_(2(0)) + Cu(CH_3COO)_2 <-> Cu(RNH_2)_2(CH_3COO)_(2(0))并对该反应的表观平衡常数及热力学函数进行了计算。通过分析萃合物的IR谱，认为Cu(RNH_2)_2(CH_3COO)_2为平面型四配位的配合物。四、(RNH_3)_2SO_4从硫酸溶液中萃取Ti（IV）的研究 在低酸度（pH：0.84）的H_2SO_4溶液中，伯胺N_(1923)对Ti（IV）具有很强的萃取能力。用化学平衡法确定其反应式为：3(RNH_3)_2SO_(4(0)) + Ti(OH)_3~+ + SO_4~(2-) <-> 2(RNH_3)_3Ti(OH_3)(SO_4)_(2(0))我们用正十二胺代替N_(1923)，合成了上述萃合物的模拟物，经元素分析确定了萃合物的分子式：(RNH_3)_3Ti(OH)_3(SO_4)_2。并较详细地分析了萃合物的NMR、IR谱。变温NMR的结果表明，萃合物中存在两种含有活泼氢的基团，用D_2O交换后的NMR的结果亦证明了这一点。从萃合物的IR谱中，可得到SO_4~(2-)是以单齿配位形式同Ti（IV）相结合的信息。这些结果为所提出的萃取机理提供了直接的证据。并求出了上述萃取反应的表观平衡常数，其对数值为10.15，该值基本不随萃取剂浓度的变化而发生改变。反应的热效应ΔH = 66.49 KJ/mol，由计算得出的ΔG值可知，上述萃取反应有很大的向右进行的趋势。五、伯胺N_(1923)在萃取分离中的应用 为了扩大N_(1923)的应用，通过上述研究，我们对其在萃取分离中的应用进行了讨论，认为在以下几方面有可能得到应用：1、从环境废水中除Hg(II)；2、Hg(II)和Zn(II)、Cd(II)在CH_3COOH体系中的分离；3、CH_3COOH体系中Cu(II)、Co(II)、Ni(II)的萃取分离；4、在较高浓度的H_2SO_4体系中，应用(RNH_3)_2SO_4进行了Ti(IV)-Fe(II)的分离。

Ln-Ba-Cu-Ag-O多元复合物制备、结构及电学性质的研究

本文合成了LnBa_2Cu_(3(1-x))Ag_xO_(7-δ) (x = 0.1,0.3,0.5, Cu = Y,Dy,Ho,Er,Gd) YBa_(2(1-x))Cu_3Ag_xO_(7-δ) (x = 0.05,0.1,0.2,0.3,0.4,0.5,0.6); Y_(1-x)Ag_xBa_2Cu_3O_(7-δ) (x = 0.05,0.1,0.2,0.3,0.5); YBa_2Cu_3O_(7-δ)Ag_x (x = 0.2～2.0), CuBaCu_3O_(7-δ)Ag_x (x = 0.5,1.0, Cu = Dy,Ho,Er)及与之对照的空白样品等一系列超导稀土复合氧化物，对它们的结构、电学性质、Ag的存在状态及Ag的加入方式进行了研究。对这方面的研究目前仍无全面系统的报道。对CuBa_2Cu_(3(1-x))Ag_xO_(7-δ)的研究表明Ag并未取代Cu的格位，少量的Ag加入（x<0.1）就使结构发生破坏，当x>0.1时样品即失去超导性，对光加Ag的YBa_(2(1-x))Cu_3Ag_(2x)Cu_3O_(7-δ)的研究表明，当x<0.6时仍为90k左右的超导体，Ag没有取代Ba的格位，Ag的加入使杂相比例加大，Ag的加入改善了样品晶粒间的弱连接状况，使电流密度明显提高，Ag以单质及复合物形式存在于样品之中。后加Ag方式对结构、电性、无影响没有提高Jc。对光加Ag的Y_(1-x)Ag_xBa_2Cu_3O_(7-δ)的研究表明，x<0.5时样品仍为90k左右超导体，Ag的加入使杂相比例减少，Ag部分以单质及与13a、Cu形成对改善弱连接状有益的复合场的形式存在，部分进入晶格可能占据了Y的格位使C轴变长。Ag的加入改善了样品晶粒间的弱连接状况，从而使Jc大幅度提高，当x=0.1时Jc = 362 A/cm~2，后加Ag的方式对结构、电性、无影响没有提高Jc。对YBa_2Cu_3O_(7-δ)Ag_x的研究表明，加Ag的样品的Jc比不加Ag样品的Jc明显加大，随着Ag量的加大Jc增加，当x=1时Jc最大，当Ag量大于2.0mol时将有大量Ag析出，Ag的加入不影响超导正交结构，部分Ag进入了晶格可能占据了Y的格位，C轴增长，部分以单质及复合物的形式存在，Ag的加入不影响样品的临界温度，使样品电阻降低，电镜分析表明，Ag的加入改善了样品晶粒间的连接状况。CuBaCu_3O_(7-δ)Ag_x与上面体子有相同的性质，在加入1mol Ag得到，Jc：DyBaCu_3O_(7-δ)Ag_(1.0) 113A/cm~2；HoBaCu_3O_(7-δ)Ag_(1.0) 164 A/cm~2 ErBaCu_3O_(7-δ)Ag_(1.0) 177A/cm~2的样品。样品加Ag后密度明显加大，最大可达6.321克/cm~3，硬度也加大具有良好的机械性能。针对在YBaCu_3O_(7-δ)样品中添加Ag，可以做为一种大幅度提高Jc的途径的特点，进行了各种工艺探索，到目前为止，合成出了临界电流密度为570 A/cm~2的样品。

哺乳动物体细胞核移植影响因素的研究

题。 在已有的基础上，建立了基于单个植入前胚胎的逆转录-聚合酶链反应（RT-PCR）技术，成功实现了针对单个猕猴植入前胚胎进行可重复的，多个特定基因的表达检测。在此基础上，对一些重要的早期胚胎发育相关基因在猕猴体细胞核移植胚胎和体外受精胚胎中的表达进行了比较研究。这其中包括核仁相关蛋白基因nucleolin，nucleophosmin，fibrillarin，PAF53，UBF和mRNA早期装配相关蛋白snrpn，这些基因被认为与植入前胚胎的再程序化有着非常密切的关系。我们的研究结果发现，相对于体外受精胚胎，被检测基因在核移植胚胎中的转录出现了不同程度的异常，表现为表达丰度相对较低，这意味着体细胞核移植植入前胚胎的再程序化，或者说供体核的再程序化可能出现了异常。通过进一步对fibrillarin（胚胎合子基因组启动的标志基因）的表达研究，比较了合子基因组启动这一再程序化分子事件在核移植胚胎和体外受精胚胎中的发生时序。研究结果证实，体细胞核移植胚胎的合子基因组启动出现了明显的滞后。我们还发现这与核移植胚胎的异常卵裂速度有着一定的关联，同时说明某些源自核移植操作技术和方法的未知因素可能是造成核移植胚胎再程序化异常的主要原因。为了验证合子基因组滞后对核移植胚胎后续发育的影响，本论文研究分析了着床相关基因Mamu-AG在猕猴核移植胚胎中的表达。研究首次发现Mamu-AG mRNA只在囊胚期开始出现，这与在人类中的情况有所不同（始于8细胞时期）。在正常体外受精囊胚中，不论发育时间如何，第6和第7天的囊胚均正常表达Mamu-AG mRNA。而在核移植囊胚中，仅有第7天的囊胚检测到该mRNA，第6天的囊胚中则没有，这进一步说明了胚胎合子基因组启动的延迟是影响核移植胚胎发育的重要环节。 本研究从分子水平上对猕猴植入前胚胎基因转录和表达进行了分析研究，首次发现了在猕猴体细胞核移植胚胎中发育相关基因表达异常，以及合子基因组启动滞后的分子证据，这为我们改进现有的猕猴核移植操作程序提供了新的思路，同时也为进一步研究猕猴植入前胚胎发育的再程序化奠定了基础。

MEASUREMENT AND SIMULATION OF THE TURN-ON DELAY TIME JITTER IN GAIN-SWITCHED SEMICONDUCTOR-LASERS

The turn-on delay time jitter of four different unbiased gain-switched laser types is determined by measuring the temporal probability distribution of the leading edge of the emitted optical pulse. One single-mode 1.5-mu-m distributed feed-back laser and three multimode Fabry-Perot lasers emitting at 750 nm and 1.3-mu-m are investigated. The jitter is found to decrease for all lasers with increasing injection current. For multimode lasers it decreases from 8 ps excited slightly above threshold down to below 2 ps at three times the threshold current. The jitter of the distributed feedback (DFB) laser is a factor of 3-5 larger than the jitter of the three multimode lasers. A new model to predict the turn-on delay time jitter is presented and explains the experiments quantitatively.

Absorption spectra of Se-8-ring clusters in zeolite 5A

Samples with different weight ratio of Se to zeolite 5A (Se concentration) have been prepared by loading Se into the pores of zeolite 5A, and the measuerments of the absorption and Raman spectra have been carried out for the prepared samples. The measured absorption edges of the samples are close to the value for monoclinic Se containing Se-8-ring, suggesting the formation of Se-8-ring clusters(1) in the pores. The continuous and broadening features of the absorption spectra are interpreted by the strong electron-nucleus coupling in the Se-8-ring cluster. The absorption edges are red shifted with the increase of the Se concentration. It is tentatively attributed to two reasons. One is the existence of the double Se-8-ring cluster in the high Se concentration samples, and the other is that for the strong electron-nucleus coupling cluster, the absorption edge of the clusters system will be red shifted with the increase of the cluster concentration in the clusters system. A single broad band at about 262 cm(-1) is observed in the Raman spectra, which further supports the formation of Se-8-ring clusters. (C) 1997 Published by Elsevier Science S.A.

Long period two-dimensional gratings for 8-12 mu m quantum well infrared photodetectors

By considering all possible high order diffracted waves, the authors investigate the spectral response of two-dimensional gratings for quantum well infrared photodetectors (QWIPs). A new method is proposed that using long period gratings may improve grating quality and reduce the resulting cross talk in grating-coupled QWIPs. A sensitivity analysis indicates that the influence of variation of the grating constant on the coupling efficiency is less sensitive for the long period gratings than for the short ones. A large coupling efficiency has been demonstrated for long period gratings. The calculated wide grating response spectra are in good agreement with the experiment result. (C) 1996 American Institute of Physics.

Absorption and Raman spectra of Se-8-ring clusters in zeolite 5A

Samples with different weight ratio of Se to zeolite 5A (Se composition) have been prepared by loading Se into the cages of zeolite 5A and the measurements of the absorption and Raman spectra have been carried out for the prepared samples. The measured absorption edges of the samples close and blue shifted to the value for monoclinic Se containing Se-8-ring, suggesting the formation of Se-8-ring clusters dagger in the cages. The continuous and broadening features of the absorption spectra are interpreted by the strong electron-phonon coupling in Se-8-ring clusters. The sample with high Se composition has a red shift of the absorption band edge relative to the samples with less Se composition. It is tentatively attributed to the reason that with different Se composition, single Se-8-ring clusters and double Se-8-ring clusters are formed in the cages of zeolite 5A. A single broad band at about 262 cm(-1) is observed in the Raman spectra, that gives the further support of the formation of Se-8-ring clusters. Copyright (C) 1996 Elsevier Science Ltd

DIFFERENT INTERDIFFUSION CHARACTERISTICS BETWEEN AG/YBA2CU3O7-X AND AL/YBA2CU3O7-X CONTACT INTERFACES

The differences between the interdiffusion characteristics of Ag/YBa2Cu3O7-x and Al/YBa2Cu3O7-x contact interfaces have been revealed by secondary ion mass spectrometry (SIMS). The different electrical properties of Ag/YBa2Cu3O7-x and YBa2Cu3O7-x films after high temperature treatment are well understood by the SIMS results.

Ag surface plasmon enhanced double-layer antireflection coatings for GaAs solar cells

Surface plasmon enhanced antireflection coatings for GaAs solar cells have been designed theoretically. The reflectance of double-layer antireflection coatings (ARCs) with different suspensions of Ag particles is calculated as a function of the wavelength according to the optical interference matrix and the Mie theory. The mean dielectric concept was adopted in the simulations. A significant reduction of reflectance in the spectral region from 300 to 400 nm was found to be beneficial for the design of ARCs. A new SiO_2/Ag-ZnS double-layer coating with better antireflection ability can be achieved if the particle volume fraction in ZnS is 1%-2%.

Ag生长温度对Ag/ZnO肖特基接触特性的影响

利用脉冲激光沉积(PLD)方法在Si衬底上制备了ZnO单晶体薄膜,并在不同温度下生长了Ag膜作为肖特基电极,研究了Ag与ZnO的接触特性.利用X射线衍射仪、扫描电子显微镜和Ⅰ-Ⅴ测试方法对样品的晶体质量、结构和电学性质进行了分析.结果表明,ZnO薄膜具有高度的c轴择优取向,Ag膜随生长温度的不同的晶体质量有较大差异.样品在室温下的Ⅰ-Ⅴ测试结果表明Ag电极的生长温度对Ag/ZnO接触性能有重要影响.在150℃和200℃生长的Ag电极实现了Ag与ZnO的肖特基接触,电极生长温度低于150℃和高于200℃的样品Ag与ZnO均为欧姆接触.经过分析,肖特基接触的形成依赖于在Ag与ZnO接触界面处形成的p型反型层.

In0.2 Ga0.8 As-GaAs复合应力缓冲层上的1.3 μmInAs/GaAs自组织量子点

用光荧光谱和原子力显微镜测试技术系统研究了在2 nm In0.2Ga0.8As和x ML GaAs的复合应力缓冲层上生长的InAs/GaAs自组织量子点的发光特性和表面形貌.采用In0.2Ga0.8As与薄层GaAs复合的应力缓冲层,由于减少了晶格失配度致使量子点密度从约1.7×109 cm-2显著增加到约3.8×109cm-2.同时,复合层也有利于提高量子点中In的组份,使量子点的高宽比增加,促进量子点发光峰红移.对于x=10 ML的样品室温下基态发光峰达到1350 nm.

7.8μm二级分布反馈量子级联激光器

报道了基于应变补偿的InP基In0.53+xGa0.47-xAs/In0.52-yAl0.48+yAs分布反馈量子级联激光器.采用二级光栅作为反馈,激射工作波长为7.8μm,在1%占空比,5kHz频率的工作条件下,在93～173K的温度范围内,单模发射光谱边模抑制比均超过20dB,调谐系数dλ/dT=0.5125nm/K.在93K时,峰值功率为30mW,直到153K时,峰值光功率仍达到12mW.

赝配GaAs/In_(0.2)Ga_(0.8)As量子阱导带不连续量的C-V和电容瞬态测量

半导体材料开放实验室基金,国家自然科学基金