无溶剂微波辅助-液相微萃取测定土壤中的滴滴涕

建立了一种快速、有效、环境友好的样品前处理方法,即无溶剂微波辅助-液相微萃取技术,并结合高效液相色谱法对土壤中的滴滴涕残留进行了测定分析,同时对影响萃取效率的相关因素,如萃取溶剂的种类、微波辐射功率、萃取时间和pH等因素进行了优化。最终确定最佳优化条件为：萃取溶剂为正庚烷,微波辐射功率为120w,萃取时间为1rain,pH为5。在最优条件下,滴滴涕的检出限（S／N=3）为0．18μg／kg,定量限（S／N=10）为0．59μg／kg,实际土壤加标回收率87．34％～96．41％之间,相对标准偏差RSDs在5．75％～6．72％之间。理论分析和实验结果表明,该方法具有操作简便,节省溶剂,快速,高效,选择性好等特点。     

SiO_2气凝胶对废水中硝基苯的吸附性能研究

选用疏水型SiO2气凝胶作为吸附剂,研究SiO2气凝胶对废水中硝基苯的吸附性能,考察溶液的pH值、温度、吸附时间、SiO2气凝胶添加量等因素对吸附率的影响,并结合Freundlich等温吸附方程,探讨SiO2气凝胶对溶液中硝基苯的吸附规律和吸附机理.结果表明,最佳吸附条件为温度25℃,pH8.35,SiO2气凝胶的添加量为3.33 g/L、振荡时间为30 min,此时疏水型SiO2气凝胶对废水中硝基苯的吸附率可达68.76%,吸附容量可达7.29 mg/g.SiO2气凝胶对废水中硝基苯的吸附性能与气凝胶的疏水性、有机溶液比表面积以及气凝胶的结构特性有关.     

高温高盐油藏可动凝胶-渗吸调驱配方体系研究与应用

通过室内试验,研究了聚合物分子量、聚合物浓度、交联剂用量及pH等因素对耐高温有机交联剂HT-2008与高分子量星形抗温耐盐聚合物CA-2588形成的凝胶黏度和成胶时间的影响,确定了尕斯库勒E_3~1油藏高温高盐可动凝胶调驱体系的基本配方及性能:环境扫描电子显微镜结果表明,高分子量星形抗温耐盐聚合物CA-2588和耐高温有机交联剂HT-2008能够形成稳定的互穿网络体型结构,该可动凝胶体系,在矿化度为117000mg/L(且钙镁离子含量高达3340 mg/L),pH为7.80,实验温度为126℃条件下,5d时黏度达到最高值43900 mPa s,180 d时凝胶黏度为43500 mPas,耐温耐盐性能好,稳定性好;通过考察不同结构的渗吸剂相态、渗吸脱油效率和长期稳定性等因素,确定了适用于尕斯库勒油田E_3~1高温高盐油藏的3种渗吸剂LF1008,AESN70和N111-2.在尕斯库勒油田E_3~1油藏进行可动凝胶.渗吸深部调驱现场应用后,取得良好效果.     

锂硼合金反应合成机制研究

提出了锂硼合金反应合成的物理模型, 反应过程中有两次放热反应, 第1次放热反应可以分成3个阶段, 第1阶段是Li与B粒在界面(~330℃)的瞬时反应, 此放热量与B粒的半径成反比关系. 第2阶段是Li液通过B粒表面反应生成的LiB₃向内扩散并与内核的B反应, 此过程可用固体反应中的Johnston模型来描述. 其反应速率常数与B粒的半径平方成反比. 第3阶段是在425℃以上LiB₃溶解到Li液体之中, 但与此同时, 第2次放热反应也开始进行. 第2次放热反应通过Li-B化合物的形核和长大来完成, 它可以分成形核孕育和爆发反应两个阶段. 有足够形核数目时, 产生爆发性反应. 温度越低, 产生爆发性反应所需时间越长. 运用该模型解释了合成实验中出现的相关现象.     

CO_2固定-甲烷蒸汽重整一体化制氢：不同吸附剂的比较

针对固定床CO2固定-甲烷蒸汽重整一体化制氢过程建立二维非等温、非等压的气固异相模型,结合实验数据,比较了Li4SiO4,CaO,Li2ZrO3和水滑石（HTC）4种CO2吸收剂在重整过程中的作用,探讨了温度、压力、水碳比（S/C）对促进制氢效率的影响.模拟结果表明,在常压及550°C温度下,以Li4SiO4,CaO,HTC为吸收剂得到高于94%的H2浓度（干燥基）;500°C～600°C的温度范围内,初始CO2吸收速率：HTC〉CaO〉Li4SiO4〉Li2ZrO3;饱和速率：HTC〉CaO〉Li4SiO4〉Li2ZrO3;提高反应温度,CaO的吸收容量和吸收速率均增加,而Li4SiO4的吸收速率增加,容量变化不大.在550°C温度下,提高反应压力,＂预穿透＂阶段Li4SiO4,HTC,Li2ZrO3的促进效率增加.在S/C=2～4.5之间存在一个最佳值,此时Li4SiO4,CaO,Li2ZrO3和水滑石（HTC）的促进效率最大.     

改性白云石制备CO_2吸收剂的活化条件优化

为了确定利用NaNO_3改性白云石制备CO_2吸收剂MgO-CaCO_3的制备工艺,本文利用热重分析仪研究了活化条件对钙镁复盐吸收剂活化程度及活化后所得吸收剂吸收性能的影响.研究结果表明活化温度越高、活化时间越长、活化气氛用空气代替N_2时,NaNO_3改性白云石制备的钙镁复盐在活化过程中的失重量越大.然而活化后所得吸收剂的CO_2吸收性能并不与样品在活化过程中的失重量成正比.结合钙镁复盐MgCO_3-CaCO_3的分解反应机制和熔融的NaNO_3通过离子液体通道促进离子扩散机制,分析了活化条件对吸收剂吸收性能的影响机理.样品活化过程过于剧烈会增大CaCO_3晶粒和MgO晶粒之间的间距,减弱CaCO_3对MgO基吸收剂CO_2吸收能力的促进作用,得到在高温条件下基本无CO_2吸收能力的独立的MgO吸收剂.     

三峡库区紫色土粘粒悬浮液的稳定性

研究了三峡库区紫色土胶体的表面电荷性质及其对变化环境的响应以及对紫色土粘粒悬浮液稳定性的影响。三种紫色土胶体在2：1型电解质中的表面电位分别约-0.14～-0.192V,1：1型电解质中约为其两倍。1：1型电解质中粘粒悬浮液完全沉降时同分剐达到40．6—47．0h,比2：1型电解质中长12．4—14．6h,电解质浓度增加,粘粒悬浮液完全沉降时间下降,稳定性减弱。pH对完全沉降时间影响强烈,当pH=5时,两种电解质体系中的粘粒悬浮液完全沉降时间减少近一半;pH=3时,60min左右悬浮液已经沉降完全。三种紫色土粘粒悬浮液稳定性是酸性紫色土〈中性紫色土〈石灰性紫色土。     

纳米TiO2/ZnO光催化降解氯胺磷的研究

采用溶胶-凝胶法制备了几种不同比例的纳米TiO2/ZnO复合半导体光催化剂及纯TiO2、ZnO单组分催化剂,并利用XRD,FE-SEM等手段对样品的结构和形貌进行表征.选用有机磷药氯胺磷为光催化降解对象,利用钼锑抗分光光度法测量并计算降解率,研究了溶液初始浓度、催化剂用量、催化剂的不同配比、热处理温度及溶液的pH值等因素对光催化降解效果的影响.实验结果表明:对于初始浓度4.5mg/L的氯胺磷溶液,催化剂用量为0.6 g·L<'-1>时,TiO2与ZnO的最佳比例为10:1,最佳热处理温度为500℃.反应进行5 h后,最大降解率可达到44.1%.在酸性及碱性介质中均有利于氯胺磷的降解,降解后溶液pH值都向中性趋近     

室温离子液体在纳米材料制备中的应用

室温离子液体作为一种新型的优良溶剂,在纳米材料合成中具有诱人的应用前景.本文简要介绍了近几年来室温离子液体在单质、氧化物、硫化物、硒化物、碲化物和含氧酸盐等纳米材料制备中应用的一些研究进展,重点介绍了我们实验室最近有关微波辅助离子液体法快速制备一维纳米材料方面的研究工作,并讨论了室温离子液体在纳米材料制备过程中的主要作用.     

稀土Ho3＋/Yb3＋共掺SrBi4Ti4O15高温铁电陶瓷的上转换发光及其温度传感特性

Sr Bi4Ti4O15是一种具有高居里温度（Tc）、高机械品质因数和大电阻率的铋层状结构铁电、压电多功能材料,通过掺入稀土离子的手段,可使其具有上转换发光的特性,并且可以在一定程度上改善其电学性能.在本文中,同时将Ho3＋和Yb3＋对A位的Bi进行取代,其中Ho3＋的取代量为0.06 mol-1,Yb3＋的取代范围为0≤x≤0.3,采用传统的固相烧结法制备了Sr Bi3.94-xHo0.06YbxTi4O15陶瓷.主要通过控制Ho3＋离子的量不变,调节Yb3＋离子的浓度来研究不同稀土离子掺杂量对Sr Bi4Ti4O15陶瓷的形貌、上转换发光特性、以及介电性能的影响.在使用980 nm的红外激光器对Sr Bi3.94-xHo0.06YbxTi4O15陶瓷进行激发下,从上转换发光图谱中可以观察到三个峰,分别为峰位在547 nm附近较强的绿色发光、659附近以及759 nm处的较弱的红色发光.同时可以看到,随着Yb3＋浓度的增加,绿色上转换发光的强度表现出先增强,后减弱的规律,且当Yb3＋取代量为x=0.15时,绿色上转换发光强度达到最大值.通过研究上转换发光强度与激发光功率的关系得到,绿色和红色上转换发光均为双光子吸收过程.在研究Sr Bi3.79Ho0.06Yb0.15Ti4O15样品上转换发光与温度的关系时,可以观测到随着温度的增加,547 nm处的绿色上转换发光和659 nm处的红色上转换发光的强度均随之减弱,且I659 nm与I547 nm的荧光强度比与温度存在线性关系,利用这种温度与上转换发光强度的关系,可将Sr Bi3.94-xHo0.06YbxTi4O15陶瓷应用于光学温度传感器.     

草石蚕水苏糖检测技术的研究

建立了我国传统植物草石蚕块茎中水苏糖的定性分析和定量检测方法。采用薄层层析（TLC）法定性分析,选择乙酸乙酯／甲醇／水／冰醋酸（3／2／1／2）为展开剂,采用二苯胺-苯胺一磷酸为显色剂。该条件下水苏糖Rf值为0．47,显色点为棕黄色,斑点清晰,与其他糖分分离良好。用高效液相色谱-示差折光检测（HPLC—RID）法定量检测,采用Kromasil NH2柱,流动相为乙腈／水（55／45,v／v）,柱温为30℃,流速为1．0mL／min,进样体积10μL,该色谱条件下,水苏糖峰出峰对称性好,时间较短（9．5min）,水苏糖浓度在1．0～8．0mg／mL范围内线性关系良好（R2=0．9996）,回收率在96．O％～102．5％之间。在生产应用中,可以根据实际采用其中一种或者两种方法结合,以满足检测需要。     

Ambiquitous behavior of rabbit liver lactate dehydrogenase

Rabbit liver mitochondrial fraction shows lactate dehydrogenase activity. The enzyme can be released from particles by increasing the pH and the ionic strength of the medium. There is a narrow range of pH (6.8-7.4) and ionic strength (20-50 mM NaCl) in which the solubilization sharply increases. It has been shown that divalent anions (SO4(2-) and cations (Mg2+, Ca2+) are highly effective specific solubilizing agents. NADH (1.5 mM) and ATP (1.0 mM) were effective in solubilizing 50% of the enzyme bound, whereas the same concentrations of the analogs NAD+ and ADP had little effect. Cytosolic lactate dehydrogenase bound to the mitochondrial fraction and a saturation of particles by enzyme was observed in all experiments performed. The in vitro binding requires a short period of incubation between the enzyme and particles and the binding is independent of the temperature in the 0-37 degrees C range. Binding was prevented by 0.15 M NaCl. The bound enzyme is approximately 20% less active than the soluble one. The results described give support to the proposal that rabbit liver lactate dehydrogenase has an ambiquitous behavior, like other glycolytic enzymes, which have not a fixed intracellular localization.     

三元体系Mg2+//Cl-,borate-H2O在308.15K时稳定相平衡研究

采用等温溶解法研究了三元体系Mg2+//C1-,borate-H20在308.15 K时的稳定相平衡;测定了上述体系液相中各组份的平衡溶解度及物化性质(密度和pH),根据实验数据绘制了相应相图和物化性质组成图.该体系在308.15 K时有1个共饱点(水氯镁石+镁硼酸盐)、2条饱和溶解度曲线和2个结晶相区,无复盐及固溶体...     

Cryo-bioorganic chemistry: freezing effect on stereoselection of l- and dl-leucine cooligomerization in aqueous solution

The chirality of l-/dl-leucine (50–50%) cooligomerization was investigated in liquid and frozen aqueous solutions. Cooligomerization was carried out by carbonyldiimidazole activation without initiator at an ambient (+22°C) and frozen (−18°C) temperature, respectively. The separated samples obtained after different time intervals of treatment were completely hydrolyzed (HCl) and the diastereomeric l- and d-leucine derivates of Marfey's reagent (1-fluoro-2,4-dinitrophenyl-5-l-alanine amide) were then traced and evaluated by RP-HPLC analysis. After 9 days of oligomerization, the l-Leu content was slightly enhanced in the liquid (57%) and somewhat more enhanced in the frozen (64%) samples. After 17 days, however, the l-Leu content had decreased in the liquid (53%) and frozen (56%) conditions. These l-enantiomer amplifications indicate that an l-antipode is preferentially incorporated into the α-helical turn of the oligomer in the earlier stage of cooligomerization, while, later, the d-antipode is also incorporated. The role of ice in the improved stereoselection is discussed. This is the first recorded example of the effect of freezing on stereoselection. Received 27 October 2000; revised 11 December 2000; accepted 4 January 2000     

Biophysikalische Studien mit synthetischem Lezithin

Summary Synthetic lecithin, dissolved in chloroform, is able to add salts which are non-soluble in chloroform and to transfer these at neutral pH from the aqueous into the lipoid phase. The effect is dependent on the cation concentrations and particularly on their valency. Calcium, barium, copper ions, etc., are about one hundred times more effective than sodium and potassium. Two-basic amines are also very effective. For experimental reasons, anion was, up to now, not varied and in all tests tropeoline was used.      

Ambiquitous behavior of rabbit liver lactate dehydrogenase

Summary Rabbit liver mitochondrial fraction shows lactate dehydrogenase activity. The enzyme can be released from particles by increasing the pH and the ionic strength of the medium. There is a narrow range of pH (6.8–7.4) and ionic strength (20–50 mM NaCl) in which the solubilization sharply increases. It has been shown that divalent anions (SO ₄ ^2– ) and cations (Mg²⁺, Ca²⁺) are highly effective specific solubilizing agents. NADH (1.5 mM) and ATP (1.0 mM) were effective in solubilizing 50% of the enzyme bound, whereas the same concentrations of the analogs NAD⁺ and ADP had little effect. Cytosolic lactate dehydrogenase bound to the mitochondrial fraction and a saturation of particles by enzyme was observed in all experiments performed. The in vitro binding requires a short period of incubation between the enzyme and particles and the binding is independent of the temperature in the 0–37°C range. Binding was prevented by 0.15 M NaCl. The bound enzyme is approximately 20% less active than the soluble one. The results described give support to the proposal that rabbit liver lactate dehydrogenase has an ambiquitous behavior, like other glycolytic enzymes, which have not a fixed intracellular localization.     

Kinetische Isotopeneffekte bei elektrophilen aromatischen Substitutionen

Summary In an aqueous buffer solution (pH 6...64) p-diazochlorbenzene reacts with 2-naphthol-6,8-disulphonic acid four times faster than with the deuterated compound 1-d-2-naphthol-6, 8-disulphonic acid. This shows that the proton loss is rate determining. Other diazo coupling reactions do not give such a kinetic isotope effect.     

Kinins in cerebrospinal fluid: reduced concentration in spontaneously hypertensive rats

Rat cerebrospinal fluid contains peptides which displace radiolabeled bradykinin from its specific antibodies. Two peptides which showed the same retention time as kallidin and bradykinin in a reverse phase high pressure liquid chromatography system were detected in cerebrospinal fluid of rats. The concentration of radioimmunologically detected kinins in the cerebrospinal fluid of spontaneously hypertensive rats of the Okamoto strain was lower than that of the Wistar Kyoto control rats.     

Circabidian rhythm: its appearance and disappearance in association with a bright light pulse

A shift from circadian to circabidian periods or vice versa was observed in the rhythm of sleep and wakefulness under temporal isolation. The shift occurred in two subjects, 3 times in association with a single bright light pulse applied, 4 times in all. The finding suggests that the bright light pulse has an additional effect to the phase shift on the human circadian system.