低温加氢裂解脱除高硅ZSM-5分子筛内TPAOH模板剂

分子筛膜的合成和应用是近年来的研究热点, 特别是具有独特孔道结构的MFI 型分子筛膜. 但由于膜内有机模板剂在高温脱除时会导致膜产生缺陷, 进而影响分子筛膜的应用. 所以分子筛膜及分子筛晶体中有机模板剂的低温脱除工艺一直是研究者们致力解决的问题之一. 本文系统考察了高硅ZSM-5分子筛晶体内有机模板剂(四丙基氢氧化铵, TPAOH)在H₂/N₂气氛下的低温裂解脱除规律, 采用低温加氢裂解工艺, 在350 ℃以下可有效脱除分子筛晶体孔道内的有机模板剂. 通过对裂解后分子筛晶体的比表面积(BET)、热失重(TG)、傅里叶变换红外(FTIR)光谱和拉曼光谱表征证实, 相比于空气和氮气气氛, 含氢还原性气氛更有利于模板剂的低温脱除, 脱除率随温度的升高而增加; 280 ℃时, 加氢裂解后晶体的BET比表面积已达到252 m²·g^-1, 仍有少量有机残余物; 350 ℃时, 加氢裂解后晶体的BET比表面积可达到399 m²·g^-1, 仅有微量无机碳残余物. 此外, 低温加氢裂解后的分子筛表面相对洁净, 且氨气程序升温脱附(NH₃-TPD)结果表明低温加氢裂解后的ZSM-5 分子筛晶体具有相对较多的酸性位.     

采用半导体激光器自身pn结特性测温的 半导体激光器恒温控制

温度对半导体激光器的发射波长有很大的影响,而很多应用都要求半导体激光器的发射波长是稳定的。针对使用测温元件作为温度传感器进行半导体激光器恒温控制中存在的温度误差,提出了以半导体激光器自身pn结作为温度检测元件进行半导体激光器恒温控制的方法,设计了半导体制冷器的驱动电路。该方法利用pn结的温度敏感特性,首先通过实际测量标定pn结的温度与其两端压降的对应关系,然后通过测量压降得出相应的实际温度。实验结果表明,采用该方法消除了使用温度传感器进行半导体激光器恒温控制中温度梯度造成的恒温误差,提高了测量速度,显著减小了超调量,消除了静差和波动。     

硫酸高铈铵分光光度法测定葡萄籽提取物中原花青素

建立了葡萄籽提取物中原花青素测定的新方法 硫酸高铈铵分光光度法。它是基于原花青素与Ce4 在强酸性介质中反应生成无色的Ce3 ,通过测定黄色高铈盐的吸光度,间接测定原花青素,Ce4 在319nm波长处具有最大吸收。该方法的线性范围为0.12～10μg mL,RSD为0.98%～1.1%,回收率为97.2%～102.8%,相关系数r=0.9992,检出限为0.04μg mL。     

胆酸和L-苯丙氨酸的固相包合作用

研究了胆酸(CA)和L-苯丙氨酸(PAA)以固相熔融法形成的固相包埋配位. 通过粉末X射线衍射图、红外光谱、粉末荧光光谱及差热分析方法, 测定了固相包埋形成的CA-PAA配合物. 同时, 用溶剂共沉淀法和机械研磨法对比了CA-PAA包埋物的形成. 结果表明, 封管固相熔融时PPA以客体形式被包合进主体CA形成的通道; 研磨法中CA部分包埋PPA; 溶剂共沉淀方法中, PPA不被主体CA包埋, 而使用的相应溶剂被CA包埋.     

Highly efficient enrichment and subsequent digestion of proteins in the mesoporous molecular sieve silicate SBA-15 for matrix-assisted laser desorption/ionization mass spectrometry with time-of-flight/time-of-flight analyzer peptide mapping

Based on a previous study of protein digestion inside the nanoreactor channels of the mesoporous molecular sieve silicate SBA-15 (Chem. Eur. J. 2005, 11: 5391), we have developed a highly efficient enrichment and subsequent tryptic digestion of proteins in SBA-15 for matrix-assisted laser desorption/ionization mass spectrometry with time-of-flight/time-of-flight analyzer (MALDI-TOF/TOF) peptide mapping. The performance of the method is exemplified with myoglobin and cytochrome c. First, protein adsorption isotherms for two standard proteins with a range of initial concentration of proteins were investigated at room temperature. The results revealed that the kinetic adsorption rate of a protein within SBA-15 was independent of initial protein concentration, and a 15-min protein enrichment within SBA-15 could be enough for protein identification in biological samples. It was noticed that no washing steps were needed to avoid protein loss due to desorption from the mesochannels into solution. Second, protein digestion inside the channels of SBA-15 was also optimized. After adsorption of proteins into SBA-15 in 15 min, the trypsin solution (pH 8) was directly added to the SBA-15 beads with immobilized proteins by centrifugation, and then the digestion was performed for 15 min at 37 degrees C. It was observed that a higher peptide sequence covering of 98% for myoglobin was obtained by MALDI-TOF/TOF analysis, compared to in-solution digestion. So the protein digestion inside SBA-15 was proved to be significantly faster and yielded a better sequence coverage. The new procedure allows for rapid protein enrichment and digestion inside SBA-15, and has great potential for protein analysis.     

Assembly-controlled biocompatible interface on a microchip: strategy to highly efficient proteolysis

A biocompatible interface was constructed on a microchip by using the layer-by-layer (LBL) assembly of charged polysaccharides incorporating proteases for highly efficient proteolysis. The controlled assembly of natural polyelectrolytes and the enzyme-adsorption step were monitored by using a quartz-crystal microbalance and atomic force microscopy (AFM). Such a multilayer-assembled membrane provides a biocompatible interconnected network with high enzyme-loading capacity. The maximum digestion rate of the adsorbed trypsin in a microchannel was significantly accelerated to 1600 mM min(-1) microg(-1), compared with the tryptic digestion in solution. Based on the Langmuir isotherm model, the thermodynamic constant of adsorption K was calculated to be 1.6 x 10(5) M(-1) and the maximum adsorption loading Gammamax was 3.6 x 10(-6) mol m(-2), 30 times more than a monolayer of trypsin on the native surface. The tunable interface containing trypsin was employed to construct a microchip reactor for digestion of femtomoles of proteins and the produced peptides were analyzed by MALDI-TOF mass spectroscopy. The efficient on-chip proteolysis was obtained within a few seconds, and the identification of biological samples was feasible.     

新型离子液体基质用于MALDI-MS高效离子化寡糖/糖肽

本研究发展了四种基于三羟基苯乙酮(THAP)的新型离子液体基质, 即2',3',4'-THAP/二甲基苯胺(DMA)、2',4',6'-THAP/DMA、2',3',4'-THAP/吡啶(Py)及2',4',6'-THAP/Py, 用于提高寡糖/糖肽在MALDI-TOF MS中的离子化效率. 与传统的固体基质2,5-二羟基苯甲酸(DHB)和2',4',6'-三羟基苯乙酮(2',4',6'-THAP)相比, 新型离子液体体系分析不同类型的寡糖链, 均可获得更高的检测灵敏度. 可使葡聚糖(dextran 1000)和环状寡聚糖β-环糊精在MALDI质谱中的信噪比提高10倍以上, RNase B的复杂寡糖链也实现了高灵敏度的检测. 在糖肽分析中, 2',3',4'-THAP/DMA离子液体高灵敏度地检测到辣根过氧化酶的7条糖肽, 而2',3',4'-THAP作为基质时却无法检测到任何信号.     

Global Insight into N-Glycome and N-Glycoproteome of Three Most Abundant Snake Venoms in Asia

Snake venom is a complex cocktail including a variety of biological active proteins and proteinaceous components, which have considerable medical and pharmacological importance. N-Glycosylation is widely impli- cated as a common modification in numerous venom proteins and impacts the in vivo venomic functions. However, systematic survey of N-glycome and N-glycoproteome on snake venoms has not been undertaken. In this study, em- ploying combination of N-glycomics and N-glycoproteomics strategies, we explored the N-glycosylation including both N-glycoproteins and N-glyco-chains in three venoms from Agkistrodon blomhoffii, Naja naja atra Cantor and Vipera russelii siamensis Smith, respectively, which are amongst the most abundant venomous snakes in Asia. As a result, numbers of N-glycoproteins and N-glycans were identified. However, the overlaps of N-glycoproteins and N-glycans of the three venoms were small. Thus, the exploration results of N-glycome and N-glycoproteome indicate that N-glycosylation increases the complexity and variety of the three venoms. Our research provided some new horizons for the comprehensive understanding of venoms variation, which is helpful for the basic venom re- search as well as the management of snake envenomation.     

Lindqvist型钼酸盐修饰的碳纳米管二阶非线性光学性质的理论研究

利用密度泛函理论(DFT)方法研究了[Mo₆O₁₉]^2-修饰的单壁碳纳米管的非线性光学(NLO)性质. 结果表明, [Mo₆O₁₉]^2-修饰的单壁碳纳米管作为特殊的有机-无机杂化体系, 具有显著的二阶非线性光学响应. 通过调整[Mo₆O₁₉]^2-与纳米管之间的角度, 体系的稳定性显示出规律性的变化趋势, 且二阶NLO响应发生了变化. 对静场二阶极化率(β_vec)有主要贡献的电子跃迁特征表明, [Mo₆O₁₉]^2-与碳纳米管之间角度的改变影响了分子内的给受体特征. 当角度达到30°时, 化合物显示出最大的β_vec值, 此时杂多阴离子簇为电子受体, 而碳纳米管为电子给体. 此外, 在碳纳米管的端位连接电子给体(如氨基)可有效地增大β_vec值.     

炮体表面瞬态温度分布的散斑干涉测试研究

为了可以实现对炮体表面瞬态温度分布变化的实时监测,同时克服传统瞬态高温测试仪器单点探测以及热惯性大等局限性,设计了基于散斑干涉与光谱频域分析相结合的瞬态温度分布测试系统。系统采用散斑干涉技术将炮体瞬态温度变化引发的微小形变转换成散斑干涉条纹,再由傅氏变换完成干涉条纹形变到光谱分布的函数转换,从而通过光谱分布函数反演任意采样时刻上的温度分布。实验采用ZX-FB1型光纤测温仪测试单点位置上瞬态温度作为标准值,再由555 nm激光器与面阵CCD采集散斑干涉条纹,分别使用图像识别法与傅氏变换法完成干涉条纹与瞬态温度的算法匹配,从而反演瞬态温度。实验结果显示,两种方法均能实现瞬态温度检测,但基于傅氏变换频谱分析的散斑干涉法精度更高,并且可以有效地克服由表面瑕疵、漆面磨损等问题造成的粗大误差。