氨基酸在乙醇/磷酸氢二钾双水相体系中分配行为

研究了5种结构和性质各异的氨基酸(谷氨酸,半胱氨酸,苯丙氨酸,赖氨酸,精氨酸)在亲水性有机溶剂乙醇和磷酸盐溶液形成的乙醇/K2HPO4双水相体系中的分配行为及其影响因素。当双水相体系中乙醇的质量分数从22%增加到30%时,半胱氨酸和苯丙氨酸的分配系数明显增大,其它三种氨基酸的分配系数变化幅度不大;当磷酸盐的质量分数从14%增加到22%时,氨基酸的分配系数的变化均不明显;双水相体系的pH值对氨基酸的分配系数影响较大,当pH增加时,5种氨基酸的分配系数均增加,但是当pH约为9.5时,苯丙氨酸、半胱氨酸的分配系数接近相等但与其它3种氨基酸的分配系数相差较多,当pH为6.0~8.0时,苯丙氨酸的分配系数远远大于另外4种氨基酸。氨基酸的支链结构中含有非极性基团将导致其分配系数的增加。     

ATR-FTIR investigation on the complexation of myo-inositol hexaphosphate with aluminum hydroxide

The adsorption isotherm of and the pH effect on the adsorption of myo-inositol hexaphosphate (myo-IP6) on amorphous aluminum hydroxide was investigated. It was found that the adsorption isotherm of myo-IP6 on aluminum hydroxide could be well fitted with the Freundlich isotherm. The amount of myo-IP6 adsorbed remained almost constant in the range of pH 4.0 to 7.0, but it decreased considerably as the initial pH was over 7. The adsorption of myo-IP6 resulted in an increase in the pH level due to the release of OH(-) ions, which suggested that the adsorption of myo-IP6 on aluminum hydroxide was caused by a ligand exchange reaction. ATR-FTIR analysis of myo-IP6 in solution and adsorbed on aluminum hydroxide at different pH were performed. The ATR-FTIR investigation indicated that myo-IP6 was adsorbed onto aluminum hydroxide by forming inner-sphere complexes and adsorption facilitated the deprotonation of phosphate groups. The asymmetric vibration of the PO bond in AlPO(-)(3) appearing at a lower frequency than that in the terminal HPO(-)(3) indicated that Al bound to the O atom not as strongly as the H atom did. The ATR-FTIR investigation and theoretical calculation (with the Gaussian 03 program) revealed that three of the six phosphate groups in myo-IP6 molecules were bound to aluminum hydroxide while the other three remained free when myo-IP6 was adsorbed on aluminum hydroxide.     

Comparison of different methods to measure contact angles of soil colloids

We compared five different methods, static sessile drop, dynamic sessile drop, Wilhelmy plate, thin-layer wicking, and column wicking, to determine the contact angle of colloids typical for soils and sediments. The colloids (smectite, kaolinite, illite, goethite, hematite) were chosen to represent 1:1 and 2:1 layered aluminosilicate clays and sesquioxides, and were either obtained in pure form or synthesized in our laboratory. Colloids were deposited as thin films on glass slides, and then used for contact angle measurements using three different test liquids (water, formamide, diiodomethane). The colloidal films could be categorized into three types: (1) films without pores and with polar-liquid interactions (smectite), (2) films with pores and with polar-liquid interactions (kaolinite, illite, goethite), and (3) films without pores and no polar-liquid interactions (hematite). The static and dynamic sessile drop methods yielded the most consistent contact angles. For porous films, the contact angles decreased with time, and we consider the initial contact angle to be the most accurate. The differences in contact angles among the different methods were large and varied considerably: the most consistent contact angles were obtained for kaolinite with water, and illite with diiodomethane (contact angles were within 3 degrees); but mostly the differences ranged from 10 degrees to 40 degrees among the different methods. The thin-layer and column wicking methods were the least consistent methods.     

无粘结剂ZSM-11催化剂上异丁烯直接胺化生成叔丁胺

叔丁胺是一种重要的化工原料和中间体,广泛应用于制备橡胶促进剂、医药、农药和着色剂等下游产品.异丁烯在分子筛催化剂上直接胺化生产叔丁胺是一个经济环保过程,其中ZSM-5和BEA分子筛的催化性能优于其它系列分子筛.ZSM-11与ZSM-5分子筛具有相似的孔道结构,我们以前的实验结果表明,与ZSM-5相比,ZSM-11表现出更优越的芳构化反应性能,在干气中乙烯低温芳构化方面也有明显优势.在此基础上,我们进行无粘结剂ZSM-11分子筛催化剂合成,并应用于异丁烯直接胺化生产叔丁胺反应.传统水热技术合成的分子筛通常为粉末,机械强度不能达到实际应用的要求,在工业化过程中分子筛粉末一般需要加入粘结剂成型使其具备一定的机械强度和形状,但是粘结剂会降低分子筛催化剂的活性和选择性,有可能会引发一些副反应,因此无粘结剂分子筛催化剂引起人们广泛关注.无粘结剂分子筛是指分子筛颗粒中不含惰性粘结剂或只含有少量粘结剂,主要依靠分子筛晶粒间的相互作用支撑存在,具有一定形状、尺寸和机械强度的催化材料.无粘结剂分子筛催化剂中分子筛含量较高,可利用的有效表面积较大,在离子交换及工业催化等方面具有明显优势.本文采用水热合成的ZSM-11分子筛原粉与二氧化硅机械混合(ZSM-11/SiO2=70/30)挤条后,通过气固相合成法制备了无粘结剂ZSM-11分子筛催化剂(Cat-C).作为对比,还分别制备了ZSM-11和SiO2机械混合(ZSM-11/SiO2=70/30)样品HZSM-11+SiO2及ZSM-11和氧化铝机械混合(ZSM-11/Al2O3=70/30)样品HZSM-11+Al2O3.利用X射线衍射、透射电镜、NH3程序升温脱附和吸附吡啶红外光谱等对分子筛催化剂的物理化学性能进行了表征.同时,以这些分子筛样品为催化剂,在固定床反应装置上进行了异丁烯胺化反应评价,反应条件为270℃,5.0 MPa,氨烯比为4和异丁烯空速0.5 h?1.结果表明,与HZSM-11+SiO2和HZSM-11+Al2O3相比,Cat-C上叔丁胺生成速率最高.关联催化剂物化性能和反应性能发现,催化剂孔道结构与叔丁胺生成并不存在明显的关联性,而较多的Br?nsted酸和较少的Lewis酸才是Cat-C具有良好反应性能的主要原因.具有一定机械强度的无粘结剂ZSM-11分子筛催化剂制备简单,在异丁烯直接胺化过程中叔丁胺生成速率高,具有很好的工业化应用前景.     

相依样本情形时的经验似然比置信区间

本文讨论了强平稳φ混合样本的经验似然比置信区间,推广了Ｏｗｅｎ（１９８８,１９９０）在独立同分布情况下的结果,指出了相依情况时经验似然比置信区间的不足并进行了合理的改进。     

粘弹性方程全离散化有限体积元格式及数值模拟

本文利用有限体积元方法研究二维粘弹性方程, 给出一种时间二阶精度的全离散化有限体积元格式, 并给出这种全离散化有限体积元解的误差估计, 最后用数值例子验证数值结果与理论结果是相吻合的. 通过与有限元方法和有限差分方法相比较, 进一步说明了全离散化有限体积元格式是求解二维粘弹性方程数值解的最有效方法之一.     

竞争-竞争-互惠交错扩散模型的整体解

应用能量估计方法和bootstrap技巧证明了竞争-竞争-互惠交错扩散模型在空间维数小于6时古典解的整体存在性.当反应函数的系数满足一定条件时,应用Lyapunov函数获得了该模型解的收敛性.     

Organophosphine bearing multiple hydrogen-bond donors for asymmetric Michael addition reaction of 1-oxoindane-2-carboxylic acid ester via dual-reagent catalysis

Multiple hydrogen bonds containing nucleophilic phosphines derived from dipeptide dual-reagents catalyzed asymmetric Michael addition reactions between indene esters and activated olefins in high yields and good to excellent enantioselectivities under mild reaction conditions. The success of current highly selective reactions should provide inspiration for expansion to other reactions and would open up new paradigms for the synthesis of indanone derivatives bearing chiral quaternary carbon centers.     

氯化钾水溶液微观结构的分子动力学模拟研究

氯化钾水溶液不同于氯化钠的,其在低温下只能形成无水盐和冰.现有研究表明在氯化钠水溶液中不仅存在着水分子连续分布的区域与离子团簇,而且这二者的物质组成也与该溶液所形成晶体的分别对应.为了探寻其他溶液中是否存在此类对应关系,并考察溶液的微观结构,本文采用分子动力学方法对氯化钾水溶液进行了研究,表明了该溶液的一些性质.氯化钾水溶液中K⁺-K⁺和Cl^--Cl^-径向分布函数的特征具有一致性,峰的最大值所对应的位置都分别相同,明显不同于氯化钠水溶液的.系列时刻下瞬态图像内O到其最近离子距离中最大值的统计结果表明氯化钾水溶液中存在着一定大小的水分子连续分布的区域,其平均尺寸至少为2.26 nm;瞬态图像中K⁺与其最近邻Cl^-之间的距离主要分布在0.28 nm～0.38 nm之间,占比约为97.4%;溶液中存在着较大和较小两类离子团簇,较大团簇的平均尺寸为1.73nm,平均离子数是25.0,其内部的离子与周围离子之间具有与氯化钾晶体类似的结构;这些结果表明氯化钾水溶液中也...     

Surface profile measurement of low-frequency vibrating objects using temporal analysis of fringe pattern

A simple and accurate algorithm (phase scanning method) is proposed for 3D surface contouring and dynamic response determination of a vibrating object. A sinusoidal fringe pattern is projected onto a low-frequency vibrating object by a programmable liquid crystal display projector. The fringe patterns are captured by a high-speed CCD camera with a telecentric gauging lens. Phase values are evaluated point by point using phase scanning method. From the phase values of each point on the object, the contour of the specimen at different instants of vibration can be retrieved. In this paper, a small vibrating coin is used to demonstrate the validity of the method and the experimental results are compared with test results on a stationary coin using four-step phase shifting and fast Fourier transform methods. The technique is especially useful in applications where the vibrating object has a complicated shape.