Kinetics of vesicle formation

 The kinetics of vesicle formation from a hydrotrope (sodium xylenesulfonate) solution of a surfactant (Laureth 4) is studied by the use of a stopped-flow apparatus combined with a dynamic light scattering device to determine vesicle size in the system. The hydrotrope system studied presents a system with a high surfactant solubilization combined with vesicle formation simply by dilution with water. The kinetic results show a single exponential decay time. The kinetic analysis indicates that the vesicles are formed from a molecular solution which resulted from the shear in the stopped-flow device and grow by monomeric association. Received: 1 October 1996 Accepted: 22 November 1996     

新型四硫代富瓦烯衍生物的合成及其性质的研究

合成了3个新的含有卤素取代基的四硫代富瓦烯衍生物及6个新的相关化合物。利用溶液的电子吸收光谱对四硫代富瓦烯衍生物的性质进行了研究。研究结果表明, 四硫代富瓦烯衍生物的分子中π轨道之间的能级差较小, 因而分子具有较高的稳定性。     

pH-sensitive polyelectrolyte complex gel microspheres composed of chitosan/sodium tripolyphosphate/dextran sulfate: swelling kinetics and drug delivery properties

Porous chitosan (CS) polyelectrolyte complex (PEC) hydrogel microspheres were prepared via either wet phase-inversion or ionotropic crosslinking with sodium tripolyphosphate (Na+ - TPP) and dextran sulfate (DS). The resulting microspheres were characterized using scanning electron microscopy (SEM) and elemental analysis (EA). The controlled release behavior of ibuprofen (IBU) from these microspheres was investigated. The PEC microspheres were about 700-950 microm in diameter with large pores and open porous structure. The CS/TPP/DS microspheres resisted hydrolysis in strong acid and biodegradation in enzymatic surroundings. The swelling kinetics for CS microspheres was close to Fickian diffusion, whereas those for CS/TPP and CS/TPP/DS were non-Fickian. Furthermore, the equilibrium water content (EWC) and water diffusion coefficient (D) increased with the pH of the media. The release profiles of IBU from CS/TPP/DS microspheres were slow in simulated gastric fluid (SGF, pH 1.4) over 3 h, but nearly all of the initial drug content was released in simulated intestinal fluid (SIF, pH 6.8) within 6 h after changing media. Overall the results demonstrated that CS/TPP/DS microspheres could successfully deliver a hydrophobic drug to the intestine without losing the drug in the stomach, and hence could be potential candidates as an orally administered drug delivery system.     

Cation-pi interactions with a model for the side chain of tryptophan: structures and absolute binding energies of alkali metal cation-indole complexes

Threshold collision-induced dissociation techniques are employed to determine bond dissociation energies (BDEs) of mono- and bis-complexes of alkali metal cations, Li+, Na+, K+, Rb+, and Cs+, with indole, C8H7N. The primary and lowest energy dissociation pathway in all cases is endothermic loss of an intact indole ligand. Sequential loss of a second indole ligand is observed at elevated energies for the bis-complexes. Density functional theory calculations at the B3LYP/6-31G level of theory are used to determine the structures, vibrational frequencies, and rotational constants of these complexes. Theoretical BDEs are determined from single point energy calculations at the MP2(full)/6-311+G(2d,2p) level using the B3LYP/6-31G* geometries. The agreement between theory and experiment is very good for all complexes except Li+ (C8H7N), where theory underestimates the strength of the binding. The trends in the BDEs of these alkali metal cation-indole complexes are compared with the analogous benzene and naphthalene complexes to examine the influence of the extended pi network and heteroatom on the strength of the cation-pi interaction. The Na+ and K+ binding affinities of benzene, phenol, and indole are also compared to those of the aromatic amino acids, phenylalanine, tyrosine, and tryptophan to elucidate the factors that contribute to the binding in complexes to the aromatic amino acids. The nature of the binding and trends in the BDEs of cation-pi complexes between alkali metal cations and benzene, phenol, and indole are examined to help understand nature's preference for engaging tryptophan over phenylalanine and tyrosine in cation-pi interactions in biological systems.     

Electrochemical Determination of Ascorbic Acid at γ-MnO<Subscript>2</Subscript> Modified Carbon Black Microelectrodes

A carbon black microelectrode modified by -MnO₂ has been prepared. The electrocatalytical oxidation of ascorbic acid (AA) at this microelectrode was investigated. The 2nd-order linear scan voltammograms of AA are recorded from –0.5 to 0.5V (vs. SCE). The relationship between the oxidation peak current of AA and its concentration in the range of 1.0×10^–64.0×10^–3molL^–1 is linear. The detection limit (3) was found to be 6.0×10^–7molL^–1. Also, the determination of AA in samples is evaluated, and the results are satisfactory.     

Linear combination of concomitants of order statistics with application to testing and estimation

Summary Let (X ₁,Y ₁), (X ₂,Y ₂),…, (X _n,Y _n) be i.i.d. as (X, Y). TheY-variate paired with therth orderedX-variateX _rn is denoted byY _rn and terms the concomitant of therth order statistic. Statistics of the form are considered. The asymptotic normality ofT _n is established. The asymptotic results are used to test univariate and bivariate normality, to test independence and linearity ofX andY, and to estimate regression coefficient based on complete and censored samples.     

PPh3催化Mannich反应机理的密度泛函研究

通过密度泛函理论研究了PPh3催化苯胺、苯甲醛和乙酰乙酸乙酯三组分Mannich反应的机理.计算结果表明该机理主要分3个步骤进行:PPh3催化乙酰乙酸乙酯发生酮式-烯醇式互变异构得到烯醇;烯醇辅助苯胺和苯甲醛缩合并脱水生成亚胺;亚胺和烯醇通过加成反应生成β-氨基羰基化合物.通过详细的机理研究,发现烯醇从亚胺的背面进攻其亲电C原子的过渡态的相对能量更低,容易得到反式的产物,对实验观察到的非对映选择性进行了合理的解释.     

Chiral coordination polymer as a luminescence sensor for small organic molecules

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两种胶原纤维固化单宁对La3+的吸附特性研究

以皮胶原纤维为基质,通过交联剂分别将黑荆树单宁和杨梅单宁固化在胶原纤维上制备吸附材料。实验表明,这两种吸附材料对稀土金属离子La^3＋有很好的吸附作用。在pH为4.5的条件下,当吸附剂用量为0.1 g,La^3＋初始浓度为9.952 mmol·L^-1,固化杨梅单宁的平衡吸附量为0.388 mmol·g^-1,比固化黑荆树单宁略大,其吸附平衡均符合Freundlich方程。进一步研究了固化杨梅单宁的吸附动力学、温度、pH值等对吸附平衡的影响。结果表明,温度对吸附平衡的影响不明显;pH值对吸附平衡有较大影响,在适当范围内提高pH值会增加平衡吸附量;吸附动力学可用拟二级速度方程来描述。当吸附温度为293 K时,由拟二级速率方程计算所得的平衡吸附量与实测的平衡吸附量误差在3%以内。同时固化杨梅单宁也具有良好的柱动力学特性。     

微波等离子体炬发射光谱法去溶系统性能的研究

用微波等离子体矩（MPT）作激发光源，等离子体的工作气体为氩气，研究了气动雾化进样去溶系统的工作参数对分析性能的影响，探讨了水冷凝与浓硫酸吸收二者协同去溶的相关性，结果表明，OH （Q1带，带头谱线为308.520nm）的发射强度即可判别样品去溶效果。