Determination of the surface tension of surfactant solutions applying the method of Lecomte du Noüy (ring tensiometer)

Summary Starting from a comparative assessment of the outstanding works on the ring method (du Noüy) for the determination of the surface tension of liquids and its solutions it is shown that the application of this method to surfactant solutions can lead to substantial errors if one follows conventional conditions. These errors are mainly connected with so far unknown phenomena occurring during the raising of the ring and concerning the influence of the hydrophilic vessel wall above the solution level and the stretching of the solution surface. This is demonstrated quantitatively with surfactant solutions of different kind and concentration. These effects can be explained theoretically very simply by introducing certain assumptions on the behaviour of a surfactant adsorption layer on the inner vessel wall. Conditions leading to the elimination of these errors are given, thus enabling the application of the ring method to the determination of the surface tension of surfactant solutions.With 10 figures and 3 tables     

Monolayer films of PS-b-PEO diblock copolymers at the air/water- and an oil/water-interface

 Amphiphilic diblock copolymers consisting of a hydrophobic polystyrene block (PS) and a hydrophilic poly(ethylene oxide) block (PEO) with block sizes of 1000 or 3000 g/mol for both blocks were studied at the air/water and toluene/water interface. Measurements of the film pressure π of spread monolayers at the water surface reveal two limiting regimes of the π−a _m isotherms, in which the mean molecular area a _m is determined either by the size of the hydrophilic or the hydrophobic blocks of the PS-PEO molecules. The interfacial activity of the block copolymers at the toluene/water interface was studied by measuring the interfacial tension σ over a wide range of concentrations. Pronounced differences in the temperature dependence of the interfacial tension were observed, depending mostly on the block length of the hydrophilic PEO block. From the temperature dependence of σ it is inferred that for the block copolymers with the PEO block size of 3000 g/mol the phase inversion temperature (PIT) is well above 60 °C while for those with a PEO block size of 1000 g/mol the PIT is below or near 25 °C in the toluene/water system. Received: 5 February 1998 Accepted: 16 February 1998     

Tween-20与牛血清白蛋白的相互作用

通过表面张力和等温滴定量热方法，研究了非离子表面活性剂Tween-20与牛血清白蛋白(BSA)的相互作用. 结果表明，BSA与Tween-20的相互作用较弱，当Tween-20浓度增大时，能将吸附于表面上的BSA分子取代. BSA/Tween-20混合体系的性质随温度的变化趋势与单一非离子型表面活性剂相似. BSA浓度在3.7×10^-5～11.1×10^-5 kg•L^-1范围内，Tween-20的cmc不随BSA浓度的变化而变化. 当Tween-20的含量一定时，Tween-20与BSA相互作用过程的热效应也与BSA 的浓度无关. BSA/Tween-20混合体系的热力学参数表明， BSA的存在使Tween-20的cmc减小，体系的熵变增大.     

Dissociation equilibrium between uncharged and charged local anesthetic lidocaine in a surface-adsorbed film

The dissociation equilibrium between uncharged local anesthetic lidocaine (LC) and charged local anesthetic LC (LCH⁺) in a surface-adsorbed film was investigated by measuring the surface tension and pH of aqueous solutions of a mixture of hydrochloric acid and LC. The surface tension values decreased slightly with increasing total molality m_t at 0X₂0.5, where X₂ is the mole fraction of LC in the mixture, while they decreased rapidly with increasing m_t at 0.5<X₂1. It was shown from the pH measurements that almost all LC molecules were changed into LCH⁺ ions by protonation at 0X₂0.5 and both forms coexisted only at 0.5<X₂1. The quantities of the respective LC and LCH⁺ transferred from the aqueous solution to the adsorbed film, i.e., their surface densities, were calculated by applying the thermodynamic equations derived to the surface tension and pH data. A greater quantity of LC than LCH⁺ existed in the adsorbed film at the coexisting composition. The partitioning behavior of LC and LCH⁺ in the adsorbed film was characterized by three composition regions: (1) slight partitioning of low surface-active LCH⁺ in the region at 0X₂0.5, (2) preferential partitioning of LC at 0.5<X₂<around 0.7, and (3) negative partitioning of LCH⁺ at around 0.7X₂1. The present results clearly indicate that uncharged local anesthetics transfer into hydrophobic environments such as cell membranes more than charged ones.     

Probing in vitro digestion at oil–water interfaces

Interfacial layers have been widely applied to study the formation and stability of emulsion-based systems. However, the application of isolated interfaces to address digestibility of emulsions is often limited because of the complexity of experimental methods and results. This review summarizes the latest developments in analytical methods and literature data on effects of digestion on interfacial layers. Particular emphasis is given to understand the changes on interfacial magnitudes during oral, gastric, and duodenal digestion, either applied separately or sequentially. Limitations of interfacial aspects and key factors that influence emulsion microstructure in bulk and lipid digestion are identified. Understanding the behavior of interfacial layers upon gastrointestinal digestion promotes an accurate tracking of the physiological fate of emulsions.     

Surface mixed adsorption films of 2,4,6- trimethylphenol–2,4,6-trichlorophenol at aqueous solution/air interface

 The results of experimental studies of the adsorption at the solution/air interface from an aqueous mixture: 2,4,6-trimethylphenol–2,4,6-trichlorophenol are presented. The surface properties of the above-mentioned mixture were studied by surface potential and surface tension measurements. These measurements were carried out as a function of the concentration of 2,4,6-trimethylphenol aqueous solution at a constant concentration of 2,4,6-trichlorophenol. Using the results obtained and based on the Gibbs equation, Helmholtz formula and Motomura’s method the relative surface excesses of adsorbed substances, effective dipole moments, surface molar fractions of solutes and miscibility of adsorbed films were determined. Received: 7 November 1997 Accepted: 26 February 1998     

Simultaneous determination of traces of heavy metals by solid-phase spectrophotometry

A coupling sensitive solid phase spectrophotometric (SPS) procedure for determination of traces of heavy metals (Me-SPS) and multicomponent analysis by multiple linear regressions (MA), a simple methodology for simultaneous determination of metals in mixtures was inaugurated. The Me-SPS procedure is based on sorption of heavy metals on PAN-resin and direct absorbance measurements of colour product Me-PAN sorbed on a solid carrier in a 1-mm cell. This methodology (Me-SPS-MA) was checked by simultaneous determination of metals in synthetic mixtures with different compositions and contents of metals important in pharmaceutical practice: Zn, Pb, Cd, Cu, Co, and Ni. Good agreement between experimental and theoretical amounts of heavy metals is obtained from the recovery test (78.3–110.0%). The proposed method enables determination of particular metal ion at the ng mL⁻¹ level and it was successfully applied to the determination impurities from heavy metal traces in pharmaceutical substances (Cu in ascorbic acid, Pb in glucose, and Zn in insulin). The proposed procedure could be possible contribution to the development of pharmacopoeial methodology for a heavy metals test.     

微量元素锌在治疗Bell麻痹中的作用

为探讨急性早期应用补锌和综合疗法治疗Bell麻痹 ,将 1 5 8例Bell麻痹患者 ,随机分成两组 :(1 )补锌组 (补锌 +综合疗法 ) ;(2 )对照组 (单纯综合疗法 )。对其进行了观察对比治疗 ,同时检测了所有患者治疗前后自身对照发锌值 ,还对所有患者进行了定位诊断、面神经电反应测试、并对面肌功能进行评分。结果表明 ,对定位诊断其病变在D段、面肌功能评分在 1 1分以下、面神经无电反应患者 ,即使给予早期综合治疗 ,效果仍较差 ,而早期给予补锌加综合治疗效果优于对照组 ,其它段内患者治疗次数和治愈天数也均优于对照组。可见微量元素锌在发挥免疫应答、免疫调控中的重要作用     

Protein surface area and retention in hydrophobic interaction chromatography

Summary Molecular surface areas accessible to a 4 ? diameter spherical probe were calculated from crystallographic data for five proteins: α-chymotrypsinogen A, lysozyme, trypsinogen, ribonuclease A and ribonuclease S. The retention factors of various proteins were measured on stationary phases having polyether- and phenylligates and with aqueous eluents containing (NH₄)₂SO₄, Na₂SO₄ or NaCl at pH 7.0. The logarithmic retention factors were plotted against the salt molality and the hydrophobic interaction parameters evaluated from the limiting slopes of the plots at high salt concentrations for the proteins in the chromatographic systems investigated. The hydrophobic interaction parameters thus obtained were linear in both the molecular surface areas of the proteins and the molal surface tension increments of the salts. The experimental results obtained with these relatively simple proteins of known molecular structure, which were available in high purity, support earlier theoretical predictions for the dependence of the hydrophobic interaction parameter on the surface area of the protein and the surface tension raising effect of the salt.     

Bayesian sequential reliability for Weibull and related distributions

Assume that the probability density function for the lifetime of a newly designed product has the form: [H(t)/Q()] exp{–H(t)/Q()}. The Exponential(), Rayleigh, WeibullW(, ) and Pareto pdf's are special cases.Q() will be assumed to have an inverse Gamma prior. Assume thatm independent products are to be tested with replacement. A Bayesian Sequential Reliability Demonstration Testing plan is used to eigher accept the product and start formal production, or reject the product for reengineering. The test criterion is the intersection of two goals, a minimal goal to begin production and a mature product goal. The exact values of various risks and the distribution of total number of failures are evaluated. Based on a result about a Poisson process, the expected stopping time for the exponential failure time is also found. Included in these risks and expected stopping times are frequentist versions, thereof, so that the results also provide frequentist answers for a class of interesting stopping rules.This research was supported by NSF grants DMS-8703620 and DMS-8923071, and forms part of the Ph.D. Thesis of the first author, the development of which was supported in part by a David Ross grant at Purdue University. The authors thank the editors and a referee for insightful comments and suggestions.