Evaluation of the interactions between lipids and γ-globulin protein at the air–liquid interface

The interactions between lipids (cholesterol, distearoylphosphatidylcholine, distearoylphosphatidylethanolamine and sphingomyelin) and the γ-globulin protein have been analyzed using the monolayer technique at the air–liquid interface. The analysis has been carried out using both state equations and an adequate thermodynamic formulation for the surface pressure (π)–molecular area (a) isotherms. Different parameters as the virial coefficients, have been estimated. For the uncharged lipid monolayers, the interactions between the molecules are of an attractive nature, at medium and long distance, and of a steric repulsive nature at short distance. At low surface pressures the lipid molecules form small domains. The net force between γ-Globulin molecules in the monolayers has been found to be attractive. Finally, it can be concluded that when the lipid monolayers are uncharged, there is practically no interaction between the protein and lipid molecules at the mentioned interface.     

Influence of temperature on surface tension of three liquid crystal polymers and polyethylene terephtalate

In this work Pressure Volume Temperature (PVT) data for three different liquid crystal polymers (LCPs), namely Vectra A950^® and two LCPs based on 4,4'-dihydroxybiphenyl (PB-n) (where n is the number of methylene units present in the polymer) and polyethylene terephtalate (PET), were obtained for temperatures ranging from 50 to 300°C and pressures ranging from 0.1 to 200 MPa. The experimental data were fitted to the Flory-Orwoll-Vrij equation of state and used to predict the influence of temperature on the surface tension of the four materials studied.

The surface tension of PET was shown to decrease linearly with increasing temperature. The surface tension of both PB-11 (γ_PB-11) and Vectra A950^® (γ_Vectra) decreased linearly with increasing temperature for temperatures corresponding to the nematic phases of the materials. Abnormal behaviour was observed for the surface tension of PB-8 (γ_PB-8): at temperatures just above T_b (the temperature at which the material became birefringent), γ levelled off and then decreased. A clear discontinuity was observed for both γ_PB-8 and γ_PB-11 near the mesophase to isotropic transition. For both PB-8 and PB-11, γ decreased linearly with increasing temperature for temperatures corresponding to the isotropic phases of the materials.     

Interaction of Bauhinia monandra lectin (BmoLL) with lipid monolayers

The interfacial behavior of the hypoglycemia lectin BmoLL purified from the leaves of Bauhinia monandra, and its ability to interact with lipid monolayers has been studied by surface tension (γ) measurements. The results of these experiments revealed that in the solution concentration range comprised between 0.2 and 1.0 mg/ml, there was an extremely pronounced increase in the BmoLL adsorption at the interface with the air phase. This adsorption at the higher studied BmoLL concentrations gave rise to a more gradual increase in the surface pressure (π = γ₀−γ). The results showed also that the surface pressure of adsorbed films was pH dependent and it substantially increased at low pHs (between pH 4.0 and pH 2.5). Independently carried out ξ potential measurements demonstrated that BmoLL was negatively charged at all pHs and borne the highest charge at the pH around 5.5. The penetrant ability of BmoLL into the two different in chemical nature monolayers: (dioleoylphosphatidylcholine and octadecylamine) have been assessed measuring Δπ increments at constant area. It was observed that, whereas the monolayers of either pure dioleoylphosphatidylcholine (DOPC) or pure octadecylamine (ODA) stimulated BmoLL adsorption, the lectin adsorption within their mixtures strongly depended on both the content of positively charged octadecylamine in a mixture and on the monolayer compressibility. These findings are discussed in terms of both the electrostatic interaction involved in adsorption of BmoLL and of changes in monolayer compressibilities brought up by the addition of ODA molecules to the phospholipid. The relevance of this work to liposome preparations is indicated in the concluding remarks.     

A method for correcting the contact angle from the θ/2 method

The θ/2 method, a widely used technique on measuring the contact angle of a sessile drop, assumes that the drop profile is part of a sphere. However, the shape profile of a sessile drop is governed by the Young–Laplace equation and is different from a sphere, especially for drops with a large bound number (e.g. large volume or small surface tension). The spherical assumption, therefore, causes errors on evaluating the contact angles. The deviation of contact angle from the θ/2 method is evaluated from a theoretical calculation in this work. A simple means is given for correcting the measurement error. The corrected angle results from the drop volume, surface tension, liquid density and the contact angle from θ/2 method. An algorithm for finding the correct contact angle without knowing the density and surface tension is also given. At the end, two examples of pendant drops are given for the illustration.     

Spreading of oil from protein stabilised emulsions at air/water interfaces

Spreading of a drop of an emulsion made with milk proteins on air/water interfaces was studied. From an unheated emulsion, all oil molecules could spread onto the air/water interface, indicating that the protein layers around the oil globules in the emulsion droplet were not coherent enough to withstand the forces involved in spreading. Heat treatment (90 °C) of emulsions made with whey protein concentrate (WPC) or skim milk powder reduced the spreadability, probably because polymerisation of whey protein at the oil/water interface increased the coherence of the protein layer. Heat treatment of emulsions made with WPC and monoglycerides did not reduce spreadability, presumably because the presence of the monoglycerides at the oil/water interface prevented a substantial increase of coherence of the protein layer. Heat treatment of caseinate-stabilised emulsions had no effect on the spreadability. If proteins were already present at the air/water interface, oil did not spread if the surface tension (γ) was <60 mN/m. We introduced a new method to measure the rate at which oil molecules spread from the oil globules in the emulsion droplet by monitoring changes in γ at various positions in a ‘trough’. The spreading rates observed for the various systems agree very well with the values predicted by the theory. Spreading from oil globules in a drop of emulsion was faster than spreading from a single oil drop, possibly due to the greater surface tension gradient between the oil globule and the air/water interface or to the increased oil surface area. Heat treatment of an emulsion made with WPC did not affect the spreading rate. The method was not suitable for measuring the spreading rate at interfaces where surface active material is already present, because changes in γ then were caused by compression of the interfacial layer rather than by the spreading oil.     

α,β,γ,δ,ε,η-Bi2O3电子结构和光学性质的第一性原理研究

基于密度泛函理论的CASTEP模块研究了α, β, γ, δ, ε和η-Bi₂O₃晶型, 计算分析了其几何结构、 能带结构、 电子态密度和光学性质. 结果表明, α, ε和η相均为层状结构, 其中, α和ε相为单层—Bi—O—结构, 而η相为双层—Bi—O—结构; β, γ和δ相为—Bi_m—O_n—交错结构, 其中δ相交错尤为密集, 呈现导体特性. 各晶相的导带均由Bi 6p态构成, 价带由O_2p态起主导作用. 电势电位分析结果表明, 6种晶相价带电位均在H₂O/O₂之下, 具有强氧化能力, 与实验报道的光催化氧化能力大小顺序γ-Bi₂O₃>β-Bi₂O₃>α-Bi₂O₃>δ-Bi₂O₃一致, 而导带还原电位低于H₂/H₂O, 预测纯Bi₂O₃很难具备催化产氢能力. 光学性质分析发现, γ和δ相的起始响应波长较大, 说明其应具备红外激发的性质. 这些结果可为获得偏红外激发和较宽光谱响应的Bi₂O₃材料研究提供理论基础, 为研发和应用Bi₂O₃及其复合物提供重要的指导.     

β-酪蛋白淀粉样纤维沉淀的形成及影响因素

利用硫磺素T(ThT)荧光分析法和透射电子显微镜检测β-酪蛋白形成淀粉样纤维沉淀(Fibril)的动力学过程, 研究了磷脂和硫酸肝素对其Fibril形成的影响. 实验结果表明, β-酪蛋白在65 ℃下, pH值为5.4~9.0的范围内, 加热252 h以上, 并未形成Fibril, 说明β-酪蛋白是一种很好的分子伴侣, 在高温、 弱酸和弱碱条件下均不形成淀粉样纤维沉淀. 甘油磷酸胆碱D6PC和D9PC可以显著地促进β-酪蛋白的Fibril的形成, 说明一定条件下蛋白质可能与细胞膜之间存在相互作用而导致其二级构象的转变. 硫酸肝素对β-酪蛋白形成Fibril具有促进作用, 在炎症组织中, 硫酸肝素表达量的增加有可能促进β-酪蛋白形成Fibril, 说明乳腺炎与乳腺中的Corpora Amylacea的形成存在一定的联系.     

Effect of pH on the electrophoretic mobility of a particle with a charge-regulated membrane in a general electrolyte solution

The electrophoretic motion of an entity comprised of a rigid, uncharged core covered by a charge-regulated membrane which simulates a biological cell, in a general a:b electrolyte solution is analyzed. The membrane carries a fixed charge which arises from the dissociation of the acidic functional group HA. We show that the higher the concentration of cations in the bulk liquid phase, the lower the absolute Donnan potential, _D, and the lower the concentration of functional group, N₀, the lower the _D. Also, the higher the pH, the higher the absolute electrical potential, and the greater the N₀, the lower the pH. The absolute mobility of a cell, μ, increases with pH, but decreases with the increase in the friction coefficient of the membrane phase, γ. For a fixed total number of HA, if γ is large, μ/μ_s is less than unity, μ_s being the mobility of the corresponding rigid particle, and it decreases with the thickness of membrane d, and the inverse is true if γ is small. For a medium γ, the variation of μ/μ_s as a function of d has a local maximum, and depending upon d, it can be either greater or less than unity.     

Interfacial characteristics of β-casein spread films at the air–water interface

Casein is well known to be a good protein emulsifier and β-casein is the major component of casein and commercial sodium caseinate. This work studies the behaviour of β-casein at the interface. The interfacial characteristics (structure and stability) of β-casein spread films have been examined at the air–water interface in a Langmuir-type film balance, as a function of temperature (5–40°C) and aqueous phase pH (pH 5 and 7). From surface pressure–area isotherms (π–A isotherms) as a function of temperature we can draw a phase diagram. β-Casein spread films present two structures and the collapse phase. That is, there is a critical surface pressure and a surface concentration at which the film properties change significantly. This transition depends on the temperature and the aqueous phase pH. The film structure was observed to be more condensed and β-casein interfacial density was higher at pH 5. β-Casein films were stable at surface pressures lower than equilibrium surface pressure. In fact, no hysteresis was observed in π–A isotherms after continuous compression-expansion cycles or over time. The relative area relaxation at constant surface pressure (10 or 20 mN m⁻¹) and the surface pressure relaxation at constant area near the monolayer collapse, can be fitted by two exponential equations. The characteristic relaxation times in β-casein films can be associated with conformation–organization changes, hydrophilic group hydration and/or surface rheology, as a function of pH.     

A density functional study of N NQR parameters of imidazole derivatives and extrapolation to PfHRP2–Fe-PPIX complex

In this paper, density functional theory (DFT) was used to calculate ¹⁴N nuclear quadrupole coupling constants (NQCC), χ, and asymmetry parameters, η, for a series of imidazole derivatives: imidazole, 5-methylimidazole and histidine. These calculations were carried out with the PW91P86 method via the Gaussian 98 package. A systematic theoretical investigation of the different environmental effects on (χ, η) values of amino ¹⁴N1 and imino ¹⁴N2 of imidazole ring of these compounds, reveals that the local surrounding of nitrogen atoms play an important role in determining their χ and η values. Our calculations in solution show that adding explicit solvent molecules to the polarizable continuum model (PCM) has a strong effect on (χ, η) values, thereby indicating that for long-range effects, PCM, is not sufficient to describe the whole solvent effects. We also evaluate the influence of [Fe³⁺ (S = 1/2)] on the (χ, η) values of proximal and remote nitrogens of an axial ligand and compare with those of free ligands. The results show that Fe³⁺ has a strong effect on the (χ, η) values of proximal nitrogen unlike remote nitrogen. Finally, our results predict (χ = 1.56 MHz, η = 0.690) for proximal nitrogen and (χ = 2.75 MHz, η = 0.169) for remote nitrogen in PfHRP2–Fe³⁺-PPIX complex.     

Effect of film ageing on the surface properties of lactoglobulin and lactoglobulin+sucrose stearate monolayers

The change in β-lactoglobulin and β-lactoglobulin+sucrose stearate spread monolayers over time (ageing effect) at room temperature was studied. Measurements of the surface pressure π-mean area per molecule A isotherms of the monolayers were used to probe any time dependent changes. The increase of the protein film area with time was attributed to protein unfolding. At certain ratios of surfactant to protein, a higher film area increase was observed. This correlated well with the excess film areas of 45 h aged films. The excess film areas for newly spread films of the same composition seemed to follow the opposite trend indicating that the protein–surfactant interactions change as the conformational changes of the protein molecules progress.     

Estimation of speed of sound of ionic liquids using surface tensions and densities: A volume based approach

The limited availability of experimental data and their quality have been preventing the development of predictive methods and Computer Aided Molecular Design (CAMD) of ionic liquids (ILs). Based on experimental speed of sound data collected from the literature, the inter-relationship of surface tension (σ), density (ρ), and speed of sound (u) has been examined for imidazolium based ILs containing hexafluorophosphate (PF₆), tetrafluoroborate (BF₄), bis(trifluoromethanesulphonyl) amide (NTf₂), methyl sulphate (MeSO₄), ethyl sulphate (EtSO₄), and trifluoromethanesulphonate (CF₃SO₃) anions, covering wide ranges of temperature, 278.15–343.15 K and speed of sound, 1129.0–1851.0 m s⁻¹. The speed of sound was correlated with a modified Auerbach's relation, by using surface tension and density data obtained from volume based predictive methods previously proposed by the authors. It is shown that a good agreement with literature data is obtained. For 133 data points of 14 ILs studied a mean percent deviation (MPD) of 1.96% with a maximum deviation inferior to 5% was observed. The correlations developed here can thus be used to evaluate the speeds of sound of new ionic liquids.     

改性钛基PbO2电极的制备及其对COD的快速检测

通过制备Ti/α/β-PbO₂、Ti/Ag/β-PbO₂这两种含有不同中间层的钛基二氧化铅电极来探究电催化氧化技术快速测定葡萄糖模拟废水中有机物(COD)含量的可行性。为了评估两种电极的各项性能,首先采用扫描电镜(SEM)、X射线衍射(XRD)对电极进行形貌表征,其次进行电化学性能测试包括线性伏安曲线(LSV)、塔菲尔曲线(Tafel)、循环伏安曲线(CV)以及交流阻抗测量分析。结果表明,Ti/α/β-PbO₂电极表面晶体结构更加均匀,晶粒尺寸偏小,具有更大的电活性表面积。Ti/α/β-PbO₂电极的析氧电位为1.77 V,为·OH的产生提供良好条件。在Tafel、CV测试中,Ti/α/β-PbO₂电极的交换电流密度i₀及比电容C_p分别为0.0995 A·cm^-1、0.004098 F·cm^-1均高于Ti/Ag/β-PbO₂电极,说明Ti/α/β-PbO₂电极的耐腐蚀性以及释放电子的能力优异。最终选用Ti/α/β-PbO₂电极为工作电极。Ti/α/β-PbO₂电极检测COD的最佳条件为：氧化电位1.30 V、电解时间150 s、电解液浓度0.03 mol·L^-1 硝酸钠(NaNO₃)。电化学法与比色消解法测定COD的相关系数可达0.9909,同时具有良好的重现性与相关性,COD的检测范围为0 mg·L^-1 ~ 500 mg·L^-1。在误差允许的范围内可以替代标准的重铬酸钾法,为实现COD的在线快速检测提供参考价值。     

Second hyperpolarizability of phenalenyl radical system involving acetylene π-conjugated bridge

The static second hyperpolarizability (γ) of a singlet diradical system involving phenalenyl radicals linked with acetylene π-conjugated bridge, BPLE, is investigated as well as reference closed-shell systems, BPRY1 and BPRY2, by the hybrid density functional theory method. The γ value of BPLE with intermediate diradical character is shown to be about four times as large as that of BPRY1 with similar π-conjugation length and to be about twice as large as that of BPRY2 with longer π-conjugation length. This feature is in agreement with our prediction that the molecules with intermediate diradical characters enhance γ values compared to the closed-shell molecules.     

一种新型钼钒多酸化合物的合成、结构与荧光性能

采用水热技术,合成了一种新型四帽Keggin结构多酸化合物[H₃Mo₈^ⅥV₈^ⅣO₄₀(AsO₄)](en)₂(4,4-bipy)₇·9H₂O(en:乙二胺;bipy:联吡啶)(1),并对化合物进行了元素分析、红外光谱、X射线光电子能谱和X射线单晶结构分析。 晶体结构分析表明, 化合物属三斜晶系,P1空间群,晶胞参数a=1.47395(5) nm,b=1.48172(6) nm,c=1.62881(7) nm,α=66.16(3)°,β=87.15(2)°,γ=63.42(1)°,V=2.8723(2) nm³,Z=1,R₁=0.0728,wR₂=0.2014。 化合物由四帽Keggin多酸阴离子、4,4'-联吡啶、乙二胺和结晶水分子构成,化合物分子间存在大量的氢键,使化合物1形成3-D超分子结构。 荧光测试表明,化合物1能发出较强的荧光,有可能成为潜在的光活性材料。     

一种阳离子Gemini型沥青乳化剂的合成及性能

以苯胺、环氧氯丙烷和十四烷基二甲基叔胺为原料,合成了含有苯环的阳离子Gemini型沥青乳化剂3,3'-苯基亚氨基-(二(2-羟基丙基-十四烷基二甲基)氯化铵)(G-T)。 采用傅里叶红外光谱(FT-IR)、质谱(MS)和核磁共振谱(¹H NMR)对产物进行了结构表征。 研究了其Krafft点、乳化性能和乳化沥青时的相关性能,并测定了25~40 ℃的临界胶束浓度(cmc)、平衡表面张力(γ_cmc)及计算了相应的热力学函数。 结果表明,G-T的Krafft点低于0 ℃,乳化分水时间为309 s。 25 ℃时,cmc为1.269×10^-3 mol/L,γ_cmc为38.33 mN/m。 随着温度的升高,cmc增大、γ_cmc减小、饱和吸附量(Γ_max)减小、极限占有面积(A_min)增大。 乳化沥青测试表明,G-T拌和时间为255 s,是慢裂型沥青乳化剂。 所制备的乳化沥青满足微表处技术规范。     

Blocking and ripening of colloids in porous media and their implications for bacterial transport

A model accounting for the dynamics of colloid deposition in porous media was developed and applied to systems containing similarly charged particles and collectors. Colloid breakthrough and intracolumn retention data confirmed that blocking reduced overall colloidal adhesion to soil. The surface coverage at which blocking occurred varied for the type of colloid, as shown by changes in the clean-bed collision efficiency, _0, and the excluded area parameter, β. Excluded area parameters were relatively high due to unfavorable interactions between particles and collectors, and ranged from 11.5 for one bacterium (Pseudomonas putida KT2442) to 13.7 and 24.1 for carboxylated latex microspheres with differing degrees of charged groups on their surfaces. Differences in β values for the three colloids were correlated with electrophoretic mobility, with the most negatively charged colloid (carboxylated latex; CL microspheres) having the highest β. No correlation between hydrophobicity and ₀ or β was found. Besides using colloidal particles capable of blocking, the addition of chemical additives to the soil has been suggested as a means for reducing attachment of colloids to porous media. Dextran addition caused an order-of-magnitude reduction in the overall (for carboxylated-modified latex; CMLs). This reduction was not attributed to blocking, but to the sorption of dextran to the soil which lowered ₀. The filtration-based numerical model used to fit the ₀ and β parameters was used to demonstrate that blocking could result in significantly enhanced bacterial transport in field situations.     

Kinetic analysis of thermogravimetric data obtained under linear temperature programming—a method based on calculations of the temperature integral by interpolation

A new technique, called interpolation method, with general application in the kinetic analysis of processes studied by thermogravimetry (TG) under linear temperature programming is developed. It is based on the linear relationship, with slope 1, between log g() and log I(γ, θ) for the appropriate kinetic function, where I(γ, θ) is the normalized temperature integral, θ the normalized temperature (θ=T/T₀) and γ a dimensionless activation energy (γ=E/RT₀). Values of log I(γ, θ) are calculated by linear interpolations in a pre-built table. This method can easily be programmed and implemented in a personal computer, where the results (kinetic parameters and quality of regressions for the kinetic functions considered) are typically obtained in a very short time. The method is validated by analyzing different simulated thermogravimetric curves and comparing the results with those determined with some classic methods taken from the literature. In addition, the results are compared with the values obtained by a similar method, also developed and explained in this paper, which involves the evaluation of all the values of the temperature integral by numerical integration, therefore, demanding a much larger calculation time. The interpolation method is found to be more accurate than other published methods, particularly in the case of thermogravimetric curves corresponding to processes with low activation energies. The results obtained are always similar to those determined by the integration method, which is taken as reference. Application of the technique to experimental data for various types of reactions shows that the results are in agreement with the published parameters and kinetic laws.     

Application of the ISM EoS for polymer solutions and blends

A method for predicting an analytical equation of state for polymer mixtures and blends from surface tension and liquid state density at normal (ordinary) temperature (γ_n, ρ_n), as scaling constants, is presented. B₂(T) follows a promising corresponding-states principle. Calculation of (T) and b(T), the two other temperature-dependent constants of the equation of state, are made possible by scaling. As a result, γ_n and ρ_n are sufficient for determination of thermophysical properties of polymer mixtures and blends.

We applied the procedure to predict liquid density of poly(ethylene glycol) (PEG-200) + 1-octanol solutions and poly(propylene glycol) (PPG) + poly(ethylene glycol) (PEG-200) blends at compressed state with temperature range from 298.15 to 338.15 K and pressures up to 40 MPa. In this work, the ISM EoS is extended to polymer mixtures and blends as well as pure case without proposing any mixing rule.