盐酸胍/Ⅰ型胶原分散体系的流变性

采用胃蛋白酶降解法从猪皮中提取了胶原蛋白, 用十二烷基硫酸钠-聚丙烯酰胺凝胶电泳(SDS-PAGE)确定为Ⅰ型胶原; 红外及紫外光谱表明胶原分子中存在三螺旋结构. 分别采用小幅振荡剪切法、 恒定剪切速率法及滞后环法研究了盐酸胍浓度及作用时间对Ⅰ型胶原蛋白体系流变性的影响. 研究表明, 随盐酸胍浓度的增大及作用时间的延长, 盐酸胍/胶原分散体系由假塑性流体逐渐接近于牛顿流体. 在所研究的盐酸胍浓度范围(0~6.0 mol/L)内, 盐酸胍/胶原分散体系的触变性类型随盐酸胍浓度的增大发生正触变性-复合触变性-负触变性的转变; 随盐酸胍作用时间的延长(6~48 h), 盐酸胍浓度为1.0 mol/L的胶原分散体系的触变性类型发生复合触变性-负触变性的转变. 本文的研究结果有助于加深对触变性产生机理的认识.     

Mg-Al-MMH-高岭土分散体系触变性研究

触变性是分散体系流变学研究的重要内容之一,在外切力作用下,若体系的粘度随时间下降,静止后又恢复,即具有时间因素的切稀现象,称为正触变性（positive thixotropy);反之,若体系的粘度或切力上升,静止后又恢复,即具有时间因素的切稠现象,称之为负触变性（Negative thixotropy)^[1],若在外切力作用下,某个特定体系的粘度或切力随时间先后呈现出正触变性和负触变性特征,则称之为复合触变性（Complex thixotropy)^[2,3],目前,对各种触变性机理的认识尚不统一。     

盐酸胍/Ⅰ型胶原分散体系的流变性

采用胃蛋白酶降解法从猪皮中提取了胶原蛋白,用十二烷基硫酸钠-聚丙烯酰胺凝胶电泳(SDSPAGE)确定为Ⅰ型胶原;红外及紫外光谱表明胶原分子中存在三螺旋结构.分别采用小幅振荡剪切法、恒定剪切速率法及滞后环法研究了盐酸胍浓度及作用时间对Ⅰ型胶原蛋白体系流变性的影响.研究表明,随盐酸胍浓度的增大及作用时间的延长,盐酸胍/胶原分散体系由假塑性流体逐渐接近于牛顿流体.在所研究的盐酸胍浓度范围(0~6.0 mol/L)内,盐酸胍/胶原分散体系的触变性类型随盐酸胍浓度的增大发生正触变性-复合触变性-负触变性的转变;随盐酸胍作用时间的延长(6~48 h),盐酸胍浓度为1.0 mol/L的胶原分散体系的触变性类型发生复合触变性-负触变性的转变.本文的研究结果有助于加深对触变性产生机理的认识.     

Mg-Fe-MMH-钠质蒙脱土分散体系的触变性研究

触变性是分散体系一种复杂的流变学性质,指流变性质随剪切时间而发生变化的现象。以往研究过程中,先后发现了切稀现象和切稠现象,即正触变性和负触变性。最近,我们又发现了复合触变性,即一个体系可先后呈现正触变性和负触变性特征。研究了Mg-Fe型混合金属氢氧化物(简称MMH)-钠质蒙脱土(简称MT)分散体系的触变性,发现在不同MMH/MT质量比条件下,可分别呈现正触变性、负触变性,另外双观察到了复合触变性。在所研究的MMH/MT质量比范围(0～0.5)内,随MMH/MT质量比增大,体系的触变性发生负触变性-正触变性-复合触变性-负触变性的转化。考察了电解质NaCl对触变性的影响,发现不改变触变性的类型。探讨了各种触变性产生的原因,提出了“分散粒子-空间连续网络结构-密实聚集体”机理,较合理地解释了观察到的复合触变现象。     

Fe-Al-Mg-MMH/钠质蒙脱土分散体系触变性研究

研究了Fe-Al-Mg型混合金属氢氧化物(简称MMH)/钠质蒙脱土(简称MT)分散体系的触变性,发现在不同MMH/MT质量比(R)条件下,分散体系可分别呈现正触变性和负触变性.在所研究的R范围(0～0.091)内,随R增大,体系的触变性发生正触变性-复合触变性-负触变性的转化.考察了高速剪切分散后,测定粘度变化前的静置时间(ts)和测定粘度时的剪切速率(DL)对触变性的影响.探讨了各种触变性产生的原因,提出了“分散粒子-空间连续网络结构-密实聚集体”和“分散粒子-密实聚集体-密实聚集体簇”机理,较合理地解释了观察到的复合触变现象.     

Volumetric and Viscosimetric Measurements for Methanol + CH 3 –O–(CH 2 CH 2 O) n –CH 3 ( n = 2, 3, 4) Mixtures at (293.15–303.15) K and Atmospheric Pressure: Application of the ERAS Model

Densities, $$\rho$$, and kinematic viscosities, $$\nu$$, have been determined at atmospheric pressure and at 293.15–303.15 K for binary mixtures formed by methanol and one linear polyether of the type CH3–O–(CH2CH2O)n–CH3 (n = 2, 3, 4). Measurements on $$\rho$$ and $$\nu$$ were carried out, respectively, using an Anton Paar DMA 602 vibrating-tube densimeter and an Ubbelohde viscosimeter. The $$\rho$$ values were used to compute excess molar volumes, $$V_{{\text{m}}}^{{\text{E}}}$$, and, together with the $$\nu$$ results, dynamic viscosities ($$\eta$$). Deviations from linear dependence on mole fraction for viscosity, $$\Delta \eta$$, are also provided. Different semi-empirical equations have been employed to correlate viscosity data. Particularly, the equations used are the: Grunberg–Nissan, Hind, Frenkel, Katti–Chaudhri, McAllister and Heric. Calculations show that better results are obtained from the Hind equation. The $$V_{{\text{m}}}^{{\text{E}}}$$ values are large and negative and contrast with the positive excess molar enthalpies, $$H_{{\text{m}}}^{{\text{E}}}$$, available in the literature, for these systems. This indicates that structural effects are dominant. The $$\Delta \eta$$ results are positive and correlate well with the difference in volumes of the mixture compounds, confirming the importance of structural effects. The temperature dependences of $$\eta$$ and of the molar volume have been used to calculate enthalpies, entropies and Gibbs energies, $$\Delta G^{*}$$, of viscous flow. It is demonstrated that $$\Delta G^{*}$$ is essentially determined by enthalpic effects. Methanol + CH3–O–(CH2CH2O)n–CH3 mixtures have been treated in the framework of the ERAS model. Results for $$H_{{\text{m}}}^{{\text{E}}}$$ are acceptable, while the composition dependence of the $$V_{{\text{m}}}^{{\text{E}}}$$ curves is poorly represented. This has been ascribed to the existence of strong dipolar and structural effects in the present solutions.     

Thermal analysis of PVA/CNTs 2D membrane

The power–time curves of micellar formation of two anionic surfactants, sodium laurate (SLA) and sodium dodecyl sulfate (SDS), in N,N-dimethyl acetamide (DMA) in the presence of various long-chain alcohols (1-heptanol, 1-octanol, 1-nonanol and 1-decanol) were measured by titration microcalorimetry at 298 K. The critical micelle concentrations (CMCs) of SLA and SDS under various conditions at 298 K were obtained based on the power–time curves. Thermodynamic parameters (, and ) for micellar systems at 298 K were evaluated according to the power–time curves and the mass action model. The influences of the number of carbon-atom and the concentration of alcohol were investigated. Moreover, combined the thermodynamic parameters at 303, 308 and 313 K in our previous work and those of 298 K in the present work for SLA and SDS in DMA in the presence of long-chain alcohols, an enthalpy–entropy compensation effect was observed. The values of the enthalpy of micellization calculated by direct and indirect methods were made a comparison.     

Aqueous polysaccharide blends based on hydroxypropyl guar gum and carboxymethyl cellulose: synergistic viscosity and thixotropic properties

Aqueous polysaccharide blends, formed from 2.5% (w/v) solution of hydroxypropyl guar gum (HPG) and 2.5% (w/v) solution of carboxymethyl cellulose (CMC) according to different blending ratios, were investigated at 20 °C in terms of their shear-dependent viscosity and thixotropic properties. The Cross viscosity equation was found to fit the shear-dependent viscosity data with reasonable accuracy. When the HPG solution with the mass fraction (f _HPG) of 0.87 was mixed, the zero shear viscosity (η _o) of the corresponding blend was found to be 168.5753 Pa s, while the η _o values of component HPG and CMC solutions were found to be 3.3859 and 98.6525 Pa s, respectively. For the aqueous HPG/CMC blends investigated, the resulting zero shear viscosity was observed to be much greater than the combined zero shear viscosity of the component polysaccharide solutions, showing a synergistic viscosity property. The quantitative determination of the hysteresis loop area, developed during viscometer tests on shear rate–shear stress reverse paths, was used to describe the thixotropic behavior. When compared with aqueous solutions of the component polysaccharides, these polysaccharide blends could afford enhanced thixotropic property. Maximum thixotropy synergism was observed for the HPG/CMC blend with the f _HPG of 0.67.     

Thixotropy of Aqueous Suspensions Containing Mg‐Al Hydrotalcite‐like Compound and Low‐substituted Cationic Starch: Comparison between Oscillatory Shear and Thixotropic Loop Measurements

The rheological properties of aqueous suspensions consisting of positively charged aluminum magnesium hydrotalcite‐like compound (HTlc) and low‐substituted cationic starch (LCS) were investigated. Special emphasis was placed on the thixotropic phenomenon. Thixotropic behavior was investigated by two thixotropic methods: thixotropic loop and oscillatory shear measurements. LCS molecules could be adsorbed onto HTlc particles due to the hydrogen bonding between ether groups or hydroxyl groups of LCS and hydroxyl groups of HTlc. The elastic dynamic response of the HTlc/LCS suspension increased with increasing mass ratio (R) of HTlc and a three‐dimensional network structure could be formed in the suspension with higher R value. The thixotropic type of the HTlc/LCS suspension transformed from negative to positive and then to complex thixotropy when R changed from 0 to 0.5. By comparing between the thixotropic results obtained by thixotropic loop and oscillatory shear measurements, it was validated that the thixotropic loop for the suspension showing complex thixotropy had a crossover point.     

Thixotropic Behavior of Hydrotalcite-Like Compound/Cationic Starch Suspensions: Effects of Mass Ratio of Hydrotalcite-Like Compound to Cationic Starch,Electrolyte, and Temperature

The thixotropic behavior of Mg-Al hydrotalcite-like compound (HTlc)/cationic starch (CS) suspensions was investigated as a function of the mass ratio (> 0.08) of HTlc to CS, the electrolyte and the temperature, respectively. The thixotropy was studied by monitoring viscosity (η) change during the recovery process as a function of time (t) after the cessation of intensive shear. The results showed that the strength of negative thixotropy of the CS solution decreased with the increasing of electrolyte (NaCl, CaCl₂, or AlCl₃) concentration and the temperature. The thixotropic type of the HTlc/CS suspensions could transform from negative to complex, positive, complex, and then to negative thixotropy with the increasing of HTlc content if CS was the main component of the suspensions. In addition, the thixotropic type of the HTlc/CS suspensions transformed from original type to positive thixotropy with the increasing of electrolyte concentration and the temperature.     

Sol–gel behavior of a novel nanodroplet biomaterial for drug delivery

Nanodroplets can be considered as those nano/microemulsions in which the oil itself forms the active agent and the droplet size ambits in the nanometer range. Eugenol is an anti-inflammatory agent and its nanodroplet gel (NDG) has immense potential for topical use. Topical gels oblige some rheological characteristics to nail down the demands of proper application, stability and storage. Thus, the purpose of our study was to comprehend the effect of eugenol on the sol–gel tranisition properties of its NDGs. Towards this goal nanodroplets of eugenol were prepared and evaluated and the three selected nanodroplet formulations with 5, 10 and 5% v/v eugenol were converted into topical gel formulation using 1% w/w Carbopol 940. The NDGs were characterized using frequency sweep, creep recovery and thixotropy. All these tests pointed out that eugenol concentration has significant effect on the sol–gel behavior of NDGs. The NDGs exhibited more viscous (sol) properties than elastic (gel) properties as observed from the frequency sweep studies. The thixotropy of the NDGs was found to decrease with increase in eugenol concentration. Efforts have been made to explain the study results using mechanistic approach. The outcomes of our research studies could be of great use in future endeavors towards development of a topical NDG of eugenol with tailored sol–gel behavior.     

Solvent effects on the dielectric dispersion of poly(vinyl pyrrolidone)-poly(ethylene glycol) blends

The complex relative dielectric function , loss tangent , complex electric modulus and alternating current electrical conductivity dispersion behaviour of liquid poly(vinyl pyrrolidone)-poly(ethylene glycol) (PVP–PEG) blends in water, ethyl alcohol and 1,4–dioxane solvent over the entire volume mixture concentration range has been investigated in the frequency range of 20 Hz to 1 MHz at 25 °C. The PVP–PEG blends show the dielectric dispersion corresponding to the micro-Brownian motion of the PVP chain in the upper frequency region, whereas in the lower frequency region, dielectric dispersion is due to ionic conduction and electrode polarization phenomena. Results show that the conductivity values of these blends in water and dioxane can be monitored with the change in the solvent concentration, whereas it has a small variation with ethyl alcohol concentration. The comparative dielectric dispersion shape study confirms that the chain dynamics of polymers blend is influenced by heterogeneous interactions and solvent polar strength.     

添加剂对TiO2/水分散体流变性的影响

研究了TiO₂生产中有关助剂对其流变性能的影响,得到了TiO₂/水分散体的流变性能与三乙醇胺用量之间的关系,并找到了最佳用量.实验发现,六偏磷酸钠为分散剂时,其使用效果有时间依赖性;碳酸铵作絮凝剂时则对分散体的流变性能和形成的絮凝体有影响.     

Interaction of a finite quantum system with an infinite quantum system that contains a single one-parameter eigenvalue band

Interaction of a finite quantum system that contains ρ eigenvalues and eigenstates with an infinite quantum system that contains a single one-parameter eigenvalue band is considered. A new approach for the treatment of the combined system is developed. This system contains embedded eigenstates with continuous eigenvalues , and, in addition, it may contain isolated eigenstates with discrete eigenvalues . Two ρ × ρ eigenvalue equations, a generic eigenvalue equation and a fractional shift eigenvalue equation are derived. It is shown that all properties of the system that interacts with the system can be expressed in terms of the solutions to those two equations. The suggested method produces correct results, however strong the interaction between quantum systems and . In the case of the weak interaction this method reproduces results that are usually obtained within the formalism of the perturbation expansion approach. However, if the interaction is strong one may encounter new phenomena with much more complex behavior. This is also the region where standard perturbation expansion fails. The method is illustrated with an example of a two-dimensional system that interacts with the infinite system that contains a single one-parameter eigenvalue band. It is shown that all relevant completeness relations are satisfied, however strong the interaction between those two systems. This provides a strong verification of the suggested method.     

Effect of Water Fraction on Rheological Properties of Waxy Crude Oil Emulsions

This article discusses the effect of water fraction on the rheological properties of waxy crude oil emulsions including gel point, yield stress, viscosity, and thixotropy. The experimental results reveal that the rheological behaviors of the w/o emulsion samples all intensify with the increase of water volume fraction within 60%. Of more significance is that a correlation for w/o emulsions between yield stress and water volume fraction is put forward with an average relative error of 6.75%. In addition, some mainstream viscosity prediction models of w/o emulsions are evaluated, and Elgibaly model is the best-fit for the emulsions in this study.     

Interaction of glycine with cationic, anionic, and nonionic surfactants at different temperatures: a volumetric, viscometric, refractive index, conductometric, and fluorescence probe study

A number of thermodynamic parameters viz. apparent molar volumes, ϕ _v , partial molar volumes, , transfer volumes, , Falkenhagen coefficients, A, Jones–Dole coefficients, B, free energies per mole of solute, , and per mole of solvent, , molar refraction, R _D , and limiting molar conductivity, , have been calculated by using the experimentally measured densities, ρ, viscosities, η, refractive indices, n _D , and specific conductivities, κ, data of glycine (0.02–0.10 m) in 0.01 m aqueous sodium dodecyl sulphate, cetyltrimethylammonium bromide, and triton X-100 (TX-100) solutions at 298.15, 303.15, 308.15, and 313.15 K. The above calculated parameters were found to be sensitive towards the interactions prevailing in the studied amino acid–surfactant–water systems. Moreover, fluorescence study using pyrene as a photophysical probe has also been carried out, the results of which support the conclusions obtained from other techniques.     

铝/镁混合金属氢氧化物正电胶体粒子体系的触变性

采用恒定低剪切速率方法和动态实验方法研究了铝/镁混合金属氢氧化物(MMH)悬浮体的流变性,着重考察了剪切历史和恢复时间等因素对悬浮体触变性的影响,发现MMH粒子深度的增加使得悬浮体从粘性流体变为“类固体”;恒定低剪切速率方法和动态实验方法研究悬浮体的结构恢复过程给出了不同的结果,唯象地解释了MMH悬浮体触变性产生的原因,认为触变性结构是由于粒子间的静电排斥作用而形成的,与粘土悬浮体相比,两者的流变性具有诸多相似之处,只是所带电荷符号相反。     

Study on the thixotropy of aluminum magnesium hydroxide– Na-montmorillonite suspension

 In this paper, the thixotropy of the aqueous suspension consisting of aluminum magnesium hydroxide (AMH) possessing permanent positive charges and Na-montmorillonite possessing permanent negative charges was studied. Besides positive thixotropy and negative thixotropy, a novel thixotropic phenomenon was found, i.e., a given system studied may display, early and late, positive M28.8nthixotropic character and negative thixotropic character, we describe it as “complex thixotropy”. The content of the suspension and electrolyte may influence the forms of thixotropy of the suspension studied. Received: 4 February 1997 Accepted: 15 October 1997     

Relative thermodynamic stabilities of the isomeric dihydrofurans and isomeric dihydropyrans. An experimental and DFT study

The relative thermodynamic stabilities of 2,5-dihydrofuran (1) and 2,3-dihydrofuran (2), and of 3,4-dihydro-6H-pyran (3) and 3,4-dihydro-2H-pyran (4), were determined at several temperatures by base-catalyzed equilibration in DMSO solution. For 1 → 2, = –15.4±0.1 kJ mol⁻¹, =–12.6±0.5 kJ mol⁻¹, and =9.5±1.3 J K⁻¹ mol⁻¹ at 298.15 K. The second-law reaction enthalpy agrees with literature data based on calorimetric enthalpies of hydrogenation of the isomeric forms in hexane. For 3 → 4, =–19.3±0.2 kJ mol⁻¹, = –18.9±1.1 kJ mol⁻¹ and =1.1±3.0 J K⁻¹ mol⁻¹ at 298.15 K: the experimental reaction enthalpy is in marked disagreement with literature data based on estimation. On the other hand, both of the experimental reaction enthalpies of the present study are in good agreement with DFT calculations using the B3LYP functional and 6-311+G(2d,p) basis set.