阳离子双子表面活性剂C18-4- C18•2Br的流变性

对阳离子双子表面活性剂四亚甲基-1,2-双(十八烷基二甲基烷基溴化铵)(C18-4-C18.2Br)的流变特性进行了研究,考察了表面活性剂质量分数、水杨酸钠质量分数及温度对表面活性剂溶液黏度和黏弹性的影响。C18-4-C18.2Br溶液的黏度随着质量分数的增加而增加。随着水杨酸钠质量分数的增加,C18-4-C18.2Br溶液的黏度和黏弹性出现先增加后下降的过程。温度对C18-4-C18.2Br溶液的黏度有较大影响,水杨酸钠的加入可明显提高C18-4-C18.2Br溶液的抗温性。TEM结果表明,适量的水杨酸钠能够促进C18-4-C18.2Br胶束从球形向蠕虫状转变,过量的水杨酸钠又会使蠕虫状胶束向囊泡转变。     

离子液体对溶菌酶晶体形态和活性的影响

以鸡蛋清溶菌酶为模型蛋白,采用冷却结晶法结晶以及浊度法测定酶活性,研究了分别添加4种亲水性离子液体(1-丁基-3-甲基咪唑四氟硼酸盐([C₄mim]BF₄)、1-丁基-3-甲基咪唑氯盐([C₄mim]Cl)、1-丁基-3-甲基咪唑溴盐([C₄mim]Br)和1,3-二甲基咪唑碘化物([dmim]I))条件下溶菌酶晶体形态和晶体活性的变化。利用光学显微镜对溶菌酶结晶过程的晶体形态进行分析,结果表明添加离子液体会影响溶菌酶的晶体形态和尺寸。离子液体[C₄mim]BF₄介导的溶菌酶形成棒状晶体。与未添加离子液体相比,[C₄mim]Cl和[C₄mim]Br均未改变溶菌酶晶体形态,均呈块状晶体,但[C₄mim]Cl和[C₄mim]Br促进溶菌酶晶体生长,晶体尺度均增加。而添加[dmim]I,溶菌酶呈现针状晶体。采用浊度法测定溶菌酶晶体活性,结果表明不同的离子液体对溶菌酶晶体的活性...     

木瓜蛋白酶在离子液体双水相中的分配行为

采用离子液体双水相提取木瓜蛋白酶。首先考察不同浓度、pH、温度的离子液体对木瓜蛋白酶活性的影响, 其次考察不同离子液体双水相体系、离子液体侧烷基链长度及浓度、酶添加量、pH、温度对木瓜蛋白酶分配行为的影响。结果表明:[C₄mim]Cl和[C₄mim]Br体系萃取木瓜蛋白酶的效果比[C₄mim]BF₄体系好;高温(≥60℃)对离子液体双水相体系萃取木瓜蛋白酶不利。离子液体双水相萃取木瓜蛋白酶的最佳工艺条件:0.25 g·ml^-1的[C₄mim]Cl, 0.35 g·ml^-1的K₂HPO₄, pH 8.0, 酶添加量2.0 mg·ml^-1, 30℃。此条件下木瓜蛋白酶的酶活性回收率达到95.16%, 纯化因子达到1.5。为今后进一步研究该体系的放大实验或规模化生产奠定了基础。     

溴化1-辛基-3-甲基咪唑聚集状态对蛋白质结晶的影响研究

研究了离子液体溴化1-辛基-3-甲基咪唑（［C₈mim］Br）添加剂的聚集状态对蛋白质结晶过程的影响。实验发现［C₈mim］Br可以改善溶菌酶晶体形貌,影响晶体数量和晶体尺寸。通过测定不同浓度［C₈mim］Br下溶菌酶的溶解度、结晶动力学、聚集状态和ζ-电势,揭示了离子液体［C₈mim］Br对溶菌酶结晶的影响机理。结果表明,［C₈mim］Br与溶菌酶的作用方式随［C₈mim］Br的聚集状态而改变。当［C₈mim］Br浓度较低（<0.1 mol/L）时,［C₈mim］⁺与溶菌酶分子之间存在疏水作用,可以促进蛋白质分子聚集,促进结晶过程。当［C₈mim］Br浓度较高（>0.1 mol/L）时,［C₈mim］⁺自发聚集成胶束,并与蛋白质分子相互作用形成溶菌酶-胶束复合物;动态光散射（DLS）结果显示结晶过程以溶菌酶-胶束复合物为基本单元聚集,因此结晶过程减缓,晶体质量提高。     

环保型MES粘弹性胶束溶液的流变性

用流变学方法研究了可生物降解阴离子表面活性剂脂肪酸甲酯磺酸钠（MES）在NaCl溶液中从球状胶束转变成蠕虫状胶束的生长过程,分析了两性表面活性剂十二烷基甜菜碱（BS-12）对MES胶束溶液流变行为的影响机制。首先,测量了MES粘弹性胶束体系剪切粘度（η）和剪切速率的关系,得到零剪切粘度（η0）;然后由动态振荡实验,得到复合粘度｜η＊｜、动态模量（储能模量G＇、损耗模量G″和结构松弛时间τs）等物理量;应用Cox-Merz规则和Cole-Cole图,证实了MES（3.0%～5.0%）/NaCl（3.0%～5.0%）/BS-12（0.5%～0.9%）体系形成蠕虫状胶束,且蠕虫状胶束的动态粘弹性在MES（3.5%～5.0%）/NaCl（3.5%～5.0%）/BS-12（0.5%～0.9%）范围是符合Maxwell模型的线性粘弹性流体。     

2,6-二甲氧基苯酚在1-丁基-3-甲基咪唑四氟硼酸盐水溶液中溶解行为的红外光谱分析

利用衰减全反射红外光谱(ATR-IR)和二维相关红外技术研究2, 6-二甲氧基苯酚(2, 6-DMP)在1-丁基-3-甲基咪唑四氟硼酸盐([C₄mim]BF₄)水溶液(离子液体摩尔分数x_IL=1.0～0.02)中的溶解行为。随着水量增大, 2, 6-DMP溶解度先增大而后急剧减小, 对应的x_IL阈值为0.1。2, 6-DMP与[C₄mim]BF₄之间存在强相互作用, 2, 6-DMP上的甲氧基是重要作用位点之一;当少量的水加入[C₄mim]BF₄(x_IL=0.1～1.0), 致密的离子簇结构被解离, 2, 6-DMP容易与[C₄mim]BF₄作用, 溶解度增大;随着大量水加入(0.02IL<0.1), 离子簇完全解离为大分子水簇包围的离子对, 憎水的2, 6-DMP与[C₄mim]BF₄作用困难, 溶解度减小。这种由于水量改变引起的[C₄mim]BF₄水溶液微观结构变化影响2, 6-DMP溶解行为。     

[Cnmim]Br/FeCl3型离子液体萃取脱除二苯并噻吩

合成了6种咪唑型离子液体[C_3-8mim]Br/FeCl₃,采用红外光谱和拉曼光谱对其进行表征,并考察了离子液体对二苯并噻吩的萃取脱除效果。结果发现,[C₃mim]Br/FeCl₃的萃取脱硫效果最佳,升高温度和增大剂油比均有利于脱硫率的提高,剂油比1:1(体积比)时,萃取时间达到12 min就可使脱硫率高达92%。且萃取反应完成后,离子液体不做处理继续重复使用,重复使用5次,脱硫率可以达到60%。     

Wormlike Micelles in Mixed Amino Acid‐Based Anionic Surfactant and Zwitterionic Surfactant Systems

The formation of wormlike micelles in aqueous solutions of an amino acid‐based surfactant, sodium lauroyl sarcosinate (LS) and a zwitterionic surfactant, cocamidopropyl betaine (CAPB) has been investigated. Holding the total concentration of LS and CAPB constant at 12 wt%, the synergistic effects of mass ratio of CAPB and LS and pH of the micelle solution on rheological behaviors of CAPB/LS micelles were studied. The viscosity of CAPB/LS micelle systems with a mass ratio from 4:8 to 9:3 increases to maximum values and then decreases as pH increases from 4.0 to 5.6. The maximum viscosity of the transparent CAPB/LS micelle solution is nearly 5500 mPa·s with a mass ratio of CAPB/LS = 8:4 at pH 5.10. It is suggested that the proper pH for CAPB and LS to form wormlike micelles should be close to the isoelectric point of the CAPB/LS solution. The results of thixotropy measurements show that the appropriate mass ratio of CAPB/LS can improve the stability of the network structure of wormlike micelles. In addition, viscosity curves of CAPB/LS wormlike micelles follow a nonlinear co‐rotational Jeffreys model, and the linear viscoelasticity of CAPB/LS wormlike micelles can be described by a linear viscoelastic Jeffreys model. The network of wormlike micelles is confirmed by Cryo‐TEM images.     

Optimization on the Conversion of Bamboo Shoot Shell to Levulinic Acid with Environmentally Benign Acidic Ionic Liquid and Response Surface Analysis

Levulinic acid (LA) has been identified as a promising green, biomass derived platform chemical. Response surface analysis (RSA) with a four-factor-five-level central composite design (CCD) was applied to optimize the hydrolysis conditions for the conversion of bamboo (Phyllostachys Praecox f. preveynalis) shoot shell (BSS) to LA catalyzed with ionic liquid [C₄mim]HSO₄. The effects of four main reaction parameters including temperature, time,C_[C4mim]HSO4(initial [C₄mim]HSO₄ concentration) and X_BSS (initial BSS intake) on the hydrolysis reaction for yield of LA were analyzed. A quadratic equation model for yield of LA was established and fitted to the data with an R² of 0.9868, and effects of main factors and their corresponding relationships were obtained with RSA. Model validation and results of CCD showed good correspondence between actual and predicted values. The analysis of variance (ANOVA) of the results indicated that the yield of LA in the range studied was significantly (P<0.05) affected by the four factors. The optimized reaction conditions were as follows: temperature of 145 ℃, time of 103.8 min,C_[C4mim]HSO4 of 0.9 mol·L^-1 and X_BSS of 2.04% (by mass), respectively. A high yield [(71±0.41)% (by mol), triplicate experiment] was obtained at the optimum conditions of temperature of 145 ℃, time of 104 min,C_[C4mim]HSO4 of 0.9 mol·L^-1 and X_BSS of 2% (by mass), which obtained from the real experiments, concurred with the model prediction [73.8% (by mol) based on available C₆ sugars in BSS or 17.9% (by mass) based on the mass of BSS], indicating that the model was adequate for the hydrolysis process.     

温度和剪切协同作用对十六烷基三甲基氯化铵溶液表观黏度的 影响

深入研究表面活性剂的流变特性，对于理解湍流减阻机理和改进制药、化工等领域的产品质量具有重要意义。本文研究了相同升温速率、不同剪切速率以及相同剪切速率、不同升温速率对阳离子表面活性剂十六烷基三甲基氯化铵（CTAC）溶液表观黏度的影响。研究表明：当温度较低时，剪切速率对表面活性剂溶液表观黏度的影响起主导作用；随着温度的升高，高温对胶束的影响增强导致溶液在高温处出现剪切稀化现象。当浓度为0.3125mmol/L时，溶液临界温度随剪切速率的升高保持恒定；但当浓度升高至0.6250～1.2500mmol/L时，在高温和高剪切的作用下，黏度曲线出现“平台”和短暂的增稠现象。对于中等浓度表面活性剂溶液，浓度升高导致蠕虫状胶束出现分支并抑制了“平台”的产生；随着升温速率的增大，胶束结构的响应时间滞后于升温速率，但当γ=150s^?1时，滞后效应减弱，高剪切对胶束结构的破坏占主导作用。     

芥酸钾/三羟乙基苄基氯化铵蠕虫状胶束的黏度行为

以阴离子表面活性剂芥酸钾(KEU)与有机反离子三羟乙基苄基氯化铵(BTHEAC)通过自组装形成的蠕虫状胶束为主要研究对象,苯乙烯与N,N-孪尾取代丙烯酰胺(DiC_nAM)为可聚合单体,偶氮二异丙基咪唑啉盐酸盐(VA-044)为引发剂,在一定温度下,合成了系列增溶单体并聚合的蠕虫状胶束,通过黏度法研究了该合成条件对蠕虫状胶束表观黏度的影响。结果表明,当单体增溶并聚合后,蠕虫状胶束表观黏度显著增大。当苯乙烯的浓度为0.02mol/L、摩尔比n(KEU):n(BTHEAC)=5:3、n(苯乙烯):n(DiC₈AM)=5:2时,合成的蠕虫状胶束表观黏度最大,为1320mPa·s,明显大于KEU/BTHEAC蠕虫状胶束的表观黏度,且耐温性能良好。     

Rheological Properties of Wormlike Micelles Formed in Aqueous Systems of 3‐Alkoxy‐2‐hydroxypropyl Trimethyl Ammonium Bromides in the Presence of Sodium Octanoate

The rheological properties of aqueous systems composed of each of the four homologous cationic surfactants (3‐alkoxy‐2‐hydroxypropyl trimethyl ammonium bromides, C_nHTAB, n = 12, 14, 16 and 18) in the presence of an anionic surfactant, sodium octanoate (SO), have been studied by using steady state and frequency sweep rheological measurements. The effects of surfactant concentration, hydrophobic chain length and temperature were investigated. In C₁₄HTAB solution, the viscosity shows shear thinning in the concentration range of C_C14HTAB >320 mmol/kg. Addition of SO promotes the micellar growth and results in the generation of wormlike micelles. Zero‐shear viscosity (η₀) of the binary surfactant system exhibits a maximum point in the investigated concentration range, suggesting the interaction between C₁₄HTAB and SO molecules is strongest at the optimal ratio of C₁₄HTAB with SO. The decrease in viscosity was attributed to be the transition from entangled wormlike micelles to branching micelles after the maximum point, cryo‐TEM images revealed the changes in the structure of the wormlike micelles.     

不同NaCl浓度下十二烷基硫酸钠的理化参数和热力学行为

为了更好地研究不同NaCl浓度对阴离子表面活性剂胶束理化性质和结构稳定性的影响,以阴离子表面活性剂十二烷基硫酸钠（C₁₂H₂₅SO₄Na）在不同温度下的临界胶束浓度为基础,分别测试并得出了不同NaCl浓度与不同温度作用下溶液的表面张力、泡沫半衰期和黏度变化规律。在此基础上通过分析得出NaCl作用下溶液的黏度活化能、标准熵变、标准焓变等热力学参数及变化规律。结果表明：C₁₂H₂₅SO₄Na降低表面张力的效率由温度效应和盐效应共同控制,随着温度的升高,温度效应发挥的作用越来越大;黏度最大值所对应的表面活性剂浓度为该温度和NaCl浓度下的临界胶束浓度;C₁₂H₂₅SO₄Na胶束化过程的影响随着温度的升高由熵驱动逐渐转化为焓驱动,这种转化过程随着NaCl浓度的升高越来越提前。掌握温度和NaCl浓度的耦合作用对C₁₂H₂₅SO₄Na理化性质的影响,以期为进一步研究其热力学行为奠定基础。     

Vapor pressure measurement and correlation of acetonitrile+1-butyl-3-methylimidazolium chloride,+1-butyl-3-methylimidazolium tetrafluoroborate,and+1-hexyl-3-methylimidazolium chloride

Vapor pressures were measured for acetonitrile+1-butyl-3-methylimidazolium chloride ([C4mim][Cl]),+1-butyl-3-methylimidazolium tetrafluoroborate ([C4mim][BF4]) and+1-hexyl-3-methylimidazolium chloride ...     

Synergistic Behavior and Microstructure Transition in Mixture of Zwitterionic Surfactant,Anionic Surfactant,and Salts in Sorbitol/H<Subscript>2</Subscript>O Solvent: 1. Effect of Surfactant Compositions

The phase behavior and rheological properties of a multi-component system, made of a zwitterionic surfactant cocoamidopropyl betaine (CAPB), an anionic surfactant sodium lauryl sulfate (SLSS), and mixed salts (tetrasodium pyrophosphate, sodium acid pyrophosphate, sacharrin, and sodium fluoride) in sorbitol/H₂O mixed solvent at different mass fraction of SLSS (X _SLSS) were systematically investigated by steady and dynamic rheology, dynamic light scattering, and diffusion ordered spectroscopy (DOSY). When fixing the salt concentration and the mass ratio of sorbitol in mixed solvent (R), the zero-shear viscosity increases first and then decreases showing a maximum with increasing X _SLSS, resulting from the formation and entanglement of wormlike micelles. Especially when X _SLSS is between 0.33 and 0.80, the mixture is dominated by entangled wormlike micelles coexisting with small micelles and separated wormlike micelles, and shows high viscoelasticity. The maximum of the zero-shear viscosity is ca. 5 orders of magnitude larger than that of sorbitol/H₂O mixed solvent or the CAPB/SLSS aqueous solution. The characteristic structural parameters for the micellar solutions at different X _SLSS are also estimated from further analysis of the rheological results, and indicate the stronger network structures of the wormlike micelles are formed in our systems compared with the wormlike micelles formed by a traditional zwitterionic/anionic surfactant aqueous solutions. The great improvements of rheological properties are attributed to the strong screening effects of the mixed salts and the strong solvophobic effect of sorbitol on the electrostatic and hydrophobic interaction between the CAPB and SLSS molecules. The present work has improved our understanding about the aggregation behavior of zwitterionic/anionic mixed surfactants with salts in less polar solvent/H₂O mixture, which would be of widely practical importance to optimize the formulation of products for personal care and household cleaning.     

Contrasting the Effects of Hydrophobicity and Counterion Size on Anionic Wormlike Micelle Growth

Rheological measurements were performed to understand the effect of benzyltrimethyl ammonium bromide (BTAB) and NaBr on the growth of wormlike micelles formed by sodium oleate (NaOA). Both salts can make the micellar solution viscoelastic, and the rheological responses verify the formation of wormlike micelles. The viscoelastic solution follows the Maxwell model of a single stress relaxation mode in the low-frequency region. In comparison, the BTAB system exhibits stronger viscoelasticity than the NaBr system at constant salt concentration, but the critical overlapping concentration shows no significant difference; less BTAB can induce the solution to be more viscous than NaBr, but the viscosity maximum of the BTAB system is remarkably lower than that of NaBr at fixed NaOA content. The puzzling result is attributed to the effect of the composition on the packing parameter. In addition, it is shown that the zero-shear viscosity of the two salt systems decreases upon heating, following the Arrhenius mode well.     

1-丁基-3-甲基咪唑氯盐离子液体水溶液对纤维素的作用

在温度90℃, 压力1 MPa条件下, 研究[C₄mim]Cl-水溶液对纤维素的溶解和结构变化的影响。在离子液体含量为60%～95%时, 无定形纤维素可以部分溶解, 并且加去离子水后有纤维素再生。经过[C₄mim]Cl-水溶液处理一段时间后, 微晶纤维素的晶型并没有发生改变, 但纤维素的结晶指数和晶粒尺寸的大小都有明显的变化, 纤维素的分子内和分子间氢键相对强度也有明显变化。离子液体含量不同对微晶纤维素的作用程度不同。     

基于“lock-in”效应的阳离子三联表面活性剂蠕虫状胶束流变性能

以三联阳离子表面活性剂双(2-羟基-二亚甲基醚)-α,ω,γ-三(十六烷基二甲基氯化铵)(16-4(OH)-16-4(OH)-16)在水杨酸钠(NaSal)及氯化钠(NaCl)作用下形成的蠕虫状胶束为研究对象,向该体系中增溶苯乙烯(S_t)引发聚合,探讨了聚合前后胶束溶液的流变性能。通过表观黏度法研究了16-4(OH)-16-4(OH)-16/NaSal/NaCl及十六烷基三甲基溴化铵(CTAB)/NaSal两种体系聚合后溶液的耐温(T)及耐剪切性,并利用流变测试对16-4(OH)-16-4(OH)-16/NaSal/NaCl体系增溶S_t聚合前后溶液性能进行了表征。结果表明:CTAB/NaSal胶束体系中S_t最佳增溶量为0.05 g,T=100℃或剪切90 min,聚合后溶液表观黏度(η_a)分别为66.9、15.5 mPa·s;而16-4(OH)-16-4(OH)-16/NaSal/NaCl胶束中S_t 最佳增溶量为0.10 g,T=100℃且连续剪切90 min后,聚合后溶液的η_a 始终维持在99.1 mPa·s,该体系聚合后稳态模量(G₀)高于未增溶S_t体系,由此说明蠕虫状胶束内S_t聚合物链可以产生对其微结构的“lock-in”效应。     

Rheological Investigation of Wormlike Micelles Based on Gemini Surfactant in EG–Water Solution

The self‐assembly behavior of gemini surfactants in ethylene glycol (EG)‐water (5/95, v/v) mixed solvent was investigated by rheological measurements at 10 °C. The influence of molecular structure of the gemini surfactant and added hydrotrope on the solution properties was studied. Sodium salicylate (NaSal) showed stronger ability to induce 2‐hydroxyl‐propanediyl‐α,ω‐bis‐(dimethyldodecylammonium bromide), referred to as 12‐3(OH)‐12, to form wormlike micelles than sodium benzoate. Less NaSal is required to promote a sphere to rod transition and to reach the peak viscosity. Moreover, the concentrations of hydrotrope and gemini surfactant are both lower than conventional single‐chain surfactant systems to reach a comparable viscosity. The strong hydrophobicity of gemini surfactants and hydrotropes is responsible for the high efficiency in forming wormlike micelles in EG/water systems. The geometric structure of gemini surfactants also plays a vital role in self‐assembly into wormlike micelles. Dimethylene‐1,2‐bis‐(dodecyl dimethylammonium bromide), referred to as 12‐2‐12, shows absolute superiority over 12‐3(OH)‐12 in constructing wormlike micelles. The present study will be helpful for developing de‐icing fluids and anti‐freezing solutions, which need rheology control in EG‐aqueous medium at low temperature.     

Effect of Silica Nanoparticles on Wormlike Micelles with Different Entanglement Degrees

Enhancing the viscoelastic properties of wormlike micelles by adding nanoparticles has been widely reported. Various mechanisms have been proposed to explain how nanoparticles strengthen the network formed by wormlike micelles. It remains unclear whether nanoparticles produce the same effect on systems with different entanglement degrees. To clarify this issue, the concentration of potassium chloride was used to control the entanglement degree of wormlike micelles. The rheological behavior of different nanoparticle-enhanced wormlike micellar systems (NEWMS) was investigated using rheology. Three critical parameters including zero-shear viscosity (η₀), relaxation time (τ_R), and contour length (L) were calculated to analyze the effect of nanoparticles on the different wormlike micellar systems. An appropriate mechanism describing the interaction between nanoparticles and wormlike micelles with different structures was proposed.