反胶团二壬基萘磺酸萃取镁的机理研究

为了确定反胶团二壬基萘磺酸萃取水相中Mg~(2+)的过程机理,以二壬基萘磺酸为萃取剂、磺化煤油为稀释剂所组成的反胶团有机相对水中的Mg~(2+)进行了萃取研究。考察了反胶团的皂化率、水相中镁盐阴离子种类等对萃取率的影响,同时考察了萃取温度、水相中pH值对分配比的影响,萃取饱和容量随萃取剂浓度的变化情况以及Mg~(2+)在两相中的分配情况。研究结果显示,反胶团的皂化率、水相中镁盐阴离子种类对萃取过程无明显影响;萃取分配比随萃取温度的升高而增大;在萃取体系中水相pH值低于4时,分配比随pH值的增加而增大,pH值大于4后,分配比变化幅度较小;萃取饱和容量随萃取剂浓度的增加而增大,且与萃取剂浓度呈线性关系。二壬基萘磺酸从水相介质中萃取Mg~(2+)的过程是吸热反应,其萃取过程热效应(?H)为5.135k J/mol。研究表明,反胶团二壬基萘磺酸萃取Mg~(2+)的过程为阳离子交换,这一研究结果为二壬基萘磺酸从冶金废水中萃取回收镁提供了理论基础和借鉴。     

增溶甲苯对聚氧乙烯-聚氧丙烯嵌段共聚物胶团的影响

用动态光散射, 测定聚氧乙烯-聚氧丙烯嵌段共聚物水溶液胶团增溶不同量的甲苯后, 其平均流体力学半径R_h的变化, 以及温度对它们的影响。实验结果表明, 25 ℃时胶团水化度高, R_h数值大, 增溶不同量的甲苯对R_h的影响较小。温度升高,胶团的水化度降低, R_h变小, 当温度接近浊点, 水化作用降至最低。因温度升高引起的胶团聚集数增加以及增溶的甲苯进入胶团内部的胀大作用, 使R_h随增溶量增加近于线性的上升。     

反胶团萃取铅的动力学机理研究

利用恒界面池研究了二壬基萘磺酸(DNNSA)反胶团溶液萃取模拟电池废水中铅离子的动力学。考察了搅拌转速、DNNSA、初始铅离子浓度以及温度对萃取速率的影响,得到了DNNSA反胶团萃取废水中铅离子的动力学方程并对萃取机理进行了探讨。结果表明,当搅拌速率在200r/min时出现与搅拌强度无关的动力学"坪区",萃取过程为化学反应控制。在动力学"坪区",铅离子萃取速率随着萃取剂DNNSA浓度和水相铅离子浓度增加而增加,温度升高萃取速率加快,萃取反应活化能为35.11k J/mol。     

高浓度区正负离子表面活性剂混合胶团的形状与大小变化

本文研究高浓度区正、负离子表面活性混合胶团的形态及大小随浓度的变化规律。根据正、负离子表面活性剂混合体系的相行为,胶团溶液的光散射以及流变性质测量,提出了混合胶团的棒-球转变模型。认为在较高浓度,随浓度增大,混合胶团经历了一个长棒变短,短棒变为球状的转变过程。     

Pluronic嵌段共聚物F127胶团对布洛芬的增溶(英文)

研究了PluronicF127胶团溶液对药物布洛芬(IBU)的增溶作用.通过芘探针荧光法测定了不同温度下F127在水溶液和0.01mo·lL-1pH7.4磷酸盐缓冲生理(PBS)溶液中的临界胶束浓度(cmc),采用高效液相色谱(HPLC)测定了F127溶液中布洛芬的溶解度,并依据公式计算了增溶参数(摩尔增溶量c和胶团-水分配系数K),考察了温度、溶剂和F68的加入对F127胶团化行为及其对布洛芬增溶作用的影响.结果表明:布洛芬的溶解度随F127质量分数的提高线性增加;随着温度升高,cmc急剧下降,胶团内核的疏水性增强,χ和K稍有增大;与水溶液相比,在PBS溶液中cmc减小,χ几乎不变,K显著降低;F68的加入对F127胶团的性质几乎无影响,对增溶的影响也不明显.对增溶参数的分析表明,K反映的是药物布洛芬的性质,χ则可反映嵌段共聚物F127的溶解效能,并证实了布洛芬是通过F127胶团的内核和栅栏层而实现增溶的.     

稀土与酸性萃取剂形成的溶液聚集态结构

用Fourier变换红外光谱(FT—IR)和光子相关光谱(PCS)研究了皂化的有机磷酸酯类萃取剂和环烷酸萃取剂在正庚烷或正庚烷与2-辛醇的混合溶剂中所形成的聚集物,以及萃取稀土元素后有机相聚集物的变化.结果表明,有机磷酸酯在正庚烷中皂化后形成反向胶团((?)_h<5.0nm),其平均流体力学半径与萃取剂分子的长度相当;2-辛醇的加入可增大反向胶团的粒径.环烷酸皂化后能在混合溶剂中形成W/O型微乳状液(5.0 nm<(?)_h<100 nm).皂化萃取剂萃取稀土元素后,有机相中形成不稳定的聚集物,继而产生聚凝.讨论了聚凝过程的可能机理.     

C12-s-C12·2Br与低碳醇混合水溶液胶团化行为的温度效应和焓/熵补偿

季铵盐Gemini表面活性剂C12-s-C12·2Br(s=2,3,4,6)与丙醇、丁醇、戊醇、己醇混合水溶液的In(cmc)随温度升高而逐渐增大.计算所得热力学数据表明,C12-s-C12·2Br与醇混合胶团化过程服从熵驱动机理,也出现了焓/熵补偿现象.随着温度上升,熵驱动力增大,在指定温度时,醇分子烷烃链上碳原子数n增大使△Gm0值减小,胶团结构更加稳定;而增加s使值增大,胶团稳定性下降.     

正负离子表面活性剂反胶团与反相微乳研究

研究了以癸烷为油相的十一烯酸癸胺正负离子表面活性剂体系对水的加溶作用。结果表明此体系在一定组成范围内可以形成均匀透明的反胶团或反相微乳液。升高温度和添加酸、碱、盐可以使形成反胶团或反相微乳的组成范围扩大。在正负离子表面活性剂中加入离子型表面活性剂、特别是负离子型表面活性剂,也有类似的作用。     

ABTT浊点萃取分光光度法测定水样中镉

利用非离子表面活性剂Triton X-114在温度高于其浊点时形成相分离行为,建立了浊点萃取-分光光度法测定水样中痕量镉的新方法,优化了以1-偶氮苯-3-噻唑-三氮烯(ABTT)为显色剂,Triton X-114浊点萃取富集痕量镉的实验条件.在最大吸收波长λ=520 nm,其表观摩尔吸光系数为6.84×105L·mol...     

浊点萃取-荧光光度法测定苯酚

基于非离子表面活性剂TritonX-100,以浊点萃取结合荧光光度法测定水中的苯酚,考察影响浊点萃取的各种因素。最佳实验条件为：pH=3.0的磷酸氢二钠-磷酸二氢钾缓冲溶液中,5%的TritonX-100用量2.0mL、平衡温度82℃、平衡时间8min。在此条件下,苯酚被萃取到TritonX-100表面活性剂相与水相分开。     

Diffusivity of whey protein and gum arabic in their coacervates

Structural properties of whey protein (WP)/gum arabic (GA) coacervates were investigated by measuring the diffusivity of WP and GA in their coacervate phase as a function of pH by means of three different complementary techniques. The combination of these measurements revealed new insights into the structure of coacervates. Nuclear magnetic resonance (NMR) measured the self-diffusion coefficient of the GA in the coacervate phase prepared at various pH values. Fluorescence recovery after photobleaching (FRAP) was measured using a confocal scanning laser microscope. The WP and GA were covalently labeled with two different dyes. The time of fluorescence recovery, related to the inverse of the diffusion coefficient, was evaluated from the measurements, and the diffusivity of the WP and GA on a long time scale could be individually estimated at each pH value. Diffusing wave spectroscopy (DWS) combined with transmission measurement was carried out in the coacervate phase, and the diffusion coefficient, corresponding to the averaged diffusion of all particles that scattered in the system, was calculated as a function of pH. Independently of the technique used, the results showed that the diffusion of the WP and GA within the coacervate phase was reduced as compared to a diluted biopolymer mixture. NMR, DWS, and FRAP measurements gave similar results, indicating that the biopolymers moved the slowest in the coacervate matrix at pH 4.0-4.2. It is assumed that the diffusion of the WP and GA is reduced because of a higher electrostatic interaction between the biopolymers. Furthermore, FRAP results showed that in the coacervate phase WP molecules diffused 10 times faster than GA molecules. This result is very relevant because it shows that WP and GA move independently in the liquid coacervate phase. Finally, DWS measurements revealed that the coacervate phase rearranged with time, as evidenced by a decrease of the diffusion coefficient and a loss of the turbidity of the sample. A more homogeneous transparent coacervate phase was obtained after a few days/weeks. Faster rearrangement was obtained at pH 3.0 and 3.5 than at higher pH values.     

Microchannel emulsification using gelatin and surfactant-free coacervate microencapsulation

In this study, we investigated the use of microchannel (MC) emulsifications in producing monodisperse gelatin/acacia complex coacervate microcapsules of soybean oil. This is considered to be a novel method for preparing monodisperse O/W and W/O emulsions. Generally, surfactants are necessary for MC emulsification, but they can also inhibit the coacervation process. In this study, we investigated a surfactant-free system. First, MC emulsification using gelatin was compared with that using decaglycerol monolaurate. The results demonstrated the potential use of gelatin for MC emulsification. MC emulsification experiments conducted over a range of conditions revealed that the pH of the continuous phase should be maintained above the isoelectric point of the gelatin. A high concentration of gelatin was found to inhibit the production of irregular-sized droplets. Low-bloom gelatin was found to be suitable for obtaining monodisperse emulsions. Finally, surfactant-free monodisperse droplets prepared by MC emulsification were microencapsulated with coacervate. The microcapsules produced by this technique were observed with a confocal laser scanning microscope. Average diameters of the inner cores and outer shells were 37.8 and 51.5 microm; their relative standard deviations were 4.9 and 8.4%.     

Preparation of zinc sodium polyphosphates glasses from coacervates precursors. Characterisation of the obtained glasses, and their applications

A soft chemistry route is described to obtain glasses in the P₂O₅–Na₂O–ZnO–H₂O. It is based on the addition of zinc salts to coacervates prepared from sodium polyphosphate. The processing of these coacervates leads to polyphosphate glasses with the same properties as those of glasses prepared in the classical way. So far, little work has been implemented in this system using ‘coacervate route’. However, it makes an attractive method for coating and joining processes on the industrial scale. As the anion associated to zinc may take part in the adhesion mechanism, coacervate formation has been studied using zinc chloride, nitrate and sulphate as starting materials. The physical properties of the glasses obtained by this method are reported and potential applications of zinc and silver coacervate are described.     

Coacervation of copolymer of diallyldimethylammonium chloride and sodium styrenesulfonate aqueous solution

Coacervate behavior of polyelectrolyte complexes has been studied by many papers. Few studies have focused on the coacervate behavior of amphoteric polymer. In this study, amphoteric copolymer of diallyldimethylammonium chloride (DM) and sodium styrenesulfonate (SS) (the copolymer was noted as DMS) was synthesized with the mole content of SS to DM ranged from 0 to 10%. Firstly, DMS was characterized by static light scattering, FTIR, ¹H-NMR, TGA and DSC. Then, its phase and coacervate behaviors were studied. Turbidity was utilized as an indicator for the coacervate formation. It was found that when the SS content was more than 4 mol%, DMS coacervate would be formed in deionized water at a certain concentration. Temperature and pH have no effect on the formation of DMS coacervate. Meanwhile, salts has a great influence on the DMS coacervation. Unlike the results of the other polyelectrolyte complexes, Na₂SO₄, Na₂HPO₄, NaCOOCH₃, sodium citrate and NaI cannot prevent the DMS coacervate formation. However, the addition of NaCl, NaNO₃, NaBr and NaSCN can prevent the coacervate formation. The influence cannot be described by Hofmeister-like behavior. Results of surface tension and fluorescence spectrum presented that the driving forces to formation of DMS coacervate are the electrostatic interaction and the intermolecular hydrophobic interaction.     

Conductivity and structure of a group of lipid coacervates

Some theories concerning the structure and properties of coacervates are discussed. The preparation of a type of lipid coacervate, suitable as a biological model, especially for olfactory transduction, is described. When organic substances are added, the conductivity of the coacervate decreases roughly in proportion to the amount of additive. The sensitivity to 20 different additives has been investigated. In general, the sensitivity was greater, the longer the chain of the additive. The sensitivity pattern was also dependent on the composition of the coacervate and although the dependence appeared to be very complex, some clear traits could be distinguished. Experimental studies on the optical and diffusional properties and composition of the coacervate are presented. The coacervate was found to be optically isotropic. Its total Na⁺ concentration was about the same as in the equilibrium liquid, whereas the Cl⁻ concentration in coacervate water was lower than in equilibrium liquid. Both remained fairly constant as the coacervate shrank under the influence of added toluene. The diffusion velocities of tartrazine and Sudan black B in coacervate were of the same order of magnitude, which suggests that the lipids may form a continuous network throughout the coacervate phase, rather than discrete micelles.     

Three-phase interactions and interfacial transport phenomena in coacervate/oil/water systems

Complex coacervation is an associative liquid/liquid phase separation resulting in the formation of two liquid phases: a polymer-rich coacervate phase and a dilute continuous solvent phase. In the presence of a third liquid phase in the form of disperse oil droplets, the coacervate phase tends to wet the oil/water interface. This affinity has long been known and used for the formation of core/shell capsules. However, while encapsulation by simple or complex coacervation has been used empirically for decades, there is a lack of a thorough understanding of the three-phase wetting phenomena that control the formation of encapsulated, compound droplets and the role of the viscoelasticity of the biopolymers involved. In this contribution, we review and discuss the interplay of wetting phenomena and fluid viscoelasticity in coacervate/oil/water systems from the perspective of colloid chemistry and fluid dynamics, focusing on aspects of rheology, interfacial tension measurements at the coacervate/solvent interface, and on the formation and fragmentation of three-phase compound drops.     

Cloud point extraction of aloe anthraquinones based on non-ionic surfactant aqueous two-phase system

Non-ionic surfactant-based aqueous two-phase system had been investigated to extract aloe anthraquinones. It had the advantage of using a single auxiliary chemical to induce phase separation above cloud point at a low concentration. Non-ionic surfactant Triton X-114 was chosen for its excellent phase-separating ability and low cloud point. The main factors affecting the cloud point extraction were discussed such as equilibrium temperature and time, concentrations of surfactant and inorganic electrolytes, pH, etc. Under the optimised conditions, the highest extraction yield 96.93% was obtained. The reverse extraction of anthraquinones from surfactant-rich phase was achieved with a recovery of 70.35% by adjusting pH. Compared with conventional purification methods, this CPE technique can be completed in one operation; besides, it is a low-cost method and an environment friendly one.     

Reversible pH-Responsive Coacervate Formation in Lipid Vesicles Activates Dormant Enzymatic Reactions

In situ, reversible coacervate formation within lipid vesicles represents a key step in the development of responsive synthetic cellular models. Herein, we exploit the pH responsiveness of a polycation above and below its pK_a, to drive liquid–liquid phase separation, to form single coacervate droplets within lipid vesicles. The process is completely reversible as coacervate droplets can be disassembled by increasing the pH above the pK_a. We further show that pH-triggered coacervation in the presence of low concentrations of enzymes activates dormant enzyme reactions by increasing the local concentration within the coacervate droplets and changing the local environment around the enzyme. In conclusion, this work establishes a tunable, pH responsive, enzymatically active multi-compartment synthetic cell. The system is readily transferred into microfluidics, making it a robust model for addressing general questions in biology, such as the role of phase separation and its effect on enzymatic reactions using a bottom-up synthetic biology approach.