反离子对胶团生长影响的研究

本文采用粘度法研究反离子对胶团生长的影响。通过粘度测量, 利用Missel等提出的热力学模型, 求算了支配球-棒转变的平衡常数K和胶团的重均聚集数n_w. 同价反离子促使溴化十四烷基吡啶胶团长大的能力为ClO_3~->NO_3~->Br~-. 在0.5 molL~(-1)的NaBr和KNO_3的介质中, 参数K在一定的胶团浓度范围内保持为常量, K值与n_W值随活性剂浓度的变化, 与光散射相应结果相当一致; 在0.5 molL~(-1)KClO_3介质中, K值明显地有浓度依赖性, 所得n_W值两法相差较大, 上述模型不再适用。     

溴代十四烷基吡啶胶团长大的光子相关谱研究

本文用光子相关谱方法在15—85 ℃温度范围内, 研究了溴代十四烷基吡啶(TPB)胶团在高盐量介质(0.5—2.0M NaBr)中的长大规律。自光子相关实验测定了胶团的平均流体力学半径。增加盐量、降低温度和增大活性剂浓度均使胶团变大。TPB胶团长大时由球转变为棒。自实验测量结果求算了在0.5 M和1.0 M盐中支配球-棒转变的平衡常数及热力学函数值。本文检验了梯子模型对TPB体系的适用性, 并对2 M盐介质中TPB胶团的长大具有不同的特征作了讨论。     

正、负离子表面活性剂混合胶团棒-球转变模型

提出正、负离子表面活性剂混合胶团的棒-球转变模型，认为在溶液浓度较高时，随浓度进一步增大，正、负离子表面活性剂混合胶团经历了一个长棒变短、短棒变为球状的转变过程，并通过混合胶团溶液的相行为、光散射及流变性质测定等加以证实。     

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。     

非离子表面活性剂的吸附机理和表面胶团化对二氧化硅悬浮液稳定性的影响

测定了CAB-O-SIL在290.7K和304.2K时自水和1mol/LNaCl溶液中吸附非离子表面活性剂TritonX-100(TX100)的吸附等温线。结果表明,吸附量随温度升高而增加。NaCl的存在也使吸附量增加。运用生成表面胶团的吸附理论处理了实验结果,求得了表面胶团化的平衡常数、表面胶团的平均聚集数、临界表面胶团浓度和表面胶团化的标准热力学函数。实验表明,随TX100浓度的增大,CAB-O-SIL悬浮液稳定性出现不规则的变化。加入NaCl的效应是使悬浮液的稳定性下降和促进表面胶团的形成。结合吸附研究结果,提出了一个涉及表面胶团的颗粒相互作用模型,合理地解释了悬浮液稳定性的实验结果。     

动态光散射法研究季铵盐Gemini表面活性剂的胶团化行为

用动态光散射技术在10～70℃温度范围内,通过测定胶团的平均流体力学半径随温度、盐浓度和联接基团长度的变化情况,研究联接基团为聚亚甲基链的阳离子季铵盐Gemini表面活性剂胶团在无机盐介质中的长大规律.实验结果表明,增加盐量、降低温度和减小联接基团的长度均使平均流体力学半径变大,Gemini表面活性剂胶团长大时是由球状转变为棒状.从实验测定的平流体力学半径求算了支配球-棒转变的平衡常数及热力学函数值,并用NNLS(non-negatively constrainedleast square)算法对胶团的粒径分布情况进行了分析.此外,对具有短联接基团的Gemini表面活性剂胶团长大所具有的独特性质进行了讨论.     

无机盐和尿素对直链烷基苯磺酸钠浓溶液粘度性质的影响

在303.2±0.1K,测定了直链烷基苯磺酸钠(SLABS),硫酸锂.硫酸钠,碘化钠和尿素溶液对水的相对粘度-浓度曲线;SLABS与添加剂的混合溶液对原SLABS溶液的相对粘度-浓度曲线,测定表明,无机盐对SLABS浓溶液有显著的增粘效果, 各种艳所达到的最大粘度有显著差别,盐达到一定浓度会与SLABS形成沉淀, 其增粘能力达到极限,这些结果用胶团溶液结构,离子与胶团的相互作用,离子的水合能力,水结构改变和活度积效应来解释,尿素明显地降低SLABS浓溶液的粘度.用硫酸钠增粘时,尿素浓度越高最大粘度越低,相应的盐浓度越高.这些结果用尿素与水合单体(表面活性剂)形成尿合单体,使参与水合单体与胶团平衡的SLABS实际浓度降低来解释.     

十二烷基硫酸钠与溴化正辛基三甲基铵混合表面活性剂水溶液的表面吸附及胶团形成

本文研究了盐存在时不同比例的十二烷基硫酸钠(简称12CH)和溴化正辛基三甲基铵(简称C8NBr)混合物的表面活性、表面吸附以及胶团形成等性质,结果表明:(1)正、负离子表面活性剂混合物具有很高的表面活性,不论其混合比例如何,临界胶团浓度(cmc)及cmc时溶液的表面张力(γcmc)皆较任何单一组分时小;(2)不论体相中比例如何,表面层中12CH和C8NBr的饱和吸附量的摩尔比皆～1.7且总饱和吸附量亦皆～5.2x10[-10]mol.cm[-2].由此求得表面层中分子截面积为32A[2],与由分子结构计算的数据相近,说明正、负表面活性离子排列紧密;(3)与碳链长相同的正、负离子型表面活性剂混合水溶液比较,本体系反应离子浓度对cmc有明显影响,证实表面层带电,胶团也带电;(4)计算了离子强度相同,温度不同时和温度相同、离子强度不同时的热力学量,得出离子强度大者易形成胶团。     

金纳米球和金纳米棒的制备及其光热催化性能

以氯金酸(HAuCl_4)为原料,硼氢化钠(NaBH_4)为还原剂,聚乙烯吡咯烷酮K30(PVP)为稳定剂制备了尺寸5 nm的金纳米球;以阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)为模板剂和油酸钠(NaOL)稳定剂,用种子生长法制备了不同长径比(R=2.5~4)的金纳米棒。在2 W·cm~(-2)的808 nm激光照射10 min条件下,C(0.4 mg·mL~(-1))浓度金纳米球溶液升温10.2℃,该溶液可催化血液中亚硝基硫醇释放NO,最大释放量可达1.42 nmol·L~(-1);相同光热及催化条件下,C(0.4 mg·mL~(-1))浓度金纳米棒(R=3.01)溶液升温41.3℃,该溶液催化血液中亚硝基硫醇释放NO最大释放量可达1.89 nmol·L~(-1)。金纳米球和金纳米棒的光热及催化性能随着浓度增加而增强,金纳米棒的光热及催化性能要优于金纳米球。     

庚烷中C12-EOx-C12•2Br反胶团的形成

在助表面活性剂正己醇存在下, 季铵盐Gemini表面活性剂C12-EOx-C12•2Br(x=1, 2, 3)在正庚烷中形成了反胶团. 以碘光谱法测定了临界反胶团浓度(cmch), 该值小于它们在水中形成正胶团时的临界浓度(cmcaq), 但两者随x的变化规律一致, 均呈单调增长. 反胶团饱和增溶水量随x增加或温度升高而增大.     

Are large micelles rigid or flexible? A reinterpretation of viscosity data for micellar solutions

Surfactant solutions in which large cylindrical micelles form are characterized by two essential features, namely, they are polydisperse and the average micelle size is proportional to the square root of the micelle concentration. These features of the cylindrical micelles imply that the intrinsic viscosities of these micellar solutions should also depend on the concentration of micelles. This fact has been ignored in all past treatments of micellar viscosity data. Here, viscosity data available in literature were reexamined in terms of concentration-dependent intrinsic viscosity so as to evaluate the rigidity or the flexibility of the large micelles. It is found that the interpretation of viscosity data assuming that the large micelles are rigid rods is in very good agreement with the theoretically anticipated essential features of large micelles. It is concluded that large micelles can be satisfactorily represented by rigid rods rather than by flexible rods or coils.     

Effect of Temperature on Micelle Formation in Aqueous NaBr Solutions of Octyltrimethylammonium Bromide

Association processes in aqueous solutions of octyltrimethylammonium bromide, C(8)TAB, have been studied in aqueous NaBr solutions at temperatures from 20 to 55 degrees C. The values of the critical micelle concentration, CMC, were determined from the intersections of two straight line portions of the plots of the relationship between adiabatic compressibility of the solutions and surfactant concentration. The value of the CMC thus determined exhibits minima at a certain temperature, T(min). The value of T(min) shifts toward a lower temperature with increasing NaBr concentration. Based on the most probable micelle size model, the values of thermodynamic functions of micelle formation have been estimated at various temperatures. Copyright 2001 Academic Press.     

激光散射研究单价盐对C8-卵磷脂胶团形成的影响

用激光散射测量确定C_8-卵磷脂临界胶团浓度及其随温度、盐离子的变化。从中导出了胶团分子量, 形成因子, 能量梯级间隔以及标准焓等反映该溶液内分子相互作用的重要参量, 从而导出单价盐调控胶团大小以至形成和解体的规律和方法。     

Polymorphism of Micelles in Aqueous Cetyltrimethylammonium Bromide Solutions

A viscometric study was made of the polymorphous transformation of micelles in an aqueous solution of cetyltrimethylammonium bromide in the presence of NaBr and sodium methylbenzenesulfonate. The effects of temperature and nature and concentration of additives on the second critical micelle concentration were studied. The thermodynamic characteristics of the micellar transition are estimated.     

Sphere-to-rod transition of non-surface-active amphiphilic diblock copolymer micelles: a small-angle neutron scattering study

Micellization behavior of amphiphilic diblock copolymers with strong acid groups, poly(hydrogenated isoprene)-block-poly(styrenesulfonate), was investigated by small-angle neutron scattering (SANS). We have reported previously (Kaewsaiha, P.; Matsumoto, K.; Matsuoka, H. Langmuir 2005, 21, 9938) that this strongly ionic amphiphilic diblock copolymer shows almost no surface activity but forms micelles in water. In this study, the size, shape, and internal structures of the micelles formed by these unique copolymers in aqueous solution were duly investigated. The SANS data were well described by the theoretical form factor of a core-shell model and the Pedersen core-corona model. The micellar shape strongly depends on the hydrophobic chain length of the block copolymer. The polymer with the shortest hydrophobic chain was suggested to form spherical micelles, whereas the scattering curves of the longer hydrophobic chain polymers showed a q-1 dependence, reflecting the formation of rodlike micelles. Furthermore, the addition of salt at high concentration also induced the sphere-to-rod transition in micellar shape as a result of the shielding effect of electrostatic repulsion. The corona thickness was almost constant up to the critical salt concentration (around 0.2 M) and then decreased with further increases in salt concentration, which is in qualitatively agreement with existing theories. The spherical/rodlike micelle ratio was also constant up to the critical salt concentration and then decreased. The micelle size and shape of this unique polymer could be described by the common concept of the packing parameter, but the anomalously stable nature of the micelle (up to 1 M NaCl) is a special characteristic.     

Effect of salt and surfactant concentration on the structure of polyacrylate gel/surfactant complexes

Small-angle X-ray scattering was used to elucidate the structure of crosslinked polyacrylate gel/dodecyltrimethylammonium bromide complexes equilibrated in solutions of varying concentrations of surfactant and sodium bromide (NaBr). Samples were swollen with no ordering (micelle free), or they were collapsed with either several distinct peaks (cubic Pm3n) or one broad correlation peak (disordered micellar). The main factor determining the structure of the collapsed complexes was found to be the NaBr concentration, with the cubic structure existing up to approximately 150 mM NaBr and above which only the disordered micellar structure was found. Increasing the salt concentration decreases the polyion mediated attractive forces holding the micelles together causing swelling of the gel. At sufficiently high salt concentration the micelle-micelle distance in the gel becomes too large for the cubic structure to be retained, and it melts into a disordered micellar structure. As most samples were above the critical micelle concentration, the bulk of the surfactant was in the form of micelles in the solution and the surfactant concentration thereby had only a minor influence on the structure. However, in the region around 150 mM NaBr, increasing the surfactant concentration, at constant NaBr concentration, was found to change the structure from disordered micellar to ordered cubic and back to disordered again.     

Tautomerization equilibria in aqueous micellar solutions: a spectrophotometric and factor-analytical study

The keto-enol equilibria of benzoylacetone (BZA) as a model for 1,3-dicarbonyl compounds are studied in aqueous acid and cationic micellar solution. Evolving factor analysis (EFA), multivariate curve resolution-alternating least-squares (MCR-ALS), and rank annihilation factor analysis (RAFA) are used for complete resolving of measured spectrophotometric data. The acidity constants of the enolic, KaE, and ketonic, KaK, forms of BZA and also the tautomerization constant, Kt, and its related thermodynamic parameters have been determined by using EFA and MCR-ALS methods and spectral variation of BZA solutions in various pHs and temperatures. The concentration and spectral profiles of all species were calculated without any assumption about chemical models. The spectral variation of BZA solutions as a function of cationic micelle concentration sufficiently beyond its critical micelle concentration is analyzed according to the partition model for distribution between water and micellar pseudo-phase and RAFA. The outputs of using RAFA on measured rank deficient data are the spectrum of enolic form in the micellar pseudo-phase, free from contribution of the enolic form in the aqueous phase, the partition coefficient of enolic form, KdE, between the micelle and water phases, and the tautomerization constant in the micellar pseudo-phase, Ktm.