Synergism in mixtures of n-octyl-β-d-thioglucoside and different n-alkyltrimethylammonium bromides: effect of the alkyl chain length

Mixtures of n-octyl-β-d-thioglucoside with three different n-alkyltrimethylammonium bromides (n?=?12 (DTAB), 14 (TTAB), and 16 (CTAB)) have been studied by using fluorescence spectroscopic techniques. The critical micelle concentration values of pure and mixed systems were determined by the pyrene 1:3 ratio method. The experimental results were treated by using thermodynamic mixing approaches based on the pseudophase separation model. It was found that all the mixed systems show a negative deviation from ideal behavior, more pronounced as the larger the alkyl tail of the co-surfactant. It was also observed that the three mixed systems fulfill the conditions of synergism, this behavior being also dependent on the alkyl chain length. By using the static quenching method, the mean micellar aggregation numbers of mixed micelles were obtained. In all the cases, it was observed that the aggregation number is initially reduced with the participation of the cationic surfactant, remaining almost constant and close to the aggregation number of the pure cationic micelles. The local viscosity of pure and mixed micelles was examined by the photophysical response of the hydrophobic probe coumarin 6 solubilized in the micellar medium. It was found that the participation of the ionic component induces the formation of a less ordered structure than that of pure nonionic micelles. This effect being less pronounced as the chain hydrocarbon length of the co-surfactant increases.     

荧光探针法研究新型Gemini表面活性剂在水溶液中的聚集行为

以芘为荧光探针、二苯酮为猝灭剂,用稳态荧光探针法测定了新型Gemini表面活性剂的临界胶团浓度(CMC)、胶团聚集数(N_agg)及胶团微极性.研究了Gemini表面活性剂结构和氯化钠浓度对CMC、N_agg、胶团微极性的影响.结果表明,新型Gemini表面活性剂的CMC比常规表面活性剂的CMC低1—2个数量级.当疏水基碳原子数增加时,CMC依次降低,N_agg增大,胶团微极性减小.当氯化钠浓度增大时,N_agg增大,胶团微极性减小.     

稳态荧光探针研究支链烷基苯磺酸钠的聚集行为

以芘为荧光探针、二苯酮为猝灭剂,用稳态荧光探针法测定了合成的4种带干扰基(磺酸基邻位的短链烷基)的支链烷基苯磺酸钠的临界胶团浓度、合适猝灭剂浓度下的胶团聚集数以及在不同浓度氯化钠水溶液中的胶团聚集数.结果表明,支链烷基苯磺酸钠分子中长链烷基碳数增加,临界胶团浓度大幅度降低,胶团聚集数减小;分子中短链烷基碳数增加,临界胶团浓度降低幅度小,胶团聚集数增大;胶团聚集数随氯化钠浓度增大而增大.     

外缘烷基链长对共轭有机小分子聚集行为及光电性质影响

改变分子化学结构和调控分子结构聚集态行为从而影响或改变材料的化学和物理性质, 是开发新型高效有机光电功能材料的重要手段. 在共轭有机分子外缘引入烷基链一般是为了改进材料溶解性能, 但近来的一些研究表明, 烷基链长对一些共轭有机小分子固态聚集行为和光电性质具有重要影响, 烷基链扮演着显著调控材料光电性质的“功能基团”作用. 本文以聚集诱导发光（aggregation-induced emission, AIE）/聚集强化荧光（aggregation enhanced emission, AEE）发射共轭有机小分子为重点, 对近年来有关烷基链长对共轭有机分子聚集形态和光电性质影响的一些典型事例进行评述, 旨在使人们在进行共轭有机分子设计合成及其结构与性能关系研究中能够关注烷基链的因素, 使烷基链变化作为功能导向晶态共轭有机材料设计合成及其可控制备的一种手段.     

离子液体表面活性剂1-丁基-3-甲基咪唑烷基硫酸酯的合成及其在水溶液中的聚集行为

采用离子交换法,由1-丁基-3甲基咪唑氯盐（C4mimCl）和烷基硫酸钠合成了一系列无卤素的阴离子表面活性离子液体—1-丁基-3-甲基咪唑烷基硫酸酯[C4mim][CnH2n 1SO4](n=8,12,16),利用表面张力仪、稳态荧光光谱等手段考察了表面活性离子液体在水溶液表面及体相中的聚集行为,结果表明,与传统无机反离子相比,有机咪唑阳离子[C4mim] 作为反离子的离子液体型表面活性剂具有较高的表面活性,[C4mim] 产生的氢键引起的抑制分子规则排列的作用小于其促进分子有序排列的疏水作用。长烷基链的阴离子是界面膜及胶束的主要组成成分,阴离子疏水烷基碳链的增长虽然可促进胶束的形成,但却在一定程度上抑制[C4mim] 离子参与界面或胶束的形成;阴离子所带烷基链越长,越不利于阳离子[C4mim]＋参与界面膜或胶束的形成,界面膜或胶束中表面活性剂排布越松散,即界面张力越大,体系中胶束聚集数较小。     

Estimation of the critical micelle concentrations and the aggregation numbers of sodium alkyl sulfates by capillary-type isotachophoresis

The analytical procedure for the separation and quantification of bulk and micellar phases for sodium alkyl sulfates has been investigated by a capillary-type isotachophoresis using a potential gradient detector. Monomer solutions were distinguished from micellar solutions at pH 5.5–6.0; hydrochloric acid — L-Histidine mixture was used as the leading electrolyte and 2-(N-Morpholino) ethanesulfonic acid as the terminating electrolyte.The potential unit value (PU value) due to the monomer solutions was larger than that due to the micellar solutions. The zone length due to monomer solutions increased with increasing concentration of surfactant until a given concentration (CMC); beyond this point the values became constant. On the other hand, the zone length due to micellar solutions increased from this point. We report an applicability of capillary-type isotachophoresis to determination of the CMC's and aggregation number for various sodium alkyl sulfates.     

Hemimicelle shape and size

Based on the assumption of spherical hemimicelle with a hydrophobic core of diameter of maximum hydrocarbon chain length of surfactant, the aggregation numbers of hemimicelles have been calculated for several values ofn, the carbon atoms of surfactant alkyl chain. The results are in reasonable good agreement with the hemimicelle aggregation number from experimental data for several corresponding systems. The other possibilities of the hemimicelle shape which allow to incorporate a larger number of hydrocarbon chains in a hemimicelle have also been discussed.On leave from Department of Chemistry, Peking University, Beijing, China     

Langmuir monolayers of the long-chain alkyl derivatives of a nucleoside analogue and the formation of self-assembled nanoparticles

The long-chain alkyl derivatives of a nucleoside analogue-acyclovir were prepared in the paper. One is stearyl-glycero-succinyl-acyclovir (SGSA) with a single 18-carbon length (C18) alkyl chain. Another is dioctadecyl-aspartate-succinyl-acyclovir (DASA) with double C18 alkyl chains. They were prepared by the esterification of succinyl-acyclovir with the lipids, and sodium salts of them were also prepared. Guanine moieties and alkyl moieties bring the derivatives intermolecular hydrogen bonding and hydrophobic interaction in water separately. The forces are influenced by the number of alkyl chains and the charged state, and determine the solubility and the self-assembly behavior of the derivatives. The double alkyl-chain derivatives (DASA and DASA-Na) formed rigid Langmuir monolayers on air/water surface, while the single alkyl chain derivatives (SGSA and SGSA-Na) did not. However, cholesterol (Chol) could assist SGSA to form rigid monolayers through inserting into the alkyl chains of SGSA to mimic the second alkyl chain. SGSA self-aggregates in water were prepared by the injection method with tetrahydrofuran as solvent. Cuboid-like shape and nanoscale size demonstrated that SGSA self-aggregates were self-assembled nanoparticles. Shape, particle size, zeta potential and phase transition of the nanoparticles were characterized. And they showed an average size of 83.2 nm, a negative surface charge of -31.3-mV zeta potential and a gel-liquid crystalline phase transition of 50.38 degrees C. The formation mechanism of self-assembled nanoparticles was analyzed. Hydrophobic interaction of alkyl chains improves SGSA molecules to form bilayers, and then cuboid-like nanoparticles were obtained by layer-by-layer aggregation based on inter-bilayers hydrogen bonding. However, the charged guanine moieties make SGSA-Na lose the function of hydrogen bonding so that SGSA-Na only forms vesicles in water based on hydrophobic interaction. Strong hydrophobicity and wide-open rigid double alkyl chains of DASA and DASA-Na restrict self-assembly in water media, and no homogeneous suspensions were obtained. Therefore, the molecular self-assembly behavior of the long-chain alkyl derivatives of nucleoside analogues on water surface or in water media is determined by the number of alkyl chains and the charged state.     

Aggregation of Sodium 2,4,5-(tri-n-Alkyl)-benzene Sulfonates in Aqueous Solution: Micellization and Microenvironment Characteristics Studied by Electron Paramagnetic Resonance and Steady-State Fluorescence Quenching

The aggregation behaviors and microenvironmental characteristics of five sodium tri-n-alkylbenzene sulfonates (STABS) micelles have been investigated by electron paramagnetic resonance (EPR) and steady-state fluorescence quenching (SSFQ) techniques. The results indicated that the micropolarity of STABS micelles was less sensitive to the increase of the alkyl chain length, and showed slight decrease with the increasing solution concentration. The microviscosity of STABS micelles increased with the increase of the long alkyl chain length, decreased with the increase of the short alkyl chain length, and exhibited little increase when increase the solution concentration. The salinity of added inorganic salt exhibited obvious effect on the decrease of micropolarity and increase of microviscosity of STABS. These results suggested that these different alkyl chains showed different effects on the micellization of STABS and the salinity's effect was even bigger.     

A stimulus-responsive shape-persistent micelle bearing a calix[4]arene building block: reversible pH-dependent transition between spherical and cylindrical forms

A series of cationic calix[4]arene-based lipids with alkyl chains of varying length were newly synthesized, and the ones with propyl and hexyl tails, denoted by CaL[4]C3 and C6, respectively, were found to form spherical micelles at low pH (protonated state of the amine headgroup). Upon deprotonation with increasing pH, CaL[4]C3 showed a sphere-to-cylinder transition, while CaL[4]C6 changed from sphere, to cylinder, to monolayer vesicle. Synchrotron small-angle X-ray scattering (SAXS) patterns from both spherical and cylindrical CaL[4]C3 micelles exhibited a sharp intensity minimum, indicating shape monodispersity. The monodispersity of the CaL[4]C3 spherical micelles was further confirmed by analytical ultracentrifugation (AUC). SAXS, AUC, and static light scattering agreeingly indicated an aggregation number of 6. In contrast, CaL[4]C6 exhibited polydispersity with an average aggregation number of 12. When the number of carbons of the alkyl chain was increased to 9 (CaL[4]C9), cylinder formed at low pH, while at high pH, no clear morphology could be observed. The present results indicate that a very precise combination of tail length, head volume, and rigidity of the building block is required to produce shape-persistent micelles and that the shape-persistence can be maintained upon a structural transition. An attempt to reconstruct a molecular model for the spherical CaL[4]C3 micelle was made with an ab initio shape determining program.     

Are hydrotropes distinct from surfactants?

The physicochemical properties of a homologous series of sodium p-n-alkylbenzoates have been investigated. The objective was to determine whether there is a clear transition point from hydrotropic to surfactant-like behavior with increasing alkyl chain length n, so as to shed clear light on the aggregation mechanism of so-called "hydrotropes". Electrical conductivity measurements were used for a first estimation of the critical aggregation concentrations (cac). As for classical surfactants, log(cac) depends on alkyl chain length n, but two branches of behavior were observed: one having a gradient typical of long chain fatty acid salts and the other with a more shallow dependence. Surface tension (γ) measurements of high purity aqueous solutions were used to generate limiting headgroup areas A(cac), which were in the range (40-50 ?(2)) being consistent with monolayer formation. Small-angle neutron scattering conclusively shows that the lower chain length homologues (classed as hydrotropes) exhibit sharp transitions in aggregation as a function of bulk concentration, typical of regular surfactants. As such, there is little to suggest from this study that hydrotropes differ in association behavior from regular surfactants.     

Characterization and application of sodium di(2-ethylhexyl) sulfosuccinate and sodium di(2-ethylhexyl) phosphate surfactants as pseudostationary phases in micellar electrokinetic chromatography

Sodium di(2-ethylhexyl) sulfosuccinate (DOSS) and sodium di(2-ethylhexyl) phosphate (NaDEHP) surfactants, with double alkyl chains and negatively charged headgroups, were characterized using fluorescence quenching, densitometry, and tensiometry techniques to determine their aggregation number, partial specific volume, and critical aggregation concentration. These two surfactants were then applied as pseudostationary phases in micellar electrokinetic chromatography (MEKC) for separations of alkyl phenyl ketones. The aggregation number of NaDEHP was found to be more than two-fold higher than that of DOSS. The partial specific volumes of NaDEHP and DOSS were found to be 0.9003 and 0.8371 mL/g, respectively. The critical aggregation concentrations are 5.12 and 1.80 mM for NaDEHP and DOSS, respectively. The DOSS surfactant provided a wider separation window and had a greater hydrophobic environment than the NaDEHP surfactant under the MEKC experimental conditions studied.     

Aggregation of sodium 1-(n-alkyl)naphthalene-4-sulfonates in aqueous solution: micellization and microenvironment characteristics

In aqueous solution, the micellization and microenvironment characteristics of the micelle assemblies of three anionic surfactants, sodium 1-(n-alkyl)naphthalene-4-sulfonates (SANS), have been investigated by steady-state fluorescence and time-resolved fluorescence decay techniques using pyrene, Ru(bpy)3(2+), and 1,6-diphenyl-1,3,5-hexatriene as fluorescence probes. The critical micelle concentrations (cmc's), effective carbon atom numbers (neff's), hydrophilic-lipophilic balances (HLBs), mean micelle aggregation numbers, micropolarities, and microviscosities of these surfactant micelles have been determined. The logarithmic cmc of the alkylnaphthalene sulfonates decreases linearly with an increase in the neff. The logarithmic aggregation number of the alkylnaphthalene sulfonates increases linearly with an increase in the neff. However, in contrast to the alkylsufonates and the alkylbenzene sulfonates, the aggregation for these alkylnaphthalene sulfonate molecules is less sensitive to the increase in the neff. The micropolarity of these alkylnaphthalene sulfonate micelles is less sensitive to the increase in the alkyl chain length and is lower than that of sodium dodecyl sulfate (SDS). The microviscosity of these alkylnaphthalene sulfonate micelles increases with an increase in the alkyl chain length and is lower than those of nonionic surfactants and zwitterionic surfactants. These results suggest that naphthyl rings have a notable effect on the micellization of SANS.     

N-烷基化聚对苯二甲酰对苯二胺梳状高分子中烷基侧链对刚性主链堆积行为的影响

基于聚对苯二甲酰对苯二胺(PPTA), 采用N-烷基化方法制备了系列PPTACns(烷基侧链碳原子数n=8, 10, 12, 14, 16, 18)刚性主链梳状高分子, 利用DSC, XRD和FTIR等方法研究了其主链堆积行为、 分子链构象及热性能等与烷基侧链长度及结晶特性之间的关系. XRD和DSC结果表明, 当烷基侧链碳原子数达到14时, 烷基侧链发生结晶. XRD结果显示, PPTACns具有层状结构, 烷基侧链长度对主链层间距影响显著. FTIR研究发现, 烷基侧链的聚集状态对PPTACns分子链的构象产生较大影响, 伴随着烷基侧链结晶的熔融, PPTACns的分子链构象发生显著改变. 烷基侧链处于熔融状态的PPTACns的ν_C=O和γ_C-H谱带峰位与烷基侧链不结晶的PPTACn接近.     

Effect of side chain length on the morphology of blends of 2,5‐bis(3‐alkylthiophen‐2‐yl)thieno[3,2‐b]thiophene oligomers and fullerene derivatives

Using molecular dynamics simulations we study blends of oligomers of 2,5‐bis(3‐alkylthiophen‐2‐yl)thieno[3,2‐b]thiophene, BTTT, and fullerene derivative based acceptors to understand the role of oligomer length and alkyl side chain (SC) length on the morphology of their blends. We use a validated coarse‐grained model of BTTT and fullerene derivatives presented in recent work along with direct comparison of morphology between simulations and experiments. In this article, we predict computationally that short alkyl SCs (6 alkyl groups) decrease the propensity of fullerene derivative acceptors to intercalate between SCs on the BTTT backbone compared to longer alkyl SCs (9 or 12 alkyl groups), and as a result increase acceptor aggregation. The decreasing acceptor intercalation and increasing acceptor aggregation do not significantly impact the positional or orientational order of the BTTT backbones. However, the BTTT oligomer backbones order better with increasing SC length in both neat systems and in blends, with the blends exhibiting higher positional order than neat systems. While these qualitative trends are similar both in 2mer blends and 4mer blends, we see a larger extent of acceptor intercalation and as a result, smaller acceptor cluster sizes in the 4mer blends. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 89–97     

AFM and electron microscopy study of the unusual aggregation behavior of metallosurfactants based on iron(II) complexes with bipyridine ligands

The aggregation behavior in water-rich solutions of five iron(II) complexes with alkylated derivatives of 2,2'-bipyridine was studied by electron microscopy (cryo-SEM, SEM, and TEM) and AFM. The results obtained by cryo-SEM on frozen colloidal solutions show that the morphology of the aggregates strongly depends on the length of the alkyl chains in the bipyridine ligands, with shorter alkyl chains forming rod-like structures, whereas for compounds with longer alkyl chains, only spherical structures were detected. The self-aggregates were further characterized by SEM and TEM. The results show that their overall morphology depends only on the length of the alkyl chain of the bipyridine ligands and that the samples show a broad size distribution. In addition, TEM and SEM were used to study the stability of the self-aggregates in solution, the effect of addition of methanol, and the temperature used in the preparation of the colloidal solutions. AFM studies of the aggregates either dried in ambient conditions or dehydrated by long drying under vacuum showed partially collapsed self-aggregates in the latter case, showing that the aggregates contain water in their core, indicating that the self-aggregation leads to vesicle-type structures.     

On the self-aggregation and fluorescence quenching aptitude of surfactant ionic liquids

The aggregation behavior in aqueous solution of a number of ionic liquids was investigated at ambient conditions by using three techniques: fluorescence, interfacial tension, and (1)H NMR spectroscopy. For the first time, the fluorescence quenching effect has been used for the determination of critical micelle concentrations. This study focuses on the following ionic liquids: [Cnmpy]Cl (1-alkyl-3-methylpyridinium chlorides) with different linear alkyl chain lengths (n=4, 10, 12, 14, 16, or 18), [C12mpip]Br (1-dodecyl-1-methylpiperidinium bromide), [C12mpy]Br (1-dodecyl-3-methylpyridinium bromide), and [C12mpyrr]Br (1-dodecyl-1-methylpyrrolidinium bromide). Both the influence of the alkyl side-chain length and the type of ring in the cation (head) on the CMC were investigated. A comparison of the self-aggregation behavior of ionic liquids based on 1-alkyl-3-methylpyridinium and 1-alkyl-3-methylpyridinium cations is provided. It was observed that 1-alkyl-3-methylpyridinium ionic liquids could be used as quenchers for some fluorescence probes (fluorophores). As a consequence, a simple and convenient method to probe early evidence of aggregate formation was established.     

Temperature behavior of the electric field-induced entropy increment within a homologous series of nematogenic compounds

Based on the temperature behavior of the entropy increment induced by the probing electric field in the isotropic phase of mesogenic compounds belonging to the homologous series C(n)H(2n+1)PhCOOPhCN ( n = 4-10), it is found that an ability to the dipolar aggregation of the molecules depends on the alkyl tail length, and, in particular, the ability is strongly reinforced when the number n changes from 7 to 8. The role of the molecular structure in the self-assembling process is discussed.     

Aggregation Processes of Perylene Bisimide Diimidazolium Salts

The supramolecular aggregation of three diimidazolium‐functionalized perylene bisimides, differing in the alkyl chain length was investigated. These salts form aggregates in solvents like chloroform, dichloromethane, and glycerol. Solvent‐, concentration‐, and temperature‐dependent spectroscopic studies were carried out, evidencing the occurrence of an isodesmic, enthalpy‐driven aggregation process, underpinned by π–π stacking and hydrogen bonding. Moreover, dynamic light scattering (DLS) measurements and SEM images revealed that these salts aggregate in chloroform into elongated structures.     

Aggregation behavior of pyridinium based ionic liquids in water--surface tension, 1H NMR chemical shifts, SANS and SAXS measurements

The aggregation behavior of short alkyl chain ionic liquids (ILs), namely 1-butyl, or 1-hexyl or 1-octylpyridinium and 1-octyl-2-, or -3-, or -4-methylpyridinium chlorides, in water has been assessed using surface tension, electrical conductance, (1)H NMR, small angle neutron scattering (SANS) and small angle X-ray scattering (SAXS) measurements. Critical aggregation concentrations (CACs), adsorption (at air/water interface) and thermodynamic parameters of aggregation have been reported. The values of CAC and area per adsorbed molecule decrease with the number of carbon atoms in the alkyl chain. The aggregation process is driven by both favorable enthalpy and entropy contributions. An attempt was made to examine the morphological features of the aggregates in water using SANS and SAXS methods. SANS and SAXS curves displayed diffuse structural peaks that could not be model fitted, and therefore, we calculated the mean aggregation numbers from the Q(max) assuming that IL molecules typically order into cubic type clusters.