可聚硼酸酯表面活性剂的表面化学性质及与LAS相互作用

用表面张力法研究了可聚合硼酸酯表面活性剂(BES)水溶液不同温度下(288-313 K)的表面活性和热力学函数变化；考察了BES与十二烷基苯磺酸钠(LAS)在0.5 mol·L-1 NaCl溶液中的相互作用. 结果表明, 298 K时, BES临界胶束浓度cmc达到0.066 mmol·L-1, γcmc为29.2 mN·m-1；在所考察的温度范围内BES胶束形成自由能(ΔG0m)在-22.4 - -25.8 kJ·mol-1之间, 胶束形成是熵驱动过程. BES/LAS混合体系为具有较大负偏差的非理想体系, BES/LAS分子间平均相互作用参数βm=-3.48；当溶液体相中BES摩尔分数αBES＝0.5时, 混合胶束中BES摩尔分数X1m为0.46, |βm|达到最大, 而且此时混合溶液cmc为0.017 mmol·L-1, 达到最低, γcmc为27.8 mN·m-1.     

N-辛基-β-D-吡喃葡萄糖苷与BSA相互作用的研究

通过稳态荧光法、紫外-可见光谱法和表面张力法研究了N-辛基-β-D-吡喃葡萄糖苷(OGP)与牛血清白蛋白(BSA)在缓冲液中的相互作用. 根据OGP溶液和OGP/BSA混合溶液的表面张力曲线可以看出, 蛋白质的加入改变了单一表面活性剂溶液的表面张力曲线. 蛋白质的加入还使混合体系的临界胶束浓度(cmc*)大于单一表面活性剂的临界胶束浓度(cmc), 这主要是由于OGP与蛋白质结合减少了单体OGP分子的浓度所致. 加入荧光探针芘测量了OGP和OGP/BSA溶液的I₁/I₃值, 结果也表明BSA的加入增大了OGP的聚集浓度, 其原因与表面张力的变化原因是相同的. 在OGP/BSA体系中, 随着OGP浓度的增大, 紫外吸收减弱、荧光强度有规律的降低, 而且荧光发射峰位发生蓝移, 说明它们的结合部位趋向于Trp残基上|同时通过同步荧光和I^－猝灭实验, 进一步证明了OGP与BSA的结合部位是在BSA的疏水空腔内的色氨酸残基上.     

烷基芳基磺酸盐相对分-T质量及其分布与表面性能的关系

测定了自制的9种烷基芳基磺酸盐复配体系在25℃下的临界胶束浓度cmc(1×10<'-5>moL/L)及临界胶束浓度下的表面张力γ<,cmc>(mN/m).研究了烷基芳基磺酸盐相对分子质量及其分布与表面性能的关系.平均相对分子质量432的5种分布cmc和γ<,cmc>值分别为:2.341和28.96(递增型分布);2.4...     

溴化1-十二烷基-3-甲基咪唑与甲基橙的相互作用

利用电导法和表面张力法,研究了离子液体表面活性剂溴化1-十二烷基-3-甲基咪唑(C12mimBr)与阴离子染料甲基橙(MO)之间的相互作用。 通过分别测定C12mimBr、MO以及C12mimBr与MO混合溶液的电导率,计算了C12mimBr与MO的结合特性。 C12mimBr与MO以等摩尔比结合,在288.1、298.1和308.1 K下的结合常数分别为4.89×105、4.88×104和5.76×103 L/mol,该结合反应属于焓驱动的自发放热反应。 分别测定了C12mimBr与MO等摩尔混合体系及其在NaBr溶液中的临界胶束浓度(cmc),加入MO使C12mimBr的cmc从9.1×10-3 mol/L降低到7.3×10-5 mol/L,显著提高了C12mimBr的表面活性。     

磺酸基丙烯酸酯三元无规共聚物胶束的聚集行为

采用自由基溶液共聚合法,合成了系列磺酸基丙烯酸酯三元无规共聚物表面活性剂(APSA).利用FTIR、1H-NMR、13C-NMR、GPC及元素分析证实了APSA的结构及组成.APSA胶束为核壳结构,随磺酸基含量增加,亲水层增厚.低剪切速率下,APSA溶液的黏度随磺酸基含量的增加而增加,胶束间的相互作用增强,假塑行为增强;高剪切速率下,黏度基本保持一致.DLS和表面张力表明,APSA1可将水溶液的表面张力降至43.26 m N/m.随亲水基团增加,表面张力增加,临界胶束浓度(cmc)增加.溶液浓度在cmc以下时,光散射强度较低且变化缓慢,高于cmc后,光散射强度呈现急剧的线性增长趋势,胶束聚集数急剧增加.随溶液浓度和亲水基团增加,胶束尺寸和分布系数增加.荧光光谱表明,随APSA浓度增加,I1/I3值从1.8降低到约1.2,芘的(0,0)吸收峰从334 nm迁移到338 nm,I338/I334值从0.7增大到1.45,表明疏水基团聚集形成疏水微区,芘分子从水相极性环境转移到胶束疏水内核.随亲水基团含量增加,分子聚集形成胶束的难度增加,速率降低.     

稳态荧光探针法测定三聚季铵盐表面活性剂的胶束聚集数

以芘为荧光探针, 十六烷基氯化吡啶(CPC)为猝灭剂, 以芘的饱和水溶液为溶剂配制表面活性剂溶液, 根据芘的荧光强度之比I1/I3随表面活性剂水溶液浓度的变化, 测定了三聚季铵盐表面活性剂CTTTA的cmc值, 测定值与表面张力法测定的cmc值一致；当猝灭剂CPC的浓度取0.1~0.3 mmol·L-1范围时, 用稳态荧光探针法测定了CTTTA的胶束聚集数. 实验数据表明, 表面活性剂溶液浓度为6~10倍cmc时, 胶束聚集数N随表面活性剂浓度增大而线性增大, 并用外推法得到CTTTA的临界胶束聚集数.     

全氟辛酸钠与十二烷基三甲基溴化铵混合胶束微环境性质的NMR, ESR研究

应用表面张力法、NMR法和ESR法研究了全氟辛酸钠(SPFO)-十二烷基三甲基溴化铵(DTAB)混合体系水溶液胶束形成及混合胶束的微环境性质(微观粘度、微观极性等).结果表明,碳氟表面活性剂碳氟链和碳氢表面活性剂碳氢链之间具有强烈的相互作用,DTAB与SPFO在水溶液中形成混合胶束.DTAB与SPFO混合体系的表面活性高于单一的DTAB或SPFO,混合体系cmc较单一的DTAB和SPFO低.DTAB与SPFO混合胶束的微观粘度较DTAB胶束的大,而微观极性较DTAB的小.     

手性赖氨酸基Gemini表面活性剂的表面性能

用表面张力法、电导法和稳态荧光法研究了手性Gemini表面活性剂[C₁₂-m-C₁₂] Na₂（m=2,4,6）和[C₁₂-T-C₁₂] Na₂的表面性能及临界胶束聚集数,并计算胶束形成的热力学参数,用圆二色谱法考察了[C₁₂-2-C₁₂] Na₂在不同浓度下的立体构型. 结果表明,手性Gemini表面活性剂的临界胶束浓度（cmc）和临界表面张力γ_cmc随着连接基链长增加或刚性增强而增大;ΔG_m⁰和ΔH_m⁰为负值,|ΔH_m⁰|比|-TΔS_m⁰|小很多,说明胶束化过程为熵驱动的自发放热过程;随着连接基链长增加或刚性增强,ΔG_m⁰和ΔH_m⁰逐渐增大,ΔS_m⁰和临界胶束聚集数逐渐减小,表明其胶束化能力随之降低;当浓度大于cmc时,手性Gemini表面活性剂可形成手性超分子聚集体.     

十四烷基芳基磺酸盐形成的分子有序组合体

以表面张力法、碘光谱法、水增溶法和相态图法研究了自制的三种十四烷基芳基磺酸盐在不同条件下形成的分子有序组合体(胶束、反胶束和微乳液),并考察了分子结构、溶剂、无机盐和短链醇等对其的影响.结果表明:增加十四烷基芳基磺酸盐分子亲油基支化度,不利于其在水溶液或混合极性溶剂(乙二醇-水)中形成胶束而有利于其在非极性溶剂正庚烷中形成反胶束;溶剂极性的降低,促使表面活性剂溶液由胶束溶液→单体溶液→反胶束溶液转变;无机盐或短链醇的加入促进了水溶液中胶束的形成,且反离子价态数或醇烷基碳原子数越大,越有利于胶束形成;无机盐浓度的增加导致表面活性剂/正丁醇/正辛烷/NaCl/水形成的微乳液体系在一定温度下发生由WinsorI→WinsorIII→WinsorII型的转变.     

全氟辛酸钠与十二烷基三甲基溴化铵混合胶束微环境性质的NMR,ESR研究

应用表面张力法、NMR法和ESR法研究了全氟辛酸钠(SPFO)-十二烷基三甲基溴化铵(DTAB)混合体系水溶液胶束形成及混合胶束的微环境性质(微观粘度、微观极性等)。结果表明, 碳氟表面活性剂碳氟链和碳氢表面活性剂碳氢链之间具有强烈的相互作用, DTAB与SPFO在水溶液中形成混合胶束。DTAB与SPFO混合体系的表面活性高于单一的DTAB或SPFO, 混合体系cmc较单一的DTAB和SPFO低。DTAB与SPFO混合胶束的微观粘度较DTAB胶束的大, 而微观极性较DTAB的小。     

Thermodynamics of micelle formation of the counterion coupled gemini surfactant Bis(4-(2-dodecyl)benzenesulfonate)-Jeffamine salt and its dynamic adsorption on sandstone

A novel counterion-coupled gemini (cocogem) surfactant, DBSJ, was synthetized via the 2:1 coupling reaction between 4-(2-dodecyl)benzenesulfonic acid (Lutensit A-LBS) and polypropyleneglycol-bis(2-aminopropyl) ether (Jeffamine D230). The surfactant had a polydispersity index of Mw/Mn = 1.04, as determined by electrospray-ionization mass spectrometry. The micellar properties of DBSJ in water were investigated in the temperature range 283-348 K by conductometry and titration microcalorimetry. The critical micelle concentration (cmc) of the cocogem was found to be more than 1 order of magnitude less than that of monomeric sodium 4-(2-dodecyl)benzenesulfonate (SDBS). The mean degree of dissociation in the temperature range studied proved to be alpha = 0.39. The calorimetric enthalpies of micelle formation agreed well with the enthalpies calculated via the van't Hoff relation. The cmc versus T curve passes through a minimum just below room temperature, after which the micelle formation changes from endothermic to exothermic. The Gibbs free energy of micelle formation was nearly constant as the temperature was increased, due to enthalpy/entropy compensation. The isotherm for DBSJ adsorption from aqueous solution onto sandstone was determined by continuous flow frontal analysis solid/liquid chromatography at 298 K and 60 bar. The adsorption of DBSJ on sandstone followed an S-type isotherm. Surface aggregation occurred over an extended range of concentration. Surface saturation was reached at a solution concentration more than 1 order of magnitude less than for monomeric SDBS. This finding is a point of concern in the chemical flooding of oil reservoir rocks to enhance oil recovery.     

Characterization,solution properties,and morphologies of a hydrophobically associating cationic terpolymer

The acrylamide‐based terpolymers (PADB) with 4‐butylstyrene (BST) as the hydrophobic monomer and dimethyldiallyammonium chloride (DMDAAC) were synthesized by the micellar free radical technique. The polymer was determined by UV, FT‐IR and ¹HNMR, and the hydrophobic microblock structure of PADB was characterized successfully by the conventional DSC measurement. The use of DMDAAC improves the water solubility and intermolecular association of terpolymers. The feed amount of BST affects greatly the apparent viscosity of PADB solution. The polymer exhibits good viscosification property, salt resistance, temperature‐thickening, thixotropy, pseudoplastic behavior and shear‐thickening at low shear rate. The apparent viscosities of PADB solution remarkably increase by the addition of a small amount of surfactant. AFM measurements show that hydrophobic aggregates have been formed in 0.1 g dL^?1 PADB aqueous solution, indicative of strong associations of hydrophobic groups, which are reinforced with increasing PADB concentration. The microstructures of PADB are disrupted by the addition of small amounts of salt, resulting in the decrease in solution viscosity. However, with increasing NaCl concentration, the tree‐like associating structures are formed, leading to the increase in the solution viscosity of PADB. The AFM results reveal that the solution properties of PADB are due to the associating structures in the aqueous solution and brine solution. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 826–839, 2007     

硼酸镁过饱和水溶液稀释和酸化过程中的Raman光谱

用纯水和恒沸点盐酸对六硼酸镁过饱和水溶液进行稀释和酸化,使用激光Raman光谱记录反应过程。对光谱峰进行归属。讨论了溶液中含硼量和pH值对硼氧配阴离子存在形式的影响,对多聚硼氧配阴离子在溶液中的存在形式及其相互作用机理进行了初步探讨。     

BSA和SDBS在水溶液与空气界面的相互作用

表面活性剂与蛋白质在界面处的相互作用在许多应用里都会遇到．如去污、药品或生物制剂的制备和提纯、某些开科手术等等[1]这常常涉及到表面活性剂与蛋白质在界面的吸附，蛋白质大分子在界面吸附层的取向和构象．对于这两种物质在界面处可能发生的相互作用的性质，是表面活性剂     

A carbonate controlled-addition method for amorphous calcium carbonate spheres stabilized by poly(acrylic acid)s

Stable amorphous calcium carbonate (ACC) composite particle with a size-controlled monodispersed sphere was obtained by a new simple carbonate controlled-addition method by using poly(acrylic acid) (PAA) (Mw = 5000), in which an aqueous ammonium carbonate solution was added into an aqueous solution of PAA and CaCl2 with a different time period. The obtained ACC composite products consist of about 50 wt % of ACC, 30 wt % of PAA, and H2O. Average particle sizes of the ACC spheres increased from (1.8 +/- 0.4) x 102 to (5.5 +/- 1.2) x 102 nm with an increase of the complexation time of the PAA-CaCl2 solution from 3 min to 24 h, respectively. The ACC formed from the complexation time for 3 min was stable for 10 days with gentle stirring as well as 3 months under a quiescent condition in the aqueous solution. Moreover, the ACC was also stable at 400 degrees C. Stability of the amorphous phase decreased with an increase of the complexation time of the PAA-CaCl2 solution. No ACC was obtained when the lower molar mass PAAs (Mw = 1200 and 2100) were used. In the higher molar mass case (Mw = 25 000), a mixture of the amorphous phase and vaterite and calcite crystalline product was produced. The present results demonstrate that the interaction and the reaction kinetics of the PAA-Ca2+-H2O complex play an important role in the mineralization of CaCO3.     

Temperature-swing solid-phase extraction of heavy metals on a poly(N-isopropylacrylamide) hydrogel

The feasibility of temperature-swing adsorption of heavy metals on a thermosensitive N-isopropylacrylamide (NIPA) hydrogel was examined. We have proposed a novel temperature-swing solid-phase extraction (TS-SPE) technique. First, a metal ion in an aqueous solution is complexed with an extractant. Subsequently, the metal-extractant complexes (or micelles) are adsorbed onto the NIPA hydrogel through a hydrophobic interaction above the lower critical solution temperature (LCST). Finally, the metal-extractant complexes are desorbed from the NIPA hydrogel after it is cooled below the LCST. In a model system consisting of Cu(II) ions, sodium n-dodecylbenzenesulfonate (SDBS), and NIPA hydrogel, the proposed TS-SPE technique has been successfully conducted. The following observations can be made: the amount of adsorbed Cu(II) ions increases with the increase in temperature, the maximum adsorption is attained at a temperature above the LCST, and the hydrogel adsorbs and desorbs Cu(II) ions reversibly due to the temperature-swing between 10 and 40 degrees C. The LCSTs of poly(NIPA) in aqueous SDBS solutions with/without CuCl2 and the surface tensions of their solutions suggest that the hydrophobicity of the complex Cu(DBS)2 is greater than the hydrophobicities of SDBS and DBS. In addition to the separation of heavy metals, TS-SPE is potentially applicable to cases such as the separation of biological molecules by means of metal-ion affinity.     

盐卤硼酸盐化学──ⅩⅩⅧ.氯柱硼镁石的激光拉曼光谱

本文研究了氯柱硼镁石硼酸和硼砂的晶体和它们在水溶液中的激光拉曼光谱，并与某些阴酸盐的谱图进行对比．初步提出硼氧配阴离子的聚合形式，为进行氯柱硼镁石结构分析提供实验依据．     

薄层法研究十二烷基苯磺酸钠对硝基苯/水界面电子转移的影响

用薄层法研究了阴离子表面活性剂十二烷基苯磺酸钠(SDBS)对硝基苯/水界面电子转移的影响. 实验结果表明, 随着水相中十二烷基苯磺酸钠浓度的增加, 有机相中十甲基二茂铁(DMFc)和水相中Fe(CN)₆^3-发生的界面双分子反应的阴极平台电流呈现递减趋势, 但是界面双分子反应速率常数却呈递增趋势. 这是由于阴离子表面活性剂十二烷基苯磺酸钠在硝基苯/水界面形成了修饰层, 影响了界面双电层结构. SDBS在液/液界面的吸附为Langmuir吸附.     

Preparation of glycerol dimethacrylate-based polymer monolith with unusual porous properties achieved via viscoelastic phase separation induced by monodisperse ultra high molecular weight poly(styrene) as a porogen

The preparation of polymer-based monolith capillary was examined by the use of glycerol dimethacrylate (GDMA) as monomer and monodisperse standard polystyrene (PS) solution in chlorobenzene as porogen. Poly-GDMA monoliths were prepared in situ in test tubes with standard PS having the variety of molecular weight (defined as Mw hereafter) from 50,000 to 3,840,000, and their morphology was compared to that of poly-GDMA monolith prepared in situ with a poor porogenic solvent of GDMA. According to scanning electron micrograph (SEM) observation, the structure of poly-GDMA monolith prepared in situ with toluene as a poor porogenic solvent showed a typical agglomerated globular structure, whereas the morphology of poly-GDMA monolith prepared in situ with the polymer (PS) porogenic solution was transformed from the aggregated globule form to three dimensionally (3D) continuous skeletal structure with the increase of Mw of standard PS utilized. Along with this morphological transformation or change, in the case of poly-GDMA monolith prepared in situ with ultra high Mw standard PS porogenic solution, the pore size distribution showed a sharp bimodal distribution, with one peak being located around 4 nm in the mesopore range (2-50 nm) and the other peak located around 1-2 microm in the macropore range (>50 nm), respectively. The poly-GDMA capillaries were prepared in situ with toluene, low Mw (50,000, 600,000) PS solution in chlorobenzene and the above mentioned ultra high Mw PS solution in chlorobenzene as a porogen, respectively, and measured by mu-HPLC with benzene and n-alkyl phenyl ketone as solutes for the evaluation in aqueous methanol (MeOH/H(2)O = 50/50-80/20, v/v). The permeability of capillaries prepared in situ with ultra high Mw standard PS polymer porogenic solution was much larger, compared to those of the capillaries prepared in situ with low Mw standard PS polymer porogenic solution or with toluene as porogen. On the other hand, the column efficiency was better in the case of the capillary prepared in situ with the ultra high Mw PS solution than in the latter capillaries. Those observations indicated that the ultra high Mw standard PS polymer porogenic solution should delay dynamically the phase separation of polymerizing mixture because of its visco-elasticity and should contribute to the creation of three dimensionally continuous skeletal monolith structure better to afford high separation efficiency.     

Synchronous-scan fluorescence as a selective detection method for sodium dodecylbenzene-sulfonate and pyrene in environmental samples

Synchronous-scan fluorescence spectra of dodecylbenzene sulfonic acid sodium salt (SDBS) and pyrene in aqueous solution were studied. The concentration ranges of SDBS and pyrene in aqueous solutions were 0.01-10.00 and 0.001-0.050 mg L⁻¹, respectively. The optimized wavelength differences (Δλ) of 46-55 and 38 nm were maintained between excitation and emission wavelengths for SDBS and pyrene, respectively, and they were found to be suitable for effective determination of SDBS and pyrene without mutual interferences; the peaks were observed at λ_ex 229-232 nm (SDBS) and λ_ex 335 nm (pyrene). Linear relationships between synchronous-scan fluorescence spectroscopy (SFS) intensity and concentration of SDBS or pyrene in aqueous solution (Milli-Q water, river water, and mucus of fish gills) were established. It was demonstrated that SFS method was effective for simultaneous analyses of SDBS and pyrene in mixed solution.