半微分电分析研究CTAB/n-C_4H_9OH/n-C_7H_(16)/H_2O微乳结构

制备了十六烷基三甲基溴化铵/正丁醇/正庚烷/水四组分体系的相图。讨论了 体系中助表面活性剂与表面活性剂的质量比k_m对形成微乳状液单相区域大小的影 响。以二茂铁为电活性探针用半微分电分析法测定系列微乳样品的表观扩散系数 D_(app)，从表观扩散系数D_(app)随含水量Φ_w的变化确定微乳液的微结构和结构 转变。电导率数据证实了半微分电分析的实验结果。     

不同阴/阳离子表面活性剂复配体系的缔合结构研究

测定了十二烷基磺酸钠(AS)/十六烷基三甲基溴化铵(CTAB)/正丁醇(n-C4H9OH)/正庚烷(n-C7H16)/水(H2O),十二烷基硫酸钠(SDS)/十六烷基三甲基溴化铵(CTAB)/正丁醇(n-C4H9OH)/正庚烷(n-C7H16)/水(H2O)体系的微乳液正四面体相图,并用电导法划分了AS/CTAB/n-C4H9OH/n-C7H16/H2O体系微乳液的结构(W/O,B.C.和O/W);同时研究AS/CTAB/n-C4H9OH/n-C7H16/H2O/盐类(NaCl,CaCl2或AlCl3)体系和SDS/CTAB/n-C4H9OH/n-C7H16/H2O/盐类(NaCl,CaCl2或AlCl3)体系形成中相微乳的盐宽,从中得出上述两体系中相微乳的盐宽随盐类阳离子价态的增大而的规律。     

Interaction of methemoglobin with GDA/n-C5H11OH/water assemblies

In the present paper, we studied the interaction between n-dodecylammonium alpha-glutamate (GDA)/n-C5H11OH/H2O assemblies and methemoglobin by UV-vis spectroscopy, X-ray diffraction, electron spin resonance (ESR), rheology, and freeze-fractured transmission electron microscopy (FF-TEM). It is found that W/O microemulsion forms at a lower n-pentanol content and O/W microemulsion forms at a lower water content with the addition of methemoglobin. The existence of methemoglobin reduces the hexagonal liquid crystal region, while the lamellar liquid crystal region is little changed in the presence of methemoglobin. Moreover, methemoglobin and GDA/n-C5H11OH/H2O assemblies can affect their structures and properties and the change in behavior is dependent on the content of methemoglobin and the composition and structure of the GDA/n-C5H11OH/H2O system. The relationship among the changes in the structure and properties of GDA/n-C5H11OH/H2O assemblies, the content of methemoglobin, and the composition and structure of GDA/n-C5H11OH/H2O assemblies may provide some important theoretical information for elucidation of the interaction between methemoglobin and blood cell membrane and may also be helpful for the cure of some blood diseases.     

Inhibition of Triton X-100／n-C5H11OH／H2O System on Hydrolysis of Cephanone

The hydrolysis of cephanone in Triton X-100 micelle and Triton X-100/n-C5H11OH/H2O(O/W) microemulsion were studied by means of UV-Vis absorption spectroscopy. The results show that compared with water, Triton X-100 micelle and Triton X-100/n-C5H11OH/H2O (O/W) microemulsion can inhibit the hydrolysis of cephanone. The inhibition effects of Triton X-100 micelle and Triton X-100/n-C5H11OH/H2O (O/W) microemulsion on the hydrolysis of cephanone are related to the location of cephanone in the interphases of Triton X-100 miceUes and Triton X-100/n-C5H11OH/H2O(O/W) microemulsion droplets.     

Transfer and distribution of L-tryptophan between W/O and O/W, and between W/O and bicontinuous microemulsions through the study of interphase electric properties

The influence of L-tryptophan (L-Trp) on the interphase electric properties of sodium dodecyl sulfate (SDS)/n-pentanol (n-C(5)H(11)OH)/water (H(2)O) system was studied by the method of AC impedance, and the distribution of L-Trp between the microemulsion phases with different structures in SDS/n-C(5)H(11)OH/H(2)O system was determined by UV-vis spectroscopy. The results show that L-Trp transfers from the lower phase (O/W or bicontinuous) to the upper phase (W/O), and that a small amount of SDS transfers from the upper phase to the lower phase correspondingly with the increase of the total SDS content at a constant weight ratio of n-C(5)H(11)OH/H(2)O=50/50 and a total L-Trp concentration of 1.0 x 10(-4) mol/L. In addition, the concentrations of L-Trp in both the upper and lower phases increase, but the SDS content decreases slightly in the upper phase and increases appreciably in the lower phase with the increase of the total L-Trp concentration at a constant total content of SDS. The interphase capacitance and the interphase charge-transfer current of the system increase, but the interphase resistivity decreases.     

Tween80/BmimPF6/醇/甲苯体系的相行为

以环境友好型的Tween80为表面活性剂, 以醇(乙醇、正丁醇、正己醇、正辛醇、正癸醇和异戊醇)为助表面活性剂, 对离子液体1-丁基-3-甲基咪唑六氟磷酸盐(bmimPF6)和甲苯进行了微乳化实验, 绘制了不同条件下Tween80离子液体的微乳体系的拟三元相图, 考察了醇的种类、含量对单相微乳区的影响, 并用电导法研究了在乙醇为助表面活性剂情况下, 单相微乳区的结构转变. 结果表明, 当醇(异戊醇)固定时, 随着表面活性剂/醇的质量比增加, 单相微乳区的面积逐渐增大; 不同链长的直链醇对单相微乳区的面积影响与该醇在离子液体中的溶解情况有关, 单相微乳区的面积随着直链醇链长的增加而越小; 当乙醇作助表面活性剂时, 所得到的单相微乳区的面积最大, 且单相微乳区存在着O/IL(oil-in-ionic liquid)、双连续相和IL/O(ionic liquid-in-oil)三种微结构. 尤其对离子液体微乳体系的电导随油的含量的增加而最初增大的现象进行了解释, 这一现象是由于油主要起到减少离子液体中离子对或离子的积聚, 提高带电离子淌度的作用.     

DEA与SDS/n-C5H11OH/H2O微乳液的相互作用

以循环伏安法研究了N,N-二乙基苯胺（DEA）与十二烷基硫酸钠（SDS）/正戊醇（n-C5H11OH）/H2O体系O/W和W/O结构微乳液的相互作用.结果表明,DEA在SDS/n-C5H11OH/H2O体系微乳液中有两种定位方式:其一,DEA分子在微乳液液滴膜相中定位于表面活性剂和助表面活性剂的极性基团附近;其二,DEA分子在微乳液液滴膜相中定位于表面活性剂疏水基团一侧.两种定位的分布与微乳液的结构和组成相关.     

Microstructure and structural transition in microemulsions stabilized by aldonamide-type surfactants

Significant efforts were undertaken to characterize the microstructure and structural properties of water-in-oil (w/o), oil-in-water (o/w), and bicontinuous (bc) microemulsions composed of N-alkyl-N-methylgluconamides (n-alkyl = n-C(12)H(25), n-C(14)H(29), n-C(16)H(33)) and n-alcohols (ethanol, n-propanol, n-butanol) or iso-alcohols (iso-propanol, iso-butanol) as cosurfactants, as well as iso-octane and water. The internal structure of so created four-component system was elucidated by means of an analysis of isotropic area magnitudes in phase diagrams and conductivity measurements. Dynamic light scattering (DLS) measurements provided the microemulsion size and polydispersity. Polarity and viscosity of microemulsion microenvironment were acquired by means of electron paramagnetic resonance (EPR), UV-vis absorption spectroscopy (in the case of w/o droplets), and steady-state fluorescence (SSF) (in the case of o/w droplets). The results show that both the surfactant and the cosurfactant types affect the shape and extent of microemulsions. The size of droplets depends strongly on the type of examined microemulsion and the type of cosurfactant (linear or brunched) but is almost independent of the length of the surfactant alkyl chain. The size of microemulsion droplets ranges from 8.1 to 22.6 nm and from 3.7 to 14.3 nm respectively, for o/w and o/w microemulsions, making them good candidates for both template-based reactions and household components solubilizing media.     

微乳液相行物为结构的研究:氯化钠/水/十二烷基硫酸钠/正丁醇/正辛烷系统

本文报道NaCl/H2O/SDS/n-C4H90H/n-C8H18系统在WC4H9OH/WSDS=4时, 不同盐浓度下的相图, 结果表明, 卤水中NaCl浓度的增大导致这个系统相分裂区域扩在, 并在一定范围内产生三相共存和出现中相微乳液。中相微乳液的密度, 粘度, 电导率和折光率与最佳盐浓度以及微观物型转变有对应关系, 红外光谱测定表明, 油相中氢键的缔合强度比中相微乳液显著增强。     

Structure Properties for SDS/ n-C4H9OH/ H20 Microemulsion

The structure properties of isotropic solution are studied with the electrochemical methods for SDS/ n-C₄H ₉OH/H ₂0 system. The measurements of the conductivity show that the isotropic range in the phase diagram is composed of three areas with different structures: OAV structure connecting with water corner, bicontinuous structure in the middle area and W/ O structure connecting with n-C ₄H ₉OH corner. This result has been proved by the measurements of eletrochemical diffusion coefficient. The middle phase microemulsion shows bicontinuous structure. The solubilization fraction of n-C ₄H ₉OH in SDS micelle is about 0.98.     

维生素C在CTAB／n—C5H11OH／H2O体系中的增稳作用

在ＣＴＡＢ／ｎ－Ｃ５Ｈ１１ＯＨ／Ｈ２Ｏ体系中，维生素Ｃ存在于Ｏ／Ｗ、Ｗ／Ｏ液滴的内侧，Ｃ５Ｈ１１ＯＨ则存在于液滴的外侧，阻碍渗透进入膜相中的水与维生素Ｃ的接触，从而在幅芳降低了维生素Ｃ在水体系中的氧化程度，提高了其稳定性，Ｏ／Ｗ、Ｗ／Ｏ微乳液对维生素Ｃ分子艇的机理亦从层状液晶对其增稳作用中得到证明。     

青霉素G钾盐在CTAB/n-C5H11OH/H2O体系中的水解及 其抑制

应用紫外光谱法研究了青霉素G钾盐在十六烷基三甲基溴化铵(CTAB)/n-C5H11OH/H2OO/W微乳液中的水解反应。结果表明,CTAB/n-C5H11OH/H2OO/W微乳液对青毒素G钾盐的水解具有抑制作用,此结果与此O/W微乳液能降低青霉素G钾盐(Pen-K)分子极性基团的电荷密度,减少Pen-K所处微环境的质子浓度有关。     

阴离子型微乳液的电导行为及其溶液结构

根据电导测量,研究了属于W/O→双连续→O/W一类微乳液的十二烷基硫酸钠(SDS)/正丁醇/辛烷/水体系的溶液结构.并探讨了表面活性剂离子对微乳液导电行为的贡献,以及表面活性剂与助表面活性剂含量、油含量对微乳液溶液结构的影响.微乳液的导电行为在W/O子区域中主要是由于SDS阴离子和在O/W子区域中是由于Na离子的影响.在双连续区(IZ)中SDS阴离子和Na阳离子都能影响导电行为增加表面活性剂含量有助于形成O/W微乳液,而助表面活性剂和油含量都增加有助于于形成W/O微乳液.     

The Catalysis of Sodium Dodecyl Sulfate／1-Pentanol／Water W／O Microemulsion on the Photoisomerization of trans-Stilbene

The photoisomerization of trans-stilbene was studied in the water in oil (W/O) microemulsion formed by SDS (sodium dodeeyl sulfate), n-C5H11OH (1-pentanol) and H2O. The experimental results show that after 2-minute UV-irradiation, the yield of cis-stilbene is higher in W/O mieroemulsion than in homogeneous solvent-n-C5H11OH.     

O／W微乳液对Zn（Ⅱ）—PAR的增敏作用

研究了十六烷基三甲基溴化铵９ＣＴＭＡＢ）／正戊醇／正庾烷／水组成的阳离子型Ｏ／Ｗ微乳液对以４－（２－吡啶偶氮）间苯二醇（ＰＡＲ）为显色剂，光度法测定锌的增敏作用。结果，方法简便、快速，与相应的胶束体系为介质比较，提高了测定灵敏度，结果可靠。通过对显色剂在水－微乳液和在水－胶束相中分配系数的测定，初步了微乳液的增敏作用机理。     

维生素C对表面活性剂体系相行为的影响

维生素Ｃ（ＶＣ）能提高表面活性剂十六烷基三甲基溴化铵（ＣＴＡＢ）在水中的溶解度,具有助溶作用;且能提高ｎ－Ｃ５Ｈ１１ＯＨ在Ｏ／Ｗ微乳液中的增溶量和水在Ｗ／Ｏ微乳液中的增溶量,Ｏ／Ｗ与Ｗ／Ｏ微乳液区域同时扩大,具有助溶－增溶作用。ＶＣ的助溶作用与助溶－增溶作用均具有一定的选择性,只对阳离子表面活性剂ＣＴＡＢ体系有效,ＶＣ助溶－增溶作用的机理是同时增加Ｗ／Ｏ和Ｏ／Ｗ微乳液的稳定性和层状液晶向双连续结构     

Location of phenothiazine in sodium dodecyl sulfate/n-pentanol/water microemulsions

The location of phenothiazine (PTZ) in sodium dodecyl sulfate (SDS)/n-pentanol (n-C5H11OH)/water microemulsions is studied by cyclic voltammetry at a Pt electrode. The results indicate that PTZ exists in the membrane phase of microemulsion droplets with its N atom or S atom toward the polar head of the surfactant. In addition, we examine the effect of the compositions and structures of the microemulsions, pH, temperature, and the inorganic salts on the location distribution for PTZ in the membrane phase of the microemulsions. The results show that the location distribution for PTZ in the membrane phase of the microemulsions is mainly dependent on the hydrogen bond between the -NH in PTZ and n-pentanol (or the -SO4- of SDS) and on the electrostatic interaction between the S atom (or N atom) in PTZ and the polar head of SDS.     

Structures, electron affinities, and harmonic vibrational frequencies of the simplest alkyl peroxyl radicals and their anions

The molecular structures and electron affinities of the R-OO/R-OO(-) (R = CH3, C2H5, n-C3H7, n-C4H9, n-C5H11, i-C3H7, t-C4H9) species have been determined using seven different density functional or hybrid Hartree-Fock density functional methods. The basis set used in this work is of double-zeta plus polarization quality with additional diffuse s-type and p-type functions, denoted DZP++. The geometries are fully optimized with each density functional theory method. Harmonic vibrational frequencies were found to be within 3.1% of available experimental values for most functionals. Two different types of the neutral-anion energy separations reported in this work are the adiabatic electron affinity and the vertical detachment energy. The most reliable adiabatic electron affinities obtained at the DZP++ BP86 level of theory are 1.150 (CH3OO), 1.124 (C2H5OO), 1.146 (n-C3H7OO), 1.173 (n-C4H9OO), 1.184 (n-C5H11OO), 1.145 (i-C3H7OO), and 1.114 eV (t-C4H9OO). Compared with the experimental values, the average absolute error of the BPW91 method is 0.05 eV.     

Novel superstructure of nondiscoid mesogens: uneven-parallel association of half-disk molecules, 3,4,5-trialkoxybenzoic anhydrides, to a columnar structure and its one-directionally geared interdigitation

Compact and simple nondiscoid mesogens, trialkoxybenzoic anhydrides 2-11 ((RO)(3)C(6)H(2)-CO-O-CO-C(6)H(2)(OR)(3), R = C(2)H(5), n-C(3)H(7), n-C(4)H(9), n-C(6)H(13), n-C(8)H(17), n-C(10)H(21), n-C(12)H(25), n-C(14)H(29), n-C(16)H(33), and (S)- and (R)-3,7-dimethyloctyl) were designed and synthesized, and their superstructures were investigated by polarized light microscopy, differential scanning calorimetry, calculation (MM2 and AM1), circular dichroism spectroscopy, and X-ray diffraction. As the result, in the cases of 5-9 and 11, the half-disk molecules in the liquid crystal phases were self-assembled by the dipole-dipole interaction between their carbonyl groups to a column in which the molecules were piled up in an alternately antiparallel manner, and the columns were interdigitated each other. The observed interdigitations were highly directional in the perpendicular direction to the column axis. In the case of compound 11 which has (S)- or (R)-3,7-dimethyloctyl groups, a helical organization of the molecules in the column was estimated from the peaks in the circular dichroism spectra. This is the first report of a one-directionally interdigitated columnar phase, and these compounds are the first liquid crystalline acid anhydrides. It was demonstrated that a -CO-O-CO- moiety is useful as a polar junction in liquid crystalline compounds.     

铜(Ⅱ)-硫氰酸盐-乙基紫-微乳液分光光度法测定钢样中的微量铜

在非离子型微乳液(OP/n-C5H11OH/n-C7H16/H2O)存在下,Cu2+与硫氰酸盐形成络阴离子[Cu(SCN)4]2-,在pH 3.6乙酸盐缓冲溶液中,该络阴离子再与乙基紫(EV)形成吸附型离子络合物,该络合物的组成为[Cu(SCN)4]2-:EV=1:2,最大吸收波长为660nm,表观摩尔吸光系数ε660为1.08×l05L.mol-1.cm-1,Cu2+含量在1.7～18.0μg/50 mL范围内符合比尔定律,检出限为0.5μg/50 mL,用该方法测定了钢中的铜,相对标准偏差小于2%。