甲基丙烯酸3-三甲氧基硅丙酯/苯乙烯细乳液共聚合过程中的水解及缩合反应

研究了甲基丙烯酸3-三甲氧基硅丙酯(MPS)和苯乙烯(St)细乳液聚合过程中的水解及缩合反应.用气相色谱仪测定聚合过程中水解产物——甲醇的含量来研究MPS的水解度.MPS分子主要在细乳液液滴与水的界面以及乳胶粒与水的界面上发生水解反应.MPS和St比例、介质pH值、乳化剂用量、引发剂类型和用量都会影响MPS的水解程度.缩合产物用29Si固态核磁共振表征,中性条件下,缩合反应受到抑制,在高MPS/St比例的体系中也只生成少量缩合产物.酸性和碱性条件下,缩合产物量均增加,但碱性条件下,体系中仍有一定数量未缩合的硅氧烷存在,这与细乳液聚合独特的液滴成核机理及聚合过程中较少液滴间物质交换有关.     

牛血清白蛋白在气-液界面上的吸附行为及其与含芘手性探针分子的相互作用研究

利用表面压力-时间曲线对牛血清白蛋白(BSA)在气液界面上的吸附行为和对手性探针分子D/L-[4-(1-芘基)]丁酰基-苯丙氨酸(PPs)的界面手性识别, 以及由此引起的气液界面上BSA的构象变化进行了研究. 结果表明, 界面上形成的稳定单层膜经历了漫长的构象调整过程; BSA的表面压力的变化说明其对亚相中的探针分子很强的浓度依赖性和对手性分子的区分能力. 在较高的PLP和PDP探针分子浓度下, BSA的成膜性均受到了很大抑制, 但较低的PLP和PDP探针分子浓度却转而对BSA成膜有利; 与PLP相比, PDP能更有效地与BSA在界面结合, 其复合膜的稳定性更好.     

气/液界面Langmuir单分子膜的原位拉曼光谱

提出了一种原位测量气/液界面Langmuir单分子膜拉曼光谱的新方法, 即利用SERS技术, 通过降低亚相的方法来获得气/液界面Langmuir单分子膜的原位拉曼光谱. 利用这种方法, 用原位拉曼光谱测量系统得到了信噪比较好的十八胺及二棕榈酰磷脂酰胆碱单分子膜的拉曼光谱, 在分子水平上获取了单分子膜中的结构信息.     

分子动力学模拟研究荧光分子芘在磺基甜菜碱胶束中的增溶

采用分子动力学模拟研究了荧光分子芘在磺基甜菜碱两性表面活性剂聚集体中的增溶现象．结果表明,芘分子自发地自溶液中增溶进入胶束疏水内核的栅栏层区域．当胶束溶液中芘分子的局部浓度增大时,两个芘分子可以同时增溶进胶束的栅栏层区域,此时两个芘分子形成π-π共轭堆积的激发态络合物．但是由于荧光分子之间的弱兀．兀相互作用,激发态络合物在胶束中是不稳定的,表现为两个芘分子的多次结合和分离．模拟表明,分子动力学方法可以在分子水平上研究荧光探针分子在表面活性剂胶束中的增溶位点,解释荧光分子在胶束中的动力学现象．     

疏水作用对光化学和光物理过程的影响 Ⅶ.芘基烷基酮的荧光光谱及其在不良溶剂中的簇集

溶剂的极性对芘基烷基酮的单体荧光和激基缔合物荧光有很大影响,在非极性溶剂中单体荧光很弱,随着溶剂极性增大,单体荧光增强,单体荧光和激基缔合物荧光明显红移。利用芘基烷基酮荧光的这些性质研究了长链分子在二甲基亚砜-水(DMSO-H₂O)中的簇集现象。在浓度非常低的情况下,长链芘基烷基酮发射激基缔合物荧光,单体荧光也明显蓝移,表明芘基烷基酮形成了簇集体。长链饱和烷烃和芘基烷基酮发生共簇集,簇集体内的极性比环己烷的极性稍大。     

杯芳烃-卟啉化合物及其金属配合物的Langmuir-Blodgett膜研究

通过对杯芳烃-卟啉化合物及其锌、钯配合物LB膜的表面压-表面积等温线、紫外可见光谱和傅里叶变换红外光谱的检测,研究了它们在气/液界面和Langmuir-Blodgett膜中的性质,并用量子力学方法优化了杯芳烃-卟啉化合物的构型.结果表明,成膜时3种化合物分子中卟啉环都倾斜地排列在亚相表面,且卟啉环间存在π-π相互作用.连接杯芳烃和卟啉之间的碳氢链在膜性质中起着重要的作用,杯芳烃-卟啉化合物分子中这种碳氢链的有序性小于其锌、钯配合物分子中的这种碳氢链有序性.     

酸性有机磷类萃取剂单分子膜的气-液界面行为:亚相pH和铺展溶剂的影响

液-液两相萃取过程中,有机磷类萃取剂分子的界面行为决定了其以何种形式参与到界面萃取反应中.为了阐明萃取剂分子界面行为的变化特点,采用Langmuir单分子膜技术研究了单分子膜中P507分子在气-液界面的吸附和聚集行为随亚相pH、有机溶剂极性的变化.通过测定表面压-分子面积等温线,并采用界面红外反射吸收光谱（IRRAS）分析表征气-液界面P507分子间相互作用,结果发现,以正己烷作铺展溶剂时,随亚相pH的降低,P507单分子膜质子化程度提高,P507分子极性端水化能力削弱,分子间相互作用增强,单分子膜中形成含有分子间氢键的聚集体.但采用极性有机溶剂（二氯甲烷和氯仿）铺展P507单分子膜,膜内P507分子界面聚集状态发生变化.铺展溶剂极性增强,单分子膜内会含有更多极性端水化能力强的P507分子单体,并且亚相pH降低,单分子膜不会出现类似正己烷条件下的π-A曲线收缩和P-O-H基团峰位红移现象.这证实了有机铺展溶剂极性可以改变P507单分子膜中分子界面存在形式和聚集状态.本工作为深入理解溶剂萃取过程中水油两相界面处酸性有机磷类萃取剂分子的聚集行为变化及其对界面反应活性的影响机制奠定了基础.     

藻胆蛋白的Langmuir-Blodgett膜——Ⅰ.R-藻红蛋白单分子膜及蛋白构象变化的研究

测定了R-藻红蛋白(R-PE)在气/液界面上的表面压-面积曲线(tt-A等温线),结果表明R-PE具有很好的成膜性能,且由n-A等温线求得的单分子占有面积与R-PE以盘状形态“平躺”于液面上时的分子占有面积相同。R-PELB膜的透射电子显微镜(TEM)图象和椭圆偏振关于R-PE单分子膜厚度的测定,说明R-PE分子在基片上的取向是其盘平面与基片表面平行。根据这些依据,提出了R-PE单分子膜的结构。将R-PE在气/液界面上形成的单分子膜在适当表面压下用LB技术转移到基片上,测得了蛋白累积单分子膜的吸收及荧光光谱,R-PE单分子膜的吸收和荧光光谱与其在水溶液中无显著差别。膜的CD光谱与R-PE水溶液的CD光谱比较说明,当R-PE成膜后其二级结构发生了变化,即蛋白的p-折叠片构象组分增加。     

疏水作用对光化学和光物理过程的影响 Ⅱ.不良溶剂中长链水杨酸烷基酯的簇集和荧光光谱的变化

前文报道了长链β-萘甲酸烷基酯在不良溶剂中形成激基缔合物,为长链分子在不良溶剂中发生簇集提供了新的证据.本文报道证明长链分子在不良溶剂中发生簇集的另一个实验事实.长链水杨酸烷基酯在二甲基亚砜-水(DMSO-H_2O)和乙二醇-水(EG-H_2O)混合溶剂中的荧光光谱分布以及荧光量子产率与短链水杨酸烷基酯的显著不同,这些差别可以用长链分子发生簇集来加以解释.     

对-三氰基乙烯基-N,N-二烷基苯胺的分子内光致电荷分离

本文以对-三氰基乙烯基-N,N-二烷基苯胺为模型化合物,开展共轭π电子体系分子内光致电子转移及电荷分离的研究。通过吸收光谱和荧光光谱探讨了这类分子的电荷分离作用以及在DMSO-H_2O中的簇集作用。     

Fluorescent probe as reporter on the local structure and dynamics in hydrolysis-condensation process of organotrialkoxysilanes

To get some information on the aggregation behaviors of the products derived from different organotrialkoxysilanes, the hydrolysis-condensation processes of some organotrialkoxysilanes have been examined by means of pyrene as fluorescent probe. The organotrialkoxysilanes used in the research were n-octadecyltri-methoxysilane (ODTMS), n-octyltrimethoxysilane (OTMS), 3-glycidoxypropyltrimethoxysilane (GTMS), 3-methacryloxypropyltrimethoxysilane (MAPTMS), and propyltrimethoxy-silane (PTMS). The results show that pyrene as fluorescence probe can respond sensitively not only to the organization state of the hydrolysates but also to the change in the organization state during the condensation process. The organization states during the hydrolysis and condensation can be explained in terms of structures of the products. In the initial stage, the silanols with long organic chains are amphiphilic molecules, and such nature of the silanols can be compared to that of a surfactant. Therefore, the excimer emission of pyrene is extremely obvious because of such silanols being prone to form aggregates. In the case of silanols having short alkyl groups or epoxy groups, these silanols homogenously disperse in solution, which results in the appearance of an only monomer emission of pyrene. In the late stage, the fluorescence behavior of pyrene is also sensitive to structural evolution of the silicates. The fluorescence spectra of pyrene during the condensation of the silanols with short alkyl groups or epoxy groups are almost in silence, indicating that the condensation products, with a low condensation degree, homogeneously disperse in solution. For the silanols with long hydrophobic substituents in different lengths, the changes in fluorescence spectra of pyrene during the condensation are varied. Commonly, the excimer emission is noticeable, implying that the condensation products with high condensation degree inhomogenously disperse in solution. However, the relative excimer/monomer fluorescence intensity is alkyl chain-length dependent. The longer alkyl chains in the condensation products result in the appearance of the obvious excimer emission. These phenomena imply that the condensation degree of the products increases with the length of the alkyl chains. Additionally, the distorted spectrum of pyrene appears in the case of the organotrialkoxysilanes with side chain substituent, illustrating that the steric hindrance between the substituents can be monitored by fluorescence of pyrene. All these results are verified by the fluorescence-quenching measurements. The approach in the present study gives new insights into the local structure and dynamics in hydrolysis-condensation process of organotrialkoxysilanes and emphasizes the influence of the self-assembling behavior.     

Pyrene fluorescence at air/sodium dodecyl sulfate solution interface

The dependence of pyrene fluorescence spectra on the concentration of sodium dodecyl sulfate (SDS) was observed, where the solution was prepared from water saturated with pyrene. The values of the I(1)/I(3) ratio from the bulk solution and from the upper meniscus region in an optical cell were similar but decreased rapidly around the critical micelle concentration (cmc) of SDS, indicating that pyrene molecules preferred to be solubilized in the micelles having a lower dielectric constant. The fluorescence intensity of the excimer indicated the concentration of pyrene molecules at the air/solution interface or the surface activity of pyrene molecules. In addition, the intensity from the meniscus region is much larger than that from the bulk at the concentrations below the cmc, whereas there was no difference in the intensity between the bulk and the meniscus above 8 mmol dm(-3) of SDS. The analysis of the fluorescence intensity from the excimer strongly suggests the presence of molecular aggregates that are favorable to the pyrene molecules just like the micelles in the bulk, making them less movable.     

Spectroscopic probes of the quasi-liquid layer on ice

Raman spectra of the water OH-stretch region were acquired at air-ice and air-water interfaces at a glancing angle, which allowed observation of surface characteristics. The shapes of the OH-stretch bands indicate that the environment at the air-ice interface is different from that at the air-water interface and from that seen in bulk water. Water spectra measured at the surface of dodecane under low relative humidity indicate that this method is sensitive to fewer than 50 monolayers of water. Changes in the local environment of the surfacial water molecules may be induced by the presence of different solute species, giving rise to changes in the shape of the band. Dissolved sodium chloride disrupts hydrogen bonding in liquid water and has the same effect at the air-ice interface. However, when either HCl or HNO(3) is adsorbed from the gas phase onto an ice surface, the opposite effect is seen: Their presence appears to increase the extent of hydrogen bonding at the ice surface. At the same time, shifts in the laser-induced fluorescence spectra of acridine, a fluorescent pH-probe present at the air-ice interface, indicate that dissociation of acids occurs there. These observations suggest that the formation of hydronium ions at the air-ice interface enhances the hydrogen bonding of surfacial water molecules.     

Tunable pK of amino acid residues at the air-water interface gives an L-zyme (langmuir enzyme)

Various amino acid-carrying amphiphiles were synthesized, and the pK values of the attached amino acid residues were investigated at the air-water interface and in aqueous vesicles using pi-A isotherm measurements, (1)H NMR titration, and IR spectroscopy in reflection-adsorption mode. The epsilon-amino group of the Lys residue embedded at the air-water interface displays a significant pK shift (4 or 5 unit) compared with that observed in bulk water, while the pK shift in aqueous vesicles was not prominent (ca. 1 unit). Moreover, pK values of the amino acids at the air-water interface can be tuned simply by control of the subphase ionic strength as well as by molecular design of the amphiphiles. A simple equation based on the dominant contribution by the electrostatic energy to the pK shift reproduces well the surface pressure difference between protonated and unprotonated species, suggesting a reduction in the apparent dielectric constant at the air-water interface. Hydrolysis of a p-nitrophenyl ester derivative was used as a model reaction to demonstrate the use of the Lys-functionalized monolayer. Efficient hydrolysis was observed, even at neutral pH, after tuning of pK for the Lys residue in the monolayer, which is a similar case to that occurring in biological catalysis.     

Effect of the air-water interface on the structure of lysozyme in the presence of guanidinium chloride

We report observations of the changes in the surface structure of lysozyme adsorbed at the air-water interface produced by the chemical denaturant guanidinium chloride. A primary result is the durability of the adsorbed surface layer to denaturation, as compared to the molecule in the bulk solution. Data on the surface film were obtained from X-ray and neutron reflectivity measurements and modeled simultaneously. The behavior of lysozyme in G.HCl solutions was determined by small-angle X-ray scattering. For the air-water interface, determination of the adsorbed protein layer dimensions shows that at low to moderate denaturant concentrations (up to 2 mol L(-1)), there is no significant distortion of the protein's tertiary structure at the interface, as changes in the orientation of the protein are sufficient to model data. At higher denaturant concentrations, time-dependent multilayer formation occurred, indicating molecular aggregation at the surface. Methodologies to predict the protein orientation at the interface, based on amino acid residues' surface affinities and charge, were critiqued and validated against our experimental data.     

Comparison between inhomogeneous adsorption of charged surfactants on air-water and on solid-water interfaces by self-consistent field theory

We use a realistic molecular model to study the interfacial behavior of hydrocarbon sulfate surfactants within a self-consistent field model and consider the adsorption both at the air-water interface and at a hydrophobic solid-water interface. We focus on the structural properties of the hemimicelles at the critical interface aggregation concentration (CIAC) for the air-water system and the critical surface aggregation concentration (CSAC) for the solid-water system. The major difference between the two systems is that the liquid interface is penetrable but the solid surface is intrinsically impenetrable for the molecular species. At the LG interface the hemimicelles have a lens shape with their centers of mass positioned slightly toward the aqueous side and feature an aspect ratio of approximately 2, with the long dimension parallel to the interface. Hemimicelle formation occurs below a critical (interfacial) area per molecule and above a critical surface pressure depending on tail length and ionic strength. Hemimicelles are not expected at air-water interfaces for a surfactant with a tail length ( t) lower than 15 CH2 units. In contrast, at a hydrophobic solid the formation of laterally inhomogeneous micelles even takes place for surfactants with the tail length as short as t = 12. This difference is attributed to the screening of the lateral interactions in the vapor phase. The shape of surface hemimicelles is caplike (or half-lens) with an aspect ratio lower than 2 and the long dimension parallel to the solid surface. The tail length, the ionic strength, the adsorption energies, and the surfactant concentration have an effect on the surface micelle properties such as the aggregation number and size and shape.     

Interactions between a lipase and charged surfactants--a comparison between bulk and interfaces

The interaction between a charged surfactant and a lipase has been investigated by several methods. Interactions in aqueous bulk phase was studied by NMR and by microcalorimetry. Surface tension and neutron reflectivity were used for studies at the air-water interface. Interactions at the interface between a hydrophobic solid surface and water was investigated by ellipsometry. The results obtained are as follows. The cationic surfactant, tetradecyltrimethylammonium bromide (iodide in the NMR experiments), showed strong interaction at the air-water and the hydrophobic solid-water interfaces but no clear indication of an interaction in bulk phase was seen. The anionic surfactant showed no interaction with the lipase neither at the interfaces, nor in bulk. The difference in behavior of the system cationic surfactant-lipase in bulk and at the interfaces may be due to the change in enzyme conformation that is known to occur at interfaces between water and an apolar phase.     

Aggregation behaviors of gemini nucleotide at the air-water interface and in solutions induced by adenine-uracil interaction

Cationic gemini surfactants having nucleotides as counterions (called nucleo-gemini hereafter) were synthesized and their aggregation behavior at air-water surfaces as well as in bulk solutions were studied. Fluid solutions of these nucleo-gemini surfactants show transitions to hydrogels upon addition of complementary nucleoside bases or other nucleo-gemini surfactants having complementary bases as counterions. The FTIR-ATR measurements show that the carboxylate groups of uridine form hydrogen bonds with the amine groups of adenosine. The aggregation behavior was also confirmed at the air-water interface by Brewster angle microscopy as well as surface pressure measurements; the monolayer of a gemini nucleotide was observed to undergo a transition to multilayers when nucleosides with complementary bases were added into the subphase. Isotherm curves of surface pressure monitored in parallel show a decrease in molecular area upon addition of such nucleosides.     

Interfacial microgels formed by oppositely charged polyelectrolytes and surfactants. 1. Influence of polyelectrolyte molecular weight

The synergistic adsorption and complexation of polystyrene sulfonate, PSS (a highly charged anionic polyelectrolyte), and dodecyltrimethylammonium bromide, C12TAB (a cationic surfactant), at the air-water interface can lead to interfacial gels that strongly influence foam-film drainage and stability. The formation and characteristics of these gels have been studied as a function of PSS molecular weight by combining surface tension, ellipsometry, and foam-film drainage experiments. Simultaneously the solution electromotive force has been measured to track the polymer-surfactant interactions in the bulk solution. It has been found that there is a critical molecular weight for surface gelation as well as for bulk precipitation and aggregation. Furthermore, we show that for the lowest molecular weights, PSS adsorbs with C12TAB in compact layers at the air-water interface. In particular, for mixtures of C12TAB with the monomer compound of the PSS repeat unit (e.g. Mw = 208), interfacial complexation is found to be similar to that of catanionic mixtures (mixtures of surfactants of opposite charge).     

Theoretical consideration on preparing silver particle films by adsorbing nanoparticles from bulk colloids to an air-water interface

In our previous paper, a method for preparing enormous surface-enhanced Raman scattering (SERS) active substrates through the aggregation of silver particles trapped at an air-water interface was reported. Here, further efforts were devoted to investigate the origin of assembling silver particle films by adsorbing nanoparticles from bulk colloids to the air-water interface. It was revealed that it is thermodynamically favorable for a colloidal particle in bulk colloids to adsorb to the air-water interface; however, a finite sorption barrier between it and the nearby particles usually restrains the adsorption process. When an electrolyte such as KCl, which is commonly used as an activating agent for additional SERS enhancement, was added into silver colloids, it largely reduced the sorption barrier. Thus, silver nanoparticles can break through the sorption barrier, pop up, and be trapped at the air-water interface. The trapped silver particles are more inclined to aggregate at the interface than those in bulk colloids due to the increase of van der Waals forces and the reduction of electrostatic forces. The morphology of the as-prepared silver particle films was characterized by scanning electron microscope, and their SERS activity was tested using NaSCN as a probe molecule. The surface enhancement of the silver particle films is about 1-2 orders of magnitude higher compared with that of silver colloids, because most of the silver particles in the films are in the aggregation form that provides enormous SERS enhancement. Furthermore, the stability of such type of films is much better that of colloid solutions.