绿色离子液体介质中有序分子聚集体构建

 离子液体具有很多物理、化学特性且环境友好,被广泛应用于化学、化工、材料、生物、环境等领域。评述了非质子化离子液体、质子化离子液体等作为绿色介质在构建胶束、溶致液晶、囊泡、微乳液和乳状液等有序分子聚集体方面的研究进展。简述了两亲分子和有序分子聚集体的基本概念、分类及发展,对各种离子型表面活性剂、非离子型表面活性剂及聚合物类表面活性剂在非质子化离子液体、质子化离子液体及水溶液中自组装有序分子聚集体的类型、结构、影响因素、驱动力、机制等进行对比分析,并对其应用领域和研究趋势进行展望。     

Biomimetic self-templating supramolecular structures

In nature, helical macromolecules such as collagen, chitin and cellulose are critical to the morphogenesis and functionality of various hierarchically structured materials. During tissue formation, these chiral macromolecules are secreted and undergo self-templating assembly, a process whereby multiple kinetic factors influence the assembly of the incoming building blocks to produce non-equilibrium structures. A single macromolecule can form diverse functional structures when self-templated under different conditions. Collagen type I, for instance, forms transparent corneal tissues from orthogonally aligned nematic fibres, distinctively coloured skin tissues from cholesteric phase fibre bundles, and mineralized tissues from hierarchically organized fibres. Nature's self-templated materials surpass the functional and structural complexity achievable by current top-down and bottom-up fabrication methods. However, self-templating has not been thoroughly explored for engineering synthetic materials. Here we demonstrate the biomimetic, self-templating assembly of chiral colloidal particles (M13 phage) into functional materials. A single-step process produces long-range-ordered, supramolecular films showing multiple levels of hierarchical organization and helical twist. Three distinct supramolecular structures are created by this approach: nematic orthogonal twists, cholesteric helical ribbons and smectic helicolidal nanofilaments. Both chiral liquid crystalline phase transitions and competing interfacial forces at the interface are found to be critical factors in determining the morphology of the templated structures during assembly. The resulting materials show distinctive optical and photonic properties, functioning as chiral reflector/filters and structural colour matrices. In addition, M13 phages with genetically incorporated bioactive peptide ligands direct both soft and hard tissue growth in a hierarchically organized manner. Our assembly approach provides insight into the complexities of hierarchical assembly in nature and could be expanded to other chiral molecules to engineer sophisticated functional helical-twisted structures.     

Free-standing mesoporous silica films with tunable chiral nematic structures

Chirality at the molecular level is found in diverse biological structures, such as polysaccharides, proteins and DNA, and is responsible for many of their unique properties. Introducing chirality into porous inorganic solids may produce new types of materials that could be useful for chiral separation, stereospecific catalysis, chiral recognition (sensing) and photonic materials. Template synthesis of inorganic solids using the self-assembly of lyotropic liquid crystals offers access to materials with well-defined porous structures, but only recently has chirality been introduced into hexagonal mesostructures through the use of a chiral surfactant. Efforts to impart chirality at a larger length scale using self-assembly are almost unknown. Here we describe the development of a photonic mesoporous inorganic solid that is a cast of a chiral nematic liquid crystal formed from nanocrystalline cellulose. These materials may be obtained as free-standing films with high surface area. The peak reflected wavelength of the films can be varied across the entire visible spectrum and into the near-infrared through simple changes in the synthetic conditions. To the best of our knowledge these are the first materials to combine mesoporosity with long-range chiral ordering that produces photonic properties. Our findings could lead to the development of new materials for applications in, for example, tuneable reflective filters and sensors. In addition, this type of material could be used as a hard template to generate other new materials with chiral nematic structures.     

Amplification of chirality in two-dimensional enantiomorphous lattices

The concept of chirality dates back to 1848, when Pasteur manually separated left-handed from right-handed sodium ammonium tartrate crystals. Crystallization is still an important means for separating chiral molecules into their two different mirror-image isomers (enantiomers), yet remains poorly understood. For example, there are no firm rules to predict whether a particular pair of chiral partners will follow the behaviour of the vast majority of chiral molecules and crystallize together as racemic crystals, or as separate enantiomers. A somewhat simpler and more tractable version of this phenomenon is crystallization in two dimensions, such as the formation of surface structures by adsorbed molecules. The relatively simple spatial molecular arrangement of these systems makes it easier to study the effects of specific chiral interactions; moreover, chiral assembly and recognition processes can be observed directly and with molecular resolution using scanning tunnelling microscopy. The enantioseparation of chiral molecules in two dimensions is expected to occur more readily because planar confinement excludes some bulk crystal symmetry elements and enhances chiral interactions; however, many surface structures have been found to be racemic. Here we show that the chiral hydrocarbon heptahelicene on a Cu111 surface does not undergo two-dimensional spontaneous resolution into enantiomers, but still shows enantiomorphism on a mesoscopic length scale that is readily amplified. That is, we observe formation of racemic heptahelicene domains with non-superimposable mirror-like lattice structures, with a small excess of one of the heptahelicene enantiomers suppressing the formation of one domain type. Similar to the induction of homochirality in achiral enantiomorphous monolayers by a chiral modifier, a small enantiomeric excess suffices to ensure that the entire molecular monolayer consists of domains having only one of two possible, non-superimposable, mirror-like lattice structures.     

非离子双子表面活性剂的合成研究进展

 双子表面活性剂是由间隔基团通过化学键联接两个疏水基团和两个亲水基团的离子头基构成的一类新型表面活性剂。与传统的单基表面活性剂相比,双子表面活性剂具有较低的临界胶束浓度、降低水溶液表面张力或者水油之间界面张力的性能更强、更好的水溶性等优点。国内外有许多关于阴离子和阳离子双子表面活性剂的合成和性能的报道,但关于非离子双子表面活性剂的合成还较少。非离子双子表面活性剂主要分为两大类：一类是醇醚、酚醚型,另一类是糖类衍生物。本文分别从联接基团加入法、极性头基加入法、疏水链基加入法等合成方法的角度,对不同类型的非离子双子表面活性剂的合成路线及性能进行了概述。其中,联接基团加入法是在两个现成的两亲分子之间插入一个联接基团,将这两个两亲分子联接起来。极性头基加入法则是联接基团先连接两条疏水链,再把两个极性头基加上去,一般是环氧乙烷或者是环氧丙烷加入的方法。疏水链基加入法所采用的原料化合物中含有联接基,并且已经和两个极性基团联接在一起,只是缺了两条碳氢疏水链。最后,对研究中存在的问题和今后的发展方向提出了一些看法,以期对新型双子表面活性剂的工业化有所促进。     

新型阴离子-非离子表面活性剂界面张力的研究

实验考察了5种自制的阴离子-非离子表面活性剂与桩西106-15-X18脱水原油在55℃下的动态界面张力与水相矿化度之间的关系.阴离子-非离子表面活性剂在水相中的质量浓度为1g.L-1.实验发现:所研究的表面活性剂与原油之间的动态界面张力受矿化度的影响明显,一定范围内,矿化度的增加有利于界面张力的降低,当矿化度增加到一定程度时界面张力又呈现增大的趋势.对于9AS-0-4、12AS-0-4、13AS-0-4三种表面活性剂,在相同的矿化度条件下,9AS-0-4的界面活性最好,12AS-0-4则略差;表面活性剂亲油基相同的情况下,随分子中氧丙烯链节长度的增加,表面活性剂的最佳盐含量依次降低,可以通过在表面活性剂中引入氧丙烯链节的方式来达到调节表面活性剂亲水亲油平衡之目的.     

基于界面相互干扰能分析法的二乙醇胺水溶液自发浸润聚偏氟乙烯疏水微孔膜的机理研究

通过van Oss范德华表面张力拟合法,拟合出了聚偏氟乙烯（PVDF）疏水微孔膜和润湿PVDF膜的各界面张力,证实了表面活性剂的吸附入侵机理同样适用于二乙醇胺（DEA）溶液浸润PVDF膜。通过吸附实验和HyperChem软件的分子优化推算出了DEA分子在固液界面的相互干扰能,利用Hamaker算法计算了DEA分子与PVDF膜的相互干扰能。结合DEA分子的固液、固气相互干扰能和Starov界面吸附常数方程,定量计算出了DEA分子在PVDF膜上的固气界面吸附常数几乎为0,即DEA分子在自发浸润过程中吸附在固气表面的可能性极小,从而证实了DEA溶液缓慢浸润PVDF疏水微孔膜的机理是由于固液界面吸附导致固液界面张力下降而引起的液气界面附加压力反向。从相互干扰能的角度研究了润湿现象,并基于所得机理提出了抵抗润湿的方法。     

驱油用表面活性剂的发展及界面张力研究

综述了驱油用磺酸盐表面活性剂、羧酸盐表面活性剂、非离子-阴离子两性表面活性剂、烷基多糖苷表面活性剂、Gemini表面活性剂、甜菜碱表面活性剂的发展,指出Gemini表面活性剂、甜菜碱表面活性剂在油田中应用需解决的问题和国外近年较重视驱油用非离子-阴离子表面活性剂的趋势;总结了表面活性剂分子结构与降低界面张力性能的关系,指出研究甜菜碱类表面活性剂低界面张力形成机理对指导新型表面活性剂的合成有重要意义.     

表面活性剂对气体水合物界面张力的影响

表面活性剂能够减小液体的表面张力以及两相液体间的界面张力,界面张力的减小有利于促进气体水合物快速形成和提高水合物储气能力.为定量研究两相液体间界面张力对气体水合物形成的影响,用界面张力仪实测不同温度时蒸馏水、HCFC-141b的表面张力以及HCFC-141b/蒸馏水、HCFC-141b/十二烷基硫酸钠溶液(0.247%)、HCFC-141b/十二烷基磺酸钠溶液(0.245%)、HCFC-141b/十二烷基苯磺酸钠溶液(0.057 6%)的界面张力,测试结果表明,表面活性剂对降低两相液体间界面张力的作用十分明显,其中十二烷基苯磺酸钠溶液对降低界面张力最为突出,降到HCFC-141b/蒸馏水界面张力值的9%左右,为定量研究气体水合物等优选表面活性剂提供了科学的依据.     

烃基苯磺酸盐表面活性剂AS的合成及其水溶液与原油的界面活性

以石油中间产品为原料合成了烃基苯磺酸盐表面活性剂 AS- 4,AS- 5,AS- 6。实验表明 ,AS水溶液 /碱 /原油体系具有 1 0 -2 m N/m以下的最小界面张力。讨论了异构体组分相对含量 ,合成的起始原料 ,平均分子量对 AS产物水溶液与原油的界面活性的影响。     

Modular and predictable assembly of porous organic molecular crystals

Nanoporous molecular frameworks are important in applications such as separation, storage and catalysis. Empirical rules exist for their assembly but it is still challenging to place and segregate functionality in three-dimensional porous solids in a predictable way. Indeed, recent studies of mixed crystalline frameworks suggest a preference for the statistical distribution of functionalities throughout the pores rather than, for example, the functional group localization found in the reactive sites of enzymes. This is a potential limitation for 'one-pot' chemical syntheses of porous frameworks from simple starting materials. An alternative strategy is to prepare porous solids from synthetically preorganized molecular pores. In principle, functional organic pore modules could be covalently prefabricated and then assembled to produce materials with specific properties. However, this vision of mix-and-match assembly is far from being realized, not least because of the challenge in reliably predicting three-dimensional structures for molecular crystals, which lack the strong directional bonding found in networks. Here we show that highly porous crystalline solids can be produced by mixing different organic cage modules that self-assemble by means of chiral recognition. The structures of the resulting materials can be predicted computationally, allowing in silico materials design strategies. The constituent pore modules are synthesized in high yields on gram scales in a one-step reaction. Assembly of the porous co-crystals is as simple as combining the modules in solution and removing the solvent. In some cases, the chiral recognition between modules can be exploited to produce porous organic nanoparticles. We show that the method is valid for four different cage modules and can in principle be generalized in a computationally predictable manner based on a lock-and-key assembly between modules.     

聚氧丙烯醚型表面活性剂结构及矿化度对油水界面张力的影响

实验选用9AS-n-0、13AS-n-0系列氧丙烯聚醚型表面活性剂,使用Texa-500型界面张力仪在55℃时不同矿化度条件下,测定了表面活性剂水溶液与桩西106-x18-15脱水原油间的界面张力,研究了矿化度及表面活性剂分子结构与油水界面张力的关系.研究发现,随着矿化度的增加,界面张力不断降低,在某一特定值时,界面张力达到最小值;随着氧丙烯链的增长,达到低界面张力所需矿化度的区域是逐渐降低的;研究还发现,含有分支结构的13AS-n-0系列表面活性剂的界面活性要比9AS-n-0好.     

羧甲基化的非离子型表面活性剂与石油磺酸盐的复配试验

对羧甲基化的非离子型表面活性剂进行了应用研究.考察了这种非离子- 阴离子两性活性剂的耐盐能力和界面张力,研究了其与石油磺酸盐复配的性能.试验表明,这种两性活性剂与石油磺酸盐复配,不仅能大大改善石油磺酸盐的耐盐性能,而且由于存在界面张力协同效应,不需添加低分子量的醇即能使复配体系与癸烷的界面张力达到超低,适合于高矿化度地层驱油.此外还进行了高矿化度条件下的模拟驱油试验,取得好的效果.     

脂肪醇聚醚磺酸盐水溶液与烷烃之间界面张力研究

测定了30℃时不同条件下脂肪醇聚氧乙烯醚磺酸盐(AES系列)和脂肪醇聚氧丙烯醚磺酸盐(APS系列)与正辛烷、正癸烷和正十二烷之间的界面张力.结果表明:APS比AES具有更好的界面活性,用HLB值基团计算法证明了这一结论;疏水基链长的APS对于长链烷烃有较好的选择性,疏水基链短的APS对于链较短的烷烃有较好的选择性;同一表面活性剂溶液的最佳盐含量与烷烃碳数ACN有明显的对应关系;APS、AES水溶液的最佳矿化度均较高,在低矿化度条件下不易与烷烃形成超低界面张力.     

壬基酚聚醚硫酸酯/Φ-磺酸钠盐表面活性剂的构效关系

以壬基酚为原料,通过烷氧基化加成、磺化或硫酸酯化、再经中和反应合成了4种结构的表面活性剂,分别为:壬基酚聚氧乙烯醚(3)硫酸酯钠(NPES-3)、壬基酚聚氧乙烯醚(3)-Φ-磺酸钠(Φ-NPES-3)、壬基酚聚氧丙烯醚(3)硫酸酯钠(NPPS-3)、壬基酚聚氧丙烯醚(3)-Φ-磺酸钠(Φ-NPPS-3).测定其γcmc,Ccmc,耐盐能力、抗硬水能力、pH水解稳定性、热水解稳定性及油水界面张力.实验结果表明,含聚氧乙烯醚结构的表面活性剂耐盐能力和抗硬水能力均优于聚氧丙烯醚结构;降低油水界面张力则以含聚氧丙烯醚结构更好,尤其是NPPS-3的平衡界面张力达到9.88×10-3 mN/m的超低范围.     

螺旋结构手性材料的手性参数实验研究

利用微波圆波导测量系统，在８．５～１１．５ ＧＨｚ 频段内测量了螺旋结构手性材料的手性参数．研究了手性掺杂体的螺径、螺距和线径对手性参数的影响．结果表明，随着螺旋体结构参数的变化，有Ｃｏｔｔｏｎ 效应出现． 实验结果为手性材料的设计提供了实验依据．     

润湿反转机理的研究进展

介绍了近年来国外针对润湿反转作用提高采收率的研究进展.首先介绍了一种测定润湿角的方法——双滴双晶法(DDDC).对比了近几年国外常用的几种润湿反转剂.研究表明:阳离子、阴离子以及非离子表面活性剂在有效作用浓度以及作用机理上存在明显区别.综合各种试验结果,认为含有聚氧乙烯(丙烯)基的阴离子或是非离子活性剂具有较好的应用前景.最后通过分析固体表面润湿反转导致的油珠剥离过程,以及不同阶段的力学变化规律,发现润湿反转作用主要受到固液界面张力的影响,而油水界面张力并不是决定性的影响因素.因此,有必要进一步研究表面活性剂对固液界面张力的影响规律.     

表面活性剂对长庆超低渗砂岩油藏化学渗吸的影响

以长庆油田超低渗储层Y284区块为研究对象,通过静态渗吸、油水界面张力、润湿性以及油水黏度比测量等实验,研究了表面活性剂性能对化学渗吸采收率的影响。结果表明:在超低渗Y284砂岩储层中,阴离子型表面活性剂的渗吸效果最好,并且阴离子亲油基碳链长度的增加可以增强渗吸作用;溶液p H大于两性离子等电点时,甜菜碱型表面活性剂可促进渗吸作用;阳离子表面活性剂不适用于砂岩油藏的化学渗吸采油中;当界面张力处于10-1m N/m数量级时,界面张力下降,渗吸采收率升高,当界面张力处于10-2m N/m数量级时,界面张力上升,渗吸采收率升高;表面活性剂可以改善岩石表面润湿性,增强渗吸作用;给出了油砂静态渗吸的毛管数表达式,润湿相黏度的适当增加或非湿相黏度的降低有利于毛管数的增加,可以增大渗吸采收率。     

改性木质素磺酸盐表面活性剂合成及性能研究

以草浆或木浆碱木素为原料,经过与脂肪多胺的曼尼希反应、与油酰氯的酰化反应和磺甲基化反应,合成了一系列含有酰胺结构的改性木质素磺酸盐表面活性剂．对改性木质素磺酸盐界面性能进行了测试,讨论了表面活性剂质量分数及碱质量分数对界面张力的影响．结果表明改性产品具有非常优良的界面活性,单独使用即可在较宽的表面活性剂质量分数和碱质量分数的变化范围内,形成超低油-水界面张力,符合三次采油的基本要求．