水溶性聚合物和两亲聚合物18.2—丙烯酰胺基烷磺酸类两亲单体

２－丙烯酰胺基烷磺酸的溶解行为和胶体化学性质明显随烷基长短而异，由于手性碳原子的存在，与其相邻亚甲基的质子峰在ＨＮＭＲ谱上清楚地发生分裂，研究了２－丙烯酰胺基十六烷磺酸（ＡＭＣ１６Ｓ）在水／二氧六环混合溶剂中的聚合动力学和胶体化化学性质，发现聚合速度和所得聚合物分子量均均在水／二氧六环体积比为１～１／２时出现最小值，临界胶束浓度随混合溶剂中二氧六环含量的增加而增加，当水／二氧六环体积比为１／２～１     

含金鸡钠碱的光活性聚合物：2.含辛可宁的两亲单体及其两亲聚合物

通过两亲单体２－丙烯酰胺基烷磺酸与辛可宁成盐后再聚合，或ＡＭＣｎＳ聚合成梳型两亲聚合物后再生ＣＮ成盐，可获得含辛可宁的两亲聚合物。ＡＭＣｎＳ－ＣＮ盐及其相应的两亲聚合物具有比ＣＮ好得多的溶解性，易溶于氯仿、ＴＨＦ、乙醇、ＤＭＦ和ＤＭＳ等极性不同的溶剂。ＡＭＣｓＳ－ＣＮ盐好得多的溶解性，易溶于氯仿、ＴＨＦ、乙醇、ＤＭＦ和ＤＭＳＯ等极性不同的溶剂。ＡＭＣｎＳ－ＣＮ盐在乙醇／氯仿（Ｖ／Ｖ＝１／２）中比旋     

水溶性聚合物和两亲聚合物：23.两亲聚合物PAMC16S对螺恶嗪？…

研究了两亲聚合物聚（２－丙烯酰胺基十六烷磺酸）（ＰＡＭＣ１６Ｓ）存在下１－乙基－２,３－二甲基螺［吲哚啉－萘并恶嗪］（ＳＯ－Ｅ）在水溶液中的增溶作用及ＰＡＭＣ１６Ｓ对ＳＯ－Ｅ化学和光化学性质的影响。ＰＡＭＣ１６Ｓ明显增加了ＳＯ－Ｅ在水相的溶解性,ＳＯ－Ｅ的最大增溶浓度随ＰＡＭＣ１６Ｓ浓度增加呈线性增加规律。在ＰＡＭＣ１６Ｓ存在下,新配制的ＳＯ－Ｅ溶液显示可逆的光致变色性,显色体呈红色,最大吸收峰位     

水溶性聚合物和两亲聚合物：聚（丙烯酰胺－co－丙烯酸钠）－g－聚（β－胺基丙酸）接枝共聚物

合成了端丙烯酰胺基聚（β－胺基丙酸）大分子单体，用端基滴定法和１Ｈ－ＮＭＲ法测定了大分子单体的分子量，用＾１＾３Ｃ－ＭＮＲ和氢氧化钠水解法测定了支化度，在水溶液中用硫酸亚铁／异丙苯过氧化氢氧化还原引发体系引发丙烯酰胺，丙烯酸钠与聚（β－胺基丙酸）大分子单体的共聚反应，合成了聚（丙烯酰胺－ｃｏ－丙烯酸钠）－ｇ－聚（β－胺基丙酸）用１Ｈ－ＮＭＲ和滴定法测定了接枝共聚物的组成。溶液性质的数据表明，与部分     

嵌段共聚物微胶束行为的研究Ⅰ．体积排斥色谱法研究聚（苯乙烯－异成二烯）二嵌段共聚物在选择性溶剂中微胶束的形成过程

采用体积排斥色谱研究聚（苯乙烯－异成二烯）二嵌段共聚物在选择性溶剂－二氧六环／甲醇混合体系中以ＰＩ为核ＰＳ为壳的微胶柬形成过程，以及在正庚烷／乙酸异戊酯混合体系中以ＰＳ为核ＰＩ为壳的微胶束形成过程。讨论了温度、混合溶剂的配比和共聚物分子量对微胶束形成的影响。根据体积排斥色谱图估算了形成微胶束时的表观缔合能和微胶束的表观缔合数．     

1-硝基蒽醌的高效液相色谱分析

用Ｖ（Ｎ,Ｎ－二甲基酰胺）：Ｖ（１,４－二氧六环）：Ｖ（二甲基亚砜）＝５：２：１混合溶剂溶解试样,利用Ｗａｔｅｒｓ Ｎｏｖａ－ｐａｋ Ｃ１８色谱柱,以１,４－二氧六环／甲醇／水＝１５／４５／４０（体积比）混合溶液为流动相,对１－硝基蒽醌样品进行了高效液相色谱法分离与分析研究。在所确定的色谱分离体系中,样品中各组分全部出峰且基本上达到基线分离,对定量方法进行了讨论,加标回收率除１,７－二硝基蒽醌外其     

水溶性聚合物和两亲聚合物：聚（丙烯酰胺－co－丙烯酸钠）－g－聚（β－胺基丙酸）接枝共聚物

合成了端丙烯酰胺基聚（β－胺基两酸）大分子单体，用端基滴定法和１Ｈ—ＮＭＲ法测定了大分子单体的分子量，用１３Ｃ—ＮＭＲ和氢氧化钠水解法测定了支化度．在水溶液中用硫酸亚铁／异丙苯过氧化氢氧化还原引发体系引发丙烯酸胺、丙烯酸钠与聚（β－胺基丙酸）大分子单体的共聚反应，合成了聚（丙烯酰胺－ｃｏ－丙烯酸钠）－ｇ－聚（β－胺基丙酸）接枝共聚物．用１Ｈ—ＮＭＲ和滴定法测定了接枝共聚物的组成．溶液性质的数据表明，与部分水解聚丙烯酰胶相比，聚（β－胺基丙酸）含量较高的接枝共聚物具有较好的耐盐性和优异的贮存稳定性．     

原子转移自由基聚合合成(甲基)丙烯酸酯类模型聚合物及其动力学研究

本文采用一种新颖的活性自由基聚合—原子转移自由基聚合（ＡＴＲＰ）的方法，以１－溴代苯乙烷作为引发剂，过渡金属卤化物与配位剂络合物（ＣｕＢｒ／２，２’－联吡啶）为催化体系，环己酮为溶剂，进行了甲基丙烯酸正丁酯（ＢＭＡ）和丙烯酸正丁酯（ＢＡ）的活性聚合。得到具有指定分子量和窄分子量分布（１．２＜Ｍｗ／Ｍｎ＜１．５）的模型聚合物。计算并讨论了两聚合体系的ＡＴＲＰ的动力学数据     

单体极性对甲基丙烯酸甲酯/丙烯酸丁酯/甲基丙烯酸钠无皂乳液共聚合的影响

研究了少量甲基丙烯酸钠（ＮａＭＡ）存在下单体极性对甲基丙烯酸甲酯（ＭＭＡ）／丙烯酸丁酯（ＢＡ）无皂乳液共聚合的影响．单体极性降低，使粒径减小、聚合速率提高、乳液表面张力和粘度降低、粒子表面电荷密度增大、聚合物分子量提高．ＭＭＡ／ＮａＭＡ无皂乳液聚合物只呈现一个玻璃化温度Ｔｇ，ＢＡ／ＮａＭＡ无皂乳液聚合物呈现两个Ｔｇ，ＭＭＡ／ＢＡ比为２∶１～１∶２的ＭＭＡ／ＢＡ／ＮａＭＡ无皂乳液聚合物呈现四个Ｔｇ，这是由于粒子外面相对富含ＯＳＯ－３和ＣＯＯ－基聚合物的亚层溶解了较多的水，使ＢＡ向粒子中心扩散，ＭＭＡ向外扩散，造成组成差异和相分离而引起的．     

嵌段共聚物微胶束行为的研究Ⅱ．动态激光光散射法研究聚（苯乙烯－异戊二烯）二嵌段共聚物在选择性溶剂中微胶束的形成过程

采用动态激光光散射研究聚（苯乙烯－异成二烯）（ＰＳ－ＰＩ）二嵌段共聚物在选择性溶剂二氧六环／甲醇混合体系中微胶束的形成过程。讨论了温度、混合溶剂的组成和共聚物分子量对形成微胶束的影响。并对与体积排斥色谱法得到结果的差异进行了讨论，从而提出临界接触浓度的概念。还就实验测得的分子链尺寸和微胶束尺寸进行理论估算，结果符合Ｆｌｏｒｙ无扰链模型。     

Amphiphilic Dipyrrinones

Summary. Replacing the typical lactam β-alkyl substituents of xanthobilirubinic acid and kryptopyrromethenone, two bilirubin analogs long used as model compounds in studies of its photochemistry and metabolism, leads to increased amphiphilicity. Synthesized by base-catalyzed condensation of 3,4-dimethoxypyrrolin-2-one with the appropriate pyrrole α-aldehyde, the 2,3-dimethoxyl analogs of xanthobilirubinic acid and kryptopyrromethenone are yellow-colored dipyrrinones that form intermolecular hydrogen-bonded dimers in the solid, as determined by X-ray crystallography, and in CHCl₃, as revealed by ¹H NMR and vapor pressure osmometry. These two new dipyrrinones are approximately ten times more soluble in water than their parent dipyrrinones.     

Amphiphilic Bistable Rotaxanes

Two molecular shuttles/switches—a slow one and a fast one—in the shape of amphiphilic, bistable [2]rotaxanes have been synthesized and characterized. Both [2]rotaxanes contain a hydrophobic, tetraarylmethane and a hydrophilic, dendritic stopper. They are comprised of two π‐electron‐rich stations—a monopyrrolotetrathiafulvalene unit and a 1,5‐dioxynaphthalene moiety—which can act as recognition sites for the tetracationic cyclophane, cyclobis(paraquat‐p‐phenylene), to reside around. In addition, a model [2]rotaxane, incorporating only a monopyrrolotetrathiafulvalene unit in the rod section of the amphiphilic dumbbell component and cyclobis(paraquat‐p‐phenylene) as the ring component, has been investigated. The dumbbell‐shaped components were constructed using conventional synthetic methodologies to assemble 1) the hydrophobic, tetraarylmethane stopper and 2) the hydrophilic, dendritic stopper. Next, 3) the hydrophobic stopper was fused to the 1,5‐dioxynaphthalene moiety and/or the monopyrrolotetrathiafulvalene unit by appropriate alkylations, followed by 4) attachment of the hydrophilic stopper, once again by alkylation to give the dumbbell‐shaped compounds. Finally, 5) the [2]rotaxanes were self‐assembled by using the dumbbells as templates for the formation of the encircling cyclobis(paraquat‐p‐phenylene) tetracations. The two [2]rotaxanes differ in their arrangement of the π‐electron‐rich units, one in which the SMe group of the monopyrrolotetrathiafulvalene unit points toward the 1,5‐dioxynaphthalene moiety ( 2 ?4 PF₆) and another in which it points away from the 1,5‐dioxynaphthalene moiety ( 3 ?4 PF₆). This seemingly small difference in the orientation of the monopyrrolotetrathiafulvalene unit leads to profound changes in the physical properties of these rotaxanes. The bistable [2]rotaxanes were both isolated as brown solids. ¹H NMR and UV‐visible spectroscopy, and electrochemical investigations, reveal the presence of both possible translational isomers at ambient temperature. As a consequence of the existence of both possible translational isomers in these bistable [2]rotaxanes, they exhibit a complex electrochemical behavior, which is further complicated by the presence of folded conformations wherein the monopyrrolotetrathiafulvalene unit is involved in an “alongside” interaction with the tetracationic cyclophane. In the molecular shuttle/switch 2 ?4 PF₆ a “knob”, in the shape of the SMe group, is situated between the monopyrrolotetrathiafulvalene and the 1,5‐dioxynaphthalene recognition sites, making it possible to isolate both translational isomers ( 2 ?4 PF₆?GREEN and 2 ?4 PF₆?RED) and to investigate the kinetics of the shuttling of the cyclobis(paraquat‐p‐phenylene) tetracation between the two recognition sites. The shuttling processes, which are accompanied by clearly detectable color changes, can be followed by ¹H NMR and UV‐visible spectroscopy, allowing the rate constants and energies of activation for the translation of the cyclobis(paraquat‐p‐phenylene) tetracations between the two recognition sites to be determined. In the molecular shuttle/switch 3 ?4 PF₆, there is no “knob” situated between the 1,5‐dioxynaphthalene and the monopyrrolotetrathiafulvalene recognition sites, resulting in a considerably faster shuttling of the cyclobis(paraquat‐p‐phenylene) tetracation between these two sites, making the separation of the two possible translational isomers of 3 ?4 PF₆ impractical. However, the shuttling of the cyclobis(paraquat‐p‐phenylene) tetracation can be followed by dynamic ¹H NMR spectroscopy. At low temperatures, the major translational isomer is 3 ?4 PF₆?RED, while 3 ?4 PF₆?GREEN is the major isomer at higher temperature. In the bistable [2]rotaxanes shuttling of the cyclobis(paraquat‐p‐phenylene) tetracations can be driven by electrochemical oxidation of the monopyrrolotetrathiafulvalene unit. In complexes in which one of the two dumbbell stoppers is missing, electrochemical oxidation causes dethreading.     

两亲性树状聚合物*

树状聚合物及其功能化是近年来高分子科学界的研究热点之一。本文综述了不同类型的树状聚合物,分别有聚酯、聚丙三醇、聚乙烯亚胺等超支化聚合物,聚酰胺-胺、聚丙烯亚胺等树枝状聚合物。通过对树状聚合物末端大量官能团的亲水（亲油）改性可以制备两亲性树状聚合物,改性方法主要有酰胺化反应、酯化反应、麦克尔加成反应等。与通过缩聚反应所得到的上述树状聚合物不同,近年来配位聚合领域出现的通过“链行走”机理形成的树状聚乙烯,引起了高度关注,这方面着重介绍了乙烯与极性单体直接共聚合或者采用链行走与原子转移自由基聚合联用制备两亲性树状乙烯聚合物。最后对两亲性树状聚合物领域的发展前景进行了展望。     

Amphiphilic dendronized homopolymers

A series of second generation of amphiphilic dendronized homopolymers are efficiently synthesized, and their thermoresponsiveness in aqueous solutions and secondary structures in methanol solutions are described. These polymers are constructed in each repeat unit with various generations of hydrophobic 4-aminoproline and hydrophilic oligoethylene glycol (OEG)-based dendrons, and their over-all hydrophilicity is tuned by varying these dendron generations. Polymers with or without the first generation of proline dendron show good water solubility at room temperature, but exhibit typical thermoresponsive behaviors at elevated temperatures as characterized by turbidity measurements using UV-vis spectroscopy, while the polymer with the secondary generation of proline dendron is not soluble in water. All polymers show ordered secondary structures as evidenced by the optical rotation and circular dichroism experiments. Finally, assembly of these amphiphilic homopolymers into porous films via breath figure (BF) technique is described, and polymer structures are found to show significant influence on the morphology of porous film.     

Amphiphilic Patchy Composite Colloids

A new approach to fabricate patchy silica/polymeric gel composite colloids with amphiphilic performance is reported. The amphiphilic performance is rendered by selectively modifying the silica framework with a silane that contains an oleophilic alkyl chain. The patchy composite colloids are dispersible in both water and oil, and may be used as a solid particle surfactant. The modified silica framework can also assist other functional materials to disperse in a desired media. The corresponding silica/carbon composite colloids become amphiphilic after a sequential activation of carbon and modification of silica, and meanwhile possess as good electron conductivity as the as‐prepared silica/carbon composite colloids.