(2-羟基-3-丁氧基)丙基-羧甲基壳聚糖的合成及表面性质

(2-羟基-3-丁氧基)丙基-羧甲基壳聚糖的合成及表面性质;壳聚糖衍生物; (羟基丁氧基)丙基-羧甲基壳聚糖;表面活性;表面压     

两亲性壳聚糖衍生物的合成及其自聚集现象

以壳聚糖为主链, 聚乙二醇单甲醚为亲水性链段, 癸二酸为疏水链段, 合成了一系列两亲性壳聚糖衍生物. 通过FTIR, 1H NMR和X射线粉末衍射等手段对壳聚糖衍生物进行了结构表征, 由元素分析方法计算出衍生物的取代度. 采用直接溶解法制备了壳聚糖衍生物的空白胶束, 通过透射电子显微镜(TEM)观察了胶束的形态. 由动态光散射(DLS)测定了胶束的粒径及分布, 并以芘为分子探针, 通过荧光光谱法测定了壳聚糖衍生物的临界聚集浓度(CAC). 研究结果表明, 壳聚糖主链上疏水链段的取代度越大, 其衍生物的临界聚集浓度越低, 相同浓度下的胶束的粒径也越小.     

羧甲基壳聚糖衍生物及其振动光谱的理论研究

用量子化学从头算STO 3G法研究了羧甲基壳聚糖及其衍生物的结构和稳定性，计算结果表明:1)壳聚糖单体经羧甲基化后，得到2种可能的产物，其中羧甲基在壳聚糖单体2位氨基上的取代产物较6位羟基上的取代产物稳定； 2)以羧甲基壳聚糖为母体经加成反应，得到羧甲基壳聚糖衍生物（2 羟基 3 丁氧基）丙基 羧甲基壳聚糖的2个异构体， 其中构型1更稳定.在优化构型的基础上，计算所得的构型1的振动光谱与实验结果相吻合.     

新型含胍基和季铵基团壳聚糖衍生物的合成

N,N-二甲基-1,3-丙二胺与单氰胺经亲核加成反应制得中间体N,N-二甲基-N′-胍基-1,3-丙二胺（2）; 以壳聚糖为起始原料,依次与氯乙酸、环氧氯丙烷经取代反应制得N-（1-羟基-3-氯丙基）-羧甲基壳聚糖（4）; 4与2经季铵化反应合成了一系列含有胍基和季胺基团的羧甲基壳聚糖衍生物（5）,其结构经¹H NMR, IR和元素分析表征。研究了反应配比［γ=m（2）∶m（4）］和反应时间对5取代度的影响,结果表明,当γ为3∶1,反应时间为10 h时,取代度最高(73%)。     

N-烷基壳聚糖的合成及其溶致液晶行为

合成了一系列具有不同取代基(甲基、乙基、丙基、丁基)的壳聚糖衍生物——N 烷基壳聚糖,通过控制反应物摩尔比获得了一系列不同取代度的产物.不同取代基及不同取代度的衍生物均具有溶致液晶性,考察了同一碳链不同取代度和相近取代度不同碳链长度的衍生物对其液晶临界行为的影响.结果表明：同一碳链长度时,取代度对临界浓度的影响不大;而当取代度相近时,随着碳链长度增加,临界浓度也随之增大.此结果与Onsager和Flory的刚性棒理论相符.粉末X射线衍射实验进一步证实了这一结果.     

新型两亲性壳聚糖衍生物的合成、表征及对难溶性药物的增溶性

以天然可生物降解的壳聚糖为原料, 通过在壳聚糖6位羟基上引入羧甲基, 在2位氨基上引入疏水烷基链, 制得N-辛基-O,N-羧甲基壳聚糖(OCC)两亲性衍生物, 分别用FTIR、1H NMR和元素分析等技术对其结构进行表征, 用广角X射线衍射(WAXD)和差示扫描量热法(DSC)对其物理性质进行分析, 并考察其在各种溶剂中的溶解性能及其对难溶性药物的增溶能力. 所制备的OCC羧甲基取代度为115.9%, 取代主要发生在6位羟基上; 辛基取代度58.0%, 取代主要发生在2位氨基上; 与壳聚糖相比, OCC分子间/内氢键作用减弱; OCC在常用的有机溶剂中不溶, 但在水中溶解度增加, 能够形成具有淡蓝色乳光的纳米胶体溶液, 对难溶性抗肿瘤药物紫杉醇具有优越的增溶能力, 使紫杉醇在水中的溶解度提高近500倍, 载药量为34.6%(质量分数), 包封率为89.9%. OCC是潜在的优良的难溶性药物增溶载体材料.     

一种新型疏水改性的两亲性壳聚糖衍生物的表面活性研究

鉴于甲壳质的生物降解性、生物活性和生物相容性等诸多特性 ,其开发利用正受到人们的广泛重视[1] .具有不同性能和功效的衍生物已在医药、食品、日用化工、纺织、水处理等领域发挥了重要的作用 [2～ 4 ] .然而具有表面活性的两亲性衍生物却少见报道 [5,6] .本文将羧甲基壳聚糖进行疏水改性 ,使其分子上同时具有亲水基和疏水基 ,从而具有两亲性质 ,可以降低溶液的表面张力 ,并在溶液中形成胶束 .可望在日用化工、医药、食品等领域起到降低表面张力、增稠、乳化和增溶等作用 .1　实验部分1 .1　原料及仪器　羧甲基壳聚糖 (CMCHS,青岛生化制…     

新型羧甲基壳聚糖水凝胶流变性能,药物释放及细胞相容性研究

羧甲基壳聚糖含有丰富的羧基和氨基, 通过1-乙基-(3-二甲基氨基丙基)碳二亚胺盐酸盐(EDC)和N-羟基琥珀酰亚胺(NHS)共催化交联羧甲基壳聚糖形成新型水凝胶. 调节EDC/NHS用量, 制备不同交联度的羧甲基壳聚糖水凝胶(CMCS hydrogels). 研究水凝胶的流变行为, 结果表明, 高交联度的水凝胶具有较好的弹性形变能力, 较高的储存模量, 这是因为随着交联度的升高, 羧甲基壳聚糖水凝胶化学交联网络结构趋于完善. 以胸腺五肽(TP-5)为模型药物, 初步评价CMCS水凝胶药物释放行为, 结果表明水凝胶交联度越高, 胸腺五肽释放速度越慢. MTT法初步评价了水凝胶细胞毒性, 细胞形态和细胞相对增值速率, 结果表明水凝胶毒性很低. 由此可见, 水凝胶具有良好的生物相容性, 在药物缓释和组织工程领域具有广阔的应用前景.     

葛根素衍生物的合成、表征及衍生化反应机理

合成了葛根素的7,4'-二丙基(Ⅰ), 7-单丙基(Ⅱ)和4'-单丙基(Ⅲ)三种取代衍生物. 其中7-丙基葛根素Ⅱ属于新型取代衍生物; 变温1H NMR和理论计算结果表明, 在300 K时, 葛根素和4'-丙基葛根素(Ⅲ)以单一构型存在; 而7,4'-二丙基葛根素(Ⅰ)和7-丙基葛根素(Ⅱ)则存在两种核磁可分辨的旋转异构体, 当温度升至330 K时, 两种异构体可以相互转化; 通过对比分析葛根素及其衍生物脱质子产物的紫外可见吸收光谱并结合理论计算, 确定了A环上7位酚羟基比B环上4'位酚羟基先脱去质子, 并由此进一步阐明了葛根素衍生化反应机理以及在抗氧化作用中可能的活性位点和结构活性关系.     

微波消解-石墨炉原子吸收光谱法测定壳聚糖凝胶中7种金属元素的含量

<正>壳聚糖化学名为β-1,4-2-氨基-2-脱氧-D-葡聚糖,是甲壳质经浓碱脱乙酰基后得到的衍生物。壳聚糖的羟基或氨基上的氢被羧甲基取代后成为羧甲基壳聚糖,在生物医学及制药等方面的应用极其广泛。医用壳聚糖凝胶以羧甲基壳聚糖为主要成分,是一种具有良好的溶解性、生物相容性、可降解性、抑菌性和抗感染性能的新型生物材料,用于手术创面、烧伤、烫伤等创面修复。目前我国有关壳聚糖的标准YY/T 0606.7-2008《组织工程医疗产品第七     

The aggregation behavior between anionic carboxymethylchitosan and cetyltrimethylammonium bromide: MesoDyn simulation and experiments

The aggregation behavior between carboxymethylchitosan (CMCHS) and cetyltrimethylammonium bromide (CTAB) is investigated by MesoDyn simulation and experimental techniques, for increasing CTAB concentrations. Mixed CMCHS/CTAB bulk aggregates are formed in the solution. Simulation results give the morphologies of aggregates clearly and illustrate the two stages for the formation of aggregates: the first stage is CTAB molecules aggregating on the CMCHS chain and the second stage is the equilibrium stage. A viscosity maximum and a hydrodynamic radius minimum at a certain CTAB concentration reveal the bridging structure of the polymer chains by the micelles. Transmission electron microscopy (TEM) images give the bridging structure clearly. At higher surfactant concentrations, light scattering and TEM show the existence of larger structures, whose size increases with CTAB concentration. According to the simulation and experimental results, the process of aggregate formation and aggregation mechanism are analyzed. Initially CMCHS and CTAB form network structure due to the bridge action of CTAB micelles, while the network structure disappears gradually and is replaced by ellipsoidal CMCHS/CTAB aggregate structure with CTAB concentration increasing.     

Simulating the effect of surfactant structure on bending moduli of monolayers

We have used dissipative particle dynamics to simulate amphiphilic monolayers on the interface between oil and water. An ultralow interfacial tension is imposed by means of Monte Carlo to resemble the amphiphilic films that separate oil and water regions in microemulsions. We calculate the bending modulus by analyzing the undulation spectrum. By varying the surfactant chain length and topology we investigate the effect of surfactant structure and composition of the monolayer on the bending moduli. We find that increasing the thickness has a larger effect than increasing the density of the layer. This follows from the observations that at a given interfacial tension, the bending modulus increases with chain length and is larger for linear than branched surfactants. The increase with chain length is approximately linear, which is slower than the theoretical predictions at a fixed area. We also investigated a binary mixture of short and long surfactants compared to pure layers of the same average chain length. We find a roughly linear decrease in bending modulus with mole fraction of short surfactants. Furthermore, the mixed film has a lower bending modulus than the corresponding pure film for all mole fractions. Linking the bending moduli to the structure of the surfactants is an important step in predicting the stability of microemulsions.     

Association behavior of fluorine-containing and non-fluorine-containing methacrylate-based amphiphilic diblock copolymer in aqueous media

Fluorine-containing amphiphilic block copolymers, poly(sodium methacrylate)-block-poly(nonafluorohexyl methacrylate) (NaMAm-b-NFHMAn) (m:n = 61:12, 72:33, 64:57), and the corresponding non-fluorine-containing amphiphilic block copolymer, poly(sodium methacrylate)-block-poly(hexyl methacrylate) (NaMAm-b-HMAn) (m:n = 64:10, 69:37, 67:50), were synthesized. Both polyNaMA-b-polyNFHMA and polyNaMA-b-polyHMA formed micelles above critical micelle concentrations, (cmc's), around 3 x 10(-5) to 1 x 10(-4) mol/L, while neither polymer decreased surface tension of aqueous solutions. The size and shape of the micelles were examined by dynamic light scattering, small-angle neutron scattering, and small-angle X-ray scattering. PolyNaMA-b-polyHMA appeared to form only spherical micelles, while polyNaMA-b-polyNFHMA with a long NFHMA segment formed both spherical and rodlike micelles. The micelles of fluorine-containing block copolymers were obviously larger than those of non-fluorine-containing block copolymers with the same chain length and the same hydrophilic/hydrophobic chain ratio. The fluorine-containing block copolymer selectively solubilized fluorinated dye into the water phase when a mixture of decafluorobiphenyl and 2,6-dimethylnaphthalene was added to the micelle solution.     

Non-surface activity and micellization of ionic amphiphilic diblock copolymers in water. Hydrophobic chain length dependence and salt effect on surface activity and the critical micelle concentration

We reported previously (Macromolecules 2003, 36, 5321; Langmuir, 2004, 20, 7412) that amphiphilic diblock copolymers having polyelectrolytes as a hydrophilic segment show almost no surface activity but form micelles in water. In this study, to further investigate this curious and novel phenomenon in surface and interface science, we synthesized another water-soluble ionic amphiphilic diblock copolymer poly(hydrogenated isoprene)-b-sodium poly(styrenesulfonate) PIp-h2-b-PSSNa by living anionic polymerization. Several diblock copolymers with different hydrophobic chain lengths were synthesized and the adsorption behavior at the air/water interface was investigated using surface tension measurement and X-ray reflectivity. A dye-solubilization experiment was carried out to detect the micelle formation. We found that the polymers used in this study also formed micelles above a certain polymer concentration (cmc) without adsorption at the air-water interface under a no-salt condition. Hence, we further confirmed that this phenomenon is universal for amphiphilic ionic block copolymer although it is hard to believe from current surface and interface science. For polymers with long hydrophobic chains (more than three times in length to hydrophilic chain), and at a high salt concentration, a slight adsorption of polymer was observed at the air-water interface. Long hydrophobic chain polymers showed behavior "normal" for low molecular weight ionic surfactants with increasing salt concentration. Hence, the origin of this curious phenomenon might be the macroionic nature of the hydrophilic part. Dynamic light scattering analysis revealed that the hydrodynamic radius of the block copolymer micelle was not largely affected by the addition of salt. The hydrophobic chain length-cmc relationship was found to be unusual; some kind of transition point was found. Furthermore, very interestingly, the cmc of the block copolymer did not decrease with the increase in salt concentration, which is in clear contrast to the fact that cmc of usual ionic small surfactants decreases with increasing salt concentration (Corrin-Harkins law). These behaviors are thought to be the special, but universal, characteristics of ionic amphiphilic diblock copolymers, and the key factor is thought to be a balance between the repulsive force from the water surface by the image charge effect and the hydrophobic adsorption.     

Synthesis and Amphiphilic Behavior of N,N‐Bis‐glucosyl‐1,5‐benzodiazepin‐2,4‐dione

Abstract

Glucosyl‐1,5‐benzodiazepin‐2,4‐diones were synthesized in order to study the influence of the glucidic moiety on the amphiphilic behaviour. The glucosyl groups include 6‐deoxy‐D‐glucopyranos‐6‐yl and 6‐deoxy‐3‐O‐R‐D‐glucopyranos‐6‐yl (R = n ? C _n H _2n+1; n = 1, 8, 10 and 12). Variation in the length of the hydrocarbon chain allowed comparison of such amphiphilic data as water solubility (Sw) and surface tension (γ) values. At 25°C, the glucopyranosyl benzodiazepines with R = H and CH₃ show a higher water solubility than the starting 1,5‐benzodiazepin‐2,4‐diones. Some other glucidic benzodiazepine derivatives with an appropriate alkyl chain at C‐3 carbon of the D‐glucopyranose present a variable hydrosolubility and surface tension γ values close to 43 to 46 mN · m^?1 at the corresponding saturation. Moreover, according to preliminary tests, these compounds seem to show a better affinity for the blood brain barrier.     

丙烯酰胺-苯乙烯双亲嵌段共聚物的微结构及水溶液行为

通过改变丙烯酰胺(AM)与苯乙烯(St)的投料比、苯乙烯与表面活性剂的加入量之比及引发剂加入量,在微乳液中制备了分子链微结构系列变化的丙烯酰胺-苯乙烯双亲嵌段共聚物(PAM-b-PSt),用荧光探针法与表面活性测定法详细地研究了共聚物中PSt嵌段长度、含量及分子量等微结构因素对共聚物在水溶液中的疏水缔合性与表面活性的影响.结果表明,当共聚物水溶液的浓度高于临界缔合浓度时,PAM-b-PSt的疏水缔合作用以分子间的缔合为主.若共聚物中PSt嵌段含量及分子链长一定时,随着PSt疏水嵌段长度增长,PAM-b-PSt的疏水缔合性增强,而对共聚物的表面活性影响很小.若共聚物中PSt疏水嵌段长度及分子链长一定时,PAM-b-PSt的疏水缔合性随着PSt嵌段含量的变化而变化,当PSt嵌段含量一定时,使大分子链之间产生最强的疏水缔合作用;而其表面活性则随着PSt嵌段含量的增大而增强.若共聚物中PSt疏水嵌段长度及含量一定时,分子量对其表面活性有较大的影响,分子量越高,表面活性越差;同时,在较稀的溶液浓度范围内,分子量对PAM-b-PSt的疏水缔合性的影响则很小.     

Studies on microstructure and aqueous solution properties of block copolymer of acrylamide-styrene

Three series of block copolymers of acrylamide (AM) and styrene (St) as hydrophobic comonomer with varied microstructures were prepared in microemulsion medium by changing feed ratio of monomers, ratio of St to surfactant, and amount of initiator, respectively. The effects of microstructure factors of the amphiphilic block copolymers PAM-b-PSt on their aqueous solution properties were investigated by fluorescence probe technique and surface tension measurement in detail. The experimental results show that the aqueous solution properties of PAM-b-PSt are strongly dependent on their microstructure factors, such as the length and content of PSt hydrophobic blocks in the copolymers and their molecular weight. It was found that the main microstructure factors which effect the hydrophobic association behavior of the copolymer PAM-b-PSt are the length and content of PSt hydrophobic blocks in the copolymer, whereas the hydrophobic association behavior of the copolymer is not affected nearly so much by molecular weight in more dilute regions. At the same time, it was also found that the main microstructure factors which affect the surface activity of the copolymer are the content of PSt hydrophobic blocks in the copolymer and molecular weight, whereas the length of PSt blocks in copolymer does not affect surface activity of the copolymer nearly so much under fixed content of PSt hydrophobic blocks and molecular weight in the copolymer.