κ-卡拉胶热可逆凝胶的非遍历行为研究

采用散射斑纹(speckle)技术,即散射光强涨落法,研究了κ-卡拉胶(KC)热可逆凝胶的非遍历行为.证明了非遍历性的存在,并研究了浓度、温度等条件对该非遍历性的影响.结果表明:该物理凝胶存在非遍历性,并随KC浓度增加,凝胶非遍历性增大;随温度升高,凝胶非遍历性逐渐减小,直至消失.     

κ-卡拉胶热可逆凝胶化行为研究

用固体小角激光散射方法研究κ 卡拉胶 (KC)的热可逆凝胶化行为 .以散色斑点的突停点温度为体系的凝胶化点Tgel,考察了溶液中加入Na+ ,K+ ,NH+4,Ca2 + ,Cu2 + ,Zn2 + 等抗衡离子对Tgel的影响 .结果是随抗衡离子浓度增大Tgel上升 ;Tgel与Na+ 的浓度呈线性关系 ,与K+ ,NH+4,Ca2 + ,Cu2 + ,Zn2 + 等离子浓度的平方根成线性关系 ;另外 ,还得到 30℃时KC在KCl盐溶液中的溶胶 凝胶相图 ,并对比了KC在NaCl溶液中透析前后Tgel的变化 .     

有机盐对水/AOT/醇反相微乳体系电导行为的影响

用二(2-乙基己基)琥珀酸酯磺酸钠(AOT)为表面活性剂研究了以正构醇(己醇、庚醇、辛醇、癸醇)为连续相的微乳体系的电导行为, 结果表明只有水/AOT/癸醇体系有水诱导的电导渗滤现象. 研究了有机盐(胆酸钠、水杨酸钠)及温度对电导行为的影响, 发现庚醇、辛醇体系电导率随胆酸钠浓度的增加而减小, 而癸醇体系电导率不受影响; 庚醇、癸醇体系的电导率随水杨酸钠浓度的增加而增大; 在5～40 ℃范围内lnσ(电导率的自然对数)与温度成很好的线性关系, 无论有机盐存在与否都没有温度诱导的渗滤现象. 根据Arrhenius-type公式估算了体系的电导活化能.     

辐射交联制备改性CMC水凝胶的溶胀行为研究

利用丙烯酰胺 (AAm)接枝改性纤维素 ,然后进行羧甲基化反应得到高取代度的丙烯酰胺 羧甲基纤维素钠 (AAm CMC Na) .对该材料进行γ射线辐照制备出新型改性CMC水凝胶 .研究了这种水凝胶的溶胀动力学、交联动力学以及温度、pH值和无机盐浓度对水凝胶溶胀行为的影响 ,并与CMC Na水凝胶进行了比较 .结果表明 ,该水凝胶和CMC Na水凝胶相比 ,优点在于辐照交联所用的剂量下降 ,而且所需的CMC浓度减少 .AAm CMC Na水凝胶的溶胀度随温度升高而增大 ,在pH为 6～ 8范围内达到最大值 ,并随无机盐浓度与吸收剂量增加而下降 ,表现出较好的温度敏感性和pH敏感性 ,可望作为吸水材料和水保持剂     

K-型卡拉胶/聚乙烯吡咯烷酮共混水凝胶的辐射合成

采用辐射技术合成了K 型卡拉胶 (KC) /聚乙烯吡咯烷酮 (PVP)共混水凝胶 ,研究了天然高分子KC、单体N 乙烯基吡咯烷酮 (N VP)、交联剂二甲基丙烯酸十四甘醇酯 ( 1 4G) ,辐照剂量以及剂量率等对辐射合成的KC/PVP共混水凝胶性质的影响 .实验发现 ,KC与适当比例的N VP共混后在一定剂量范围内辐照可得到高强度、高溶胀行为的KC/PVP共混水凝胶 ,随着共混凝胶内KC含量的相对增加 ,凝胶强度及溶胀性的能均显著提高 ,但合成该共混凝胶的最佳剂量却相对提前 ;加入 1 4G后降低了KC/PVP共混凝胶辐射合成最佳剂量 ,同时使KC/PVP共混凝胶的强度进一步提高 ;剂量、剂量率对KC/PVP共混凝胶的性质亦有很大的影响 .分析表明 ,KC与N VP共混后 ,在较低剂量下KC的降解被抑制 ,从而获得一种由物理交联的KC和化学交联的PVP形成的互穿网络 (IPN)凝胶     

十六烷基二苯醚二磺酸钠表面化学性质及胶团化作用

用滴体积法通过表面张力的测定, 系统地研究了十六烷基二苯醚二磺酸钠(C₁₆-MADS)在不同温度(298.0～318.0 K)和不同NaCl浓度(0～0.50 mol•L^-1)下的表面活性. 结果表明, 温度升高使C₁₆-MADS溶液的临界胶束浓度(cmc)略有增大, 表面极限吸附量(Γ_∞)降低. cmc随NaCl浓度的增大从1.45×10^-4 mol•L^-1降至4.10×10^-5 mol•L^-1, 但最低表面张力(γ_cmc)基本不受影响. 在298.0 K与303.0 K时, NaCl浓度的增大, Γ_∞增大; 在308.0、313.0与318.0 K时, NaCl浓度的增大, 出现了Γ_∞从2.27 μmol•m^-2降低至1.41 μmol•m^-2的“反常”现象. 胶团形成自由能(ΔG_m⁰)随温度和NaCl浓度增加负值增大(－63.98～－76.20 kJ•mol^-1), 胶团的形成主要是熵驱动过程.     

β-环糊精与两性表面活性剂相互作用

用表面张力法研究了β-环糊精与十一烷基酰胺甲酸钠(C₁₁H₂₃CONHCOONa,SF)两性表面活性剂在不同温度下的包结作用。结果表明:SF的表面张力值(β)及表观临界胶束浓度(cmc^*)加入β-CD后增加,β-CD浓度越大,γ和cmc^*增加越多,且SF的cmc^*与β-CD浓度存在线性关系,随温度的升高,两性表面活性剂的表面张力值降低,意味着它们的表面活性随温度升高而增强。利用表面张力测定了β-CD-SF体系在不同温度下的包结形成常数K_a,进而求得了包结过程的焓变和熵变,结果表明,该过程是焓和熵均有利的过程,进一步说明疏水作用是形成包结物最重要的的作用力之一。     

十八烷基-L-苯丙氨酸齐聚物在有机溶剂中的自组装

由L-苯丙氨酸和二(三氯甲基)碳酸酯反应得到的L-苯丙氨酸-N-羧基-环内酸酐(L-Phe-NCA), 在十八胺的引发下开环聚合得到十八烷基-L-苯丙氨酸齐聚物(简称L-Phe-R18). ¹H NMR (300 MHz)和FT-IR表征了产物结构, 是平均聚合度为5的齐聚物. L-Phe-R18能在多种有机溶剂中发生聚集和自组装, 并进而在这些有机溶剂中形成热可逆的物理凝胶. 其中, 该齐聚物能在氯苯、二苯醚、甲苯等溶剂中形成透明凝胶. 也能在苯、硝基苯、醋酸丁酯等溶剂中形成非透明凝胶. L-Phe-R18在这些有机溶剂中的最低凝胶化浓度(MGC)在w＝0.3%～1%之间. X射线衍射(XRD)数据和场发射扫描电镜(FE-SEM)以及分子模拟表征了L-Phe-R18聚集体的微观形态和可能的聚集方式. 认为L-Phe-R18在有机溶剂中通过分子间氢键、π-π堆积等非共价键相互作用聚集、组装成厚度约为20 nm左右的带状纤维, 溶剂分子以毛细力存在于相互缠绕的纤维网络结构中, 使体系形成稳定的凝胶.     

三嵌段共聚物PAN-b-PEG-b-PAN的合成及其自组装行为的研究

利用原子转移自由基聚合(ATRP)制得了分子量可控、分子量分布窄的聚丙烯腈-b-聚乙二醇-b-聚丙烯腈P(AN-b-PEG-b-PAN)嵌段共聚物. 通过¹H NMR, FTIR, 凝胶渗透色谱(GPC)对所得产物的结构和分子量进行了表征并通过TG和DTA考察了该嵌段共聚物的热稳定性; 运用透射电子显微镜(TEM)、荧光探针技术和动态光散射(DLS)研究了P(AN)₂₇-b-P(EG)₄₅-b-P(AN)₂₇在溶剂水中胶束的形成、结构、形貌和胶束粒径. 结果表明, 三嵌段共聚物P(AN)₂₇-b-P(EG)₄₅-b-P(AN)₂₇的热稳定性较纯聚乙二醇P(EG)好, 且柔性链PEG的引入对嵌段共聚物的放热峰位置没有显著的影响. 当改变此嵌段共聚物溶液浓度时, 该嵌段共聚物会自组装成不同形状的胶束, DLS测量的胶束粒径大于TEM观察的结果, 其临界胶束浓度(cmc)约为4.46×10^－4 g•L^－1.     

κ-型卡拉胶/聚乙烯吡咯烷酮共混水凝胶的辐射制备及性质研究

采用辐射技术制备了κ-型卡拉胶 ( KC) /聚乙烯基吡咯烷酮 ( PVP)共混水凝胶 ,研究了共混凝胶内 KC含量、PVP的分子量和辐照剂量等对 KC/ PVP共混水凝胶性质的影响 .实验发现 ,KC与高分子量的 PVP( k-90 )共混后在一定剂量范围内辐照可得到高强度、高溶胀行为的 KC/ PVP共混水凝胶 ,随着共混凝胶内KC含量的增加 ,凝胶强度及溶胀性能均显著提高 .分析表明 ,KC与高分子量的 PVP共混后 ,在较低剂量下 KC的降解被抑制 ,从而获得一种由物理交联的 KC和化学交联的 PVP形成的互穿网络 ( IPN)凝胶 .     

Temperature-induced association and gelation of aqueous solutions of pectin. A dynamic light scattering study

Dynamic light scattering (DLS) measurements were carried out on aqueous solutions of low-methoxyl pectin at different temperatures and polymer concentration. Low temperature and increased polymer concentration promote the formation of multichain aggregates. The time correlation data obtained from the DLS experiments revealed, for all polymer solutions, the existence of two relaxation modes, one single exponential at short times followed by a stretched exponential at longer times. In the semidilute regime, a temperature reduction induced enhanced chain associations in the solutions with high values of the slow relaxation time and a strong wave vector dependence of the slow mode. These features could be rationalized in the framework of the coupling model of Ngai. At low temperatures (10 °C), gelation occurs in the semidilute regime and a transparent gel is formed. In this state, the profile of the correlation function changes and nonergodic signs are observed. The conjecture is that the association complexes and the gel network are stabilized through intermolecular hydrogen bonds, which are broken-up at higher temperatures. The hydrogen-bonded structures are formed in a process where the polymer chains have been “zipped” together in a cooperative manner.     

Core-corona structure of cubic silsesquioxane-poly(ethylene oxide) in aqueous solution: fluorescence, light scattering, and TEM studies

Well-defined amphiphilic cubic silsesquioxane-poly(ethylene oxide) (CSSQ-PEO) was prepared from octakis (dimethylsiloxy)octasilsesquioxane (Q8M8(H)) and allyl-PEO through a hydrosilylation reaction. The structure of CSSQ-PEO was characterized by nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FTIR), and gel permeation chromatography (GPC). The amphiphilic properties and aggregation process of CSSQ-PEO in aqueous solution were investigated by fluorescence, dynamic and static light scattering (DLS and SLS), and transmission electron microscopy (TEM). The critical aggregation concentration (CAC) determined by fluorescence measurements was found to be 0.28 mg/mL. Combinations of DLS, SLS, and TEM studies showed the existence of core-corona micelle with hydrophobic CSSQ as the core and hydrophilic PEO as the corona in aqueous solution. The observation of two size distribution peaks from DLS measurements revealed the coexistence of small amounts of unassociated unimolecular micelles (approximately 10% of the scattered intensity) together with micellar aggregates when the CSSQ-PEO concentration was < or = 2 mg/mL. The hydrodynamic radii (R(h)) of unassociated unimolecular micelle and micellar aggregates were found to be 26 and 79 nm, respectively. A large R(g)/R(h) ratio (1.46) and the extremely small value of average chain density (4 x 10(-4) g/cm3) indicate the small hydrophobic CSSQ core was surrounded by the extended PEO coronae. The aggregation number (N(agg)) of CSSQ-PEO in aqueous solution was found to be 38 +/- 2 from SLS and 31-40 from TEM, respectively. The long PEO segments act as a spacer between the spherical aggregates, which facilitate the formation of a network-like structure at high concentration.     

Preparation and characterization of temperature and pH-sensitive chitosan material and its controlled release on coenzyme A

A novel copolymer P(CS–Ma–DMAEMA) was synthesized with chitosan (CS), maleic anhydride (Ma) and 2-(dimethylamino)ethyl methacrylate (DMAEMA) by grafting and copolymerization. The copolymer obtained was analyzed by FT-IR, ¹H NMR and UV, and the molecular weight and polydispersity were determined by gel permeation chromatography (GPC). The average size and distribution of copolymer micelles were determined by dynamic light scattering (DLS). Their aqueous solution properties and controlled coenzyme A delivery were also studied. It was found that the copolymer had temperature sensitivity and pH sensitivity. The factors affecting release behavior, such as concentration, pH and temperature were discussed in this paper. The higher concentration of the copolymer aqueous solution absorbed more coenzyme A than the lower one. The increasing temperature accelerated the drug release from the copolymer. The pH of the copolymer solution had significant impact on the release of coenzyme A. The results suggested that the novel copolymer could be used as drug delivery carrier.     

Non-surface activity and micellization behavior of cationic amphiphilic block copolymer synthesized by reversible addition-fragmentation chain transfer process

Cationic amphiphilic diblock copolymers of poly(n-butylacrylate)-b-poly(3-(methacryloylamino)propyl)trimethylammonium chloride) (PBA-b-PMAPTAC) with various hydrophobic and hydrophilic chain lengths were synthesized by a reversible addition-fragmentation chain transfer (RAFT) process. Their molecular characteristics such as surface activity/nonactivity were investigated by surface tension measurements and foam formation observation. Their micelle formation behavior and micelle structure were investigated by fluorescence probe technique, static and dynamic light scattering (SLS and DLS), etc., as a function of hydrophilic and hydrophobic chain lengths. The block copolymers were found to be non-surface active because the surface tension of the aqueous solutions did not change with increasing polymer concentration. Critical micelle concentration (cmc) of the polymers could be determined by fluorescence and SLS measurements, which means that these polymers form micelles in bulk solution, although they were non-surface active. Above the cmc, the large blue shift of the emission maximum of N-phenyl-1-naphthylamine (NPN) probe and the low micropolarity value of the pyrene probe in polymer solution indicate the core of the micelle is nonpolar in nature. Also, the high value of the relative intensity of the NPN probe and the fluorescence anisotropy of the 1,6-diphenyl-1,3,5-hexatriene (DPH) probe indicated that the core of the micelle is highly viscous in nature. DLS was used to measure the average hydrodynamic radii and size distribution of the copolymer micelles. The copolymer with the longest PBA block had the poorest water solubility and consequently formed micelles with larger size while having a lower cmc. The "non-surface activity" was confirmed for cationic amphiphilic diblock copolymers in addition to anionic ones studied previously, indicating the universality of non-surface activity nature.     

Light scattering and luminescence studies on self-aggregation behavior of amphiphilic copolymer micelles

The self-aggregation behavior of three amphiphilic graft copolymers, oligo(9,9-dihexyl)fluorence-graft-poly(ethylene oxide) (OHF-g-PEO), with different architectures was studied by dynamic and static light scattering (DLS and SLS) in combination with fluorescence spectroscopy and transmission electron microscopy (TEM). The formation of self-assembled polymeric micelles was confirmed by SLS and TEM. DLS and SLS analyses showed that the architecture of graft copolymers has a dramatic effect on critical aggregation concentration (CAC), micelle size distribution, apparent aggregation number (Nagg app), and apparent molecular weight of polymer aggregates (Mw,agg app). An architecture-dependent excimer emission, resulting from the pi-pi stacking of the oligofluorene backbones, was also observed from the photoluminescence spectra of the micelle aqueous solutions, which indicated a strong intermolecular interaction among the polymeric molecules. The excimer emission was further investigated by time-resolved fluorescence spectroscopy.     

Thermo-Responsive Hydrogels Based on Branched Poly(L-lactide)-poly(ethylene glycol) Copolymers

Summary: Branched poly(L -lactide)-poly(ethylene glycol) (PLLA-PEG) block copolymers were synthesized from trifunctional PLLA and amine functionalized methoxy poly(ethylene glycol)s. The copolymers in water formed hydrogels that showed thermo-responsive behavior. The hydrogels underwent a gel to sol transition with increasing temperature as determined with the vial tilting method and oscillatory rheology. For all copolymers, the transition temperature increased with increasing copolymer concentration. The transition temperature of corresponding branched copolymers also increased with increasing PEG molecular weight, and surprisingly decreased with increasing molecular weight of the PLLA branches. In general, the gel-sol transition is explained by disruption of micellar or aggregate interactions because of partial dehydration and shrinkage of the PEG chains. An increase in the molecular weight of the PLLA branches led to the formation of micelles and aggregates as observed with DLS at low concentrations. It is speculated that the non-uniform size distribution and possible crystallization of longer PLLA blocks may have a negative effect on the formation of micellar packing upon gelation, allowing the disruption of micellar or aggregate interactions to occur at lower temperatures. The transition temperature of the gels could be tuned closely to body temperature by varying the concentration of the solution or the molecular weight of the PEG block and the PLLA blocks, which implies that these polymers may be used as injectable systems for in-situ gel formation.     

Aggregation behavior of amphiphilic random copolymer of 2‐(acrylamido)‐2‐methylpropanesulfonic acid and tris(trimethylsiloxy)silylpropylmethacrylate in aqueous solution

Aggregation behavior including dilute solution property and surface‐activity of the amphiphilic random copolymer composed of 2‐(acrylamido)‐2‐methylpropanesulfonic acid and tris(trimethylsiloxy)silylpropylmethacrylate (AMPS/TRIS copolymer) in aqueous solution were studied by static light scattering (SLS), dynamic light scattering (DLS), surface tension measurement, and transmission electron microscopy (TEM). The surface tension measurement made it clear that AMPS/TRIS copolymer exhibited weaker surface‐activity than a typical low‐molecular weight surfactant sodium dodecyl sulfate in water, that is, there were no plateau of surface tension γ versus concentration and no critical micelle concentration (CMC) in the whole concentration studied. SLS and DLS analyses, and TEM revealed that AMPS/TRIS copolymer self‐associated into imperfect core‐shell micelles having hydrophobic TRIS core surrounded by hydrophilic AMPS shell in water. AMPS shell was considered as a hard shell due to the stiffness of AMPS chain in water. TRIS chain could not densely aggregate in water due to the large steric hindrance between bulky trimethylsiloxy groups despite its hydrophobic nature, thereby providing TRIS core with less‐dense structure. The balance between the spreading force of stiff AMPS chain and the cohesion force of bulky TRIS chain provides the driving force for forming the unique micelle having less‐dense TRIS core and hard AMPS shell. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Unusual behavior in light scattering experiments of poly(<Emphasis Type="Italic">N</Emphasis>-vinylimidazole) prepared by precipitation polymerization

Poly(N-vinylimidazole) (PVI) was synthesized by the precipitation polymerization using 2,2’-azobis(isobutyronitrile) (AIBN; initiator) and benzene (solvent) at two different monomer/initiator ratios. The solution polymerization was also performed with the following initiator/solvent systems: AIBN/water–methanol mixture (1:1 by volume) and 4,4’-azobis(4-cyanovaleric acid)/aqueous HCl solution (pH 0.8). All the four preparations of PVI in ethanol and in 0.2 M NaCl (pH 3 with HCl) were examined by dynamic light scattering (DLS). The CONTIN analysis of DLS data for each preparation from the solution polymerization showed a unimodal distribution in both ethanol and aqueous solvents. A good agreement was obtained between the molar masses in these different solvents by static light scattering (SLS). However, the polymers from the precipitation polymerization exhibited a heterogeneous bimodal distribution in DLS under the same conditions as above, indicating that the SLS data as in reference [6] (Savin et al. Macromolecules 37:6565) cause a serious error in the understanding of solution behavior of PVI.     

Formation of intra- and interparticle polyelectrolyte complexes between cationic nanogel and strong polyanion

Polyelectrolyte complex formation of a strong polyanion, potassium poly(vinyl alcohol) sulfate (KPVS), with positively charged nanogels was studied at 25 degrees C in aqueous solutions with different KCl concentrations (C(s)) as a function of the polyion-nanogel mixing ratio based on moles of anions versus cations. Used as the gel sample was a polyampholytic nanogel consisting of lightly cross-linked terpolymer chains of N-isopropylacrylamide, acrylic acid, and 1-vinylimidazole; thus, the complexation was performed at pH 3 at which the imidazole groups are fully protonated to generate positive charges. Turbidimetric titration was employed to vary the mixing ratio. Also employed for studies of the resulting complexes at different stages of the titration were dynamic light scattering (DLS) and static light scattering (SLS) techniques. It was found from the titration as well as DLS and SLS that there is a critical mixing ratio (cmr) at which both the size and molar mass of the complexed gel particles abruptly increase. The value of the cmr at C(s) = 0 or 0.01 M (mol/L) was observed at approximately 1:1 mixing ratio of anions versus cations but at lower mixing ratios than the 1:1 ratio under conditions of C(s) = 0.05 and 0.1 M. At the mixing ratios less than the cmr, the molar mass of the complex agrees with that of one gel particle with the calculated amount of the bound KPVS ions, indicating the formation of an "intraparticle" KPVS-nanogel complex, by the aggregation of which an "interparticle" complex is formed at the cmr. During the process of the intraparticle complex formation, both the hydrodynamic radius by DLS and the radius gyration by SLS decreased with increasing mixing ratio, demonstrating the gel collapse due to the complexation. At C(s) = 0 or 0.01 M and under conditions where the amount of KPVS bindings was less than half of the nanogel cations, however, the decrease of the hydrodynamic radius was very small, while the radius gyration fell monotonically. These results were discussed in connection with a collapse of dangling chains attached to the nanogel surface by the binding of KPVS.