原位聚合法制备壳聚糖/聚丙烯酸水凝胶磁微球及其性能表征

为了避免制备过程中有机试剂对水凝胶磁微球生物安全性的影响,采用原位聚合法,在水溶液体系中制备了壳聚糖/聚丙烯酸(CS/PAAc)水凝胶磁微球.首先将壳聚糖(CS)包覆于纳米磁微球(Fe3O4)表面,随后加入丙烯酸单体,使其在壳聚糖磁微球上吸附并且原位聚合,然后经戊二醛交联得到了CS/PAAc水凝胶磁微球.用红外光谱、扫描电镜对合成的水凝胶磁微球进行了结构表征和形貌观察,并且进行了热重分析、元素分析、磁性能测试和粒度分析;研究了pH对水凝胶磁微球溶胀性能的影响.结果表明CS/PAAc水凝胶磁微球具有较好的球形结构,大小在500 nm左右;Fe3O4含量约为73%,具有良好的顺磁性质,磁饱和强度为45 emu·g-1;呈现出良好的pH敏感性,当pH=3时,CS/PAAc水凝胶磁微球的溶胀率达到最小.     

聚丙烯酸镍纳米微球的制备及表征

本文以低分子量聚丙烯酸 (PAA)和氯化镍 (NiCl2 ·6H2 O)为主要原料 ,通过控制体系的 pH值下合成聚丙烯酸镍纳米微球。实验结果表明 ,PAA—Ni在该体系中 ,具有较好的分散性 ,通过TEM观察尺寸达 2 0nm左右。用IR、原子吸收分光光度法研究了Ni与聚丙烯酸 (PAA)间的配位作用、所形成的配位聚合物的组成和结构 ,确定了Ni与PAA分子间以配位键相结合形成Ni—PAA配聚物 ,配聚物的配位单元由 1个Ni与 2个PAA单体单元的羧基 (—COOH)形成螯合双齿结构。     

壳聚糖微球的制备

用甲醛作为交联剂,通过悬浮交联法制备粒径不同的壳聚糖微球。通过控制反应条件,可以得到单分散性的微米级微球。通过光学显微镜及红外光谱仪等仪器对所得的产物进行了表征。     

水溶性壳聚糖及磁性壳聚糖微球的制备

以废弃蟹壳为原料制备出了高脱乙酰度壳聚糖和脱乙酰度50%的水溶性壳聚糖,通过电位滴定、红外光谱等对产物的脱乙酰度、功能基团作了表征,测定了产物的黏度,结果表明制备的水溶性壳聚糖的动力黏度为82.9 mPa.s。以0.01 mol/L硝酸钴和0.02 mol/L硝酸铁的混合溶液,采用微乳液法制备了纳米铁酸钴,以水溶性壳聚糖为原料制备了壳聚糖/纳米铁酸钴复合微球,TEM结果显示该磁性壳聚糖微球为规则球形,粒径13μm左右,分散性好。     

壳聚糖微球的制备研究

利用液体石蜡作有机分散介质,甲醛、戊二醛作交联剂,通过反相悬液交联法制备了微米级窄分布壳聚糖微球,对合成最佳条件进行了实验选择,并对产物的形态、红外光谱特性及吸附行为进行了初步表征     

壳聚糖/明胶复合微球的制备及吸附性能研究

以壳聚糖和明胶为原料,span 80为乳化剂,戊二醛为交联剂,采用乳化交联法制备了壳聚糖/明胶复合微球并用于Cr(Ⅵ)的吸附。考察了复合微球的各制备因素对微球形貌的影响,通过单因素分析研究了壳聚糖与明胶的比例、乳化剂用量、乳化时间对复合微球吸附性能的影响。结果表明,壳聚糖与明胶的比例为1∶2、span80用量为6mL、乳化时间为50min时,制备的复合微球对Cr(Ⅵ)的吸附性能良好,吸附量较大,Cr(Ⅵ)的去除率可达95.3%。     

聚乳酸-壳聚糖共聚物载药微球的制备及性能研究

为了改善聚乳酸(PLLA)的组织相容性及细胞亲和性,提高盐酸乌拉地尔生物利用率,文中在催化剂4-(二甲胺基)吡啶与N,N'-二环己基碳酰亚胺共同作用下,将含亲水基团的碱性聚电解质壳聚糖(CS)与PLLA共聚,制备了聚乳酸-壳聚糖接枝共聚物(PLCS),采用溶剂挥发法制备盐酸乌拉地尔PLCS微球并对其结构进行了表征,同时对微球的包封率和药物释放进行了测试。通过有机相加入乙醇的方法可以提高微球对药物的包封率。结果表明,当无水乙醇与三氯甲烷的体积比为1∶2时,制得的微球包封率最高,达到34.86%。体外药物释放结果表明,PLCS微球具有明显的缓释作用,其释药动力学满足Higuchi方程。     

热固性聚丙烯酸酯/铝粉微球的制备研究

利用聚丙烯酸酯乳液与铝粉浆共混,再加入固化剂,采用离心喷雾干燥工艺,成功制备了热固性聚丙烯酸酯包覆铝粉微球。考察了铝粉种类与用量、固化剂用量等对包覆微球粒径和表面形貌的影响。结果表明,随着固化剂的引入,包覆微球的粒径及其分布和微观形貌变化不大;铝粉的粒径对包覆微球粒径影响较小,但是铝粉粒径太大导致微球包覆不完全,出现片状物;随着微球中铝粉含量增加,微球的粒径增加,粒径分布变宽,微球规整度降低,破裂增多。当铝粉含量为5%,微球的包覆效果较好。     

壳聚糖缓释微球的制备与表征

以壳聚糖(Chitosan)、戊二醛(Glutaraldehyde)、尿素(Urea)为主要原料,采用乳化-化学交联法制备尿素-壳聚糖缓释微球.通过红外光谱测试,分析缓释微球的结构特征;通过扫描电镜测试,观察微球的微观形貌;通过交联度测试确定戊二醛的最佳用量;通过缓释测试,测定壳聚糖微球的缓释效果.结果表明:采用乳化-...     

羧甲基壳聚糖离子配位微球的制备及性能研究

以羧甲基壳聚糖(CMCHS)为主要原料,采用静电脉冲液滴发生器制备羧甲基壳聚糖离子配位微球。光学显微镜观察微球具备规整形貌,扫描电镜分析显示干球粒径约为100μm且表面呈多孔结构;红外光谱证明其内部具有由CMCHS上的羧酸根与Ca^2 配位形成的羧酸盐结构。溶胀实验表明,CMCHS溶液浓度、金属离子种类及其浓度等制备条件均影响微球的溶胀性能．且其溶胀行为对pH值较敏感。药物体外释放初步研究表明,CaCl2浓度和释放介质pH值均对微球的释放性能产生影响。研究对其进一步应用于药物释放等领域具有重要意义。     

Hot Melt Reactive Extrusion of Chitosan with Poly(acrylic acid)

The hot melt reactive extrusion of blends of chitosan and poly(acrylic acid) (PAA) was carried out without any process additives such as organic solvent or plasticizer. The maximum amount of chitosan in the blend during the extrusion process was kept at 40 wt%, since the melt viscosity of a system containing 50 wt% of chitosan exceeded the torque limitation of the equipment. The carboxylic groups of PAA interacted with the amine groups of chitosan during the melt process, and the system exhibited good melt flow. The interactions between these two polymers were explained by investigating the results obtained by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The thermal transition behavior of PAA was altered with a decrease of more than 10°C in the peak melting point after extrusion. The infrared (IR) spectroscopic data confirmed the existence of a complex formation and possible hydrogen bonding between chitosan and PAA during the melt process. Scanning electron microscopy (SEM) micrographs indicated that chitosan was well-dispersed in the PAA blends up to 30 wt% chitosan, with no indication of loose particles or other disruptions on the upper and lower fractured faces. This smooth interface might have been caused by the interaction between amide bonds of chitosan and carboxylic groups of PAA.     

Polyion Complex Nanofibrous Structure Formed by Self‐Assembly of Chitosan and Poly(acrylic acid)

Summary: An ideal scaffold design has a nanofibrous structure that can replace the natural extracellular matrix (ECM) until host cells can repopulate and resynthesize a new natural matrix. In this study, chitosan (CS)‐poly(acrylic acid) (PAA) nanofibers with diameters that range from 50 to 150 nm are synthesized successfully by a modified dropping method. Exactly how various carboxylic acid solvents affect the formation of CS‐PAA nanofibrous complex is also discussed. The results show that using adipic acid as a solvent to dissolve CS, adjusting the final pH value of the CS solution to 3, and then dropping the CS solution into the PAA solution at a ratio of 3:1, cause a significant reaction of CS with PAA and the nanofibers are dispersed uniformly. After freeze‐drying, a 3‐D interconnected CS‐PAA nanofibrous scaffold with a fiber diameter that ranges from 50 to 200 nm can be obtained. The CS‐PAA nanofibrous matrix is of particular interest in tissue engineering for controlled drug release and tissue remodeling.

Nanofibrous structure via polyion complex formation between chitosan and poly(acrylic acid).     

Poly(acrylic acid)-grafted magnetic nanoparticle for conjugation with folic acid

Poly(acrylic acid) (poly(AA))-grafted magnetite nanoparticles (MNPs) prepared via surface-initiated atom transfer radical polymerization (ATRP) of t-butyl acrylate, followed by acid-catalyzed deprotection of t-butyl groups, is herein presented. In addition to serve as both steric and electrostatic stabilizers, poly(AA) grafted on MNP surface also served as a platform for conjugating folic acid, a cancer cell targeting agent. Fourier transform infrared spectroscopy (FTIR) was used to monitor the reaction progress in each step of the syntheses. The particle size was 8 nm in diameter without significant aggregation during the preparation process. Photocorrelation spectroscopy (PCS) indicated that, as increasing pH of the dispersions, their hydrodynamic diameter was decreased and negatively charge surface was obtained. According to thermogravimetric analysis (TGA), up to 14 wt% of folic acid (about 400 molecules of folic acid per particle) was bound to the surface-modified MNPs. This novel nanocomplex is hypothetically viable to efficiently graft other affinity molecules on their surfaces and thus might be suitable for use as an efficient drug delivery vehicle particularly for cancer treatment.     

Swelling behavior of chitosan/poly(acrylic acid) complex

This study investigates the improved swelling behavior of chitosan/poly(acrylic acid) complex by solvent (methanol, ethanol, and acetone) extraction. The complex is developed by photoinitiated free‐radical polymerization of acrylic acid in the presence of chitosan. The swelling ratio of the complexes depends on the cosolvency effect of poly(acrylic acid) to the extracted solvent, which in turn affects the polymer network structure and ionic states characterized by dynamic force microscopy (DFM), Raman, and FT‐IR spectroscopy. The DFM investigation displays the improved structural changes of the polymer network structure after solvent extraction and its relation to the improved swelling property of the chosen system in different environmental conditions (pH, solvent, and salt concentration) are discussed. A high swelling ratio of about 600 times its dry weight is observed in water as well as in low salt and solvent concentration after methanol extraction. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2930–2940, 2004     

Characterization of polyelectrolyte effect in poly(acrylic acid) solutions

The viscometric behavior of poly(acrylic acid) solutions, as well as their ion transport properties, were monitored as a function of polymer concentration and the addition of KOH in nonisoionic conditions. Polyelectrolyte effect was studied and characterized by conductivimetry as well as viscometric properties at the infinite dilution limit. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 191–196, 2003     

Synthesis and characterization of chitosan/poly(acrylic acid) polyelectrolyte complex

Polyelectrolyte complex based on chitosan and acrylic acid monomer by photoinitiated free‐radical polymerization in the absence of crosslinker showed a large transition in swelling in response to changes in pH of surrounding medium. Their ability to swell arises from polyelectrolyte interactions and molecular structure of the complex. The main properties of interest that related to the molecular structure, swelling volumes, glass transition temperature, and elastic modulus of the complex were investigated. The effect of water content, the only variable in the sample component, played an important role in molecular structure of the complex and as a consequence, the extent of intermolecular linkage, especially amide bonds which in turn governed the degree of swelling of the polyelectrolyte complex in this study. The decreased degree of swelling and higher temperature shift of glass transition temperature was found with increased water content, whereas increased modulus of elasticity of dry complex was found in lower water content of synthesis component. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1025–1035, 2002     

Preparation and characterization of chitosan-poly(acrylic acid) polymer magnetic microspheres

A modified method to prepare chitosan-poly(acrylic acid)(CS-PAA) polymer magnetic microspheres was reported in this paper. First, via self-assembly of positively charged CS and negatively charged Fe₃O₄ nanoparticles, magnetic CS cores with a large amount of Fe₃O₄ nanoparticles were successfully prepared. Subsequently, the AA monomers were polymerized on the magetic CS cores based on the reaction system of water-soluble polymer-monomer pairs. These polymer magnetic microspheres had a high Fe₃O₄ loading content, and showed unique pH-dependent behaviors on the size and zeta potential. From the magnetometer measurements data, the CS-PAA polymer magnetic microspheres also had superparamagnetic property as well as fast magnetic response. A continuous release of the entrapped ammonium glycyrrhizinate in such polymer magnetic microspheres occurred, which confirmed the potential applications of these microspheres for the targeted delivery of drugs.     

聚丙烯酸/氧化石墨烯自修复水凝胶的合成及性能

通过改进的Hummers方法成功制备了氧化石墨烯(GO)。以Fe3+为交联剂、丙烯酸(AA)为单体、GO为增强剂,采用原位聚合法制备了聚丙烯酸(PAA)/GO自修复水凝胶。考查了不同GO含量下,PAA/GO自修复水凝胶的溶胀性能,并探讨了GO含量、Fe3+含量和H2O含量对PAA/GO自修复水凝胶力学性能的影响,研究了PAA/GO自修复水凝胶的自修复性能。结果表明,Fe3+含量、GO含量和H2O单体含量分别为0.5 %（摩尔分数）、0.5 %（质量分数,下同）、80 %时,具有最佳力学性能（其拉伸强度为743.5 kPa,断裂伸长率为2940.5 %）;GO含量为0.25 %时,PAA/GO自修复水凝胶的吸水性能最大;PAA/GO自修复水凝胶具有优异的自修复性能。     

Poly(acrylic acid)–poly(vinyl alcohol) copolymers with superabsorbent properties

Biodegradable polyacrylates were produced by a series of novel copolymerization and/or crosslinking techniques using poly(vinyl alcohol) (PVA) moieties modified by the incorporation of olefinic structures. PVA was modified by a tosylation and/or detosylation reaction. The functionalized PVA was copolymerized and/or crosslinked with acrylic acid or its partially neutralized form to give crosslinked polyacrylates that could swell in water. Their swelling behavior was determined under load. Degradation studies were performed in α-chymotrypsin, trypsin, and papain solutions. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 817–829, 1998     

壳聚糖/聚丙烯酸水凝胶的制备及对Cu2 和Cd2 的吸附性能

以丙烯酸(AA)和壳聚糖(CS)为原料,N,N''-亚甲基双丙烯酰胺(MBA)为交联剂,利用辉光放电电解等离子(GDEP)技术在水溶液中一步引发制备壳聚糖/聚丙烯酸(CS/PAA)水凝胶。采用FT-IR、XRD和SEM对水凝胶的结构和形貌进行表征,考察了溶液pH、吸附时间和初始浓度对Cu2 和Cd2 吸附的影响,探讨了水凝胶的重复利用性。结果表明,丙烯酸成功接枝到壳聚糖链上,水凝胶呈现多孔的三维网络结构,CS/PAA对Cu2 和Cd2 的吸附符合Langmuir 吸附等温式和准二级动力学模型,由Langmuir 模型得到的最大理论吸附量为161.8和327.9 mg/g,该水凝胶在EDTA-4Na溶液中具有良好的再生和重复利用性。