降解壳聚糖季铵盐的制备及其在亚麻染色中的应用

降解壳聚糖季铵盐是将降解壳聚糖的氨基通过引入基团转换成季铵盐或者把一个低分子季铵盐接到氨基上而得到的一类降解壳聚糖衍生物。降解壳聚糖季铵盐在亚麻织物染色中的应用研究表明其具有一定的助染作用。国外对壳聚糖季铵盐的合成已有报道,如1985年国外报道了碘化壳聚糖季铵盐的合成方法,但得到的碘化N-三甲基壳聚糖季铵盐是不溶于水的。     

壳聚糖季铵盐的制备及应用进展

壳聚糖季铵盐是一种具有广阔应用前景的阳离子聚合物。概述了壳聚糖季铵盐的制备方法以及壳聚糖季铵盐在水处理、化妆品、制膜等领域的应用进展情况,并展望了壳聚糖季铵盐的研究趋势。     

季铵盐改性壳聚糖微球对含铬废水的吸附性能

用2,3-环氧丙基三甲基氯化铵对壳聚糖进行改性得到壳聚糖季铵盐,进一步通过乳化交联法合成壳聚糖季铵盐微球,采用傅里叶变换红外光谱（FT-IR）、差热热重分析（TG-DTG）、X-衍射衍射（XRD）和扫描电镜（SEM）对其进行表征分析。此外,研究了壳聚糖季铵盐的浓度、油水比、交联剂用量对合成的壳聚糖季铵盐微球吸附Cr(Ⅵ)性能的影响,并考察了重铬酸钾初始浓度、pH值、壳聚糖季铵盐微球添加量对Cr(Ⅵ)吸附效果的影响。结果表明：HACC浓度为0.8%(w/V)、油水比为8∶1、壳聚糖季铵盐与交联剂质量比为1.64的条件下,可以制备出球型圆整、分散性好的壳聚糖季铵盐微球。在酸性条件和较低浓度的重铬酸钾均有利于壳聚糖季铵盐微球对Cr(Ⅵ)的吸附。     

壳聚糖季铵化衍生物结构表征及特性研究

采用壳聚糖(CTS)与2,3-环氧丙基三甲基氯化铵(GTA)制备了不同取代度的水溶性壳聚糖季铵盐(HACC),通过红外、扫描电镜对壳聚糖、壳聚糖季铵盐结构进行表征,同时测试了壳聚糖季铵盐的水溶性、表面张力.结果表明:取代主要发生在壳聚糖的氨基上,改性后产物外观与粒度有很大变化;壳聚糖季铵化改性产物具有比壳聚糖更优良的水溶性、表面活性,且随着取代度的增加而提高.     

壳聚糖季铵盐的制备与应用研究进展

壳聚糖季铵盐是一种重要的壳聚糖衍生物,在环境保护、食品加工、药物负载及控释和抗菌抑菌材料的制备中有广泛应用。本文概述了壳聚糖季铵盐的基本类型及其制备方法、壳聚糖季铵盐在相关领域中的应用进展情况,并展望了壳聚糖季铵盐的研究趋势。     

壳聚糖季铵盐铜配合物的热降解行为研究

采用热重分析(TG)研究壳聚糖季铵盐铜配合物在30℃～600℃的温度范围内的热降解行为,探讨壳聚糖季铵盐铜配合物的热稳定性。研究结果表明:壳聚糖季铵盐铜配合物的热降解为一步反应,取代度对壳聚糖季铵盐的热降解有明显的影响,壳聚糖季铵盐铜配合物的特征降解温度都随取代度的增加而降低。     

壳聚糖季铵盐的微波辐射合成及应用

采用微波辐射法合成了壳聚糖季铵盐,将其作为絮凝剂对造纸白水进行处理,获得良好的效果。探讨了壳聚糖季铵盐加入量、废水pH及絮凝时间对絮凝效果的影响,确定了造纸白水的最佳处理条件。实验发现壳聚糖季铵盐能大幅降低造纸白水的COD。     

壳聚糖季铵盐对味精废水絮凝作用

用氯化三甲基壳聚糖季铵盐作絮凝剂处理味精废水。壳聚糖季铵盐适宜的pH值为9－13,CODCr去除率80％以上,高浓度壳聚糖季铵盐絮凝效果优于低浓度,延长振荡时间能提高絮凝效果,助凝剂的加入不有明显提高壳聚糖季铵盐的絮凝效果。     

壳聚糖季铵盐温敏型原位凝胶的研究

壳聚糖季铵盐是壳聚糖季铵化后的产物,已有文献报道壳聚糖(CS)/甘油磷酸盐(GP)系统是一种具有温敏性溶胶-凝胶转变的原位凝胶,本研究利用壳聚糖季铵盐与甘油磷酸盐GP组成温敏原位凝胶体系,通过改变壳聚糖季铵盐取代度和浓度,来观察不同取代度对凝胶形成和凝胶特性的影响。研究发现,壳聚糖季铵盐的不同取代度、用量以及甘油磷酸盐的量对凝胶的形成具有较为显著的影响。壳聚糖季铵盐HACC/甘油磷酸盐GP凝胶系统比壳聚糖CS/甘油磷酸盐GP凝胶系统的稳定性好。     

壳聚糖季铵盐及其衍生物的应用研究进展

壳聚糖是一种天然无毒多糖,可生物降解,具有生物相容性。在实际应用中壳聚糖水溶性差,只能在酸性介质中溶解。为了提高壳聚糖的溶解度并改善其理化及生物特性以扩大其应用范围,有必要对壳聚糖进行化学修饰。壳聚糖季铵盐是一种常见的壳聚糖修饰产物,属于水溶性壳聚糖衍生物,由于骨架上有强正电荷,因此其pH值溶解范围较宽。综述了壳聚糖季铵盐及其衍生物在抗菌活性、基因运载、给药系统、抗凝血材料、传感器等方面的应用进展,提出改进壳聚糖季铵盐及其衍生物的合成路线,可合成一系列生物学性能改良的壳聚糖季铵盐及其衍生物,有望将其应用于特殊领域。     

Preparation of nanoparticles composed of chitosan and its derivatives as delivery systems for macromolecules

Three different kinds of nanoparticles for paracellular transport were prepared using a simple and mild ionic‐gelation method. Sodium tripolyphosphate (TPP) as crosslinking agent was added into three kinds of solutions, which were chitosan solution, physical blending solution of chitosan, and glycidyl trimethylammonium chloride (GTMAC), and O‐(2‐hydroxyl) propyl‐3‐trimethyl ammonium chitosan chloride (O‐HTCC) solution respectively. O‐HTCC was synthesized by coupling of GTMAC to chitosan whose functional groups of the NH₂ groups were protected. The nanoparticles were characterized by transmission electron microscopy, atomic force microscopy, photon correlation spectroscopy, and zeta potential measurement. The results showed that increasing TPP concentration promoted the size of chitosan nanoparticles, a decrease in the size of O‐HTCC nanoparticles incurred on the contrary. The size of O‐HTCC nanoparticles is slightly bigger than that of pure chitosan nanoparticles, and smaller than that of physical blending nanoparticles (PBN). Bovine serum albumin (BSA), as a model protein drug, was incorporated into the nanoparticles. Compared with chitosan nanoparticles and PBN, high BSA loading efficiency (87.5%) and loading capacity (99.5%) are achieved by quaternized chitosan (O‐HTCC) nanoparticles, and the release profile of BSA from nanoparticles has an obvious burst effect and a slowly continuous release phase followed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

海因改性N-季铵化壳聚糖衍生物的合成及其抗菌性能

在酸性条件下,以壳聚糖与环氧季铵盐为原料反应得到水溶性良好的产物N-(2-羟丙基三甲基氯化铵)壳聚糖(HTCC),再用实验室自制的环氧海因改性,得到O-羟丙基(5,5-二甲基海因)-N-(2-羟丙基三甲基氯化铵)壳聚糖衍生物(GH-HTCC),用 FTIR、¹H NMR、UV-VIS和EA 等对产物进行表征。抗菌实验结果表明,产物对两种菌种都有一定的抗菌活性,对金黄色葡萄球菌的抗菌活性优于大肠杆菌;GH-HTCC的抗菌活性优于HTCC,并随环氧海因取代度的增加而增强;低浓度的乙二胺四乙酸(EDTA)增强了HTCC和GH-HTCC的抗菌活性,而高浓度的EDTA在一定程度上抑制了二者的抗菌活性。     

Durable antimicrobial treatment of cotton fabrics using N‐(2‐hydroxy)propyl‐3‐trimethylammonium chitosan chloride and polycarboxylic acids

N‐(2‐hydroxy)propyl‐3‐trimethylammonium chitosan chloride (HTCC), a water‐soluble chitosan quaternary ammonium derivative, was used as an antimicrobial agent for cotton fabrics. HTCC has a lower minimum inhibition concentration (MIC) against Staphylococcus aureus, Klebsiella pneumoniae, and Escherichia coli compared to that of chitosan; however, the imparted antimicrobial activity is lost on laundering. Thus crosslinking agents were utilized to obtain a durable antimicrobial treatment by immobilizing HTCC. Several crosslinkers such as dimethyloldihydroxyethylene urea (DMDHEU), butanetetracarboxylic acid (BTCA), and citric acid (CA) were used with HTCC to improve the laundering durability of HTCC treatment by covalent bond formation between the crosslinker, HTCC and cellulose. The polycarboxylic acid treatment was superior to the DMDHEU treatment in terms of prolonged antimicrobial activity of the treated cotton after successive laundering. Also, the cotton treated with HTCC and BTCA showed improved durable press properties without excessive deterioration in mechanical strength or whiteness when compared to the citric acid treatment. With the addition of only 0.1% HTCC to BTCA solutions, the treated fabrics showed durable antimicrobial activity up to 20 laundering cycles. The wrinkle recovery angle and strength retention of the treated fabrics were not adversely affected with the addition of HTCC. Therefore, BTCA can be used with HTCC in one bath to impart durability of antimicrobial activity along with durable press properties to cotton fabric. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1567–1572, 2003     

叶酸偶联N-季铵化壳聚糖的制备及其基因载体性能

首先对壳聚糖进行季铵化改性合成N-季铵化壳聚糖（HTCC）,再接枝叶酸基团制备了叶酸偶联N-季铵化壳聚糖（FA-HTCC）,用FTIR和1H NMR等对产物进行表征,并对其作为基因载体进行研究。结果表明,合成产物具有较好的水溶性,N/P为4的FA-HTCC/DNA复合物粒径为188 nm、Zeta电位为15.4 mV。与PEI和阳离子脂质体相比,FA-HTCC具有更低的细胞毒性和更高的转染效率。     

Properties of polyacrylonitrile-N-(2-hydroxy) propyl-3-trimethylammonium chitosan chloride blend films and fibers

A water-soluble chitosan derivative namely, N-(2-hydroxy) propyl-3-trimethylammonium chitosan chloride (HTCC) was synthesized by the reaction of chitosan with glycidyltrimethyl ammonium chloride in a neutral aqueous condition and solution blended with polyacrylonitrile (PAN) in an organic solvent. Polymeric films were made by casting, and they were dyed with an acid dye, a basic dye, and mixture of them. Results obtained from differential scanning calorimetry, scanning electron microscopy, and dyeing show that these polymers are immiscible even at low percentage of HTCC (lower than 20%). However, at higher ratio, the phase separation takes place. Fibers obtained from this blend system by wet-spinning technique show a good mechanical properties and increasing the amount of HTCC causes an increment in the mechanical strength of the fibers up to 20% of HTCC and beyond that due to phase separation mechanical strength reduces. Blending PAN with HTCC improves the dyeing behavior of the films and fibers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Blend fibers of polyacrylonitrile and water‐soluble chitosan derivative prepared from sodium thiocyanate solution

A water‐soluble chitosan derivative of N‐(2‐hydroxy)propyl‐3‐trimethylammonium chitosan chloride (HTCC), synthesized by the reaction of chitosan and glycidyltrimethyl ammonium chloride, and polyacrylonitrile (PAN) were blended using 46% (w/w) NaSCN aqueous solution as a common solvent. The total polymer concentration of blend solution was fixed at 12% (w/w), and the relative composition of PAN/HTCC in the blend solution varied from 0/100 to 80/20 by weight. The PAN/HTCC blend fibers with the appropriate physical property were prepared by a wet spinning and drawing process. The effect of HTCC content on the structural change, miscibility, and ability to be dyed of the blend fibers was investigated. The optical and scanning electron microscopic observation gave no indication of phase separation up to 20% HTCC content. Differential scanning calorimetry and dynamic mechanical measurements of the blend fibers show single glass transition temperatures that increase with increasing blend ratio of HTCC. All the experimental results exhibit that the blends are miscible on the molecular scale. The blend fibers could be dyed with an acid dye. This enhanced ability of the blend fibers to be dyed with acid dyes could be useful for one‐step dyeing when mixed with other fibers, such as wool and nylon. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1620–1629, 2001     

Characterization of novel quaternary chitosan derivative nanoparticles loaded with protein

The objective of this work was to characterize a novel quaternary chitosan derivative [O‐(2‐hydroxyl) propyl‐3‐trimethyl ammonium chitosan chloride (O‐HTCC)] nanoparticle system. O‐HTCC nanoparticles were prepared with a simple and mild ionic gelation method upon the addition of a sodium tripolyphosphate solution to a low‐molecular‐weight O‐HTCC solution. Highly cationic chitosan nanoparticles were prepared. Bovine serum albumin (BSA), a model protein drug, was incorporated into the nanoparticles. The physicochemical properties of the nanoparticles were determined with transmission electron microscopy (TEM), scanning electron microscopy (SEM), Fourier transform infrared analysis, differential scanning calorimetry, and X‐ray diffraction (XRD) patterns. The results showed that increasing the BSA concentration from 1.5 to 2.5 mg/mL promoted the BSA encapsulation efficiency from 57.3% to 87.5% and the loading capacity from 70.2% to 99.5%. Compared with the chitosan nanoparticles, the O‐HTCC nanoparticles had lower burst release. TEM revealed that the BSA‐loaded O‐HTCC nanoparticles were smaller than the O‐HTCC nanoparticles when the BSA concentration was 1.5 mg/mL; SEM showed that the size of the BSA‐loaded O‐HTCC nanoparticles was mostly affected by the BSA concentration, and the increase in size occurred with the concentration increasing. Thermograms and XRD of the BSA‐loaded nanoparticles suggested that polyelectrolyte–protein interactions increased with the BSA concentration increasing and greater chain realignment in the BSA‐loaded nanoparticles. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Water-soluble cationic chitosan derivative to improve pigment-based inkjet printing and antibacterial properties for cellulose substrates

The water-soluble N-(2-hydroxy)propyl-3-trimethylammonium chitosan chloride (HTCC) was prepared by chitosan and glycidyl trimethyl ammonium chloride. Fourier-transform infrared spectroscopic analysis spectrum confirmed that glycidyl trimethyl ammonium chloride was grafted to the amino groups of chitosan via substitution reaction (Zhao et al., Int J Pharm 2010, 393, 268; Montazer and Afjeh, J Appl Polym Sci 2007, 103, 178). The obtained chitosan derivative was used to modify cotton fabrics for improving aqueous pigment-based inkjet printing and antibacterial properties. Scanning electron microscope images showed that HTCC was adhered onto the cotton fabrics surface and formed film structure. The K/S value on printed cotton substrates increased from 3.20 to 4.87, which indicated that higher color yield was achieved in this way. Modified samples performed better crocking fastness and laundering fastness than the control cotton fabrics. The line definition of modified cotton fabrics respectively, improved 16.5% and 12.6% in the warp and weft direction as the specified line width was 0.5 × 10³ μm. Samples also showed good antibacterial potential, the inhibitory rate for Staphylococcus aureus and Escherichia coli were both more than 95% when the concentration of HTCC used in the pretreatment solution was 0.8%. The antibacterial effect was found to be durable for 20 laundering cycles. However, the hand feeling of modified cotton fabrics presented a slight decrease. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Modification of polyacrylonitrile (PAN) fiber by blending with N‐(2‐hydroxy)propyl‐3‐trimethyl‐ ammonium chitosan chloride

N‐(2‐Hydroxy)propyl‐3‐trimethylammonium chitosan chloride (HTCC) was synthesized by the reaction of glycidyltrimethylammonium chloride (GTMAC) and chitosan. The reaction product was a water‐soluble chitosan derivative, and showed excellent antimicrobial activity. HTCC was blended with polyacrylonitrile (PAN) using an NaSCN aqueous solution as a common solvent. The blend solution was transparent and stable up to 6 months without phase separation. The PAN/HTCC blend fibers were prepared via a wet spinning and drawing process. Thermal, electrical, and mechanical properties as well as antimicrobial activity were investigated. It was found that the antistatic property and antimicrobial activity of the blend fibers could be achieved by adding only a small amount of HTCC. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2258–2265, 1999     

2-羟丙基三甲基氯化铵壳聚糖的制备及其表征

以脱乙酰度为90%的壳聚糖(CTS)为原料,异丙醇为溶剂,w(NaOH)=40 0%的水溶液为催化剂,3 氯 2 羟丙基三甲基氯化铵(CTA)为改性剂,在m(NaOH)∶m(CTS)=1 0∶1 0,m(CTA)∶m(CTS)=4 0∶1 0,反应温度65 0℃下制备了2 羟丙基三甲基氯化铵壳聚糖(HTCC)。实验结果表明,在反应时间达到或超过9 0h时,得到的HTCC产品的接枝度超过90 0%,在pH=6 7～7 0的水中可完全溶解形成w(HTCC)=3 0%的溶液。IR和1HNMR的结果表明,接枝反应主要发生在CTS的氨基上。