The preparation and antioxidant activity of the sulfanilamide derivatives of chitosan and chitosan sulfates

Chitosan (CS) and chitosan sulfates (CSS) with different molecular weight (Mw) were reacted with 4-acetamidobenzene sulfonyl chloride to obtain sulfanilamide derivatives of chitosan and chitosan sulfates (LSACS, HSACS, LSACSS, HSACSS). The preparation conditions such as different reaction time, temperature, solvent, and the molar ratio of reaction materials are discussed in this paper. Their structures were characterized by FTIR spectroscopy and elemental analyses. The antioxidant activities of the derivatives were investigated employing various established in vitro systems, such as hydroxyl-radical (OH) superoxide anion (O-2(center dot-)) scavenging and reducing power. All kinds of the compounds (HCS, LCS, HCSS, LCSS, HSACS, LSACS, HSACSS, LSACSS) showed stronger scavenging activity on hydroxyl radical than ascorbic acid (Vc). The inhibitory activities of the derivatives toward superoxide radical by the PMS-NADH system were obvious. The experiment showed that the superoxide radical scavenging effect of sulfanilamide derivatives of chitosan and chitosan sulfates was stronger than that of original CS and CSS. All of the derivatives were efficient in the reducing power. The results indicated that the sulfanilamide group were grafted on CS and CSS increased the reducing power of them obviously. (c) 2007 Elsevier Ltd. All rights reserved.

Hydroxyl radicals scavenging activity of N-substituted chitosan and quaternized chitosan

N-substituted chitosan and quaternized chitosan were synthesized and their antioxidant activity against hydroxyl radicals was assessed, respectively. Compared with the antioxidant activity of chitosan, the results indicated that the two kinds of chitosan derivatives had different scavenging ability on hydroxyl radicals, which should be related to the form of amido in the two kinds of chitosan derivatives. (c) 2006 Elsevier Ltd. All rights reserved.

Novel derivatives of chitosan and their antifungal activities in vitro

Three kinds of Schiff bases of carboxymethyl chitosan (CMCTS) were prepared, and their antifungal activities were assessed according to Jasso de Rodriguez's method. The results indicated that 2-(2-hydroxybenzylideneamino)-6-carboxymethylchitosan (HNCMCTS) and 2-(5-chloro-2-hydroxybenzylideneamino)-6-carboxymethylchitosan (HCCMCTS) had better inhibitory effects than those of chitosan or CMCTS against Fusarium oxysporium f. sp. vasinfectum, Alternaria solani, and Valsa mali. (c) 2005 Elsevier Ltd. All rights reserved.

Recovery of silver (I) using a thiourea-modified chitosan resin

This work describes the preparation of a chelating resin from chemically modified chitosan. The resin was synthesized by using O-carboxymethylated chitosan to cross-link a polymeric Schiffs base of thiourea/glutaraldehyde and characterized by IR. Batch method was applied for testing the resin's adsorption behavior. Adsorption experiments showed the resin had good adsorption capacity and high selectivity for Ag(I) in aqueous solution. The maximum uptake of Ag(I) exhibited was 3.77 mmol/g, at pH 4.0. The results also indicated that the adsorption process was exothermic and fit well with the pseudosecond-order kinetic model. Ag(I) desorption could reach 99.23% using 0.5 M thiourea-2.0 M HCl solution. (C) 2010 Elsevier B.V. All rights reserved.

The preparation and antioxidant activity of 2-[phenylhydrazine (or hydrazine)-thiosemicarbazone]-chitosan

Chitosan (CS) with two different molecular weight were modified by reacting with methyl hydrazine-dithiocarboxylate and methyl phenylhydrazine-dithiocarboxylate to give 2-(hydrazine-thiosemicarbazone)-chitosan (2-HTCHCS, 2-HTCLCS) and 2-(phenylhydrazine-thiosemicarbazone)chitosan (2-PHTCHCS, 2-PHTCLCS). The structure of the derivatives was characterized by FT-IR spectroscopy and elemental analysis. The antioxidant activities of the derivatives were investigated employing various established systems, such as hydroxyl radical (*OH)/superoxide anion (O-2(center dot-)) scavenging/reducing power and chelating activity. All of the derivatives showed strong scavenging activity on hydroxyl radical than chitosan and ascorbic acid (Vc), and IC50 of 2-HTCHCS, 2-HTCLCS, 2-PHTCHCS and 2-PHTCLCS was 0.362, 0.263, 0.531 and 0.336 mg/mL respectively. The inhibitory activities of the derivatives toward superoxide radical by the PMS-NADH system were strong. The results showed that the superoxide radical scavenging effect of 2-[phenylhydrazine (or hydrazine)-thiosemicarbazone]-chitosan were higher than that of chitosan. The derivatives had obviously reducing power and chelating activity. The data obtained from vitro models clearly establish the antioxidant potency of 2-[phenylhydrazine (or hydrazine)-thiosemicarbazone]-chitosan. (C) 2010 Elsevier B.V. All rights reserved.

Synthesis and evaluation of a thiourea-modified chitosan derivative applied for adsorption of Hg(II) from synthetic wastewater

In this work, a thiourea-modified chitosan derivative (TMCD) was synthesized through two steps, O-carboxymethylated first and then modified by a polymeric Schiff's base of thiourea/glutaraldehyde. The adsorption behavior of mercury (II) ions onto TMCD was investigated through batch method. The maximum adsorption capacity for Hg(II) was found to be 6.29 mmol/g at pH 5.0 and both kinetic and thermodynamic parameters of the adsorption process were obtained. The results indicated that adsorption process was spontaneous exothermic reaction and kinetically followed pseudo-second-order model. The adsorption experiments also demonstrated TMCD had high adsorption selectivity towards Hg(II) ions when coexisted with Cu(II), Zn(II), Cd(II) and Ca(II) in solution and it could be easily regenerated and efficiently reused. (C) 2010 Elsevier B.V. All rights reserved.

Preparation of chitooligosaccharides from chitosan by a complex enzyme

Chitosan of 24% degree of acetylation was depolymerized by a mixture of cellulase, alpha amylase, and proteinase to give the title oligosaccharides. The removal of products by membrane separation permitted yield maximization of products having degree of polymerization in the 3-10 range. (C) 1999 Elsevier Science Ltd. All rights reserved.

壳聚糖衍生物抑菌性能及机理的研究

壳聚糖是一种天然的聚阳离子氨基多糖，由甲壳素经脱乙酰反应得到。作为天然可再生资源，壳聚糖以其特有的安全无毒、可生物降解、生物相容等特性，在农业、生物工程、制药、环保等领域引起广泛关注。随着对壳聚糖研究的不断深入，壳聚糖的抑菌活性及机理成为研究热点之一，但是，大多集中于壳聚糖分子量和脱乙酰度对其抑菌活性的影响，而对壳聚糖衍生物的抑菌性能及机理研究较少。本文合成了N–季铵盐，N,O–季铵盐，羧甲基壳聚糖希夫碱及其铜配合物，壳聚糖有机酸盐，并对它们的抑菌活性进行了研究，同时探讨了引入基团与抑菌活性之间的关系。 测定了壳聚糖及其季铵盐对黄瓜枯萎病菌、黄瓜炭疽病菌和桃褐腐病菌的抑制活性，结果表明壳聚糖季铵盐的抑制活性高于壳聚糖，其中，抑制活性最强的是N–异丁基–N,N–二甲基壳聚糖，当样品浓度为500μg/mL时，对三种病原菌的抑制率分别为：67.52%、70.42%和76.25%。壳聚糖分子带正电荷的氨基可以与菌体表面带负电的物质作用，导致菌体死亡，而壳聚糖季铵盐分子中的正电性可以加强这种作用，从而增强抑菌活性，而且随着正电性的增强，抑菌活性增强。 为了进一步研究壳聚糖季铵盐的正电性与其抑菌活性的关系，合成了含有氟、溴、氯吸电子基团苯环取代的壳聚糖季铵盐，通过计算分别得到取代基团的电负性以及氨基正电性。结果表明，随着取代基团电负性的增强，季铵盐氨基正电性增强，抑菌活性增强。其中，抑菌活性最强的是N–(2–氟)苄基–N,N–二甲基壳聚糖，当样品浓度为500μg/mL时，对三种病原菌的抑制率分别为：80.85%、100%和100%。 将壳聚糖的–NH2与有机酸的–H通过离子键结合制备得到了系列的固态壳聚糖有机酸盐：壳聚糖甲酸盐、壳聚糖乙酸盐、壳聚糖丙酸盐、壳聚糖丁酸盐和壳聚糖戊酸盐，抑菌活性结果表明，随着衍生物链长的增加，抑菌活性增强，而且衍生物抑菌活性与取代基团的电负性成正相关。 以羧甲基壳聚糖为原料，合成了羧甲基壳聚糖希夫碱及其铜配合物，各类衍生物的抑菌活性强弱顺序如下：羧甲基壳聚糖希夫碱铜配合物>羧甲基壳聚糖希夫碱>羧甲基壳聚糖，从而说明了基团的相互增效作用能增强衍生物的抑菌活性。 以N–季铵盐为原料，以环氧丙基三甲基氯化铵为改性剂合成了具有–N+(CH3)2R和–N+(CH3)3两种基团的N,O–季铵盐，抑菌活性结果表明，N,O–季铵盐的抑菌活性

Rapid quantification of total microcystins in cyanobacterial samples by periodate-permanganate oxidation and reversed-phase liquid chromatography

Microcystins (MCs) comprise a family of more than 80 related cyclic hepatotoxic heptapeptides. Oxidation of MCs causes cleavage of the chemically unique C-20 beta-amino acid (2S, 3S, 8S, 9S)-3-amino-9-methoxy-2,6,8-trimethyl-10-phenyldeca-4,6-dienoic acid (Adda) amino to form 2-methyl-3-methoxy-4-phenylbutanoic acid (MMPB), which has been exploited to enable analysis of the entire family. In the present study, the reaction conditions (e.g. concentration of the reactants. temperature and pH) used in the production of MMPB by oxidation of cyanobacterial samples with permanganate-periodate were optimized through a series of well-controlled batch experiments. The oxidation product (MMPB) was then directly analyzed by high-performance liquid chromatography with diode array detection. The results of this study provided insight into the influence of reaction conditions on the yield of MMPB. Specifically, the optimal conditions, including a high dose of permanganate (>= 50 mM) in saturated periodate solution at ambient temperature under alkaline conditions (pH similar to 9) over 1-4 h were proposed, as indicated by a MMPB yield of greater than 85%. The technique developed here was applied to determine the total concentration of MCs in cyanobacterial bloom samples, and indicated that the MMPB technique was a highly sensitive and accurate method of quantifying total MCs. Additionally, these results will aid in development of a highly effective analytical method for detection of MMPB as an oxidation product for evaluation of total MCs in a wide range of environmental sample matrices, including natural waters, soils (sediments) and animal tissues. (C) 2009 Elsevier B.V. All rights reserved.

Kinetic study of the 2-methyl-3-methoxy-4-phenylbutanoic acid produced by oxidation of microcystin in aqueous solutions

Microcystins (MCs) are a family of related cyclic hepatotoxic heptapeptides, of which more than 70 types have been identified. The chemically unique nature of the C20 beta-amino acid, (2S, 3S, 8S, 9S)-3-amino-9-methoxy-2,6,8-trimethyl-10-phenyldeca4,6-dienoic acid (Adda), portion of the MCs has been exploited to develop a strategy to analyze the entirety. Oxidation of MCs causes the cleavage of MC Adda to form 2-methyl-3-methoxy-4-phenylbutanoic acid (MMPB). In the present study, we investigated the kinetics of MMPB produced by oxidation of the most-often-studied MC variant, MC-LR (L = leucine, R = arginine), with permanganate-periodate. This investigation allowed insight regarding the influence of the reaction conditions (concentration of the reactants, temperature, and pH) on the conversion rate. The results indicated that the reaction was second order overall and first order with respect to both permanganate and MC-LR. The second-order rate constant ranged from 0.66 to 1.35 M/s at temperatures from 10 to 30 degrees C, and the activation energy was 24.44 kJ/mol. The rates of MMPB production can be accelerated through increasing reaction temperature and oxidant concentration, and sufficient periodate is necessary for the formation of MMPB. The initial reaction rate under alkaline and neutral conditions is higher than that under acidic conditions, but the former decreases faster than the latter except under weakly acidic conditions. These results provided new insight concerning selection of the permanganate-periodate concentration, pH, and temperature needed for the oxidation of MCs with a high and stable yield of MMPB.