甲壳素及其衍生物在痕量元素及其形态分析中的应用

本文对甲壳素及其衍生物在痕量元素及其形态分析中的应用研究进行了综述。引用参考文献46篇。     

Hybrid of chitin and humic acid as high performance sorbent for Ni(II)

Hybrid of humic acid (HA) and chitin has been synthesized and the hybrid material (chitin-HA) was then applied as sorbent to adsorb Ni(II). The HA was extracted from peat soil of Gambut District, South Kalimantan, Indonesia, according to the procedure recommended by IHSS (International Humic Substances Society). The chitin was isolated from crab shell waste of sea food restaurants through deproteination using NaOH 3.5% (w/v) and followed by removal of inorganic impurities using HCl 1 M. The synthesis of chitin-HA was performed by reacting gelatinous chitin solution in HCl 0.5 M and HA solution in NaOH 0.5 M. Parameters investigated in this work consists of effect of medium acidity on the sorption, sorption rate (k_s) and desorption rate (k_d) constants, Langmuir (monolayer) and Freundlich (multilayer) sorption capacities, and energy (E) of sorption. The k_s and k_d were determined according to a kinetic model of first order sorption reaching equilibrium, monolayer sorption capacity (b) and energy (E) were determined according to the Langmuir isotherm model, and multilayer sorption capacity (B) was determined based on the Freundlich isotherm model.Sorption of Ni(II) on both chitin and chitin-HA was maximum at pH 8.0. The kinetic expression resulted from the proposed kinetic model has been shown to be more applicable than the commonly known Lagergren equation obtained from the pseudo-first order sorption model. The application of the proposed model revealed that the presence of HA increased the k_s from 0.018 min⁻¹ for chitin to 0.031 min⁻¹ for chitin-HA. As for k_s, the value of b was also bigger in the presence of HA, i.e. 7.42 × 10⁻⁵ mol/g for chitin and 9.93 × 10⁻⁵ mol/g for the chitin-HA. Unlike k_s and b, the value of E slightly decreased from 23.23 to 21.51 kJ/mol for the absence and presence of HA, respectively. It can also be deduced that the presence of HA on chitin contributed more to the additional layer of Ni(II) sorbed on sorbent. Without HA, B for chitin was only 6.17 times higher than b, while with the presence of HA, the enhancement of the sorption capacity from the multilayer (B) to the monolayer (b) was 19.40. The increase of k_s, b, B, and the decrease of E would be very benefit in the real application of chitin-HA for the recovery of Ni(II) from aqueous samples.     

从鱿鱼顶骨β-甲壳素合成的丙酰化甲壳素的结晶结构

分别从α 甲壳素 (来源于蟹壳 )和 β 甲壳素 (来源于鱿鱼顶骨 )制备丙酰化甲壳素。丙酰化β 甲壳素的大角X光衍射图出现 2 0个衍射峰 ,而丙酰化α 甲壳素只在 2 0°左右出现弥散峰。发现丙酰化β 甲壳素的结晶属三斜晶系 ,a =7.997,b =1 3.0 67,c =6.31 6(任意单位 ) ,α =98°5 6′ ,β =1 0 4°1 9′,γ =82°2 6′。列表说明了各衍射峰的归属。据分析 ,每个单元晶胞内含一根分子链的 2 .5个葡萄糖残基单元。分子轴为b轴     

乙酰化甲壳素膜的制备及表征

本文报道了加入二氯甲烷可使甲壳素的乙酰化反应更顺利进行,并提高了产物的乙酰化度,通过红外、X射线衍射分析、拉伸等方法对乙酰化甲壳素膜的结晶结构和力学性能作了表征和测定。     

Synthesis of Novel Benzoylphenylurea Chitin Inhibitors From Chlorothalonil ( Ⅱ )

Six novel benzoylphenylurea chitin inhibitor derivatives were synthesized in the yields of 30%-50%from the readily available starting material chlorothalonil 1 via sequential fluorine exchange, aminolysis, hydrolysis and acylation reactions.     

Extraction and Characterization of Chitin and Chitosan from Parapenaeus longirostris from Moroccan Local Sources

The contents of the exoskeleton of Parapenaeus longirostris from Moroccan local sources were analyzed and the percentages of inorganic salt, protein, lipid, and chitin were determined. Chitin in the α form was extracted from Parapenaeus longirostris shells by 0.25 M HCl and 1 M NaOH treatment for demineralization and deproteinization, respectively. The obtained chitin was converted into the more useful soluble chitosan. The chemical structure and physico-chemical properties of chitin and chitosan were characterized using Fourier transform-infrared (FT-IR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, X-ray diffractometry (XRD), and scanning electron microscopy (SEM). The molecular weight (MW) of chitosan was determined by viscometric methods. The degree of acetylation (DA) of chitin and chitosan was determined by the ¹H NMR technique. To the best of our knowledge this is the first report on the extraction and characterization of chitin and chitosan from Parapenaeus longirostris.     

Ultrasound in the deproteinization process for chitin and chitosan production

Recently, chitin and chitosan are widely investigated for food preservation and active packaging applications. Chemical, as well as biological methods, are usually adopted for the production of these biopolymers. In this study, modification to a chemical method of chitin synthesis from shrimp shells has been proposed through the application of high-frequency ultrasound. The impact of sonication time on the deproteinization step of chitin and chitosan preparation was examined. The chemical identities of chitin and chitosan were verified using infrared spectroscopy. The influence of ultrasound on the deacetylation degree, molecular weight and particle size of the biopolymer products was analysed. The microscopic characteristics, crystallinity and the colour characteristics of the as-obtained biopolymers were investigated. Application of ultrasound for the production of biopolymers reduced the protein content as well as the particle size of chitin. Chitosan of high deacetylation degree and medium molecular weight was produced through ultrasound assistance. Finally, the as-derived chitosan was applied for beef preservation. High values of luminosity, chromatid and chrome were noted for the beef samples preserved using chitosan films, which were obtained by employing biopolymer subjected to sonication for 15, 25 and 40 min. Notably; these characteristics were maintained even after ten days of packaging. The molecular weight of these samples are 73.61 KDa, 86.82 KDa and 55.66 KDa, while the deacetylation degree are 80.60%, 92.86% and 94.03%, respectively; in the same order, the particle size of chitosan are 35.70 μm, 25.51 μm and 20.10 μm.     

A search of an optimal carrier for immobilization of chitin deacetylase

Chitin deacetylase is an enzyme that can play an important role in enzymatic deacetylation of chitosan to obtain polymers with a lower degree of acetylation. As this enzyme has never been immobilized up to now, efforts were directed towards determining both the most suitable carrier and the best method of covalent attachment to the selected carrier. In the preliminary experiments several different carriers were tested that were based on acrylic, silica-gel, agarose, dextran or cellulose materials. The best results were obtained for cellulose-based Granocel matrix. DEAE- and NH₂-Granocel activated with divinyl sulfone or glutaraldehyde were chosen for optimization of the immobilization procedure and the carrier’s superstructure. It was found that covalent binding of chitin deacetylase on DEAE-Granocel-2000 via divinyl sulfone offers preparations with the highest activity and stability. The characteristics of the selected preparation and comparison with the native enzyme show that optimal conditions are close to those for the free enzyme: the optimal pH is 4.0 for both enzymes and the optimal temperatures are 55 °C and 50 °C for native and immobilized forms, respectively. The kinetics of chitosan deacetylation for both enzymes follow the Michaelis–Menten relationship, but significant differences in the values of the equation parameters were observed.     

A comparison of glycans and polyglycans using solid-state NMR and X-ray powder diffraction

Individual polyglycans and their corresponding monomers have been studied separately for several decades. Attention has focused primarily on the modifications of these polyglycans instead of the simple relationship between the polyglycans themselves and their corresponding monomers. Two polyglycans, chitin and chitosan, were examined along with their respective monomeric units, N-acetyl-D-glucosamine (GlcNAc) and (+)D-glucosamine (GlcN) using solid-state proton decoupling Magic Angle Turning (MAT) techniques and X-Ray Powder Diffraction (XRPD). A down-field shift in isotropic (13)C chemical shifts was observed for both polymers in Cross Polarization/Magic Angle Spinning (CP/MAS) spectra. An explanation of misleading peak assignments in previous NMR studies for these polyglycans was determined by comparing sideband patterns of the polymers with their corresponding monomers generated in a 2D FIve pi REplicated Magic Angle Turning (FIREMAT) experiment processed by Technique for Importing Greater Evolution Resolution (TIGER). Structural changes in the crystalline framework were supported by XRPD diffraction data.     

甲壳素和壳聚糖作为天然生物高分子材料的研究进展

甲壳素是自然界中含量仅次于纤维素的天然高分子,壳聚糖是甲壳素脱乙酰化后带有阳离子的多糖.壳聚糖中的自由氨基以及它的高结晶性,使得它能溶于酸,而不溶于碱和绝大数的有机溶剂.同时壳聚糖具有无毒性、无刺激性、良好的生物相容性、生物可溶解性, 以及高的电荷密度,因而被作为一种新型的天然生物材料得到广泛应用.文章介绍了甲壳素和壳聚糖的结构和性质,综述分析了甲壳素和壳聚糖在制备微球和作为支架材料中的应用, 并总结了甲壳素和壳聚糖在这两个方面存在的问题和发展前景.