共查询到19条相似文献,搜索用时 62 毫秒
1.
对壳聚糖进行液态均相络合反应制得壳聚糖铜配合物,IR、UV、元素分析及热重分析等检测证实了壳聚糖铜配合物中配位键的存在,且显示壳聚糖在形成配位结构后存在有利于降解的优势构象。以H2O2对壳聚糖-Cu(Ⅱ)络合物及壳聚糖进行氧化降解,考察降解过程中粘度的变化及降解产物分子量分布,在相同的降解条件下,壳聚糖铜配合物的降解速度明显高于壳聚糖,降解产物分子量分布较壳聚糖直接降解窄,结果进一步证明壳聚糖铜配合物中存在有利于降解的优势结构,同时证明以金属离子Cu(Ⅱ)对壳聚 相似文献
2.
壳聚糖锰(Ⅱ)配位与氧化控制降解寡糖的分子量分布 总被引:4,自引:0,他引:4
Complexes of chitosan with Mn(Ⅱ) were prepared by adding Mn(OAc)2·4H2O to Chitosan solution. IR, elemental analysis and TG analysis were used to character the complex. The results showed that there were coordinate bands formed. H2O2 was used to degrade chitosan-Mn(Ⅱ) complex, and the molecular distribution of degraded products were investigated after eliminating Mn(Ⅱ) ions using the cation exchange resin column. The result suggested that the Chitosan could be degraded rapidly, the degradation started from higher molecular weight range, the molecular weight distribution of oligosaccharides was much more narrower than that of degradated products from common methods such as hydrolysis, acidic and oxidizing methods. The index of molecular weight distribution was changed with the average degradability. When exceeding 10 oligosaccharides, the smaller of the DP, the smaller of the index. 相似文献
3.
4.
5.
壳聚糖钙/锌配位降解产物的GFC及清除O-·2研究 总被引:3,自引:0,他引:3
分别将Ca(Ⅱ)和Zn(Ⅱ)加入到壳聚糖溶液中,调节pH值使壳聚糖与金属配位.加入H2O2并升高温度对处于配位缔合状态的壳聚糖进行氧化降解,测定了降解产物寡糖的数均相对分子质量和相对分子质量分布.结果表明壳聚糖在与Ca和Zn配位的情况下,可被H2O2迅速降解;降解从大相对分子质量范围开始,降解产物寡糖相对分子质量分布较窄,且聚合度(DP数)越小,寡糖相对分子质量分布指数越小.同时对两者的降解产物进行了清除超氧阴离子自由基(O2-.)的研究,研究发现两者的降解产物均对O2-.有一定的清除作用,清除率随降解产物数均相对分子质量的减小而增大.但用完全降解产物氨基葡糖形成配合物时,清除作用几乎完全消失. 相似文献
6.
7.
8.
壳聚糖镍和壳聚糖镧配位聚合物的配位数研究 总被引:6,自引:1,他引:6
从IR、ESR和XPS的测试结果可知,Ni^2+或La^3+与壳聚糖(CS)键节单元上的氨基N和仲羟基O发生配位反应,形成CS-Ni^2+或CS-La^3+配位聚合物膜。通过电导率研究其配位数,发现Ni^2+或La^3+可与壳聚糖的3个或5个键节单元配位。根据以上的实验可推定中心离子Ni^2+与壳聚糖3个键节单元上的氨基N和仲羟基O结合,形成六配位的CS-Ni配位聚合物La^3+与壳聚糖5个键节单 相似文献
9.
壳聚糖/羧甲基壳聚糖金属配合物对氧自由基的清除作用研究 总被引:9,自引:0,他引:9
以NADH-PMS-NBT体系产生超氧阴离子自由基(o2-·)和EDTANa2·Fe(Ⅱ)-H2O2体系产生 羟自由基(·OH)来研究壳聚糖Cu(Ⅱ)、Zn(Ⅱ)配合物、羧甲基壳聚糖Cu(Ⅱ)、Zn(Ⅱ)配合物时氧自由基的 清除作用。结果显示配合物对O2-·和·OH均具有明显的清除作用,其中铜(Ⅱ)配合物对O2-·的清除活 性最高,而锌(Ⅱ)配合物比铜(Ⅱ)配合物具有更强的清除·OH的能力,羧甲基壳聚糖Cu(Ⅱ)、Zn(Ⅱ)配合 物与含有相同金属离子的壳聚糖配合物相比对O2-·和·OH具有更高的抑制活性。 相似文献
10.
壳聚糖超声可控降解及降解动力学研究 总被引:1,自引:0,他引:1
通过正交实验法考察了壳聚糖溶液浓度、反应温度、超声强度以及醋酸溶液浓度对超声降解反应的影响,确定了最佳反应条件,制备了一系列不同分子量的壳聚糖.研究了壳聚糖溶液浓度、反应温度以及壳聚糖原料分子参数与降解速率常数的关系.通过红外光谱、X-射线衍射和凝胶渗透色谱对降解产物进行了表征.结果表明,超声降解壳聚糖的最佳条件为10℃,壳聚糖溶液浓度2.5g/L.降解速率常数随壳聚糖溶液浓度和反应温度的降低而增大.高分子量和低脱乙酰度的壳聚糖原料有较高的降解速率和降解速率常数,壳聚糖原料的分子量对降解速率和降解速率常数的影响大于脱乙酰度对其的影响.超声波导致了壳聚糖分子量的降低和产物晶体结构的破坏,但没有改变产物的脱乙酰度和糖残基结构. 相似文献
11.
The kinetics of the thermal degradation and thermal oxidative degradation of poly(p-dioxanone) (PPDO) were investigated by thermogravimetric analysis. Kissinger method, Friedman method, Flynn-Wall-Ozawa method and Coats-Redfern method have been used to determine the activation energies of PPDO degradation. The results showed that the thermal stability of PPDO in pure nitrogen is higher than that in air atmosphere. The analyses of the solid-state processes mechanism of PPDO by Coats-Redfern method and Criado et al. method showed: the thermal degradation process of PPDO goes to a mechanism involving random nucleation with one nucleus on the individual particle (F1 mechanism); otherwise, the thermal oxidative degradation process of PPDO is corresponding to a nucleation and growth mechanism (A2 mechanism). 相似文献
12.
Isolation of oxidative degradation products of atorvastatin with supercritical fluid chromatography 下载免费PDF全文
The isolation of four oxidative degradation products of atorvastatin using preparative high‐performance liquid chromatography applying at least two chromatographic steps is known from the literature. In this paper it is shown that the same four impurities could be isolated from similarly prepared mixtures in only one step using supercritical fluid chromatography. The methods for separation were developed and optimized. The preparation of the mixtures was altered in such a way as to enhance the concentration of desired impurities. Appropriate solvents were applied for collection of separated impurities in order to prevent degradation. The structures of the isolated impurities were confirmed and their purity determined. The preparative supercritical fluid chromatography has proven to be superior to preparative HPLC regarding achieved purity of standards applying fewer chromatographic as well as isolation steps. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
13.
Xueqin Kang Chi Yao Chunmin Yang Peizhong Feng 《International Journal of Polymer Analysis and Characterization》2017,22(5):383-393
The change in oxidative degradation and mechanical properties of ultrahigh molecular weight polyethylene (UHMWPE) samples was evaluated. The percentage of crystallinity, chemical composition, and wetting properties were performed on different UHMWPE samples. Experimental results showed that the percentage of crystallinity and O/C ratio increased after immersion in simulated body fluids (SBF) for 5 years, and this resulted in lower mechanical properties. A coarse surface quality of UHMWPE surface caused lower contact angle and higher initial friction coefficient after the coeffect of force and SBF, but other mechanical properties changed little. The wear mechanism changed when immersed in SBF for 5 years. 相似文献
14.
Huaili Qin Zhenguang Zhang Meng Feng Fangling Gong Shimin Zhang Mingshu Yang 《Journal of Polymer Science.Polymer Physics》2004,42(16):3006-3012
The photo‐oxidative degradation of polyethylene/montmorillonite (PE/MMT) nanocomposite and microcomposite has been investigated. It has been found that the rate of photo‐oxidative degradation of PE/MMT nanocomposite and PE/Mn+MMT (where Mn+ stands for multivalent transition metal cation) microcomposites is much faster than that of pure PE. For the PE/MMT nanocomposite, the acceleration of photo‐oxidative degradation is due to the influence of MMT and ammonium ion, in which the influence of ammonium is primary. The decomposition of ammonium ion may create acidic sites on layered silicates; meanwhile, the complex crystallographic structure and habit of clay minerals could also result in some active sites. The reversible photo‐redox reaction of transition metal cations has a catalytic effect in the degradation of the polymer matrix. All these catalytic active sites can accept single electrons from donor molecules of polymer matrix and induce the formation of free radical upon UV irradiation. The generation of free radical leads to the oxidization and break of molecular chain. Thus, the materials suffer degradation and their mechanical strength decreases. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3006–3012, 2004 相似文献
15.
Tian C. M. Xie J. X. Guo H. Z. Xu J. Z. 《Journal of Thermal Analysis and Calorimetry》2003,73(3):827-834
The thermal oxidative degradation of cellulose, and of cellulose ammonium phosphate and its metal complexes products were
studied by thermal analysis, infrared spectroscopy and elemental analysis. The temperature of decomposition was lower for
metal complexes of cellulose ammonium phosphate than those samples untreated by metal ions and the values of char yield were
greater for treated cellulose than those untreated. This indicates the metal ions can catalyze the reaction of degradation
and form more char.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
16.
Reaction of 3-hydrazonobutan-2-one oxime with aromatic aldehydes resulted in the formation of 1,2-bis(arylidene)hydrazine commonly referred as azine as an unexpected product, instead of expected product 3-(aryl)methylenehydrazonobutan-2-one oxime, which were subsequently oxidized to corresponding aromatic acids with an ecofriendly oxidizing agent iodobenzene diacetate. Azines and carboxylic acids were characterized by IR and NMR (1H, 13C, HMBC, and HMQC) studies. 相似文献
17.
Yinghong Chen 《Polymer Degradation and Stability》2007,92(2):280-291
The thermal oxidative degradation kinetics of pure PP and the flame-retarded (FR) PP materials with intumescent flame-retardant (IFR) master batches in situ prepared in twin-screw extruder were investigated using Kissinger method, Flynn-Wall-Ozawa method and Coats-Redfern method. The results showed that the activation energy order of PP and FR PP samples with different blowing agent/char former ratios obtained by Kissinger method agrees well with that obtained by Coats-Redfern one, which well illustrates the relationship between the composition of IFRs and their flame-retardancy, i.e. FR material with richer carbonization agent has higher activation energy for thermal oxidative degradation, hence leading to a better flame-retardancy. For Flynn-Wall-Ozawa method, due to its adoption of Doyle approximation, the obtained activation energy and its order of samples are very different from those of both Kissinger and Coats-Redfern methods. Criado method was finally used to determine the degradation reaction mechanism of various samples. 相似文献
18.
Chitosan, a natural polymer, bound Schiff base copper complexes CT‐She‐Cu, CT‐o‐Bel‐Cu, CT‐m‐Bel‐Cu were prepared and characterize by inductively coupled plasma (ICP), FT‐IR and X‐ray photoelectron spectroscopy (XPS). Their catalytic activity in the oxidation of cyclohexene with molecular oxygen was studied. All the complexes have catalytic activity and the main oxidation products are 2‐cyclohexene‐ol, 2‐cyclohexene‐one and cyclohexene hydroperoxide, which were measured by gas chromatography/mass spectroscopy (GC/MS) and GC/IR. CT‐m‐Bel‐Cu was selected to study the influence of reaction temperature, amount of catalyst and additives such as acid and base on the oxidation of cyclohexene systematically. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
19.
Ayako Yano Nobuyuki Akai Hiroshi Ishii Chikahiro Satoh Takayuki Hironiwa Keith R. Millington Munetaka Nakata 《Polymer Degradation and Stability》2013
Thermal oxidative degradation of additive-free polypropylene pellets heated isothermally in dry air at 150 and 180 °C (below and above the melting point of 163 °C) was investigated by multichannel Fourier-transform chemiluminescence spectroscopy. The initial peak wavelength of chemiluminescence emission at 490 nm remained constant during the early stages of thermal degradation, but new emissions developed with time in the red spectral region over an extended oxidation period. The time-dependent luminescence spectra were deconvoluted into three emission bands by least-squares fitting using Gaussian curves. We concluded that at least three groups of luminescent species (luminophores), having different conjugation lengths, were generated by thermal oxidation over extended periods and show luminescence around 490, 660, and 740 nm. 相似文献