羧甲基壳聚糖与钙离子络合作用的研究

羧甲基壳聚糖(carboxymethyl chitosan,CMCS)是壳聚糖Chitosan经化学改性得到的水溶性衍生物,由于羧基的引入,络合金属离子的能力及反应速度大大提高[1-6],在医药、化工、环保等领域有着广泛的应用前景。本文研究了羧甲基壳聚糖与Ca2 络合的条件,着重探讨了Pb2 在不同条件下对络合反应的影响,以期扩大羧甲基壳聚糖的应用范围。1材料与方法1.1仪器与试剂羧甲基壳聚糖(自制),其它试剂均为国产优级纯。TAS-986G原子吸收分光光度计;SX5-12箱式电阻炉;GL-20B高速冷冻离心机;Ori-on818型pH测试计。1.2实验方法1.2.1羧甲基壳聚糖与Ca2 络合…     

A study for quality evaluation of Taxilli Herba from different hosts based on fingerprint-activity relationship modeling and multivariate statistical analysis

In this study, a fingerprint-activity relationship modeling between chemical fingerprints and antirheumatic activity was established, and multivariate statistical analysis was used to evaluate the quality of Taxilli Herba (TH) from different hosts. Characteristic fingerprints of 20 batches of TH samples were generated by high-performance liquid chromatography coupled with triple quadrupole-time of flight tandem mass spectrometry (HPLC-Triple TOF-MS/MS), and the similarity analysis was calculated based on thirteen common characteristic peaks by hierarchical clustering analysis (HCA). Subsequently, nine efficacy markers were discovered by combining fingerprints and antirheumatic activity through grey correlation analysis (GCA) and bivariate correlation analysis (BCA). Meanwhile, the content of 5 constituents in 9 markers was determined by high-performance liquid chromatography coupled with triple quadrupole-linear ion trap tandem mass spectrometry (HPLC-QTRAP-MS/MS). The comprehensive quality of TH was assessed using multivariate statistical analysis, including principal components analysis (PCA) and technique for order preference by similarity to ideal solution (TOPSIS). The results showed that a high dose of TH extract could markedly ameliorate arthritis damage compared to other doses, with flavonoids playing an important role in the antirheumatic activity. The comprehensive quality of samples from Morus alba L. (SS) was superior to those from Liquidambar formosana Hance (FXS). The present study will demonstrate the markers associated with efficacy, and provide an applicable strategy for more comprehensive quality control and evaluation of TH.     

Adsorption of Hg(II) Ions onto Binary Biopolymeric Beads of Carboxymethyl Cellulose and Alginate

The removal of Hg(II) ions from aqueous solution by adsorption onto cross-linked polymeric beads of carboxymethyl cellulose (CMC) and sodium alginate was studied at fixed pH (6) and room temperature 28 ± 0.2°C. The cross-linked polymeric beads were characterized by FTIR spectra. Sorption capacity of the polymer for the mercury ions was investigated in aqueous media consisting different amounts of mercury ions (2.5 to 100 mg dm^?3) and at different pH values (2 to 8). Adsorption behavior of Hg(II) ions could be modeled using both the Langmuir and Freundlich isotherms. The dynamic nature of adsorption was quantified in terms of several kinetic constants such as rate constants for adsorption (k₁) and Lagergreen rate constant (K_ad). The influence of various experimental parameters such as effect of pH, contact time, solid-to-liquid ratio, salt effect, and temperature effect etc. were investigated on the adsorption of Hg(II) ions.     

Synthesis and characterization of folic acid‐modified carboxymethyl chitosan‐ursolic acid targeted nano‐drug carrier for the delivery of ursolic acid and 10‐hydroxycamptothecin

Carboxymethyl chitosan (CMCS), as a water‐soluble, biocompatible, and biodegradable polymer, is an excellent carrier for a sustained drug delivery system. In this study, a amphiphilic carboxymethyl chitosan‐ursolic acid nano‐drug carrier modified by folic acid (FPCU) were prepared, and then the nano‐drug carrier wrapped another anticancer drug 10‐hydroxycamptothecin were self‐assembled into nanoparticles (FPCU/HCPT NPs). The FPCU/HCPT NPs had a suitable size, high drug loading efficiency of ursolic acid (6.4%) and 10‐hydroxycamptothecin (14.1%). The drug release study in vitro indicated that the nanoparticles have obviously sustained effect and pH sensitive behaviors, the drug release amount was higher at pH 5.5 than at pH 7.4. in vitro and in vivo study showed that the nanoparticles displayed a high antitumor efficiency to tumor cells compared with free drug. The nano delivery system as a carrier for ursolic acid (UA) and 10‐hydroxycamptothecin (HCPT) has good application prospects in cancer treatment.     

基于N-羧甲基壳聚糖钆基磁共振造影剂的制备及性能

通过在DTPA配体上修饰N-羧甲基壳聚糖(NCMCS)增加配体的分子量,构建配合物Gd-(DTPA-NCMCS)。测定了Gd-(DTPA-NCMCS)及对照组Gd-DTPA与Gd-(DTPA-CS)不同浓度的弛豫时间T1,拟合了配合物的纵向弛豫率r1,结果表明Gd-(DTPA-NCMCS)纵向弛豫能力明显强于Gd-DTPA,也高于配合物Gd-(DTPA-CS),浓度梯度的体外加权成像图清晰地观察到配合物Gd-(DTPA-NCMCS)比Gd-DTPA、Gd-(DTPA-CS)对应水溶液的信号更强。MTT法测定了Gd-(DTPA-NCMCS)的IC50值为568μmol·L-1,表现出良好的生物相容性。Gd-(DTPA-NCMCS)可作为潜在的磁共振造影剂。     

Dual crosslinked pH‐ and temperature‐sensitive hydrogel beads for intestine‐targeted controlled release

Novel drug‐loaded hydrogel beads for intestine‐targeted controlled release were developed by using pH‐ and temperature‐sensitive carboxymethyl chitosan‐graft‐poly(N,N‐diethylacrylamide) (CMCTS‐g‐PDEA) hydrogel as carriers and vitamin B₂ (VB₂) as a model drug. The hydrogel beads were prepared based on Ca²⁺ ionic crosslinking in acidic solution and formed dual crosslinked network structure. The structure of hydrogel and morphology of drug‐loaded beads were characterized by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and scanning electron microscopy (SEM). The study about swelling characteristics of hydrogel beads indicated that the beads had obvious pH‐ and temperature‐sensitivity. In vitro release studies of drug‐loaded beads were carried out in pH 1.2 HCl buffer solution and pH 7.4 phosphate buffer solution at 37°C, respectively. The results indicated that the dual crosslinked method could effectively control the drug release rate under gastrointestinal tract (GIT) conditions, which was superior to traditional single crosslinked beads. In addition, the effects of grafting percentage, pH value, and temperature on the release behavior of the VB₂ were investigated. The drug release mechanism of CMCTS‐g‐PDEA drug‐loaded beads was analyzed by Peppa's potential equation. According to this study, the dual crosslinked hydrogel beads based on CMCTS‐g‐PDEA could serve as suitable candidate for drug site‐specific carrier in intestine. Copyright © 2009 John Wiley & Sons, Ltd.     

羧甲基交联壳聚糖树脂的合成、表征及其应用

羧甲基交联壳聚糖树脂(C-C-CTS)与普通壳聚糖树脂相比,既能在酸性介质中不溶又不失去其螯合性能.其合成采用简单的2步法,首先用还氧氯丙烷交联,然后羧甲基化.C-C-CTS的结构用红外光谱和X-ray光电子能谱进行表征.C-C-CTS树脂对重金属离子有很好的螯合吸附能力,每种树脂对Pb(Ⅱ),Cu(Ⅱ)和Zn(Ⅱ)的吸附能力分别为8.73,10.12和4.89 mg·g-1,并且在不同的pH条件下对Pb(Ⅱ)、Cu(Ⅱ)和Zn(Ⅱ)有很好的选择性吸附,最后还讨论了C-C-CTS树脂对Pb(Ⅱ)的吸附机理.     

Structural changes in β-lactoglobulin by conjugation with three different kinds of carboxymethyl cyclodextrins

β-Lactoglobulin-carboxymethyl cyclodextrin (β-LG-CMCyD) conjugates were prepared by using water soluble carbodiimide. Three kinds of CMCyDs differing in molecular mass were used to investigate the effects of different CMCyD contents, net charge and hydrophobicity on the structural changes in β-lactoglobulin. The effect of CMCyDs on the structure of β-lactoglobulin was utilized to investigate the contribution of hydrophobic interactions to the stability of the protein. Spectroscopic studies suggested that the conformation around had not changed in either conjugate but the α-helix content of β-LG-CMCyD conjugates had markedly increased as compared with that of β-lactoglobulin. The differential scanning calorimetry technique confirmed that the addition of one glucose unit in β-LG-CMCyD conjugates, enthalpy change of calorimetry decreased and the denaturation temperature of each conjugate was higher than that of native β-lactoglobulin. The heat contents agreed well with the conformational transition measured by molar ellipticity at 222 nm ([θ]₂₂₂) and Stoke's radius (R_S) values. Therefore, hydrophobic forces play an important role in stabilizing and shielding of the β-LG-CMCyD conjugates.     

Preparation,swelling, and stimuli‐responsive characteristics of superabsorbent nanocomposites based on carboxymethyl cellulose and rectorite

Utilization of naturally available raw materials for the fabrication of eco‐friendly functional materials has long been desired. In this work, a series of superabsorbent nanocomposites were prepared by radical solution copolymerization of sodium carboxymethyl cellulose (CMC), partially neutralized acrylic acid (NaA), and rectorite (REC) in the presence of initiator ammonium persulfate (APS) and crosslinker N,N'‐methylene‐bis‐acrylamide (MBA). The optimal reaction variables including the mass ratio of acrylic acid (AA) to CMC, MBA concentration, and REC content were explored. FTIR spectra confirmed that NaA had been grafted onto CMC and REC participated in polymerization. REC was exfoliated and uniformly dispersed in the CMC‐g‐PNaA matrix without agglomeration as shown by XRD, TEM, and SEM analysis. The thermal stability, swelling capabilities, and rate of the nanocomposites were improved after introducing REC, and the gel strength greatly depended on the concentration of crosslinker MBA. The nanocomposite showed excellent responsive properties and reversible On–Off switching characteristics in various saline, pH, and hydrophilic organic solvent/water solutions, which provided great possibility to extend the application domain of the superabsorbent nanocomposites such as drug delivery system. Copyright © 2010 John Wiley & Sons, Ltd.     

pH值对壳聚糖/羧甲基壳聚糖水凝胶溶胀行为的影响

利用壳聚糖与羧甲基壳聚糖制备了一系列新型的水凝胶，研究了pH值对水凝胶溶胀度、微观结构和基团结构的影响．结果表明，壳聚糖与羧甲基壳聚糖水凝胶的溶胀行为和微观结构均表现出pH值敏感性，但随着羧基的引入，水凝胶的最低溶胀度从pH7．O移向pH3．O．红外光谱证明，水凝胶的pH敏感行为是由基团结构的变化引起的．