Fe3O4/壳聚糖复合纳米粒子吸附剂的制备及其对Pb2+吸附性能

用乙二醇为溶剂,三氯化铁和尿素为起始反应试剂,柠檬酸为粒子表面修饰剂,通过一步溶剂热法制备Fe3 O4纳米粒子,然后以一定浓度配比的Na2 SO4与NaOH混合液为沉淀剂,通过沉淀聚合法制备Fe3 O4/壳聚糖复合纳米粒子吸附剂。利用X射线衍射仪(XRD)、红外光谱(IR)、透射电子显微镜(TEM)和物理特性测试仪(PPMS)表征样品的结构、形貌和磁性能,并使用原子吸收分光光度计(AAS)评价吸附剂对Pb2+的吸附去除性能。结果表明,Fe3O4/壳聚糖复合纳米粒子吸附剂是由磁性Fe3O4纳米球形粒子和鱼卵状壳聚糖纳米粒子聚集体复合而成,该吸附剂对Pb2+有很好的吸附去除性能,它对Pb2+的等温吸附线符合Langmuir模型,在温度298k和pH值5时,吸附剂对Pb2+的饱和吸附量为105.5mg/g。     

壳聚糖包覆磁性纳米粒子的制备和表征以及蛋白质吸附特性

制备了一种壳聚糖包覆的磁性纳米粒子,并对其进行了表征和蛋白吸附特性研究.首先通过共沉淀法制备了表面羧基功能化的磁性纳米粒子(MNP-COOH),然后通过静电相互作用将壳聚糖自组装在MNPCOOH粒子表面,在甲醛保护氨基的情况下,利用环氧氯丙烷交联粒子表面壳聚糖上的羟基,交联完成后脱去氨基保护剂,制得表面富含氨基的壳聚糖包覆磁性纳米粒子(MNP-CS).分别使用扫描电子显微镜(SEM)、X射线衍射仪(XRD)、傅里叶变换红外光谱仪(FTIR)、热重分析仪(TGA)、震动样品磁强计(VSM)和zeta电位仪等对制得的MNP-CS进行表征.结果表明,壳聚糖成功地被包裹在磁性纳米颗粒表面.颗粒可完全分散于pH=1~14的水溶液中,形成均匀溶胶,Fe3O4磁核能抵抗0.1 mol/L的HCl溶液腐蚀.MNP-CS颗粒直径为10~20 nm,饱和磁化值为50.05 emu/g,剩磁和矫顽力近似为零,具有明显的超顺磁性.制得的磁性纳米粒子吸附BSA时呈明显的S型等温吸附特性,单层吸附量约为300 mg/g.     

磁性碳包铁纳米粒子在重金属元素检测分离富集中的应用

以氩电弧等离子体法制备的碳包铁纳米粒子为固相萃取材料,采用等离子体原子发射光谱法(ICP-AES)系统研究了该材料对Cr、Ni、Cd、Pb离子的吸附性能,并确定了最佳吸附和洗脱条件。实验结果表明:当pH值为8.0～9.0时,分析物均可被碳包铁纳米粒子定量吸附;采用酸性溶液(pH=1.0～2.0)可将吸附在碳包铁纳米粒子上的金属离子完全脱附。该法对Cr、Ni、Cd、Pb的检出限分别为3.6、4.1、1.1、9.8μg/L,Cr、Ni、Cd的线性范围为1～500μg.L-1,Pb的线性范围为10～1 000μg.L-1,线性相关系数均大于0.999。方法用于自来水中Cr、Ni、Cd、Pb离子的测定,回收率可达到93%～105%;碳包铁纳米粒子对Cr、Ni、Cd、Pb离子的吸附量分别为3.6、4.8、6.3、2.1 mg/g。     

树脂填充EVAL中空纤维膜吸附剂的吸附及脱附性能研究

以亲水性乙烯-乙烯醇共聚物(EVAL)为膜吸附剂基质材料,阳离子交换树脂D061为功能树脂,采用干-湿法纺丝技术,制备了树脂填充EVAL中空纤维膜吸附剂。实验采用连续循环膜过滤工艺,研究了这种吸附剂对目标蛋白(牛血清白蛋白-BSA)的吸附和脱附性能。考察了树脂填充量、缓冲溶液pH值等对蛋白质吸附和脱附性能的影响。实验结果表明,树脂填充EVAL中空纤维膜吸附剂对目标蛋白BSA具有较高的吸附容量和脱附率,随着树脂填充量的增加,膜吸附剂对BSA吸附容量增加,并且最大吸附容量在牛血清蛋白等电点(4.8～5.2)附近出现。当树脂填充量65%,缓冲溶液pH4.5时树脂填充EVAL中空纤维膜吸附剂对BSA的吸附容量可达到71.47mgBSA/g膜吸附剂。     

壳聚糖黄原酸盐对Cu2+的吸附性能

用红外、紫外和热重分析等测试技术分别对二硫代氨基甲酸改性壳聚糖(壳聚糖黄原酸钠,DTC-CTS)进行了表征和测试.比较了DTC-CTS与未改性的壳聚糖(CTS)对水溶液中Cu2 吸附性能的差别,考察了溶液的pH值、温度、时间及取代度对其吸附性能的影响.结果表明,DTC-CTS的取代度越高,吸附性能越好,对Cu2 吸附的最佳pH值范围为6.0～7.0,最佳温度为40℃,最佳吸附时间为0.5h.在最佳吸附条件下,DTC-CTS的吸附量为349.5mg/g,比CTS提高了7%.用体积分数为10%的氨水可将吸附在DTC-CTS上的Cu2 定量的洗脱,脱附率为96%,DTC-CTS能重复使用3次.     

磁性壳聚糖去除水中腐殖酸的研究

采用高温水热法合成了磁性壳聚糖,并研究了其对水中腐殖酸(HA)的吸附、脱附行为。表征结果表明,磁性壳聚糖粒径大小为200～300nm,氨基含量1.29mmol·g-1,BET比表面积36.00m2·g-1,饱和磁化强度为38.78emu·g-1,易于磁性分离。HA在磁性壳聚糖上的吸附等温线可用Freundlich方程模拟,吸附动力学符合拟二级动力学方程。HA的吸附量随溶液pH值的升高而降低,随不同阳离子浓度增加而增加,不同类型的阳离子对HA吸附效果影响的大小顺序为:Ca2+Mg2+Na+K+。经5个脱附再生循环,磁性壳聚糖仍能保持79.8%的吸附量,表明该吸附剂再生性好,可循环使用。     

调节pH控制载银纳米TiO2表面包覆的PMMA

测定了十二烷基磺酸钠(SDS)在载银离子纳米TiO2颗粒表面的等温吸附曲线,在SDS达到临界胶束浓度(CMC)时,研究了pH=2.0(等电点以下)和pH=7.0(等电点以上)时甲基丙烯酸甲酯(MMA)在TiO2粒子表面的乳液聚合.采用改性前后TiO2的Zeta 电位的变化、红外光谱(FT-IR)及差热分析(DTA)等表征方法评价了改性效果.结果表明:PMMA成功包覆到TiO2表面,包覆率达17.8%,载银TiO2的表面由亲水变为亲油;在pH=2.0,cSDS=5.0 mmol/L时,Ag+的脱附量只有8%.     

壳聚糖/乙酰半胱氨酸纳米粒子的性质及体外释药性

制备了一种基于壳聚糖/乙酰半胱氨酸偶合物(CS-NAC)的新型巯基纳米粒子并进行了结构表征, 同时对纳米粒子的黏附性、溶胀性和药物释放进行了测试. 结果表明, 纳米粒子具有较小的粒径(140~210 nm)和正的表面电位(19.5~31.7 mV), 胰岛素的载药量达到13%~42%. 这些性质随着巯基含量的变化而变化. 与壳聚糖纳米粒子相比, 巯基壳聚糖纳米粒子表现出了更强更快的黏附性质. 体外释放研究结果表明, 巯基壳聚糖纳米粒子的胰岛素释放具有pH响应性. 在pH=6.8时, 15 min即能释放58.6 %的胰岛素; 而在pH=5.4时, 24 h内仅有不到40%的胰岛素被释放. 因此, CS-NAC纳米粒子用于胰岛素的黏膜给药体系具有很好的应用前景.     

缓冲液的组成和浓度对带正电荷纳米粒子ζ电位的影响

研究了测定介质缓冲液的组成和浓度对3种含氨基纳米粒子的ζ电位的影响,这3种纳米粒子是聚酰胺-胺树状大分子(PAMAM)、苯乙烯与甲基丙烯酸-N,N-二甲基氨基乙基酯二嵌段共聚物(PS-bPDMAEMA)胶束和壳聚糖纳米粒子.在相同的pH值下,3种纳米粒子在三(羟甲基)氨基甲烷盐酸盐(Tris)、N-(2-羟乙基)哌嗪-N′-2-乙烷磺酸(Hepes)、3-(N-吗啡啉)丙磺酸(Mops)和磷酸盐缓冲液中的ζ电位依次降低,在磷酸盐缓冲液中的ζ电位比在其他几种缓冲液中的都低很多.带有氨基的壳聚糖纳米粒子在浓度~10 mmol/L磷酸盐缓冲液(pH=7.4)中的ζ电位甚至是负值.随着缓冲剂浓度的增加(从2 mmol/L到100 mmol/L)3种纳米粒子的ζ电位都显著降低,在磷酸盐缓冲液(pH=7.4)中随着缓冲剂浓度的增加,壳聚糖纳米粒子的ζ电位由正转负,转变点的磷酸盐的浓度为~10 mmol/L.这一由正转负的现象可以归因于壳聚糖中氨基(p Ka=6.3)在pH=7.4下的低的质子化作用和存在三价的磷酸根负离子,三价磷酸根负离子牢固地结合于带正电荷的纳米粒子上,掩蔽了粒子的正电荷.还研究了不同缓冲液的pH值和离子强度对ζ电位的影响.     

纳米氢氧化铝-聚丙烯酰胺复合絮凝剂对镉离子的吸附研究

采用响应面法对纳米氢氧化铝-聚丙烯酰胺复合絮凝剂吸附Cd(II)过程进行了拟合和优化,分别以pH值、温度和Cd(II)浓度为自变量,研究了其对响应值镉离子最大吸附量的影响,并通过吸附动力学方程和吸附等温线数据对吸附机理进行了探讨。结果表明,采用响应面法对pH值、温度和Cd(II)浓度3个自变量进行优化后得出最大吸附量为79.07mg/g,其最优条件为:pH 6.35,镉离子浓度91.36mg/L,温度50℃;氢氧化铝-聚丙烯酰胺对Cd(II)的吸附在120min内达到平衡,且吸附动力学数据符合准二级动力学模型,表明吸附过程包含化学吸附;吸附速率的控制步骤是吸附脱附平衡步骤;吸附等温线数据与Langmuir吸附等温模型相一致,表明镉离子在氢氧化铝-聚丙烯酰胺表面形成的是单层吸附层。     

Nanoparticles from Chitosan

Novel biodegradable nanoparticles were synthesized by chemical modification of the chitosan linear chain. A natural dicarboxylic acid (malic acid) was used as a crosslinking agent for intramolecular covalent condensation reaction to obtain hydrophilic nanoparticles based on chitosan. A variety of methods including, solubility studies, laser light scattering (DLS), transmission electron microscopy (TEM) and nuclear magnetic resonance (NMR) was used to characterize the crosslinked macromolecules. The prepared biodegradable chitosan nanoparticles, soluble in aqueous media, might be useful for various biomedical applications, like injectable drug- or gene-delivery systems.     

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.     

Preparation,Characterization and Optimization of Chitosan Nanoparticles as Carrier for Immobilization of Thermophilic Recombinant Esterase

Immobilization of biologically important molecules on myriad nano-sized materials has attracted great attention. Through this study, thermophilic esterase enzyme was obtained using recombinant DNA technology and purified applying one-step His-Select HF nickel affinity gel. The synthesis of chitosan was achieved from chitin by deacetylation process and degree of deacetylation was calculated as 89% by elemental analysis. Chitosan nanoparticles were prepared based on the ionic gelation of chitosan with tripolyphosphate anions. The physicochemical properties of the chitosan and chitosan nanoparticles were determined by several methods including SEM (Scanning Electron Microscopy), FT-IR (Fourier Transform Infrared Spectroscopy) and DLS (Dynamic Light Scattering). The morphology of chitosan nanoparticles was spherical and the nanospheres’ average diameter was 75.3 nm. The purified recombinant esterase was immobilized efficiently by physical adsorption onto chitosan nanoparticles and effects of various immobilization conditions were investigated in details to develope highly cost-effective esterase as a biocatalyst to be utilized in biotechnological purposes. The optimal conditions of immobilization were determined as follows; 1.0 mg/mL of recombinant esterase was immobilized on 1.5 mg chitosan nanoparticles for 30 min at 60°C, pH 7.0 under 100 rpm stirring speed. Under optimized conditions, immobilized recombinant esterase activity yield was 88.5%. The physicochemical characterization of enzyme immobilized chitosan nanoparticles was analyzed by SEM, FT-IR and AFM (Atomic Force Microscopy).     

金＠壳聚糖复合材料的合成、表征及其葡萄糖选择氧化性能

采用硼氢化钠化学还原氯金酸的碱性溶液制备了纳米金溶胶, 利用紫外-可见吸收光谱研究了金与壳聚糖的相互作用. 结果表明, 壳聚糖能够捕获金纳米粒子并易于形成金@壳聚糖复合材料. 利用X-光粉末衍射(XRD)、紫外-可见漫反射光谱(UV-vis DRS)、透射电镜(TEM)、红外光谱(IR)、微分热重及差热分析(DTG-DTA)等对这种复合材料进行了表征, 发现该材料具有较小的金纳米粒子, 壳聚糖的存在改变了金纳米粒子的等离子共振吸收, 二者之间存在一定的键合作用. 以分子氧为氧化剂, 在温和条件下, 该材料对葡萄糖选择氧化制葡萄糖酸反应具有良好的催化性能.     

O-羧甲基壳聚糖纳米微粒制备及对Ni~(2+)吸附研究

将壳聚糖与氯乙酸反应,通过控制反应条件制备了取代度为0.71的O-羧甲基壳聚糖,将改性后的O-羧甲基壳聚糖与多聚磷酸钠反应,制备了粒径分布在370-710nm的O-羧甲基壳聚糖纳米微粒,透射电镜观察表明该微粒呈球状,平均粒径为450nm.在此基础上研究了O-羧甲基壳聚糖纳米微粒对工业电镀镍废水Ni~(2+)吸附性能,考察了溶液pH、Ni~(2+)起始浓度、平衡吸附时间、粒径等因素的影响,结果表明:O-羧甲基壳聚糖微粒最佳吸附条件是Ni~(2+)溶液pH为8.0、Ni~(2+)溶液起始浓度为33.28mg/ml、平衡吸附时间为0.5h、粒径较小的O-羧甲基壳聚糖纳米微粒对Ni~(2+)的吸附量要大于粒径较大的吸附量.     

Self-aggregated nanoparticles from linoleic acid modified carboxymethyl chitosan: Synthesis, characterization and application in vitro

The purpose of the present research work was to study the formation of linoleic acid (LA) modified carboxymethyl chitosan (LCC). Another objective was to evaluate effect of linoleic acid degree of substitution on loading capacity (LC), ADR loading efficiency (LE) and in vitro release profile of LCC nanoparticles. The hydrogel nanoparticles can be prepared using linoleic acid modified carboxymethyl chitosan (LACMCS) after the sonication. The critical aggregation concentration (CAC) of the self-aggregate of LA modified CMCS (LCC) was determined by measuring the fluorescence intensity of the pyrene as a fluorescent probe. The CAC values were in the range of 0.061–0.081 mg/mL. Self-aggregated nanoparticles exhibited an increased LC and LE, decreased sustained release with an increasing ratio of the hydrophobic LA to hydrophilic CMCS. LCC nanoparticles loaded with ADR exerted in vitro anticancer activity against Hela cells that was comparable to the activity of free (non-entrapped in nanoparticles) ADR.     

Chitosan nanoparticles crosslinked by glycidoxypropyltrimethoxysilane for pH triggered release of protein

pH-responsive-chitosan nanoparticles for the control release of protein drug were prepared by combining two-step crosslinking method,in which chitosan was subsequently crosslinked by sodium tripolyphosphate(TPP)and glycidoxypropyltrimethoxysilane (GPTMS).Compared with TPP crosslinked chitosan particles,the two-step crosslinked nanoparticles were not only pH-responsive but also more stable in wide pH range.Fluorescein isothiocyanate(FITC)labeled anti-human-IgG antibody was used as a model protein drug for...     

Swelling of ferrogels of poly(acrylic acid) with ferric oxide nanoparticles stabilized by chitosan

The processes of swelling of poly(acrylic acid) ferrogels prepared via radical polymerization in an aqueous suspension of ferric oxide nanoparticles with the weighted average size of 23.5 nm obtained by laser evaporation method and stabilized by chitosan (М = 5.3 × 10⁵ and degree of deacetylation of 62%) are studied. The swelling of washed ferrogels depends on the content of chitosan and decreases abruptly at a polymer concentration exceeding 1 g/L. At a chitosan concentration above 1 g/L, the chemical network of poly(acrylic acid) is formed on the fluctuation network of chitosan in solution. As pH increases, these ferrogels are contracted owing to formation of an interpolymer complex of chitosan with poly(acrylic acid) subchains.     

纳米金–壳聚糖修饰电极循环伏安法测定抗坏血酸

介绍纳米金–壳聚糖修饰电极的制备方法及其测定抗坏血酸的分析应用。采用电沉积方法,将氯金酸与壳聚糖的混合电解液直接共沉积,制备了壳聚糖–纳米金修饰玻碳电极的电化学传感器。利用循环伏安法研究了抗坏血酸浓度、p H值等对抗坏血酸在修饰电极上的电化学行为的影响。实验结果表明,修饰电极对抗坏血酸具有良好的电催化氧化作用,抗坏血酸浓度在5×10~(–5)~1×10~(–3) mol/L范围内线性良好,回归方程为I_p=0.433 8c+0.881 9,相关系数为0.998 71。该法可指导纳米金–壳聚糖修饰电极的制备及抗坏血酸含量的测定。     

Synthesis of P(AA‐SA)/ZnO composite latex particles via inverse miniemulsion polymerization and its application in pH regulation and UV shielding

Poly(acrylic acid‐co‐sodium acrylate)/zinc oxide, P(AA‐SA)/ZnO, composite latex particles were synthesized by inverse miniemulsion polymerization. The ZnO nanoparticles were prepared by hydrothermal synthesis and undergone oleic acid (OA) surface treatment. The X‐ray diffraction pattern and FT‐IR spectra characterized the crystal structure and functional groups of OA‐ZnO nanoparticles. An appropriate formulation in preparing P(AA‐SA) latex particles, ensuring the dominant in situ particle nucleation and growth, was developed in our experiment first. Sodium hydroxide was chosen as a costabilizer, because of its ability to increase the deprotonation of acylic acid and enhance the hydrophilicity of monomer, acrylic acid besides providing osmotic pressure. The growth mechanism of P(AA‐SA)/ZnO composite particles was proposed. The OA‐ZnO nanoparticles were adsorbed on or around the surface of P(AA‐SA) latex particles by hydrophobic interaction, thus enhanced the interfacial tension over latex particles. The P(AA‐SA)/ZnO composite latex particles owned better thermal stability than pure latex particles. The pH regulation capacity was excellent for both ZnO and P(AA‐SA) particles. Combining P(AA‐SA) and ZnO nanoparticles into composite particles, the performance in pH regulation and UV shielding was discussed from our experimental results. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 8081–8090, 2008