复合磁性壳聚糖微球对BSA的吸附机理研究

将脱乙酰度为85%的壳聚糖包裹在由二价和三价的铁离子共沉淀制得的Fe3O4磁子表面,用环氧氯丙烷作为交联剂进行交联制成磁性壳聚糖(简称MC),用于吸附蛋白质一磷酸氢二钠一柠檬酸缓冲溶液中的小牛白蛋白(BSA),利用TEM(透射电镜)、IR(红外光谱)、TG-DSC(失重-差热)、XRD(粉末衍射)分析微球的形貌、组成及热件能,考察了牛白蛋白的初始浓度、溶液pH及保温时间对蛋白质吸附程度的影响.结果显示,pH增大使蛋白质的吸附量减小;在一定范围内,增大蛋白质的初始浓度和延长保温时间均有利于增加蛋白质的吸附量,温度对微球吸附蛋白质的影响比较复杂.     

pH温度双敏感磁性微球的分散聚合、表征及吸附性能研究

在Fe3O4磁流体存在的条件下,以苯乙烯、甲基丙烯酸、N,N-亚甲基双丙烯酰胺、N-异丙基丙烯酰胺为共聚单体,在醇-水体系中采用分散聚合法制备了具有pH值敏感和温度敏感性的磁性高分子微球。采用扫描电镜 (SEM) 等考察了双敏感磁性微球的形态及结构,测得磁性微球的粒径约为1.5μm。研究了双敏感磁性微球对牛血清蛋白的吸附动力学性能,36h时的平衡吸附量为565.6mmol/g。吸附过程具有Freundlich等温吸附特征。     

沉积法制备Fe_3O_4/P(AA-DVB)磁性复合微球

通过静电吸附与机械力共同作用的沉积法制备得到了Fe3O4/P(AA-DVB)磁性复合微球。分别采用无皂乳液聚合和共沉淀法制备得到单分散的P(AA-DVB)胶体粒子及Fe3O4纳米粒子,在静电吸附和机械力作用下,将Fe3O4纳米粒子附着并嵌入P(AA-DVB)胶体粒子表面及内部,制备得到Fe3O4/P(AA-DVB)磁性复合微球。该方法的优势在于最终磁性复合微球的粒径及粒径分布可以由前驱体P(AA-DVB)胶体粒子调控。磁性复合微球表面和内部Fe3O4纳米粒子的分布及磁含量可以由机械力作用时间进行调节。所制备的Fe3O4/P(AA-DVB)磁性复合微球平均粒径为542 nm,磁含量范围在11%~33%内可调。     

Tween-60+Span-80/异戊醇/环己烷微乳液法制备纳米Fe3O4

采用W/O型Tween-60 Span-80/异戊醇/环己烷微乳液作为"微反应器"合成纳米磁性Fe3O4粒子。研究结果表明纳米Fe3O4粒子磁化率均随着反应温度、pH、铁离子的浓度比例ω(=[Fe2 ]/[Fe3 ])的增大先增大后减小;最优的制备条件为反应温度30℃、ω=1.2:2、pH=11。最优条件下制备的纳米Fe3O4粒子AFM图片表明所得纳米Fe3O4为均匀分散的球形微粒,平均粒径为70nm。     

沉淀聚合法制备壳聚糖磁性微球

要用共沉淀法制备Fe3O4磁性纳米粒子,并对其用油酸进行表面改性,继而采用沉淀聚合法制备壳聚糖磁性微球。考察了沉淀剂浓度、乳化剂种类、Fe3O4的改性等条件对制备微球的影响。应用扫描电镜、红外谱图、接触角仪、粒径分析仪及磁铁吸附对壳聚糖磁性微球的形态与特性进行了表征。研究结果表明,在适宜的沉淀剂浓度、复合乳化剂、Fe3O4经油酸改性等条件下,可以制得平均粒径为150nm、单分散性好且磁性明显的壳聚糖磁性微球。     

壳聚糖修饰磁性纳米粒子对BSA的吸附性能

采用化学共沉淀法制备磁性Fe3O4纳米粒子,以（3-氯丙基）三甲氧基硅烷为偶联剂将壳聚糖共价键合到磁性Fe3O4纳米粒子的表面,通过红外光谱（FTIR）、X射线衍射（XRD）、扫描电子显微镜（SEM）及热重分析（TGA）对其进行了表征。主要研究了不同影响因素（吸附时间、pH值、牛血清白蛋白浓度）下壳聚糖修饰的磁性纳米粒子对牛血清白蛋白（BSA）的吸附性能。结果得到壳聚糖修饰的磁性Fe3O4纳米粒子粒径为20 nm左右,壳聚糖在磁性Fe3O4纳米粒子表面的接枝率为15.40%。研究表明：在不同条件下,与未修饰的磁性Fe3O4纳米粒子相比,经壳聚糖修饰的Fe3O4纳米粒子对BSA均表现出较强的吸附能力。     

pH/温度双敏感磁性微球的分散聚合、表征及吸附性能

在Fe3O4磁流体存在的条件下,以苯乙烯、甲基丙烯酸、N,N-亚甲基双丙烯酰胺、N-异丙基丙烯酰胺为共聚单体,在醇-水体系中采用分散聚合法制备了具有p H值敏感和温度敏感性的磁性高分子微球。采用扫描电镜(SEM)等考察了双敏感磁性微球的形态及结构,测得磁性微球的粒径约为1.5μm。研究了双敏感磁性微球对牛血清蛋白的吸附动力学性能,36 h时的平衡吸附量为565.6 mmol/g。吸附过程具有Freundlich等温吸附特征。     

双重Pickering乳液法制备聚丙烯酰胺多孔微球及应用

采用亲水性气相二氧化硅N20和疏水性气相二氧化硅H30复配表面活性剂制备O/W/O型双重乳液,以此为模板,聚合中间相,挥发内相制备聚丙烯酰胺(PAM)多孔微球,并用于染料分子亚甲基蓝的吸附。结果表明：乳液显微镜照片显示水油比对双重乳液的形成有很大的影响,当水油比(O₁/W)/O₂为(1/2)/2时,可得到稳定的双重乳液;扫描电镜(SEM)照片显示PAM多孔微球基本呈球形,但粒径不均匀,球体表面粗糙,内部为空心结构;激光粒度仪(DLS)结果表明PAM微球平均粒径为356nm,多分散系数(PDI)为0.718,比表面积为230m²/g,粒径分布宽;在吸附温度35℃、吸附时间5min时对亚甲基蓝的吸附率为98.89%,最大吸附率超过99%,在吸附速率和吸附率上均优于传统PAM吸附剂,本研究为染料废水的处理提供了新方法。     

Fe~(3+)@酵母菌非均相UV-Fenton降解染料废水

以球形酵母菌为生物载体,饱和吸附Fe3+后,获得了Fe3+@酵母菌核壳微球。SEM,EDS及FT-IR对微球的结构进行了表征。实验研究了Fe3+@酵母菌非均相UV-Fenton降解碱性嫩黄O染料废水,考察了H2O2浓度、Fe3+@酵母菌催化剂的投加质量浓度、pH值、碱性嫩黄O染料的初始质量浓度等对反应的影响。结果表明,微球的直径在3.1—3.3μm,具有较好的球形形貌和壳壁强度。核壳结构的形成主要源自于生物吸附作用。当H2O2浓度为3.5 mol/L,pH值为3—4,催化剂质量浓度为5.5 g/L时,Fe3+@酵母菌非均相UV-Fenton降解碱性嫩黄O染料废水表现出了较好的去除效率。     

高吸附性能介孔磁性复合碳球的制备

以正硅酸乙酯(TEOS)为硅前驱体,间苯二酚-甲醛树脂(RF)为碳源,在表面活性剂十六烷基三甲基溴化铵(CTAB)的辅助作用下,采用原位聚合法制备了介孔磁性复合碳球Fe3O4@C-M。考察了醇水比〔V(乙醇)∶V(水)〕、表面活性剂用量、TEOS用量和水热温度(HT)对碳球的形貌、粒径和表面孔结构的影响。在84 mL乙醇/水混合液〔V(乙醇)∶V(水)=3∶4〕、CTAB 0.6 g、TEOS 4 mL、水热温度100℃下制备得到Fe3O4@C-M,采用TEM、XRD、XPS、BET、TGA、VSM对其进行表征。结果表明,Fe3O4@C-M的比表面积为553m2/g,较不引入硅前驱体时制备的磁性复合碳球Fe3O4@C-0增大1.7倍,介孔孔容占比由18%增大到83%。考察Fe3O4@C-M对红霉素的吸附性能,饱和吸附量为255 mg/g;用乙酸正丁酯对吸附后材料进行再生,5次循环再生后吸附量维持在初始吸附量的85%以上。     

表面带磺酸基团的聚苯乙烯微球的制备及其对蛋白质的吸附

研究了运用分散聚合法,在乙醇/水混合介质中,制备2-丙烯酰胺基-2-甲基丙磺酸(AMPS)与苯乙烯(St)的共聚微球。运用红外、核磁共振、激光光散射和扫描电子显微镜对功能微球进行表征。阐述了该微球对牛血清蛋白(BSA)的吸附量与吸附时间和pH值的关系。结果表明:功能微球对BSA的吸附先随时间的增长而增大,一段时间后达到平衡吸附。当pH值接近BSA等电点(pI=4.7)时,BSA的吸附量达到最大值。     

Congo red- and Zn(II)-derivatized monosize poly(MMA-HEMA) microspheres as specific sorbent in metal chelate affinity of albumin

Monosize poly(methylmethacrylate-hydroxyethylmethacrylate) [poly(MMA-HEMA)] microspheres (4 μm in diameter) were produced by dispersion copolymerization of MMA and HEMA in an ethanol-water medium. Congo Red was attached to the poly(MMA-HEMA) microspheres, covalently. These Congo Red-derivatized microspheres were characterized by optical microscopy, Fourier transform infrared spectroscopy, and elemental analysis. Then, Zn(II) ions were incorporated by chelating with the immobilized Congo Red molecules. Different amounts of Zn(II) ions [1.2–17.6 mg of Zn(II)/g of polymer] were conjugated on the microspheres by changing the initial concentration of Zn(II) ions and pH. Bovine serum albumin (BSA) adsorption on these microspheres from aqueous solutions containing different amounts of BSA at different pH and ionic strengths was investigated in batch reactors. The nonspecific BSA adsorption on the plain poly(MMA-HEMA) microspheres was very low (0.7 mg of BSA/g of polymer). Congo Red derivatization significantly increased the BSA adsorption (up to 35.8 mg of BSA/g of polymer). A further increase in the adsorption capacity (up to 61.0 mg of BSA/g of polymer) was observed when Zn(II) ions were incorporated. More than 90% of the adsorbed BSA was desorbed in 1 h in the desorption medium containing 1.0M NaSCN at pH 8.0. © 1997 John Wiley & Sons, Inc.     

mPEG-PLGA多孔微球的制备及其对降钙素的吸附行为

以聚乙二醇-聚(乳酸-乙醇酸)共聚物(mPEG-PLGA)为材料,采用溶剂挥发法与快速膜乳化法制备了尺寸均一的mPEG-PLGA多孔微球,用其吸附降钙素,考察了降钙素浓度、吸附时间、离子浓度、温度及pH值及微球性质对吸附的影响. 结果表明,优化的吸附条件为：降钙素浓度1.0 mg/mL, pH 7.4, NaCl浓度0.2 mol/L, 14℃下吸附8 h,该条件下,微球吸附量为48.9 mg/g;吸附量与微球比表面积正相关.     

Biomagnetic of Apatite-Coated Cobalt Ferrite: A Core–Shell Particle for Protein Adsorption and pH-Controlled Release

Magnetic nanoparticle composite with a cobalt ferrite (CoFe₂O₄, (CF)) core and an apatite (Ap) coating was synthesized using a biomineralization process in which a modified simulated body fluid (1.5SBF) solution is the source of the calcium phosphate for the apatite formation. The core–shell structure formed after the citric acid–stabilized cobalt ferrite (CFCA) particles were incubated in the 1.5 SBF solution for 1 week. The mean particle size of CFCA-Ap is about 750 nm. A saturation magnetization of 15.56 emug^-1 and a coercivity of 1808.5 Oe were observed for the CFCA-Ap obtained. Bovine serum albumin (BSA) was used as the model protein to study the adsorption and release of the proteins by the CFCA-Ap particles. The protein adsorption by the CFCA-Ap particles followed a more typical Freundlich than Langmuir adsorption isotherm. The BSA release as a function of time became less rapid as the CFCA-Ap particles were immersed in higher pH solution, thus indicating that the BSA release is dependent on the local pH.     

Human serum albumin (HSA) adsorption with chitosan microspheres

In this study, chitosan microspheres were prepared and characterized for adsorption of human serum albumin (HSA) as affinity sorbent. The chitosan microspheres were obtained with a “suspension crosslinking technique” in the size range of 30–700 μm by using a crosslinker, i.e., glutaraldehyde. The chitosan microspheres used in HSA adsorption studies were having the average size of 170 ± 81 μm. Adsorption medium pH and the initial HSA concentration in the adsorption medium were changed as 4.0–7.0 and 0.5–2.0 mg HSA/mL, respectively, to investigate the HSA adsorption capacity of chitosan microspheres. Maximum HSA adsorption (i.e., 11.35 mg HSA/g chitosan microspheres) was obtained at pH 5.0 and 1.5 mg HSA/mL of the initial HSA concentration in the adsorption medium was obtained as the saturation value for HSA adsorption. A very common dye ligand, i.e., Cibacron Blue F3GA was attached to the chitosan microspheres to increase the HSA adsorption capacity. Actually, the HSA adsorption capacity was increased up to 15.35 mg HSA/g chitosan microspheres in the case of Cibacron Blue F3GA attached to chitosan microspheres used. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3035–3039, 2002     

Preparation of polyamidoamine dendrons supported on chitosan microspheres and the adsorption of bilirubin

The aim of this study was to prepare a new adsorbent for bilirubin (BR); low generation (G, G ≤4) hexanediamine‐containing polyamidoamine (PAMAM) dendrons were supported on chitosan (CS) microspheres (CS‐Gn, n = 0,1,2,3,4). The adsorption properties of this novel adsorbent for BR in aqueous solution were examined. The adsorption percentages were over 70% at 0.5 h and over 90% at 1 h. The adsorption capacity was up to 43 mg/g and was not yet saturated. The BR adsorption increased with increasing temperature and increasing BR initial concentration and was the highest at pH 7.4; it decreased slightly with increasing ionic strength and occurred even in the presence of bovine serum albumin (BSA). We observed that the CS–Gn microspheres had satisfactory competitive abilities with BSA, although the adsorption percentage decreased a certain extent in the presence of BSA. In addition, the CS–Gn microspheres were easier to prepare than the usual PAMAM dendrimers. In summary, this adsorbent is a promising biomedical material for BR removal for artificial liver supported systems. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

氨基表面修饰的高分子乳液微球对牛血白质BSA吸附性能的研究

以苯乙烯St和甲基丙烯酸环氧丙酯GMA为单体,两性偶氮类化合物V50为引发剂,运用功能单体多段加料的无皂乳液聚合法制备亲和高分子乳液基球PSG,并选择双氨基封端的聚乙二醇作为空间臂分子,进行表面修饰反应,考察了高分子乳液微球对牛血蛋白BSA的吸附性能,并着重研究了吸附时间和温度、BSA初始浓度、离子强度等因素对吸附反应的影响。实验结果表明,空间臂表面修饰的高分子微球作为载体材料,固定药物分子等生物活性物质,可通过控制吸附条件,如pH,温度,反应时间等,减少蛋白质分子的非特异性吸附,且保持生化分子的较高活性。     

乙肝表面抗原在微球表面的吸附行为、活性和结构变化

采用快速膜乳化技术结合溶剂挥发法制备了尺寸均一的聚乳酸(PLA)微球,平均粒径为800 nm左右,并采用PLA微球对乙肝表面抗原(HBsAg)进行了吸附研究,考察了pH值、盐浓度、微球用量、HBsAg浓度及吸附温度对HBsAg吸附率、活性和结构的影响. 结果表明,在pH 6.0的磷酸缓冲溶液中,NaCl浓度为20 g/L、微球用量为20 mg/mL、HBsAg浓度为10 mg/mL、吸附温度为37℃的条件下,HBsAg吸附率可达60%左右. 4℃下,pH值为8.0及NaCl浓度为1 g/L、微球用量为2 mg/mL及HBsAg浓度为300 mg/mL时,HBsAg活性保留可达98%以上.     

双乳化-凝胶法制备单分散海藻酸钙微球及其载BSA研究

采用双乳化-凝胶法制备了单分散的海藻酸钙凝胶微球,并通过正交试验系统考察了海藻酸钠浓度、氯化钙浓度、表面活性剂浓度、搅拌速度和油水比对海藻酸钙凝胶微球粒径及形貌的影响。在优化的条件下,制备出了平均粒径为4μm、单分散和球形度好的海藻酸钙凝胶微球。包埋模型药物牛血清白蛋白(BSA)的过程中,以去离子水作为洗涤液洗涤海藻酸钙微球时,BSA的包封率仅为13%左右;当水洗液的pH值为3.2时,BSA的包封率提高到66%左右,载药率可达16%,这是海藻酸钙pH值响应溶胀和BSA与海藻酸盐之间静电作用的结果。微球中BSA的体外释放曲线表明,该系统具有在模拟胃液中释药速率慢、释药量低、模拟肠液中释药迅速的特性。因此,双乳化-凝胶法制备海藻酸钙微球有望成为制备蛋白类药物控释制剂的一种新方法,以达到靶向快速给药的目的。     

粉煤灰基地质聚合物微球吸附水中铜（Ⅱ）的研究

以粉煤灰为原料,以氢氧化钾溶液为碱激发剂,将二者按照优化配比（氧化钾与氧化铝物质的量比为1.5、水与氧化钠物质的量比为18）混合均匀后,采用悬浮固化法制备粉煤灰基地质聚合物微球,将微球用于吸附含铜废水中的铜（Ⅱ）。通过X射线衍射（XRD）仪、比表面积与孔径分析仪、BT-99型水质分析仪对微球进行了表征,探究了吸附时间、微球用量、吸附温度、铜（Ⅱ）溶液pH、铜（Ⅱ）溶液质量浓度等因素对微球吸附铜（Ⅱ）的影响。结果表明,粉煤灰基地质聚合物微球较粉煤灰原料具有更大的孔径和比表面积,具有更好的对铜（Ⅱ）的吸附效果,在最优条件下[微球用量为0.20 g、溶液pH为5、铜（Ⅱ）初始质量浓度为100 mg/L、溶液体积为100 mL、吸附温度为40℃、吸附时间为24 h]微球对铜（Ⅱ）的吸附量为45.62 mg/g、去除率达到91.46%,吸附过程遵循准二级动力学方程。