[Dye molecules/copper(II)/macroporous glutaraldehyde‐chitosan] microspheres complex: Surface characterization,kinetic, and thermodynamic investigations

Chitosan microspheres loaded Cu(II) were prepared using a precipitation method and heterogeneously crosslinked with glutaraldehyde. The abilities of the binary [Cu(II)/Glut‐chitosan] system for binding two acid dyes, that is, Acid blue 25 (AB25) and Calmagite (Calma) were investigated. Sorption experiments were performed using a batch process at 25°C and indicate pH dependence. Evidence for the modification of the raw chitosan polymer was provided by Fourier transform infra red spectral study, thermogravimetry, differential thermogravimetry, differential scanning calorimetry, and scanning electron microscopy analysis. Data gleaned from the thermal analyses, showed that the modification of the polymer decreases the thermal stability of the prepared materials with respect to that of the native one. The effecting factors during dye adsorption have been also studied. Thermodynamic and kinetic experiments were undertaken to assess the capacity and the rate of dyes removal on the surface of [Cu(II)/Glut‐chitosan]. Experimental data were mathematically described using various kinetic models. The pseudo second‐order equation was shown to fit the adsorption kinetics. The interpretation of the equilibrium sorption data complies well with the Freundlich adsorption model. Thermodynamic results indicate that the adsorption follows an exothermic process. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation and characterization of uniform molecularly imprinted polymer beads for separation of triazine herbicides

Uniform molecularly imprinted polymer beads were synthesized by precipitation polymerization for separation of triazine herbicides. A series of imprinted polymers were prepared using ametryn as template and divinylbenzene as crosslinking monomer, in combination with three different functional monomers under different solvent conditions. Under optimized reaction conditions, we obtained uniform molecularly imprinted polymer microspheres that display favorable molecular binding selectivity for triazine herbicides. The imprinted polymer beads synthesized using methacrylic acid as functional monomer in a mixture of methyl ethyl ketone and heptane showed the best results in terms of particle size distribution and molecular selectivity. Compared with nonimprinted polymer microspheres, the imprinted microspheres displayed significantly higher binding for a group of triazine herbicides including atrazine, simazine, propazine, ametryn, prometryn, and terbutryn. For the first time, precipitation polymerization has been used to produce highly uniform imprinted microspheres suitable for affinity separation of triazine herbicides. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis of monodisperse crosslinked poly(styrene‐co‐divinylbenzene) microspheres by precipitation polymerization in acetic acid

Poly(styrene‐co‐divinylbenzene) microspheres with size ranging from 1.6 to 1.8 μm were prepared in acetic acid by precipitation polymerization. The particle size and particle size distribution were determined by laser diffraction particle size analyzer, and the morphology of the particles was observed with scanning electron microscope. Besides, effects of various polymerization parameters such as initiator and total monomer concentration, divinylbenzene (DVB) content, polymerization time and polymerization temperature on the morphology and particle size were investigated in this article. In addition, the yield of microspheres increased with the increasing total monomer concentration, initiator loading, DVB concentration and polymerization time. In addition, the optimum polymerization conditions for synthesis of monodisperse crosslinked poly(styrene‐co‐divinylbenzene) microspheres by precipitation polymerization in acetic acid were obtained. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Temperature-Sensitive Microspheres for Controlled Release of Enalprilmaleate

Poly(N′-isopropylacrylamide-co–methacryl amide) has been prepared by free-radical emulsion polymerization. The copolymer was transformed into thermoresponsive microspheres by chemical crosslinking with N′, N′ Methylenebis-acrylamide (NNMBA). Enalpril maleate (ENAM), an anti-hypertensive drug, was successfully loaded into these microspheres during in-situ polymerization. DSC and X-RD analysis of the drug-loaded and plain microspheres have confirmed partial dispersion of ENAM in the microspheres. SEM confirmed the spherical nature of the particles with a mean particle size of 100 µm. Drug release profiles of these microspheres exhibited a prolonged release of ENAM for more than 12 h.     

Investigation of the surface area and polarity of porous copolymers of maleic anhydride and divinylbezene

Porous copolymers of maleic anhydride (MA) and divinylbezene (DVB) in the form of regular microspheres were prepared by suspension polymerization. During copolymerization the mixture of 1,4-dioxane and n-dodecane as a pore-forming diluent was used. It was found that specific surface area of the obtained beads is strongly dependent on the diluent system and polymerization medium and achieves a value from 4 to 535 m²/g. To determine the influence of polymerization medium on the selectivity and polarity of the copolymers, inverse gas chromatography (IGC) was applied. To determine these parameters, three procedures were applied: overall polarity, the selectivity triangle, and the ΔC method. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation of sodium alginate/poly(vinyl alcohol) blend microspheres for controlled release applications

Sodium alginate (NaAlg)/poly (vinyl alcohol) (PVA) blend microspheres (MS) were prepared by water-in-oil (w/o) emulsion method. These polymer microspheres were crosslinked with glutaraldehyde and loaded with metformin hydrochloride (MHC). The microspheres were characterized by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and X-ray diffraction (XRD) analysis to confirm the molecular dispersion of the drug, thermal stability, morphological properties, and crystallinity of the polymer matrix before and after blending. SEM of the microspheres suggested the formation of microspheres in spherical structure. Drug release data were analyzed using an empirical equation to understand the nature of drug transport through polymeric matrices. The controlled release (CR) characteristics of the polymer matrices was investigated in pH 7.4 media and from the results it was obtained that the drug was released in controlled manner up to 10 h. The physico-chemical properties of the microspheres were studied by calculating drug entrapment efficiency and drug release kinetics. Percent of encapsulation efficiency (% EE) decreased with increase in crosslinking agent (GA) and PVA content in the microspheres. The optimum % EE (80%) was observed in case of MS containing 40% of PVA with 15% MHC. The release profiles indicate that the release of MHC decreases with increasing the PVA/NaAlg (w/w) and drug/polymer ratio. At the end of 10 h, the highest release of MHC was found to be 96% for MS containing PVA/NaAlg (40 : 60) and 15 wt % drug loaded. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

不同修饰剂对β-环糊精微球吸附性能的影响

以β-环糊精为原料,通过传统的反相乳液聚合法合成β-环糊精微球,选择壳聚糖和四甲基氢氧化铵分别对其进行修饰,考察溶液的搅拌时间、吸附体系的温度、pH等条件对β-环糊精微球及其衍生物吸附甲基橙的影响。结果显示,β-环糊精微球对甲基橙吸附效果较好,修饰改性后,吸附效果增强,四甲基氢氧化铵修饰的β-环糊精微球吸附效果优于壳聚糖修饰后β-环糊精微球。     

腐植酸/淀粉复合微球的制备及工艺优化

以腐植酸(HA)和可溶性淀粉(St)为原料,N,N'-亚甲基双丙烯酰胺(MBAA)为交联剂,过硫酸钾/亚硫酸氢钠(K_2S_2O_8/Na HSO_3)为复合引发剂,采用反相乳液聚合法合成了腐植酸/淀粉复合微球(CSM)。结合响应曲面设计,探讨了m(HA)∶m(St)、K_2S_2O_8/Na HSO_3用量、MBAA用量、复合乳化剂用量、反应温度等因素对CSM吸附Cr(Ⅵ)性能的影响。结果表明,合成CSM的最佳工艺条件为:m(HA)∶m(St)=1.51∶1.00、MBAA用量40%(以St质量为基准,下同)、K_2S_2O_8/NaHSO_3用量40%/40%、复合乳化剂〔m(Span-80):m(Tween-20)=3:1〕用量80%、反应温度50℃、反应时间3 h。在该条件下合成的CSM对Cr(Ⅵ)(10 mg/L)的去除率达到99.91%,吸附量为1.9980 mg/g。利用FTIR、SEM、激光粒度分布仪、XRD和TGA对CSM进行了结构表征和性能测试,结果显示HA和St成功反应,所得CSM形状规则,表面粗糙,粒径分布均匀,平均粒径为13.79μm,结晶度(相较于St)降低,具有较好的热稳定性。     

松香基磁性微球的结构表征及其对Cr(Ⅵ)的吸附性能

以马来松香乙二醇丙烯酸酯和甲基丙烯酸为单体,Fe₃O₄为磁源,通过悬浮聚合和酰胺化反应制备出松香基磁性微球。利用热重分析仪、红外光谱、比表面积与孔隙度分析仪、扫描电镜及磁天平对磁性微球进行表征,并通过静态吸附法研究了其对Cr(Ⅵ)的吸附性能。结果显示：松香基磁性微球既具有顺磁性(磁化率为9.123×10^-4 cm³/g),又具有功能基团(氨基),比表面积、孔体积和平均孔径分别为29.73 m²/g、0.396 cm³/g和18.023 nm,表面和内部均有大量孔洞。当磁性微球粒径为72~108 μm时,在50 mL质量浓度为0.5 g/L Cr(Ⅵ)溶液中,调节pH值为2,吸附剂用量为0.8 g,25 ℃下振荡吸附,吸附平衡时间为4 h时,平衡吸附量为67.5 mg/g。动力学方程拟合结果显示吸附速率符合准一级动力学方程,吸附过程受液膜扩散和颗粒内部扩散共同影响。磁性微球循环使用5次,去除率仍达第一次吸附的85%以上,具有很好的循环使用性能。     

Preparation of Anti‐Nonspecific Adsorption Chitosan‐Based Bovine Serum Albumin Imprinted Polymers with Outstanding Adsorption Capacity and Selective Recognition Ability Based on Magnetic Microspheres

Bovine serum albumin (BSA)‐imprinted magnetic microspheres are successfully fabricated by a precipitation copolymerization, in which 2‐hydroxyethyl acrylate (HEA) and water‐soluble chitosan separately work as functional monomers and cross‐linking agents. Hydroxyl derived from HEA as well as hydroxyl, amino, and carboxyl groups, originating from chitosan on the surface of the prepared imprinted microspheres, can form hydrogen bonds and extra electrostatic interaction with proteins. The sulfobetaine methacrylate (SBMA) is introduced into the imprinted polymer as an anti‐protein segment to reduce the nonspecific adsorption and improve the selectivity. Detailed characterization demonstrates that the imprinted layer is about 10 nm, which is extremely beneficial for BSA identification and quality transmission. Furthermore, these microspheres also display an excellent selective adsorption of BSA (IF = 5.0). The results reveal that the prepared imprinted materials can be used as BSA biosensor or separation materials.