Monodisperse hydrophilic polymer microspheres having carboxylic acid groups prepared by distillation precipitation polymerization

Monodisperse hydrophilic polymer microspheres having carboxyl acid group with spherical shape in the range of 160 nm and 1.52 μm were prepared by distillation copolymerizations of (meth)acrylic acid with either ethyleneglycol dimethacrylate (EGDMA) or divinylbenzene (DVB) as crosslinker. Polymerization was carried out with 2,2′-azobisisobutyronitrile (AIBN) as initiator in neat acetonitrile without stirring. The polymer microspheres were formed and precipitated out from the reaction medium during the distillation of the solvent from the reaction system through an entropic precipitation polymerization manner. The effects of the crosslinker degree on the morphology and the loading capacity of the carboxylic acid group of the resultant polymer microspheres were investigated. The growth procedures of poly(DVB-co-AA) microspheres were traced by SEM characterization. The steric stabilization through the pendent chains and surface gel and the electrostatic repulsion from the carboxyl acid groups contribute to the formation of monodisperse polymer microspheres.     

Preparation and characterization of monodisperse molecularly imprinted polymer microspheres by precipitation polymerization for kaempferol

A new kind of molecularly imprinted polymer (MIP) microspheres for the selective extraction of kaempferol was prepared by precipitation polymerization using 4-vinylpridine (4-VP) and ethylene glycol dimethacrylate (EDMA) as functional monomer and cross-linker respectively. The synthesis conditions, such as ratios of 4-VP/EDMA and polymerization time were discussed in detail. Results showed that the 2% was the optimal concentration of co-monomers to obtain monodisperse MIP microspheres, the best ratio of 4-VP/EDMA was 1:2, and 24 h was considered as the proper polymerization time. Compared with the MIP agglomeration or coagulum particles, monodisperse MIP microspheres showed the better adsorption capacity: the saturated adsorption capacity of monodisperse MIP microspheres was 7.47 mg g^?1, the adsorption equilibrium could be obtained in 30 min. Finally, the adsorption performances of the optimal MIP microspheres were evaluated by kinetic adsorption, adsorption isotherm, and selective adsorption experiments, which indicated that the adsorption mechanism were chemical single layer adsorption and the separation factor was up to 3.91 by comparing with the structure similar compound (quercetin). The MIP microspheres exhibit prospects in the kaempferol efficient and selective separation.     

Selective solid‐phase extraction of naphazoline using imprinted polymers as matrix prepared by precipitation polymerization

The molecularly imprinted polymers (MIP) for drug naphazoline (NAZ) have been synthesized by precipitation polymerization. The effect of the dispersive solvents dichloromethane (DCM), acetonitrile (ACN), and Methanol (MeOH) on particle size and morphology of MIP (P1, P2, and P3) was investigated by scanning electron microscopy (SEM). The selectivity of P1, compared with nonimprinted polymer (NIP), C₈ and C₁₈ were evaluated via static adsorption using UV spectrophotometer. The result showed that the bond amount of P1 for NAZ was significantly higher than other sorbents. The P1 were applied as a solid‐phase extraction (SPE) stationary phase to extract the NAZ from nasal drops and recoveries of more than 89% (relative standard deviations, RSD <5%) were obtained by high performance liquid chromatograph (HPLC) analyses. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Molecularly imprinted nanoparticles prepared by core‐shell emulsion polymerization

Submicron core‐shell polymer particles, with molecularly imprinted shells, were prepared by a two‐stage polymerization process. Particles of this type, prepared with a cholesterol‐imprinted ethyleneglycol dimethacrylate shell and in the absence of porogen, were found to be 76 nm in diameter with a surface area of 82 m² g⁻¹. Cholesterol uptake from a 1 mM solution in isohexane was measured at both 10 and 30 mg mL⁻¹, with the imprinted polymer showing considerable binding (up to 57%). Imprinted but not hydrolyzed and hydrolyzed nonimprinted polymers showed very low uptakes (≤4.5%) and a phenol‐imprinted polymer showed reduced binding (36%) under the same conditions. Imprinted shells were also prepared over superparamagnetic polymer cores and over magnetite ferrocolloid alone. The cholesterol binding to magnetic particles was very similar to that of equivalent nonmagnetic materials. Magnetic particles could be sedimented in as little as 30 s in a magnetic field. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1851–1859, 2000     

Molecularly imprinted polymer beads prepared by pickering emulsion polymerization for steroid recognition

Pickering emulsion polymerization was used to synthesize molecularly imprinted polymer beads for the selective recognition of 17‐β‐estradiol under aqueous conditions. Scanning electron microscopy analysis indicated that the imprinted polymer beads had a small diameter with a narrow size distribution (18.9 ± 2.3 μm). The reduction in particle size achieved in this study was attributed to the altered polarity of the stabilizing nanoparticles used in the Pickering emulsion. The imprinted polymer beads could be used directly in water and showed a high binding affinity for the template molecule, 17‐β‐estradiol, and its structural analogs. These water‐compatible polymer beads could be used as affinity adsorbents for the extraction and analysis of low‐abundance steroid compounds in aqueous samples. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39606.     

Imprinted polymers prepared by aqueous suspension polymerization

The feasibility of preparing cholesterol‐imprinted polymers by aqueous suspension polymerization was investigated by the preparation of ethyleneglycol dimethacrylate and divinylbenzene‐based beads imprinted using cholesteryl(4‐vinyl)phenyl carbonate as the template. A low volatility porogen to replace a 4:1 hexane/toluene mixture was selected on the basis of solubility parameters and consisted of dioctyl phthalate/n‐decane 77:23 v/v. Beads were prepared using a range of porogen contents with the best results obtained at 5.5–6.5 mL /5 g of monomer. Uptake of cholesterol by suspension polymers was broadly similar to that of the corresponding “bulk” polymers, but suffered from higher nonspecific binding. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1841–1850, 2000     

Preparation of molecularly imprinted polymer microspheres via reversible addition-fragmentation chain transfer precipitation polymerization

The first combined use of reversible addition-fragmentation chain transfer (RAFT) polymerization and precipitation polymerization in the molecular imprinting field is described. The new polymerization technique, namely RAFT precipitation polymerization (RAFTPP), provides MIP microspheres with obvious molecular imprinting effects towards the template, fast template binding process and an appreciable selectivity over structurally related compounds, while only irregular MIP aggregates were obtained via traditional radical precipitation polymerization (TRPP) under similar reaction conditions. The MIP microspheres prepared via RAFTPP have proven to show improved binding capacity, larger binding constant and apparent maximum number for high-affinity sites, and significantly higher high-affinity binding site density in comparison with the MIP prepared via TRPP.     

Clozapine recognition via molecularly imprinted polymers; bulk polymerization versus precipitation method

Two clozapine (CLZ) imprinted polymers were prepared by bulk and precipitation methods. Methacrylic acid and ethylene glycol dimethacrylate (EDMA) were used as functional and crosslinker monomers, respectively. The mean diameter and particle size distribution of the imprinted (P‐MIP) and nonimprinted (P‐NIP) particles obtained in precipitation method were examined. A conventional batch‐adsorption test was applied for characterization of CLZ–polymer interaction. Dissociation constant (K_D) and maximum binding sites (B_max) were calculated using Scatchard analysis. To evaluate the recognition properties of polymers, phenytoin (PTN) binding to each polymer was also studied and compared to CLZ. The imprinting factor (IF) and selectivity factor (α) were also determined for each polymer. Average diameter and polydispersity of P‐MIP were 925 nm and 0.17, respectively. The data for P‐NIP were 1.05 μm and 0.18. The K_D, IF, and α values calculated for P‐MIP were 0.45 μM, 3.26, and 17.43, respectively. The data for imprinted polymer, prepared by bulk polymerization (B‐MIP), were 14.5 μM, 1.95, and 3.67. These results demonstrated that precipitation polymerization is a more convenient, more effective, and more reproducible method than bulk polymerization for the synthesis of uniformly sized micron and submicron‐imprinted polymer particles. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Cholesterol‐imprinted polymer receptor prepared by a hybrid imprinting method

A novel cholesterol‐imprinted polymer (CMIP‐H) was prepared by a hybrid method of covalent imprinting and non‐covalent imprinting. This approach involves the copolymerization of a template‐containing monomer, cholesteryl 2‐hydroxyethyl methacrylate carbonate, and a cross‐linker, followed by hydrolysis to afford a flexible guest‐binding site accompanied with the easy and efficient removal of a ‘sacrificial spacer’. The effect of solvent on the binding capacity of CMIP‐H towards cholesterol was studied, indicating that a good binding capacity towards cholesterol could be achieved in a less‐polar solvent. The binding experiments of CMIP‐H towards a series of structural analogues of cholesterol, including cholesterol acetate, progesterone and stigmasterol, were carried out in hexane. The results showed that CMIP‐H almost did not bind cholesterol acetate at all because the hydrogen‐bonding site is blocked. It exhibited a similar binding towards both cholesterol and stigmasterol, but much higher binding towards progesterone. Copyright © 2005 Society of Chemical Industry     

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     

Molecularly imprinted polymer microspheres with nanopore cavities prepared by precipitation polymerization as new carriers for the sustained release of dipyridamole

Imprinted polymers are now being increasingly considered for active biomedical uses such as drug delivery. In this work, the use of molecularly imprinted polymers (MIPs) in designing new drug delivery devices was studied. Imprinted polymers were prepared from methacrylic acid (MAA) (functional monomer), ethylene glycol dimethacrylate (cross‐linker), and dipyridamole (DIP) (as a drug template) using precipitation polymerization method. The influence of the template/functional monomer proportion and pH on the achievement of MIPs with nanopore cavities with a high enough affinity for the drug was investigated. The small pores (average 3.9 nm) in the imprinted microspheres show excellent retention properties for the target analyte. The polymeric devices were further characterized by FT‐IR, thermogravimetric analysis, scanning electron microscopy, photon correlation spectroscopy, Brunauer‐Emmett‐Teller analysis, and binding experiments. The imprinted polymers showed a higher affinity for DIP and a slower release rate than the nonimprinted polymers. The controlled releases of DIP from the prepared imprinted polymers were investigated by an in vitro dissolution test by measuring the absorbance at 284 nm by means of a UV–Visible spectrophotometer. Loaded imprinted microsphers showed very slow release in various solutions such as phosphate buffer solution (pH 6.8), HCl (pH 1.0) and mixture of HCl and MeOH at 37.0 ± 0.5°C and were able to prolong DIP release for more than two days. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Morphologies and binding characteristics of molecularly imprinted polymers prepared by precipitation polymerization

Molecularly imprinted polymers using L ‐2‐chloromandelic acid as templates were prepared by precipitation polymerization. The polymer particles exhibited a regular shape in the nanoscale range; moreover, the size and the uniformity of the particles were influenced by the concentration of monomers, polymerization temperature, types and concentrations of initiators. The experimental binding tests indicated that the nanospherical imprinted polymers possessed higher specific affinity to templates in comparison with traditional imprinted polymers prepared by bulk polymerization. Two classes of specific binding sites in the polymer matrix were investigated by the Scatchard method and ‘Hyperchem’ simulation studies. Copyright © 2003 Society of Chemical Industry     

Molecularly imprinted polymer prepared by Pickering emulsion polymerization for removal of acephate residues from contaminated waters

A molecularly imprinted polymer (MIP) prepared with Pickering emulsion polymerization was designed by a computational approach for removal of acephate from aqueous solution. Methacrylic acid, ethylene glycol dimethacrylate, and chloroform were screened as the optimal functional monomer, crosslinker, and porogen by the Gaussian 03 package using the density functional theory method. The polymerization was carried out in an oil‐in‐water emulsion using nano‐SiO₂ particles as stabilizer instead of a toxic surfactant. The characterization results indicated that the prepared MIP had a porous and hollow core, and the particle size was approximately 20 μm. The binding and recognition abilities of MIP for acephate were studied through equilibrium adsorption analysis and selectivity analysis. The results showed that the MIP had high binding capacity and excellent selectivity for acephate. The saturated binding amount could reach 6.59 × 10³ μg/g. The Langmuir isotherm model gave a good fit to the experimental data. Moreover, the results of a reusability analysis and practical application suggested that the prepared MIP provides the potential for removal of acephate residues from aqueous solution. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43126.     

石杉碱甲分子印迹聚合物的制备及缓释特性

石杉碱甲(Hup A)是从蛇足石杉中提取出来的可逆性乙酰胆碱酯酶抑制剂，对AD症具有良好的治疗效果。用分子印迹和沉淀聚合技术，以甲基丙烯酸为功能单体，乙二醇二甲基丙烯酸乙酯为交联剂成功制备石杉碱甲分子印迹聚合物（MIP）。通过傅里叶变换红外光谱，热重分析，扫描电子显微镜对印迹聚合物（MIP）进行了表征。通过静态吸附、动态吸附、体外释药和MTT等实验对MIP性能进行了评价。实验结果表明MIP对石杉碱甲存在特异性和非特异性两种结合位点。市售石杉碱甲片在1h内快速释放，累积释放率达90%以上，有明显的突释现象。而MIP在1h后释放平缓，在24h附近达到平衡，可以达到缓慢释放的效果。释放动力学符合Peppas模型，释放指数n=0.48，为非Fickian扩散机理。MIP生物相容性良好，L929小鼠成纤维细胞对MIP的细胞毒性数据显示，细胞存活率高于93%。     

Molecularly imprinted polymer microspheres prepared via the two-step swelling polymerization for the separation of lincomycin

A molecularly imprinted polymer (MIP) was synthesized via a two-step swelling polymerization method for the purification of lincomycin. Polystyrene microspheres were prepared by the dispersion-polymerization process and used as the substrate. Methacrylic acid was used as the functional monomer, whereas ethylene glycol dimethacrylate was the cross-linker. The MIP was structurally characterized and examined for its separation performance at different conditions (temperature, solvents, etc.). It was found that the MIP possesses the good sphericity, porosity, monodispersity, and a high adsorption capacity of (180 μmol/g) in chloroform solution. Comparison studies showed that the MIP presents a higher capacity than the NIP (non-imprinted polymer) in chloroform solution and a much higher capacity in the practical lincomycin fermentation solution extracts, confirming the underlining mechanisms of the MIP. Scatchard plot revealed two adsorption mechanisms on the MIP, whereas the isotherm is better described by Freundlich equation. The adsorption/elution kinetics demonstrated that the MIP possesses good elution/regeneration capabilities with the elution ratio > 93%. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47938.     

Surface molecularly imprinted polymer prepared by reverse atom transfer radical polymerization for selective adsorption indole

The preparation of indole molecularly imprinted polymers (indole‐MIPs) using 4‐vinylpyridine as functional monomer, silica gel as matrix were used to adsorb indole from fuel oil specifically. The reverse atom transfer radical polymerization (RATRP) technology was introduced to prepare the surface molecularly imprinted polymers, and the precipitation polymerization was adopted in the preparation process. The obtained indole‐MIPs were characterized by nitrogen adsorption, Fourier transform infrared spectrometry and scanning electron microscopy. The results show that indole‐MIPs were provided with the larger surface areas and more pores. The adsorption capacity of indole‐MIPs was 31.80 mg g^?1 at 298 K, and the adsorption equilibrium was reached in a short time. The adsorption process was spontaneous by thermodynamic analysis, and an appropriate decrease in temperature could enhance the adsorption capacity. The adsorption process obeyed pseudo‐second‐order kinetic model by kinetics analysis. The isotherm analysis results show that both Langmuir and Sips equations were suitable to experimental data. The selective adsorption and reusable performance of indole‐MIPs were favorable. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40473.     

三硝基甲苯分子印迹微球的制备与应用

以三硝基甲苯（TNT）为模板分子,丙烯酰胺（AM）为功能单体,采用沉淀聚合法制备分子印迹聚合物MIP。通过紫外光谱法研究TNT和AM之间的相互作用,结果表明TNT与AM之间作用力较强,有助于形成结构稳定、亲和性强的聚合物;利用扫描电镜观测不同制备条件下印迹聚合物的表观形貌,发现乙腈用量为100mL,缓慢的搅拌速率下制备的聚合物形貌较优异;利用红外光谱分析聚合物的结构特征,验证印迹聚合物的制备与模板分子的洗脱;平衡吸附实验表明,MIP对TNT的吸附存在两种作用位点并且吸附量随TNT初始浓度增加而增加;动力学吸附实验发现印迹聚合物对TNT的吸附速率远大于非印迹聚合物;选择性吸附实验中,MIP对TNT表现出较好的特异吸附性能,而对于TNT的结构类似物DNT、RDX吸附能力较差。     

辐射引发分散聚合反应制备聚合物微球研究进展

介绍了辐射作用原理、辐射引发分散聚合反应技术和机理、及其最新研究进展：重点阐述了超声、紫外光、γ射线、微波辐射在分散聚合中的应用。     

Preparation and evaluation of a molecularly imprinted polymer for tolazoline

A uniformly sized molecularly imprinted polymer for the peripheral vasodilator drug tolazoline (T‐MIP) was prepared, and a nonimprinted polymer (NIP) was also synthesized in the same way but in the absence of the template. The T‐MIP was prepared with methylacrylic acid as functional monomer and ethylene glycol dimethacrylate as crosslinker by a multistep swelling and polymerization method. These imprinted materials were characterized by scanning electron microscopy, nitrogen adsorption, and static adsorption experiments. Binding studies were also performed to evaluate the uptake of T‐MIP and NIP with the results that T‐MIP had a significantly higher binding capacity for tolazoline (T) than did NIP. The maximum static adsorption capacities of T‐MIP and NIP for T were 78.9 and 38.8 μmol/g, respectively. The T‐MIPs and NIPs were used as stationary phases of solid‐phase extraction (SPE), and a relative selectivity coefficient (k′) value of 5.21 was obtained, which showed that the T‐MIP sorbent had higher selectivity than the NIP sorbent. The method was applied to the determination of T in urine samples. The prepared polymer sorbent showed promise for SPE for gas chromatography determination of T in urine samples. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

沉淀聚合法制备咖啡因分子印迹聚合物微球

以咖啡因为印迹分子,甲基丙烯酸为功能单体,乙二醇二甲基丙烯酸酯为交联剂,偶氮二异丁腈为引发剂,采用沉淀聚合法在乙腈溶液中制备了针对咖啡因的分子印迹聚合物微球。对沉淀聚合中单体、引发剂、溶剂用量的比例关系进行探索,并利用平衡结合实验研究了聚合物对印迹分子的吸附性能,结果表明该印迹聚合物微球呈现出较好的结合能力。