Fabrication of temperature-sensitive imprinted polymer hydrogel

Weakly cross-linked temperature sensitive gels that memorize 4-aminopyridine molecules were designed and synthesized. The polymer gels show special selectivity, good thermo-sensitivity and reusability, which would have an enormous potential of application in drug controlled release systems.     

Molecular Imprinting of Cyclodextrin Supramolecular Hydrogels Improves Drug Loading and Delivery

Cyclodextrin‐based controlled delivery materials have previously been developed for controlled release of different therapeutic drugs. In this study, a supramolecular hydrogel made from cyclodextrin‐based macromonomers is subjected to molecular imprinting to investigate the impact on release kinetics and drug loading, when compared with non‐imprinted, or alternately imprinted hydrogels. Mild synthesis conditions are used to molecularly imprint three antibiotics—novobiocin, rifampicin, and vancomycin—and to test two different hydrogel chemistries. The release profile and drug loading of the molecularly imprinted hydrogels are characterized using ultraviolet spectroscopy over a period of 35 days and compared to non‐imprinted, and alternately imprinted hydrogels. While only modest differences are observed in the release rate of the antibiotics tested, a substantial difference is observed in the total drug‐loading amount possible for hydrogels releasing drugs which has been templated by those drugs. Hydrogels releasing drugs which are templated by other drugs do not show improved release or loading. Analysis by FTIR does not show substantial incorporation of drug into the polymer. Lastly, bioactivity assays confirmed long‐term stability and release of incorporated antibiotics.     

Nanotemplating for two-dimensional molecular imprinting

A new 2D molecular imprinting technique based on nanotemplating and soft-lithography techniques is reported. This technique allows the creation of target-specific synthetic recognition sites on different substrates using a uniquely oriented and immobilized template and the attachment of a molecularly imprinted polymer on a substrate. The molecularly imprinted polymer was characterized by AFM, fluorescence microscopy, and ATR-FTIR. We evaluated the rebinding ability of the sites with theophylline (the target molecule). The selectivity of the molecularly imprinted polymer was determined for the theophylline-caffeine couple. The molecularly imprinted polymer exhibited selectivity for theophylline, as revealed by competitive rebinding experiments. Fluorescence microscopy experiments provided complementary proof of the selectivity of the molecularly imprinted polymer surfaces toward theophylline. These selective molecularly imprinted polymers have the potential for chemical sensor applications. Because of its 2D nature, this novel chemical sensor technology can be integrated with many existing high-sensitivity multichannel detection technologies.     

环丙沙星分子印迹聚合物的合成及识别性能研究

采用分子印迹技术合成了以环丙沙星为印迹分子,以甲基丙烯酸和4-乙烯基吡啶同时为功能单体的分子印迹聚合物。运用平衡结合实验研究了印迹聚合物的吸附特性和选择识别能力。Scatchard分析表明,在所研究的浓度范围内,分子印迹聚合物中形成了两类不同的结合位点。底物选择实验表明,这种聚合物对环丙沙星呈现高的选择结合能力。     

pH/temperature - sensitive imprinted ionic poly(N-tert-butylacrylamide-co-acrylamide/maleic acid) hydrogels for bovine serum albumin

In this study, we have prepared pH/temperature-sensitive imprinted ionic poly(N-tert-butylacrylamide-co-acrylamide/maleic acid) [P(TBA-co-AAm/MA)] hydrogels for bovine serum albumin (BSA) by using molecular imprinting method. BSA adsorption from aqueous BSA solutions was investigated with two types of hydrogel systems prepared by non-imprinted and imprinted methods. Hydrogels imprinted with BSA showed higher adsorption capacity and specificity for BSA than hydrogels prepared by the usual procedure. At all studied conditions, the highest BSA adsorption was observed in the hydrogel imprinted with 8.63 wt.-% BSA. In addition, the imprinted hydrogels exhibited both for good selectivity BSA and high adsorption rate depending on the number of BSA-sized cavities. Adsorption studies showed that other stimuli, such as pH, temperature and initial BSA concentration also influenced the BSA adsorption capacity of both non-imprinted and imprinted hydrogels.     

药物头孢氨苄分子模板聚合物水中结合性质的研究

采用分子模板技术合成了以头孢氨苄为模板分子以三氟甲基丙烯酸和４－乙烯基吡啶同时为功能单体的分子模板聚合物。将得到的棒状聚合物研磨过筛后,运用平衡结合实验研究了头孢氨苄分子模板聚合物的结合性质,Ｓｃａｔｃｈａｒｄ分析表明,在所研究的浓度范围内,在聚合物中形成了两类不同的结合位点。头孢氨苄分子模板聚合物与其化学组成相同的非模板聚合物相比,有很高的结合容量。底物选择性实验表明,与其它结构相似的药物相比,     

对-特辛基酚表面印迹聚合物的制备及吸附性能评价

以对-特辛基酚为模板、甲基丙烯酸为功能单体制备了对-特辛基酚表面印迹聚合物.采用扫描电子显微镜、紫外光谱以及红外光谱对印迹聚合物进行表征,通过平衡吸附实验对聚合物的吸附性能进行评价.结果表明:该分子印迹聚合物对对-特辛基酚具有较大的吸附容量和良好的选择性,其最大吸附量Qmax约为86.12mg/g.     

A novel ion‐imprinted hydrogel for recognition of potassium ions with rapid response

A novel ion‐imprinted strategy is developed for synthesizing responsive hydrogels with rapid response to potassium ions. With potassium ions as templates, ion‐imprinted poly(N‐isopropylacrylamide‐co‐benzo‐15‐crown‐5‐acrylamide) (P(NIPAM‐co‐B15C5Am)) hydrogels are synthesized with 15‐crown‐5 crown ethers mounted on the polymer networks in pairs; therefore, it is very easy and fast for the crown ethers to capture potassium ions again by their Venus flytrap action and form stable 2:1 “host–guest” complexes with potassium ions in the ion‐recognition process. As a result, the response rate of the ion‐imprinted hydrogels to potassium ions is significantly faster than that of normal P(NIPAM‐co‐B15C5Am) hydrogels in which 15‐crown‐5 crown ethers are randomly pendent on the polymeric networks. Copyright © 2010 John Wiley & Sons, Ltd.     

二茂铁甲酸分子印迹聚合物的制备和识别机理、结合特性

以二茂铁甲酸（FCA）为模板,选用不同的功能单体制备了一系列分子印迹聚合物,用平衡结合实验考察了它们对模板分子的结合性能。 结果表明,以甲基丙烯酸为功能单体制得的印迹聚合物P1对模板分子有很好的选择性,特异性吸附量ΔCP为23.18 μmol/g,印迹因子IF为2.33,竞争性结合实验结果表明,P1可以将模板分子从结构类似物中分离出来。 Scatchard方程研究表明,在研究的浓度范围内聚合物中形成了一类等价的结合位点,其对模板分子的平衡离解常数K=1.94 mmol/L,最大表观结合量Cpmax=92.33 μmol/g。 研究还表明,FCA的羧基是在聚合物的孔穴中产生识别位点的功能基,模板分子上的羧基与MAA的羧基形成双重氢键作用是分子识别的主要作用力。     

Stimuli-responsive nanocomposite gels

A new class of polymer hydrogels, nanocomposite hydrogels (NC gels), consisting of a unique organic (polymer)/inorganic (clay) network structure, was synthesized by in situ free-radical polymerization in the presence of exfoliated clay nanoparticles in an aqueous system. The resulting NC gels overcame most of the disadvantages associated with chemically cross-linked hydrogels, such as mechanical fragility, structural heterogeneity, and slow de-swelling rate. By using thermo-sensitive poly(N-isopropylacrylamide) (PNIPA) as a constituent polymer, NC gels with remarkable mechanical, optical, and swelling properties as well as thermo-sensitivity were obtained. The various properties of NC gels, such as transparency, gel volume, cell culturing, and surface friction changed significantly in response to the temperature and surrounding conditions. All the excellent properties and new stimuli-responsive characteristics of NC gels are attributed to the unique PNIPA/clay network structure. The thermo-sensitivities and the transition temperature can largely be controlled by varying the clay content and by the addition of solutes.     

Molecularly Imprinted Nanozymes with Free Substrate Access for Catalyzing the Ligation of ssDNA Sequences

Nanozymes have attracted wide attention for the unique advantages of low cost, high stability and designability. Molecularly imprinted polymers (MIPs) have demonstrated great potential as a new type of nanozymes due to their excellent specificity and high affinity. However, effective approaches for creating molecularly imprinted nanozymes still remain limited. Herein, reverse microemulsion template docking surface imprinting (RMTD-SI) is reported as a new approach for the rational design and engineering of nanozymes with free substrate access for the ligation of ssDNA sequences. As a proof of the principle, octa-deoxyribonucleotide-imprinted nanoparticles were successfully prepared. Using tetradeoxyribonucleotides and octa-deoxyribonucleotide as substrates, the properties, catalytic activity and behavior of the imprinted nanoparticles were thoroughly investigated. The imprinted nanozyme exhibited an enhanced reaction speed (by up to 41-fold) and good sequence selectivity towards substrate tetra-deoxyribonucleotides. More interestingly, due to the open substrate access, the imprinted nanozyme also allowed the ligation of a ssDNA that fully matched with the imprinted cavity and other ssDNA substrates to form longer sequences, but at the price of substrate selectivity. Thus, this study provides not only a new avenue to the rational design and synthesis of molecularly imprinted nanozymes but also new insights of their catalytic behavior.     

Thermosensitive molecularly imprinted hydrogel cross‐linked with N‐malely chitosan for the recognition and separation of BSA

A novel temperature‐sensitive molecularly imprinted hydrogel composed of N‐isopropylacrylamide and acrylamide has been prepared by using free‐radical polymerization and was cross‐linked by modified water‐soluble N‐maley chitosan in aqueous solution. BSA (pI 4.9, MW 66.0 kDa) was used as the template protein. The produced hydrogels were characterized by environmental SEM to reveal the microcosmic morphology. A microporous structure was only found in the imprinted hydrogel, while no obvious microporous structure was found in nonimprinted hydrogels. The lower critical solution temperature of the hydrogels was 34°C, and the optimal binding conditions were tested, namely, the adsorption equilibrium time of 6 h and initial BSA concentration of 1.0 mg/mL. The adsorption capacity Q_max was determined by Langmuir isotherm plots and was 5.72 mg/g for imprinted hydrogel and 1.18 mg/g for nonimprinted hydrogels. A separation factor (β) of 4 was obtained when bovine hemoglobin (pI 6.9, MW 64.0 kDa) was selected as the particular reference protein. Molecular weights and pIs were chosen to investigate the selectivity of the hydrogels. It was shown that the shape memory and the size effect were the major factors for the recognition. This imprinted hydrogel was used to specifically adsorb the BSA from the protein mixture.     

MMTCA recognition by molecular imprinting in interpenetrating polymer network hydrogels based on poly(acrylic acid) and poly(vinyl alcohol)

A novel IPN hydrogel designed to recognize MMTCA is prepared by applying the molecular-imprinting method. The IPN is characterized by FT-IR, DSC, and SEM. Langmuir analysis shows that an equal class of adsorption is formed in the hydrogel. The adsorption equilibrium constant and the maximum adsorption capacity are evaluated, and the effect of the pH on MMTCA adsorption is discussed. The selectivity of the imprinted polymer for MMTCA is studied in aqueous solutions of MMTCA/aspirin/riboflavin. The results suggest that the MMTCA-imprinted polymer shows superior selectivity for MMTCA as compared to riboflavin and aspirin. The reproducibility of the imprinted polymer to MMTCA is also studied.     

分子印迹聚合物选择性降低烟气中稠环芳烃类物质

以芘(PYR)为模板,由热引发本体聚合合成了芘分子印迹聚合物(MIP),考察了印迹聚合物的选择性吸附性能,采用Scatchard模型分析了印迹聚合物的结合特性,用离线固相萃取实验考察了印迹聚合物对同类底物的吸附能力,并将芘分子印迹聚合物应用到卷烟滤嘴中,用GC/MS法考察了卷烟主流烟气中稠环芳烃类物质释放量的变化。 结果表明,芘分子印迹聚合物具有选择性降低卷烟烟气中稠环芳烃类物质的功能,当MIP添加量为1.5 mg时,能将卷烟烟气中的苯并[a]芘(B[a]P)、苯并(a)蒽(B[a]A)和苣(CHR)的释放量分别降低31.08%、25.69%和27.33%。     

Preparing molecularly imprinted membranes by phase inversion to separate kaempferol

Molecularly imprinted membranes (MIMs) were studied to separate special target molecule – kaempferol, an important active pharmaceutical ingredient. The kaempferol MIM were prepared by the liquid–solid phase inversion method. The effects of polyphenylene sulfone, LiCl, and ZnCl₂ on membrane performance were studied, a high Flux MIM was prepared, then the kaempferol molecularly imprinted polymer membrane, non‐molecularly imprinted membrane, and non‐molecularly imprinted polymer membrane were prepared to investigate adsorption capacity. From adsorption isotherm curve, the maximum equilibrium adsorption quantity was 890 µg/g, and it was MIM. The MIM and molecularly imprinted polymer membrane give high selectivity towards kaempferol; the non‐molecularly imprinted membrane and non‐molecularly imprinted polymer membrane showed low adsorption quantity and selectivity. The reuse experiment of the MIM indicated that it has good reuse property. All the results showed binding sites were important in the separation process of MIMs. Copyright © 2016 John Wiley & Sons, Ltd.     

Chemically Crosslinked pH- and Temperature-Sensitive (N-isopropylacrylamide-co-1-vinyl-2-pyrrolidone) Based on New Crosslinker: I. Swelling Behavior

Novel pH- and temperature-sensitive polymer matrices based on N-isopropylacrylamide have been developed. The hydrogels were prepared by bulk radical polymerization of N-isopropylacrylamide and 1-vinyl-2-pyrrolidinone in appropriate amounts of distilled water using different mol% of traditional N,N-methylene bisacrylamide (MBA) and the new synthesized N,N,N-tris acryloyl melamine (MAAm) crosslinkers. Lower critical solution transition temperatures (LCST) were measured by differential scanning calorimetry. The synthesized hydrogels have LCST lower than 40°C. The influence of environmental conditions such as temperature and pH on the swelling behavior of these polymeric gels was investigated. The swelling behaviors of the resulting gels show pH sensitivity. The crosslinked NIPAAm/VP with MAAm hydrogels exhibited more rapid deswelling rate than NIPAAm/VP hydrogels crosslinked with MBA in pure water in response to abrupt temperature changes from 20°C to 50°C.     

Molecular Recognition of the Fungicide Carbendazim by a Molecular Imprinted Polymer Obtained through a Mimic Template Approach

Abstract

A molecularly imprinted polymer recognizing the fungicide carbendazim was prepared using a mimicking template approach. Methyl-3-propylcarbamoyl-1H-benzimidazol-2-ylcarbamate was synthesized and used as a mimic template for polymer preparation. Selectivity of this polymer for carbendazim and structurally related substances (the template, fluberidazole, rabenzazole, thiabendazole, and benomyl and its two degradation products) was evaluated by liquid chromatography. Results demonstrate that imprinted polymer shows significant recognition properties for carbendazim, whereas the mimic and other carbendazim-related molecules are not recognized. This peculiar selectivity pattern can be explained as an imprinting effect due to the in situ formation of carbendazim from mimic degradation during the polymerization process.     

Noncovalently galactose imprinted polymer for the recognition of different saccharides

Molecularly imprinted polymers (MIPs) represent a new class of materials possessing high selectivity and affinity for the target molecule. The main goal of this study was to prepare a galactose imprinted polymer and its potential application for the recognition of different saccharides. The selectivity of galactose imprinted polymer for several saccharides; glucose, mannose, fructose, maltose, lactose, sucrose and raffinose was investigated. Macroporous polymer was prepared utilizing ethyleneglycoldimethacrylate as a crosslinking agent, in the presence of galactose as a template molecule with acrylamide as a functional monomer. After the synthesis of polymer, galactose was removed by methanol:acetic acid washing. The selectivity of galactose imprinted polymer for other saccharides was utilized by batch rebinding assay. The arrangement of functional groups within cavities versus shape selectivity is discussed. The results showed that, the orientation of the functional groups was the dominating factor for the selectivity of galactose imprinted polymer. The dissociation constants of polymer were determined by Scatchard analysis.     

Facile preparation of polydopamine‐coated imprinted polymers on the surface of SiO2 for estrone capture in milk samples

Estrone molecularly imprinted polymers were synthesized through the self‐polymerization of dopamine on the surface of silica gels, which had the characteristics of mild polymerization conditions, simple reaction procedure and good specific recognition ability for estrone. The estrone molecularly imprinted polymers were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, elemental analysis and nitrogen adsorption–desorption tests. The characterization confirmed that the imprinted polymers were successfully grafted on the surface of silica gels. Through investigating the adsorption performance, the prepared estrone molecularly imprinted polymers exhibited high adsorption capacity, fast mass transfer, as well as excellent selectivity toward estrone. The estrone molecularly imprinted polymers as the solid‐phase extraction adsorbent coupled with high‐performance liquid chromatography was developed to determine estrone from the milk samples. The developed estrone molecularly imprinted polymer solid‐phase extraction with high‐performance liquid chromatography method exhibited satisfactory specificity, precision, accuracy and good linearity relationship in the range of 0.2–20 μg/mL. The developed method is simple, fast, effective and high specificity method and it provides a new method to detect the residues of estrone in animal foods.     

烟碱分子烙印聚合物的吸附特性

利用分子烙印技术，以烟碱为烙印分子，甲基丙烯酸(MAA)为功能单体，乙二醇二甲基丙烯酸酯(EDMA)为交联剂，合成了对烟碱具有特异性作用的分子烙印聚合物P(Nic)；通过平衡吸附实验，评价了其对烟碱的亲和力和选择性。与非烙印聚合物相比，P(Nic)对烟碱表现了很高的亲和力；Scatchard分析表明在P(Nic)中存在对烟碱有不同的亲和力的两类作用位点。通过与氨基吡啶类物质在P(Nic)上的吸附行为比较，表明P(Nic)对烟碱具有很好的选择性。本工作证明了用P(Nic)作为固相萃取(SPE)材料选择性地从烟草烟雾中提取烟碱的可能性。