Preparation of bowl-shaped polydopamine surface imprinted polymer composite adsorbent for specific separation of 2'-deoxyadenosine

Molecularly imprinted polymers (MIPs) have great potential as adsorbents for selective adsorption and separation of nucleoside compounds,but effectively enhancing the affinity of recognition sites by adjusting the forces between template molecules and functional monomers remains an important challenge.In this work,a surface imprinting strategy was used to construct bowl-shaped molecularly imprinted composite sorbents (BHPN@MIPs) based on polydopamine (PDA) particles and have achieved selective separation and purification of 2'-deoxyadenosine (dA).Where by the base complementary pairing interaction of the combined template molecule d A and the pyrimidine functional monomer can enhance the preassembly force,and the hydrophilic bowl-shaped PDA can provide a larger storage space contact efficiency of d A in the test solution,causing the site utilization much higher and improving the kinetic adsorption performance.The equilibrium adsorption time and maximum adsorption capacity of60 min and 328.45μmol·g^(-1)were observed by static adsorption experiments,and the selectivity experimental results showed an imprinting factor IF of 1.30.After four adsorption–desorption cycles,the initial adsorption equilibrium adsorption capacity of BHPN@MIPs still retained 91.14%.By evaluating the selective adsorption of d A in spiked human serum solutions,BHPN@MIPs can be used to selectively enrich and analyze target d A in complex biological samples.

Preparation of high selective molecularly imprinted polymers for tetracycline by precipitation polymerization

High selective molecularly imprinted polymers （MIPs） for tetracycline have been prepared by precipitation polymerization. Effects of monomer and solvent, the ratio of monomer and template and the characterization of the polymer were investigated by frontal chromatography and selectivity experiment. The results clearly indicated that the polymer, which had the highest molecular recognition abilities for tetracycline antibiotics, had been received.

Tetracycline selective electrode based on molecularly imprinted polymer particles

Tetracycline selective electrode using molecularly imprinted polymer particles as quasi-ionophore was constructed the first time, and its performance was carefully characterized. Due to the specific recognition of tetracycline by the particles, the selectivity coefficients for routine interferences were less than 10-4. Benefited from the absence of tetracycline in the sensitive membrane and the optimized composition of the inner filling solution, the limit of detection of the electrode was reduced to about 2.5 × 10^-8 mol/ L. It exhibited a good electrode slope 57.6 mV/decade near the theoretical Nernstian one, with a wide linear working range from 6.0 × 10^-8 to 1.0 × 10^-3 mol/L. The fabricated electrode should be used in pH 2--4, response time of which was less than 200 s when the concentration of tetracycline was higher than 1.0 × 10^-6 mol/L and no more than 30 min at the concentration of 1.0 × 10^-8 mol/L.

Molecularly Imprinted Polymer Based on GO-QDs as Enhanced Fluorescent Nanoscale Device for Specific Recognition of Target Protein

In this work the enhanced molecularly imprinted optosensing material based on graphene oxide-quantum dots （ GO- QDs） was synthesized for highly selective and sensitive specific recognition of the target protein, bovine serum albumin （BSA）. Here, GO was introduced to enhance the efficiency of mass-transfer in recognition of target protein. Molecularly imprinted polymer coated GO-QDs using BSA as template （BMIP-coated GO-QDs ） exhibited a fast mass-transfer speed, which could be ascribed to the high volume of efficient surface area and high target recognition efficiency of the synthesized nanoscale device. Under optimal conditions, it was found that the BSA as target protein could remarkably quench the relative fluorescence intensity of BMIP- coated GO-QDs linearly in a concentration-dependent manner that was best described by a Stern-Volmer equation. The Ksv （Stern- Volmer constant） for template BSA was much higher than bovine hemoglobin （BHb） and lysozyme （Lyz）, implying a highly selective recognition ability of the BMIP-coated GO-QDs to BSA. This enhanced fluorescent nanoscale device may provide opportunities to develop a system that is efficient and effective and has potential in the design of highly effective fluorescent receptor for recognition of target protein in Droteomics studies.

Direct Synthesis of Monodisperse Hollow Molecularly Imprinted Polymers Based on Unfunctionalized SiO2 for the Recognition of Bisphenol A

A novel and effective approach was developed to synthesize monodisperse hollow molecularly imprinted polymers （MHMIPs） with unfunctionalized SiO2 spheres in a mixture of toluene and CH3CN. The factors that affected the synthesis of MHMIPs were systematically investigated. It was determined that a suitable ratio of toluene to CH3CN and the use of a functional monomer that can generate double H-bonding interactions were the critical factors to obtain MHMIPs with high uniformity and rnonodispersion. The obtained MHMIPs exhibited a fast adsorption rate and high adsorption capacity （270 μmol/g） for bisphenol A. As the shell thickness increased from 90 nm to 130 nm, the binding capacity of the imprinted shells decreased gradually. The relative selectivity coefficients of MHMIPs for tetra-brornobisphenol A （TBBPA）, phenol and p-tert-butylphenol （PTBP） were calculated as 1.53, 1.83 and 1.90, respectively. These findings indicate that MHMIPs have good adsorption performances and suggest applications in the selective removal or sensitive analysis of bisphenol A.

Preparation of High Selective Molecularly Imprinted Polymers for (S)-4-Phenyl-2-oxazolidinone

（S）-4-Phenyl-2-oxazolidinone imprinted polymers were prepared by using methacrylic acid （MAA） as the functional monomer, and divinylbenzene （DVB） as crosslinker. The factors, which influence the selectivity of the polymers were explored. Effective separation was observed for racemic 4-phenyl-2-oxazolidinone in mobile phase of acetonitrile. The investigation of mobile phase suggested that the hydrogen bonds between template and functional monomer was a primary factor in chiral recognition, while the preparation of polymers implied that the л-л stacking interaction between template and crosslinker played a role in imprinting procedure.

Molecularly Imprinted Polymer for Theophylline Retention and Molecular Recognition Properties in Capillary Electrochromatography

Molecular imprinting of theophylline in poly (methacrylic acid- ethylene dimethacrylate) as CEC stationary phases was synthesized by an in situ photo-initiated polymerization reaction. The effect of electrolyte pH on xanthine derivatives and the stability of MIP column performance were investigated. the relative standard deviation (D RS) of migration time of five consecutive runs on MIP column was in the range of 2.2%–3.1%. The reproducibility of migration time column to column of M(A) was in the range of 3.8%–4.9%. The highest column efficiency was more than 140 000 plates per meter. The MIP capillaries had showed better selective for theophylline, which comparing with the reference column. The urine sample was separated by spiked 5×10?4 mol·L?1 theophylline. Key words capillary electrochromatography - molecular imprinting polymers - theophylline CLC number O 657.8 Foundation item: Supported by the National Nature Science Foundation of China (20375028) and the Research Fund for the National High Technology Development “863” of China (2002AA2Z2004)Biography: Cai Ling-shuang (1968-), female, Associate professor, Ph. D, research direction: separation science.

Selective Recognition and Detection of L-Aspartic Acid by Molecularly Imprinted Polymer in Aqueous Solution

Molecularly imprinted polymers selective for L-aspartic acid (LAA) have been prepared using the carboxy-betaine polymer bearing zwitterionic centres along the backbone. LAA is well known to promote good me-tabolism, treat fatigue and depression along with its significance in accurate age estimation in the field of forensic science and is an important constituent of ‘aspartame’, the low calorie sweetener. In order to study the intermolecular interactions in the prepolymerization mixture between the monomer and the template (LAA)/non-template (DAA), a computational approach was developed. It was based on the binding energy of the complex between the template and functional monomer. The results demonstrate that electrostatic in-teractions primarily guide the imprinting protocol. The MIP was able to selectively and specifically take up LAA from aqueous solution, human blood serum and certain pharmaceutical samples quantitatively. Hence, a facile, specific and selective technique to detect the amino acid, LAA in the presence of various interfer-rants, in different kinds of matrices is presented.

RECENT ADVANCES IN THE PREPARATION OF MOLECULARLY IMPRINTED POLYMERS VIA CONTROLLED RADICAL POLYMERIZATION TECHNIQUES

Molecular imprinting technique is a simple and efficient method for the preparation of polymer materials (i.e., molecularly imprinted polymers, MIPs) with tailor-made recognition sites for certain target molecules. The resulting MIPs have proven to be versatile synthetic receptors due to their high specific recognition ability, favorable mechanical, thermal and chemical stability, and ease of preparation. Recent years have witnessed significant progress in the synthesis and applications of MIPs. This review focus on the recent developments and advances in the preparation of MIPs via various controlled radical polymerization techniques.

MOLECULAR IMPRINTED POLYMERS——Novel Polymer Adsorbents

Molecular imprinted polymers (MIPs) are novel functional polymer materials and known as specific adsorbents for the template molecules. These novel functional polymers have promised potential applications in racemic resolution, sensor, chromatography, adsorptive separation and other fields. This review exhibits the approach for preparing MIPs, the features of MIPs obtained by different routes and the characteristics of adsorptive separations with MIPs. The molecular recognition mechanism and the idea of the present possibilities and limitations of molecular imprinting polymerization are discussed as well.

Preparation and Electrochemical Characters of Parathion Molecule Imprinted Polymeric Sensors

A sensitive, fast and low-cost molecular imprinted polymeric sensor for quantitative determination of parathion was prepared with chitosan（CS） as function matrix and parathion（PT） as template molecule via constant potential electrochemical deposition. Sensitive response was obtained with a detection limit of 1.0× 10-7 mol/L and an excellent recognition for PT was achieved due to the good memory capacity of the sensor. The developed sensor exhibited good fabrication reproducibility and acceptable stability, which provided a new promising tool for pesticide analysis.

Enantiomeric Resolution on L-Carnitine Selective Polymers Prepared by Molecular Imprinting

L-carnitine selective polymers were prepared by molecular imprinting using methacrylic acid as the functional monomer. The acid function of the monomer is expected to form hydrogen bond and ionic interactions with the amine function of the target molecule L-carnitine. The imprinted polymers were used as stationary phases in high-performance liquid chromatography (HPLC). It was shown that L-carnitine imprinted polymer exhibited a higher affinity to its template molecule, while the non-imprinted polymer had no affinity to the compounds tested. Racemic carnitine hydrochloride was efficiently resolved on the L-carnitine imprinted polymer, and the separation factor is 1.9.

Nano-silica particles enhanced adsorption and recognition of lysozyme on imprinted polymers gels

Molecular imprinting technology has a great potential to be used in protein separation and purification. In this work, lysozyme imprinted polyacrylamide gel was prepared with silica particles as a sacrificial template to generate macro-porosity for fast adsorption. The adsorption equilibrium time and adsorption capacity were 9 h and 56 mg/g respectively, which was 2 h less and 2.3-fold more than polymers without the sacrificial template. In order to test molecular imprinting polymers （MIPs） ＇ selectivity, bovine serum albumin （BSA） was chosen as interferent for binary adsorption tests. In addition, the adsorption selectivity was further investigated using different molar ratios of lysozyme to BSA with fixed total concentration of proteins, as well as using various total concentra- tions of proteins with an equimolar ratio of lysozyme to BSA. It has been proven that the total con- centration of proteins should be larger than 1.5 × 10^-7 mol/mL, when the molar ratio of BSA to Lyz is 1： 1, in order to effectively separate Lyz from the binary protein mixture. The macro-porous lyso- zyme molecularly imprinted polymers have less adsorption time, larger adsorption capacity, and bet- ter imprinting effect.

Theoretical Researches on the Recognizing Characteristics of Atrazine Imprinted Polymers with Different Functional Monomers

As a widely used herbicide, the threat of atrazine to both environment and health of people has become the focus. Therefore, the research and analysis of atrazine are getting more important. In this work, the MIT was used to detect atrazine theoretically. Atrazine was taken as a template molecule. MAA, MMA and TFMAA were taken as the functional monomers, respectively. The geometry optimization, the nature of hydrogen bonds, the NBO charge, and the binding energies of the imprinted molecule with the functional monomers were investigated at the B3LYP/6-31g（d,p） level. Results indicated that atrazine had the strongest interaction with TFMAA. When the ratio of atrazine and TFMAA was 1：6, the amount of H-bond formed from atrazine and TFMAA was the largest. Moreover, TFMAA owned the largest binding energy with atrazine while MMA owned the smallest. The study is helpful to interpret experiment phenomena of molecular imprinting and select better functional monomers.

Preparation and Cyclic Voltammetry Characterization Of Cu-dipyridyl Imprinted Polymer

Polymer capable of specific binding to Cu-dipyridyl complex was prepared by molecular imprinting technology. The binding specificity of the polymer to the template (Cu-dipyridyl complex) was investigated by cyclic voltametric scanning using the carbon paste electrode modified by polymer particles in phosphate buffer solution. Factors that influence rebinding of the imprinted polymer were explored. The result demonstrated that the cyclic voltammetry was an efficient approach to explore interactions between template and imprinted polymers.

Preparation and adsorption behaviors of Cu(Ⅱ) ion-imprinted polymers

Imprinted polymers were prepared for selective removal of Cu（Ⅱ） ions from metal solutions. Three ion-imprinted polymers were synthesized with methacrylic acid （MAA）, acrylamide （AA） and N,N＇-methylenebisacrylamide （MBAA） respectively as the functional monomers, ethleneglycoldimethacrylate （EGDMA） as the cross-linking agent, 2,2＇- azobisisobutyronitrile （AIBN） as the initiator and Cu （Ⅱ） ion as the imprint ion. The template Cu （Ⅱ） ion was removed from the polymer by leaching with a liquid of a 1：1 volumetric ratio of HCl to ethylenediaminetetraacetic acid （EDTA）. The capacity and selectivity of Cu（Ⅱ） ion adsorption were investigated with the three imprinted polymers and their non-imprinted counterparts. The polymers have a maximum adsorption capacity at pH 7.0. The isotherm of their batch adsorption of Cu（Ⅱ） ions shows a Langmuir adsorption pattern. Imprinted polymers all have a much higher capacity and higher selectivity of Cu（Ⅱ） adsorption than nonimprinted ones. MAA polymer benefits the most from imprinting. Imprinted MAA polymer has the highest selectivity when used to rebind Cu （Ⅱ） ion from an aqueous solution in the presence of other metal ions. Ion imprinting can be a promising technique of preparing selective adsorbents to separate and preconcentrate metal in a medium of multiple competitive metal ions through solid phase extraction （SPE）.

Biosorption of Toxic Zn（ll） Ion from Water Using Ion Imprinted Interpenetrating Polymer Networks

Toxic Zn（II） ion imprinted interpenetrating polymer networks were synthesized for the selective sorption of Zn（ll） from aqueous solutions using a biopolymer alginic acid. The polymeric biosorbant was prepared using Zn（II） ion as template, acrylamide as functional monomer, cross linker NNMBA （N,N＇ Methylene-bis-acrylamide） and potassium persulphate as an initiator. The non-imprinted polymer networks were also prepared without use of the Zn（II） ion. The synthesized interpenetrating networks were characterized by various spectral techniques. Metal ion binding studies were carried out and the factors affecting binding were also optimized. Competitive sorption studies were investigated to determine the selectivity of Zn（II） ion imprinted interpenetrating polymer network. Zinc ion imprinted polymer networks showed good selectivity for the target ion.

A Novel Molecular Imprinted Polymers-Based Lateral Flow Strip for Sensitive Detection of Thiodiglycol

Traditional detection of thiodiglycol(TDG),a metabolic marker for sulfur mustard poisoning,requires not only professional operators,but also expensive reagents and large instruments.Herein,we developed a novel molecular imprinted polymers(MIPs)-based lateral flow assay(LFA)strategy for the quick,sensitive,and selective detection of TDG.Gold nanoparticles(Au NPs),MIPs,and metallothioneins(MTs)were respectively loaded on the conjugate pad,test line(T line)and control line(C line).After adding TDG,Au NPs on the conjugate pad reacted with TDG through the Au-S bond first.Then,under the action of capillary force,the conjugates of TDG and Au NPs were trapped by the MIPs as they traveled to the T line,and the residual Au NPs bound with the MTs on the C line,exhibiting two obvious red bands on T line and C line,respectively.In contrast,a single red band could be observed on C line without TDG.This method exhibited a wide linear range from 10.0 pg/m L to 10,000.0 ng/m L and its limit of detection(LOD)was as low as 0.41 pg/m L.This method was successfully utilized to detect TDG in human urine,presenting significant potential in the point-of-care testing of TDG in clinical samples of the sulfur mustard poisoning patients.

Molecular Imprinting Technique and Its Application in Food Industry

As a novel technique, molecular imprinting technique are attracting more and more attention in recent years, due to its specific recognition function to im- printed molecules. This paper firstly introduced this technique from its history, princi- ple, classification and methods, and then reviewed the application in food industry, and presented possible future research orientations.