A molecularly imprinted polymer (MIP) was formed using an inorganic polymer by a sol-gel process. The monomers which were used to synthesize the inorganic polymer were tetraethoxysilane (TEOS), triethoxymethylsilane (...A molecularly imprinted polymer (MIP) was formed using an inorganic polymer by a sol-gel process. The monomers which were used to synthesize the inorganic polymer were tetraethoxysilane (TEOS), triethoxymethylsilane (MTES), and triethoxyphenylsilane (PTES). Caffeine was chosen as a template for the molecular imprinting, and theophylline was chosen as the analogous counterpart compound. The discriminating ability of the synthesized MIP to these two-compounds was estimated in this study. The MIP showed the highest discriminating ability when the ratio of TEOS:MTES: PTES in the synthesis of the inorganic polymer was 1:1:3, the reaction temperature was 50?C, and the pH of the reaction system was ~6.5.展开更多
Urinary 8-hydroxy-2 -deoxyguanosine(8-OHdG) is an excellent marker of oxidative DNA damage.In this study,employing guanosine as dummy template a novel molecularly imprinted(MIP) monolithic capillary column had been sy...Urinary 8-hydroxy-2 -deoxyguanosine(8-OHdG) is an excellent marker of oxidative DNA damage.In this study,employing guanosine as dummy template a novel molecularly imprinted(MIP) monolithic capillary column had been synthesized,and that was used as medium of in-tube solid phase microextraction(SPME).Coupled with capillary electrophoresis-electrochemical detection(CE-ECD),the system of extraction and detection of 8-OHdG in urinary sample had been developed.Because of its greater phase ratio combined with conv...展开更多
Surface molecularly imprinted polymers (SMIPs) for selective adsorption of ampicillin sodium were synthesized using surface molecular imprinting technique with silica gel as a support. The physical and morphological...Surface molecularly imprinted polymers (SMIPs) for selective adsorption of ampicillin sodium were synthesized using surface molecular imprinting technique with silica gel as a support. The physical and morphological characteristics of the polymers were investigated by scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), elemental analysis and nitrogen adsorption-desorption test. The obtained results showed that the SMIPs displayed great adsorption capacity (13.5 lag/mg), high recognition ability (the imprinted factor is 3.2) and good binding kinetics for ampicillin sodium. Finally, as solid phase extraction adsorbents, the SMIPs coupled with HPLC method were validated and applied for the enrichment, purification and determination of anapicillin sodium in real milk and blood samples. The averages of spiked accuracy ranged from 92.1% to 107.6%. The relative standard deviations of intra- and inter-day precisions were less than 4.6%. This study provides a new and promising method for enriching, extracting and determining ampicillin sodium in complex biological samples.展开更多
Molecularly imprinted polymers using 2,4-dichlorophenoxyacetic acid (2,4-D) as templates were prepared by suspension polymerization in silicon oil. The polymer particles exhibited regular shape in the micro-scale ra...Molecularly imprinted polymers using 2,4-dichlorophenoxyacetic acid (2,4-D) as templates were prepared by suspension polymerization in silicon oil. The polymer particles exhibited regular shape in the micro-scale range. The adsorbing experiments indicated that the imprinted polymer particles possessed higher affinity to 2,4-D than the non-imprinted polymer particles.展开更多
An S-naproxen(S-NAP)molecularly imprinted monolithic stationary phase(MIMSP)with specific recognition for S-NAP and naproxen(NAP)was prepared by in situ technique,utilizing 4-vinylpridine(4-VP)as a function mo...An S-naproxen(S-NAP)molecularly imprinted monolithic stationary phase(MIMSP)with specific recognition for S-NAP and naproxen(NAP)was prepared by in situ technique,utilizing 4-vinylpridine(4-VP)as a function monomer,ethylene glycol dimethacrylate(EDMA)as a cross-linking agent,and low-polar solvents(toluene and dodecanol)as porogenic solvents.The selectivity of the polymers for S-NAP and NAP was evaluated by high performance liquid chromatography(HPLC).The binding characteristics were tested by Scatchard analysis.Racemic NAP could be specifically separated to some extent.At the same time,NAP could be separated from ibuprofen under optimized conditions.Scatchard analysis showed that two classes of binding sites existed in the S-NAP-imprinted polymers,with their dissociation constants estimated to be 1.045 and 5.496 μM,respectively.The results demonstrate that S-NAP and NAP can be recognized specifically on the obtained MIMSP.展开更多
Metsulfuron-methyl molecularly imprinted polymer(MIP)-coated stir bar was prepared for sorptive extraction of sulfonylurea herbicides in complex samples.The MIP-coating was about 21.3 μm thickness with the relative...Metsulfuron-methyl molecularly imprinted polymer(MIP)-coated stir bar was prepared for sorptive extraction of sulfonylurea herbicides in complex samples.The MIP-coating was about 21.3 μm thickness with the relative standard deviation(RSD) of 4.4%(n=10).It was homogeneous and porous with good thermal stability and chemical stability.The extraction capability of the MIP-coating was 2.8 times over that of the non-imprinted polymer(NIP)-coating in hexane.The MIP-coating exhibited selective adsorption ability to the template and its analogues.The extraction conditions,including extraction solvent,desorption solvent,extraction time,desorption time and stirring speed,were optimized.A method for the determination of six sulfonylurea herbicides by MIP-coated stir bar sorptive extraction coupled with high performance liquid chromatography(HPLC) was developed.The linear range was 10―200 μg/L and the detection limits were within a range of 2.0―3.3 μg/L.It was also applied to the analysis of sulfonylurea herbicides in spiked river water,soil and rice samples.展开更多
Moleculary imprinted polymers using p-hydroxybenzoic acid as templates wassynthesized by an in situ polymerization reaction and rendered capillary monolithic column wasused in capillary electrochromatographic mode. Go...Moleculary imprinted polymers using p-hydroxybenzoic acid as templates wassynthesized by an in situ polymerization reaction and rendered capillary monolithic column wasused in capillary electrochromatographic mode. Good molecular recognition was achieved for p-hydroxybenzoic acid and good resolution of isomers can be realized.展开更多
Fluorescent nanoparticles have good chemical stability and photostability,controllable optical properties and larger stokes shift.In light of their designability and functionability,the fluorescent nanoparticles are w...Fluorescent nanoparticles have good chemical stability and photostability,controllable optical properties and larger stokes shift.In light of their designability and functionability,the fluorescent nanoparticles are widely used as the fluorescent probes for diverse applications.To enhance the sensitivity and selectivity,the combination of the fluorescent nanoparticles with the molecularly imprinted polymer,i.e.molecularly imprinted fluorescent nanoparticles(MIFN),was an effective way.The sensor based on MIFN(the MIFN sensor)could be more compatible with the complex sample matrix,which was especially widely adopted in medical and biological analysis.In this mini-review,the construction method,detective mechanism and types of MIFN sensors are elaborated.The current applications of MIFN sensors in pharmaceutical analysis,including pesticides/herbicide,veterinary drugs/drugs residues and human related proteins,are highlighted based on the literature in the recent three years.Finally,the research prospect and development trend of the MIFN sensor are forecasted.展开更多
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 for...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.展开更多
For preparing the phenobarbital(PHN) molecularly imprinted polymers(MIPs) with higher adsorption and selectivity properties, we used the M062 X/6-31 g(d,p) method of density functional theory to predict the various pr...For preparing the phenobarbital(PHN) molecularly imprinted polymers(MIPs) with higher adsorption and selectivity properties, we used the M062 X/6-31 g(d,p) method of density functional theory to predict the various properties of PHN-MIPs. Here PHN is as the imprinted molecule and acrylamide(AM) as the functional monomer. The ethylene glycol dimethacrylate,trimethylolpropane trimethacrylate, divinyl benzene, and pentaerythritol trimethacrylate are as the cross-linking agents, respectively. The acetonitrile, chloroform, toluene, and tetrahydrofuran are used as the solvents, respectively. The configurations of the molecular imprinting self-assembly system for PHN and AM have been simulated to study their bonding sites, binding energy, amount of hydrogen bond, and interaction mechanism. The essence of imprinting interaction for PHN and AM has been revealed by the atomic in the molecule theory. Meanwhile, the analogues of PHN were used to discuss the selectivity property of the stable PHN-AM complex. The results show that the PHN interacts with AM through hydrogen bonds. When the imprinting molar ratio of PHN-AM is1:6 and the THF is as the solvent, the amount of their hydrogen bonds is the most, the binding energy is the lowest, and their configuration is the most stable. In comparison with the other cross-linking agents(EGDMA, TRIM, and DVB), the PETA is more suitable for PHN-MIPs. The selective property of PHN-MIP to PHN is excellent when PHN and DMBA exist at the same time.展开更多
A fluorescent competitive assay for melamine was first developed utilizing dummy molecularly imprinted polymers(DMIPs) as artificial antibodies. This method is based on the competition between fluorescent substances...A fluorescent competitive assay for melamine was first developed utilizing dummy molecularly imprinted polymers(DMIPs) as artificial antibodies. This method is based on the competition between fluorescent substances and the unlabeled analyte for binding sites in synthesized DMIPs and the decreased binding of fluorescent substances to DMIPs due to increased concentrations of melamine in the solutions. DMIPs for melamine were synthesized under a hot water bath in the presence of the initiator azobisisobutyronitrile(AIBN) using 2,4-diamino-6-methyl-1,3,5-triazine(DAMT) as a dummy template, methacrylic acid(MAA) as a functional monomer, and ethylene glycol dimethacrylate(EGDMA) as a crosslinking agent. The adsorption capacity and selectivity of DMIPs for melamine were evaluated by the isothermal adsorption curve and Scatchard analysis. The evaluation results showed that the synthesized DMIPs had specific recognition sites for melamine and the maximum adsorption amount was 1 066.33 μg g^(-1). Later, 5-(4,6-d ichlorotriazinyl) amino fluorescein(DTAF) with a triazine ring, which s lightly resembles m elamine, w as selected as the fluorescent substance. The fluorescent competitive assay using DMIPs as t he antibody mimics was finally established by selecting and optimizing the reaction solvents, DMIPs amount, DTAF concentration, and incubation time. The optimal detection system showed a linear response w ithin range of 0.05-40 mg L^(-1) and the limit of detection(LOD) was 1.23 μg L^(-1). It was successfully applied to the detection of melamine in spiked milk samples wi th satisfactory recoveries(71.9 to 86.3%). According to the comparative analysis, the result of optimized fluorescent competitive assay re vealed excellent agreement with the HPLC-MS/MS result for melamine.展开更多
Novel uniform-sized magnetic molecularly imprinted polymers (MMIPs) were synthe- sized for selective recognition of active antitumor ingredients of kaempferol (KMF) and protoapi- genone (PA) in Macrothelypteris ...Novel uniform-sized magnetic molecularly imprinted polymers (MMIPs) were synthe- sized for selective recognition of active antitumor ingredients of kaempferol (KMF) and protoapi- genone (PA) in Macrothelypteris torresiana (M. torresiana) by surface molecular imprinting tech- nique in this study. Super paramagnetic core-sheU nanoparticles (γ-MPS-SiO2@Fe3O4) were used as seeds, KMF as template molecule, acrylamide (AM) as functional monomer, and N, N'-methylene bisacrylamide (BisAM) as cross-linker. The prepared MMIPs were characterized by X-ray diffraction (XRD), Fourier transform infrared spectrum fiT/R), transmission electron microscopy (TEM) and thermo-gravimetric analysis (TGA), respectively. The recognition capacity of MMIPs was 2.436 times of non-imprinted polymers. The adsorption results based on kinetics and isotherm analysis were in accordance with the pseudo-second-order model (R2=0.9980) and the Langmuir adsorption model (R2=0.9944). The value of E (6.742 kJ/mol) calculated from the Dubinin-Radushkevich isotherm model suggested that the physical adsorption via hydrogen-bonding might be predominant. The Scatchard plot showed a single line (R2=0.9172) and demonstrated the homogeneous recognition sites on MMIPs for KMF. The magnetic solid phase extraction (MSPE) based on MMIPs as sorbent was established for fast and selective enrichment of KMF and its structural analogue PA from the crude extract of M. torresiana and then KMF and PA were detected by HPLC-UV. The established method showed good performance and satisfactory results for real sample analysis. It also showed the feasi- bility of MMIPs for selective recognition of active structural analogues from complex herbal extracts.展开更多
Molecularly imprinted polymers(MIPs) were applied as molecular recognition elements to an electro- chemical sensor for cinchonidine(CD). A kind of MIP was synthesized with cinchonidine as template, modified ro- si...Molecularly imprinted polymers(MIPs) were applied as molecular recognition elements to an electro- chemical sensor for cinchonidine(CD). A kind of MIP was synthesized with cinchonidine as template, modified ro- sin(ethylene glycol maleic rosinate acrylate) containing the skeleton of phenanthrene rings as cross-linker and me- thylacrylic acid as functional monomer. MIP membrane was prepared on a glassy carbon electrode for the determina- tion of CD via free radical polymerization method. Electrochemical impedance spectroscopy(EIS) and cyclic vol- tammetry(CV) were used to characterize the membrane electrochemical behavior in electrode fabrication process. The experimental conditions were discussed. Under optimum conditions, it was found that the response of peak cur- rents was linear to the concentration of CD in a range of 0.013-2.26 mmol/L. The detection limit for CD is 1 μmol/L the relative standard deviation for 100 μmol/L CD is 1.34% and the incubation time is 2 min. The sensor was applied to the determination of CD in urine samples with satisfactory results.展开更多
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, bov...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.展开更多
Surface molecularly imprinted polymers (SMIP) was prepared via the reversible addition-fragmentation chain transfer (RAFT) polymerization on the chloromethyl polystyrene resin (CPR) in the presence of the templa...Surface molecularly imprinted polymers (SMIP) was prepared via the reversible addition-fragmentation chain transfer (RAFT) polymerization on the chloromethyl polystyrene resin (CPR) in the presence of the template D-phenylalanine. The structure of SMIP was characterized by FTIR and SEM. The adsorption behavior of D-phenylalanine of SMIP was preliminarily investigated.展开更多
In the last decades, the extensive use of chemical and biological materials has not only seen to an increased transport of environmental pollutants but also, it has interfered and compromised the pristine state of dif...In the last decades, the extensive use of chemical and biological materials has not only seen to an increased transport of environmental pollutants but also, it has interfered and compromised the pristine state of different environmental matrices with emphasis on waterbodies. This has stimulated studies to develop and adopt novel techniques which consider the removal of pollutants with premium on economic feasibility, simple instrumentation, and high performance. In the treatment of water, the removal of trace concentration organic compounds and other numerous polluted water effluents is difficult due to limited affinity of trace compound ions to ion exchange resins. Because of the selective nature;recognition properties;adsorption ability;high stability;and easier preparation of molecular imprints, they are considered attractive and suitable artificial receptors to be applied in analytical separations, drug delivery, and as chemical sensors. In this review, we touch on the fundamentals of molecularly imprinted technologies and underscore some recent advances made in the development of imprinted polymers that are compatible with water and how they can be used in the clean-up of pollutants. The paper finally presents a comprehensive report on some challenges and outlook in the use of MIPs as water treatment sorbent.展开更多
Molecularly imprinted polymers(MIPs) were prepared by the bulk polymerization using crystal violet as the template molecule, and the methacrylic acid and ethylene glycol dimetheacrylate as functional monomer and cross...Molecularly imprinted polymers(MIPs) were prepared by the bulk polymerization using crystal violet as the template molecule, and the methacrylic acid and ethylene glycol dimetheacrylate as functional monomer and cross-linker, respectively. Systematic investigations of synthetic conditions were conducted. The surface morphology and recognition mechanism of the obtained polymers were studied using scanning electron microscope and spectrophotometric analysis. MIPs showed high affinity to template molecule and were successfully applied as special solid-phase extraction sorbent for selective extraction of crystal violet from natural seawater. An off-line molecularly imprinted solid-phase extraction(MISPE) method followed by high-performance liquid chromatography with diodearray detection for the analysis of crystal violet was also established. MISPE columns have good recoveries for crystal violet standard solutions and good linearity was obtained over the concentration range of 0-200 μg L-1(R2 > 0.99). Finally, two natural seawater samples were investigated. The recoveries of spiked seawater on the MISPE columns were from 44.47% to 62.34%, the relative standard deviation(n=3) being in the range of 2.89%-5.96%.展开更多
Under the condition of weak acidity of pH 5.2, a sensitive vitamin B2 electrochemical sensor based on molecularly imprinted nonconducting polymer of o-aminophenol by potentiostatic polymerization in the presence of te...Under the condition of weak acidity of pH 5.2, a sensitive vitamin B2 electrochemical sensor based on molecularly imprinted nonconducting polymer of o-aminophenol by potentiostatic polymerization in the presence of template(vitamin B2) on a glassy carbon electrode was prepared, and its performance was studied. The sensor exhibited good sensitivity and selectivity to VB2. The detection limit went down to 2.3851nM, and a linear relationship between the current incremental and the concentration was found in the range of 10~120nM. And the sensor could use in detection of VB2 real sample for a long time and show good reproducibility. The average recovery rate to VB2 was 98.41%.展开更多
The increasing application of pesticides for agricultural purposes involves serious risk to the environment and human health due to either exposure or through residues in food and drinking water. Since food safety is ...The increasing application of pesticides for agricultural purposes involves serious risk to the environment and human health due to either exposure or through residues in food and drinking water. Since food safety is of mandatory importance there is a growing interest on the development of selective, simple, rapid, cost-effective and reliable analytical methodologies in order to ensure that pesticides residues should not be found at levels above the established maximum pesticide residue limits (MRLs). In recent years, a new methodology based on the development of molecularly imprinting polymers (MIPs) allows not only pre-concentration and cleaning of the sample but also selective extraction of the target analyte, which is crucial, particularly when the sample is complex and impurities can interfere with quantification. The scope of this review is to provide a general overview on MIPs field, with emphasis on MIP preparation and its use as sorbents for solid-phase extraction. This paper will be focused on the review of the current state of the art in the use of MIPs as selective materials in molecularly imprinted solid-phase extraction (MISPE) for the analysis of pesticide residues from food matrices. A review of preparation and application of MIPs in food matrices, will also be discussed.展开更多
文摘A molecularly imprinted polymer (MIP) was formed using an inorganic polymer by a sol-gel process. The monomers which were used to synthesize the inorganic polymer were tetraethoxysilane (TEOS), triethoxymethylsilane (MTES), and triethoxyphenylsilane (PTES). Caffeine was chosen as a template for the molecular imprinting, and theophylline was chosen as the analogous counterpart compound. The discriminating ability of the synthesized MIP to these two-compounds was estimated in this study. The MIP showed the highest discriminating ability when the ratio of TEOS:MTES: PTES in the synthesis of the inorganic polymer was 1:1:3, the reaction temperature was 50?C, and the pH of the reaction system was ~6.5.
基金the support of the National Natural Science Foundation of China(No.20575051).
文摘Urinary 8-hydroxy-2 -deoxyguanosine(8-OHdG) is an excellent marker of oxidative DNA damage.In this study,employing guanosine as dummy template a novel molecularly imprinted(MIP) monolithic capillary column had been synthesized,and that was used as medium of in-tube solid phase microextraction(SPME).Coupled with capillary electrophoresis-electrochemical detection(CE-ECD),the system of extraction and detection of 8-OHdG in urinary sample had been developed.Because of its greater phase ratio combined with conv...
基金financially supported by the National Natural Science Foundation of China (Nos. 81573391 and 81173024)the National Key Projects of China (No. 812277802)
文摘Surface molecularly imprinted polymers (SMIPs) for selective adsorption of ampicillin sodium were synthesized using surface molecular imprinting technique with silica gel as a support. The physical and morphological characteristics of the polymers were investigated by scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), elemental analysis and nitrogen adsorption-desorption test. The obtained results showed that the SMIPs displayed great adsorption capacity (13.5 lag/mg), high recognition ability (the imprinted factor is 3.2) and good binding kinetics for ampicillin sodium. Finally, as solid phase extraction adsorbents, the SMIPs coupled with HPLC method were validated and applied for the enrichment, purification and determination of anapicillin sodium in real milk and blood samples. The averages of spiked accuracy ranged from 92.1% to 107.6%. The relative standard deviations of intra- and inter-day precisions were less than 4.6%. This study provides a new and promising method for enriching, extracting and determining ampicillin sodium in complex biological samples.
基金supported by the National Natural Science Foundation of China(No 20274052).
文摘Molecularly imprinted polymers using 2,4-dichlorophenoxyacetic acid (2,4-D) as templates were prepared by suspension polymerization in silicon oil. The polymer particles exhibited regular shape in the micro-scale range. The adsorbing experiments indicated that the imprinted polymer particles possessed higher affinity to 2,4-D than the non-imprinted polymer particles.
基金supported by the National Natural Science Foundations of China(No.30873193 and No.30672551)
文摘An S-naproxen(S-NAP)molecularly imprinted monolithic stationary phase(MIMSP)with specific recognition for S-NAP and naproxen(NAP)was prepared by in situ technique,utilizing 4-vinylpridine(4-VP)as a function monomer,ethylene glycol dimethacrylate(EDMA)as a cross-linking agent,and low-polar solvents(toluene and dodecanol)as porogenic solvents.The selectivity of the polymers for S-NAP and NAP was evaluated by high performance liquid chromatography(HPLC).The binding characteristics were tested by Scatchard analysis.Racemic NAP could be specifically separated to some extent.At the same time,NAP could be separated from ibuprofen under optimized conditions.Scatchard analysis showed that two classes of binding sites existed in the S-NAP-imprinted polymers,with their dissociation constants estimated to be 1.045 and 5.496 μM,respectively.The results demonstrate that S-NAP and NAP can be recognized specifically on the obtained MIMSP.
基金Supported by the National Natural Science Foundation of China(Nos.21127008,21075140,21105133,90817012)the Key Program of Natural Science Foundation of Guangdong Province,China(No.9251027501000004)+1 种基金the Cooperation Project in Industry,Education and Research of Guangdong Province and Ministry of Education of China(No.2010B090400142)the Fundamental Research Funds for the Central Universities of China
文摘Metsulfuron-methyl molecularly imprinted polymer(MIP)-coated stir bar was prepared for sorptive extraction of sulfonylurea herbicides in complex samples.The MIP-coating was about 21.3 μm thickness with the relative standard deviation(RSD) of 4.4%(n=10).It was homogeneous and porous with good thermal stability and chemical stability.The extraction capability of the MIP-coating was 2.8 times over that of the non-imprinted polymer(NIP)-coating in hexane.The MIP-coating exhibited selective adsorption ability to the template and its analogues.The extraction conditions,including extraction solvent,desorption solvent,extraction time,desorption time and stirring speed,were optimized.A method for the determination of six sulfonylurea herbicides by MIP-coated stir bar sorptive extraction coupled with high performance liquid chromatography(HPLC) was developed.The linear range was 10―200 μg/L and the detection limits were within a range of 2.0―3.3 μg/L.It was also applied to the analysis of sulfonylurea herbicides in spiked river water,soil and rice samples.
文摘Moleculary imprinted polymers using p-hydroxybenzoic acid as templates wassynthesized by an in situ polymerization reaction and rendered capillary monolithic column wasused in capillary electrochromatographic mode. Good molecular recognition was achieved for p-hydroxybenzoic acid and good resolution of isomers can be realized.
基金This work is supported by the National Natural Science Foundation of China(No.21804105)by the Fundamental Research Funds for the Central Universities(No.5003515037)supported by the Huazhong University of Science and Technology Start-up Fund to Xu YU.
文摘Fluorescent nanoparticles have good chemical stability and photostability,controllable optical properties and larger stokes shift.In light of their designability and functionability,the fluorescent nanoparticles are widely used as the fluorescent probes for diverse applications.To enhance the sensitivity and selectivity,the combination of the fluorescent nanoparticles with the molecularly imprinted polymer,i.e.molecularly imprinted fluorescent nanoparticles(MIFN),was an effective way.The sensor based on MIFN(the MIFN sensor)could be more compatible with the complex sample matrix,which was especially widely adopted in medical and biological analysis.In this mini-review,the construction method,detective mechanism and types of MIFN sensors are elaborated.The current applications of MIFN sensors in pharmaceutical analysis,including pesticides/herbicide,veterinary drugs/drugs residues and human related proteins,are highlighted based on the literature in the recent three years.Finally,the research prospect and development trend of the MIFN sensor are forecasted.
基金financially supported by the National Natural Science Foundation of China (22078132 and 22108103)Open Funding Project of the National Key Laboratory of Biochemical Engineering (2021KF-02)+3 种基金China Postdoctoral Science Foundation (2021M691301)Jiangsu Agricultural Independent Innovation Fund Project (CX(21)3079)Graduate Research Innovation Program of Jiangsu Province (KYCX20-3040)China Postdoctoral Science Foundation (2021M691301)。
文摘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.
基金supported by the Science and Technology Research Project for Education Department of Jilin Province(No.JJKH20170299KJ)the Science and Technology Development Project of Jilin Province(No.20170520145JH)
文摘For preparing the phenobarbital(PHN) molecularly imprinted polymers(MIPs) with higher adsorption and selectivity properties, we used the M062 X/6-31 g(d,p) method of density functional theory to predict the various properties of PHN-MIPs. Here PHN is as the imprinted molecule and acrylamide(AM) as the functional monomer. The ethylene glycol dimethacrylate,trimethylolpropane trimethacrylate, divinyl benzene, and pentaerythritol trimethacrylate are as the cross-linking agents, respectively. The acetonitrile, chloroform, toluene, and tetrahydrofuran are used as the solvents, respectively. The configurations of the molecular imprinting self-assembly system for PHN and AM have been simulated to study their bonding sites, binding energy, amount of hydrogen bond, and interaction mechanism. The essence of imprinting interaction for PHN and AM has been revealed by the atomic in the molecule theory. Meanwhile, the analogues of PHN were used to discuss the selectivity property of the stable PHN-AM complex. The results show that the PHN interacts with AM through hydrogen bonds. When the imprinting molar ratio of PHN-AM is1:6 and the THF is as the solvent, the amount of their hydrogen bonds is the most, the binding energy is the lowest, and their configuration is the most stable. In comparison with the other cross-linking agents(EGDMA, TRIM, and DVB), the PETA is more suitable for PHN-MIPs. The selective property of PHN-MIP to PHN is excellent when PHN and DMBA exist at the same time.
基金supported by the National Natural Science Foundation of China (31260620, 31471654)the Special Fund for Agro-scientific Research in the Public Interest of China (201203094)
文摘A fluorescent competitive assay for melamine was first developed utilizing dummy molecularly imprinted polymers(DMIPs) as artificial antibodies. This method is based on the competition between fluorescent substances and the unlabeled analyte for binding sites in synthesized DMIPs and the decreased binding of fluorescent substances to DMIPs due to increased concentrations of melamine in the solutions. DMIPs for melamine were synthesized under a hot water bath in the presence of the initiator azobisisobutyronitrile(AIBN) using 2,4-diamino-6-methyl-1,3,5-triazine(DAMT) as a dummy template, methacrylic acid(MAA) as a functional monomer, and ethylene glycol dimethacrylate(EGDMA) as a crosslinking agent. The adsorption capacity and selectivity of DMIPs for melamine were evaluated by the isothermal adsorption curve and Scatchard analysis. The evaluation results showed that the synthesized DMIPs had specific recognition sites for melamine and the maximum adsorption amount was 1 066.33 μg g^(-1). Later, 5-(4,6-d ichlorotriazinyl) amino fluorescein(DTAF) with a triazine ring, which s lightly resembles m elamine, w as selected as the fluorescent substance. The fluorescent competitive assay using DMIPs as t he antibody mimics was finally established by selecting and optimizing the reaction solvents, DMIPs amount, DTAF concentration, and incubation time. The optimal detection system showed a linear response w ithin range of 0.05-40 mg L^(-1) and the limit of detection(LOD) was 1.23 μg L^(-1). It was successfully applied to the detection of melamine in spiked milk samples wi th satisfactory recoveries(71.9 to 86.3%). According to the comparative analysis, the result of optimized fluorescent competitive assay re vealed excellent agreement with the HPLC-MS/MS result for melamine.
基金supported by grants from the National Natural Science Foundation of China(No.21105032)Doctoral Program Fund of Ministry of Education of China(No.20110142120031)
文摘Novel uniform-sized magnetic molecularly imprinted polymers (MMIPs) were synthe- sized for selective recognition of active antitumor ingredients of kaempferol (KMF) and protoapi- genone (PA) in Macrothelypteris torresiana (M. torresiana) by surface molecular imprinting tech- nique in this study. Super paramagnetic core-sheU nanoparticles (γ-MPS-SiO2@Fe3O4) were used as seeds, KMF as template molecule, acrylamide (AM) as functional monomer, and N, N'-methylene bisacrylamide (BisAM) as cross-linker. The prepared MMIPs were characterized by X-ray diffraction (XRD), Fourier transform infrared spectrum fiT/R), transmission electron microscopy (TEM) and thermo-gravimetric analysis (TGA), respectively. The recognition capacity of MMIPs was 2.436 times of non-imprinted polymers. The adsorption results based on kinetics and isotherm analysis were in accordance with the pseudo-second-order model (R2=0.9980) and the Langmuir adsorption model (R2=0.9944). The value of E (6.742 kJ/mol) calculated from the Dubinin-Radushkevich isotherm model suggested that the physical adsorption via hydrogen-bonding might be predominant. The Scatchard plot showed a single line (R2=0.9172) and demonstrated the homogeneous recognition sites on MMIPs for KMF. The magnetic solid phase extraction (MSPE) based on MMIPs as sorbent was established for fast and selective enrichment of KMF and its structural analogue PA from the crude extract of M. torresiana and then KMF and PA were detected by HPLC-UV. The established method showed good performance and satisfactory results for real sample analysis. It also showed the feasi- bility of MMIPs for selective recognition of active structural analogues from complex herbal extracts.
基金Supported by the National Nature Science Foundation of China(Nos.21065001 and 30960306)the Natural Science Foundation of Guangxi Province,China(Nos.0639025,0991084 and 0991001z)+2 种基金the Fund of Guangxi Key Laboratory of Chemistry and Engineering of Forest Products,China(No.GXFC08-06)the Project of Education Department of Guangxi Province,China(No.200812MS074)the Innovation Project of Guangxi University for Nationalities,China(No.gxun-chx2011086)
文摘Molecularly imprinted polymers(MIPs) were applied as molecular recognition elements to an electro- chemical sensor for cinchonidine(CD). A kind of MIP was synthesized with cinchonidine as template, modified ro- sin(ethylene glycol maleic rosinate acrylate) containing the skeleton of phenanthrene rings as cross-linker and me- thylacrylic acid as functional monomer. MIP membrane was prepared on a glassy carbon electrode for the determina- tion of CD via free radical polymerization method. Electrochemical impedance spectroscopy(EIS) and cyclic vol- tammetry(CV) were used to characterize the membrane electrochemical behavior in electrode fabrication process. The experimental conditions were discussed. Under optimum conditions, it was found that the response of peak cur- rents was linear to the concentration of CD in a range of 0.013-2.26 mmol/L. The detection limit for CD is 1 μmol/L the relative standard deviation for 100 μmol/L CD is 1.34% and the incubation time is 2 min. The sensor was applied to the determination of CD in urine samples with satisfactory results.
文摘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.
文摘Surface molecularly imprinted polymers (SMIP) was prepared via the reversible addition-fragmentation chain transfer (RAFT) polymerization on the chloromethyl polystyrene resin (CPR) in the presence of the template D-phenylalanine. The structure of SMIP was characterized by FTIR and SEM. The adsorption behavior of D-phenylalanine of SMIP was preliminarily investigated.
文摘In the last decades, the extensive use of chemical and biological materials has not only seen to an increased transport of environmental pollutants but also, it has interfered and compromised the pristine state of different environmental matrices with emphasis on waterbodies. This has stimulated studies to develop and adopt novel techniques which consider the removal of pollutants with premium on economic feasibility, simple instrumentation, and high performance. In the treatment of water, the removal of trace concentration organic compounds and other numerous polluted water effluents is difficult due to limited affinity of trace compound ions to ion exchange resins. Because of the selective nature;recognition properties;adsorption ability;high stability;and easier preparation of molecular imprints, they are considered attractive and suitable artificial receptors to be applied in analytical separations, drug delivery, and as chemical sensors. In this review, we touch on the fundamentals of molecularly imprinted technologies and underscore some recent advances made in the development of imprinted polymers that are compatible with water and how they can be used in the clean-up of pollutants. The paper finally presents a comprehensive report on some challenges and outlook in the use of MIPs as water treatment sorbent.
基金supported by the Natural Science Foundation of China (41076065)the Major State Basic Research Development Program of China (973 Program) (2010CB428701)
文摘Molecularly imprinted polymers(MIPs) were prepared by the bulk polymerization using crystal violet as the template molecule, and the methacrylic acid and ethylene glycol dimetheacrylate as functional monomer and cross-linker, respectively. Systematic investigations of synthetic conditions were conducted. The surface morphology and recognition mechanism of the obtained polymers were studied using scanning electron microscope and spectrophotometric analysis. MIPs showed high affinity to template molecule and were successfully applied as special solid-phase extraction sorbent for selective extraction of crystal violet from natural seawater. An off-line molecularly imprinted solid-phase extraction(MISPE) method followed by high-performance liquid chromatography with diodearray detection for the analysis of crystal violet was also established. MISPE columns have good recoveries for crystal violet standard solutions and good linearity was obtained over the concentration range of 0-200 μg L-1(R2 > 0.99). Finally, two natural seawater samples were investigated. The recoveries of spiked seawater on the MISPE columns were from 44.47% to 62.34%, the relative standard deviation(n=3) being in the range of 2.89%-5.96%.
文摘Under the condition of weak acidity of pH 5.2, a sensitive vitamin B2 electrochemical sensor based on molecularly imprinted nonconducting polymer of o-aminophenol by potentiostatic polymerization in the presence of template(vitamin B2) on a glassy carbon electrode was prepared, and its performance was studied. The sensor exhibited good sensitivity and selectivity to VB2. The detection limit went down to 2.3851nM, and a linear relationship between the current incremental and the concentration was found in the range of 10~120nM. And the sensor could use in detection of VB2 real sample for a long time and show good reproducibility. The average recovery rate to VB2 was 98.41%.
基金funding by Fundos FEDER through Programa Operacional Factores de Competitividade-COM-PETE and Fundos Nacionais through FCT-Fundacao para a Ciencia e a Tecnologia(Project PTDC/AGR-ALI/117544/2010).
文摘The increasing application of pesticides for agricultural purposes involves serious risk to the environment and human health due to either exposure or through residues in food and drinking water. Since food safety is of mandatory importance there is a growing interest on the development of selective, simple, rapid, cost-effective and reliable analytical methodologies in order to ensure that pesticides residues should not be found at levels above the established maximum pesticide residue limits (MRLs). In recent years, a new methodology based on the development of molecularly imprinting polymers (MIPs) allows not only pre-concentration and cleaning of the sample but also selective extraction of the target analyte, which is crucial, particularly when the sample is complex and impurities can interfere with quantification. The scope of this review is to provide a general overview on MIPs field, with emphasis on MIP preparation and its use as sorbents for solid-phase extraction. This paper will be focused on the review of the current state of the art in the use of MIPs as selective materials in molecularly imprinted solid-phase extraction (MISPE) for the analysis of pesticide residues from food matrices. A review of preparation and application of MIPs in food matrices, will also be discussed.