Youwen Tang

Highly ordered metal ion imprinted mesoporous silica particles exhibiting specific recognition and fast adsorption kinetics

We prepared highly ordered metal ion imprinted mesoporous silica (IIMS) through co-condensation using a combination of molecular imprinting technology and traditional mesoporous materials. Copper ion is used as the template. Besides the periodic hexagonal structure, nano-sized wall thickness, and large surface area, it is found that the IIMS has highly specific recognition ability for the template. The imprinting factor of IIMS exhibits a maximum value of 3.7 at pH 2.5. The material shows fast binding kinetics for Cu2+ (complete equilibrium reach only within 5 min) and the saturation adsorption capacity reaches up to 0.39 mmol g−1. Homogeneous binding sites are confirmed by the Langmuir isothermal model and the Langmuir–Freundlich isothermal model. The heterogeneity index is 0.992 with a value similar to those found for molecularly imprinted polymers prepared using covalent imprinting. The recovery of the silica stays above 90% after six extraction–stripping cycles. Furthermore, the silica has significant potential for water treatment applications.

Development of hybrid organic-inorganic surface imprinted Mn-doped ZnS QDs and their application as a sensing material for target proteins.

Applying molecular imprinting techniques to the surface of functionalized quantum dots (QDs) allows the preparation of molecularly imprinted polymers (MIPs) with accessible, surface exposed binding sites and excellent optical properties. This paper demonstrates a new strategy for producing such hybrid organic-inorganic imprinted Mn-doped ZnS QDs for specific recognition of bovine hemoglobin. The technique provides surface grafting imprinting in aqueous solutions using amino modified Mn-doped ZnS QDs as supports, acrylamide and methacrylic acid as functional monomers, γ-methacryloxypropyl trimethoxy silane as the grafting agent, and bovine hemoglobin as a template. The amino propyl functional monomer layer directs the selective occurrence of imprinting polymerization at the QDs surface through copolymerization of grafting agents with functional monomers, but also acts as an assistive monomer to drive the template into the formed polymer shells to create effective recognition sites. Using MIP-QDs composites as a fluorescence sensing material, trace amounts of bovine hemoglobin are signaled with high selectivity by emission intensity changes of Mn-doped ZnS QDs, which is embedded into the imprinted polymers.

Efficient removal of lead from highly acidic wastewater by periodic ion imprinted mesoporous SBA-15 organosilica combining metal coordination and co-condensation

In order to develop a highly efficient method for direct removal of lead from acidic wastewater (pH 2.0), we introduce a novel highly ordered Pb2+ imprinted mesoporous silica (PbIMS) SBA-15 combining co-condensation and functionalized iminodiacetic acid (IDA). Fourier transform infrared spectroscopy (FTIR) and energy-dispersive X-ray (EDX) analysis provided the components of PbIMS. The solid-state 13C NMR spectra demonstrated the successful embedment of IDA in the mesoporous silica. Furthermore, X-ray photoelectron spectroscopy (XPS) analysis confirmed that Pb2+ was coordinated by the N atom and carboxyl O atom of IDA. The results of transmission electron microscopy (TEM), small angle X-ray diffraction (XRD) and N2 adsorption–desorption measurement confirmed that the PbIMS preserved a highly ordered hexagonal P6mm mesostructure. The Brunauer–Emmett–Teller (BET) surface area was 762 m2 g−1. The saturated adsorption capacity of PbIMS toward lead reached up to 103 mg g−1 at pH 2.0, which was greater even than that of the simply modified SBA-15 by IDA at pH 4.5. The values of selectivity coefficients of PbIMS for six competing metal ions ranged from 67.3 to 12.7. The adsorption of Pb2+ reached equilibrium within 7 min. The adsorption efficiency of PbIMS was above 93% after six extraction–stripping cycles. The investigation conducted with real samples of strongly acidic wastewater demonstrated the ability of PbIMS to efficiently remove lead below the current China regulatory standard.

Methyl parathion imprinted polymer nanoshell coated on the magnetic nanocore for selective recognition and fast adsorption and separation in soils.

Core-shell magnetic methyl parathion (MP) imprinted polymers (Fe3O4@MPIPs) were fabricated by a layer-by-layer self-assembly process. In order to take full advantage of the synergistic effect of hydrogen-binding interactions and π-π accumulation between host and guest for molecular recognition, methacrylic acid and 4-vinyl pyridine were chosen as co-functional monomers and their optimal proportion were investigated. The core-shell and crystalline structure, morphology and magnetic properties of Fe3O4@MPIPs were characterized. The MP-imprinted nanoshell was almost uniform and about 100nm thick. Binding experiments demonstrated that Fe3O4@MPIPs possessed excellent binding properties, including high adsorption capacity and specific recognition, as well as fast adsorption kinetics and a fast phase separation rate. The equilibration adsorption capacity reached up to 9.1mg/g, which was 12 times higher than that of magnetic non-imprinted polymers, while adsorption reached equilibrium within 5min at a concentration of 0.2mmol/L. Furthermore, Fe3O4@MPIPs successfully provided selective separation and removal of MP in soils with a recovery and detection limit of 81.1-87.0% and 5.2ng/g, respectively.

Selective fluorescent sensing of α-amanitin in serum using carbon quantum dots-embedded specificity determinant imprinted polymers

α-amanitin could make patients die of acute liver failure within a short time if suitable treatment is not provided in a timely fashion. This paper demonstrates a new strategy for direct detection of α-amanitin in serum using carbon quantum dots-embedded specificity determinant imprinted polymers. According to the structure of α-amanitin, we selected a proper moiety of α-amanitin as specificity determinant to synthesize template to prepare the MIPs. The computer simulation was used to screen out acidic methacrylic acid (MAA) and basic 4-vinyl pyridine (4-Vpy) together as functional monomers, and the experiments further proved that synergistic interaction of MAA and 4-Vpy was beneficial to enhance the recognition capability of MIPs for α-amanitin. Moreover, the fluorescence intensity showed good linear correlations with the concentration of α-amanitin from 0.05 to 4.0μgmL(-1). The detection limit for α-amanitin was 15ngmL(-1). The nanoparticles were employed to directly detect α-amanitin in serum without any pretreatment with recoveries of 97.8-100.9%.

Development of surface imprinted core-shell nanoparticles and their application in a solid-phase dispersion extraction matrix for methyl parathion

Applying molecular imprinting techniques to the surface of functionalized SiO2 allows the preparation of molecularly imprinted polymers (MIPs) with accessible, high affinity and surface exposed binding sites. This paper demonstrates a new strategy for producing such hybrid organic-inorganic surface imprinted silica nanoparticles for specific recognition of methyl parathion. The technique provides surface grafting imprinting in chloroform using amino modified silica nanoparticles as supports, acrylamide as the functional monomer, γ-methacryloxypropyl trimethoxy silane as the grafting agent, and methyl parathion as a template. The amino propyl functional monomer layer directs the selective occurrence of imprinting polymerization at the silica surface through copolymerization of grafting agents with functional monomers, but also acts as an assistive monomer to drive the template into the formed polymer shells to create effective recognition sites. The resulting MIPs-SiO2 nanoparticles display three-dimensional core-shell architectures and large surface areas. The molecularly imprinted shell provides recognition sites for methyl parathion, with the materials exhibiting excellent performance for selecting the template. Using MIPs-SiO2 nanoparticles as a matrix of solid-phase dispersion extraction sorbents, trace amounts of methyl parathion are selectivity extracted from pear and green vegetable samples while simultaneously eliminating matrix interferences, attaining recoveries of 84.7-94.4% for the samples.

Binding characteristics of homogeneous molecularly imprinted polymers for acyclovir using an (acceptor-donor-donor)-(donor-acceptor-acceptor) hydrogen-bond strategy, and analytical applications for serum samples.

This paper demonstrates a novel approach to assembling homogeneous molecularly imprinted polymers (MIPs) based on mimicking multiple hydrogen bonds between nucleotide bases by preparing acyclovir (ACV) as a template and using coatings grafted on silica supports. (1)H NMR studies confirmed the AAD-DDA (A for acceptor, D for donor) hydrogen-bond array between template and functional monomer, while the resultant monodisperse molecularly imprinted microspheres (MIMs) were evaluated using a binding experiment, high performance liquid chromatography (HPLC), and solid phase extraction. The Langmuir isothermal model and the Langmuir-Freundlich isothermal model suggest that ACV-MIMs have more homogeneous binding sites than MIPs prepared through normal imprinting. In contrast to previous MIP-HPLC columns, there were no apparent tailings for the ACV peaks, and ACV-MIMs had excellent specific binding properties with a Ka peak of 3.44 × 10(5)M(-1). A complete baseline separation is obtained for ACV and structurally similar compounds. This work also successfully used MIMs as a specific sorbent for capturing ACV from serum samples. The detection limit and mean recovery of ACV was 1.8 ng/mL(-1) and 95.6%, respectively, for molecularly imprinted solid phase extraction coupled with HPLC. To our knowledge, this was the first example of MIPs using AAD-DDA hydrogen bonds.

A novel hydroquinidine imprinted microsphere using a chirality-matching N-Acryloyl-l-phenylalanine monomer for recognition of cinchona alkaloids

Using a combination of molecular imprinting technology and traditional chiral stationary phases, the synergistic effect between chiral monomer and chiral cavity of molecularly imprinted polymers in stereoselective recognition was investigated. We designed and synthesized an amino acid derivative to be used as a novel chiral functional monomer. Monodisperse molecularly imprinted core-shell microspheres using surface imprinting method on silica gel were prepared with hydroquinidine as the pseudo-template molecule for the resolution of cinchona alkaloids. The results showed a significant synergistic effect in stereoselective recognition, confirming our initial hypothesis. Furthermore, our computational simulation and experiments intensively support the hypothetical chiral recognition mechanism for the imprinted microspheres.

Preparation of core-shell magnetic molecular imprinted polymer with binary monomer for the fast and selective extraction of bisphenol A from milk.

In the current study, a new strategy for the extraction of bisphenol A (BPA) from milk has been employed by using surface-imprinted core-shell magnetic beads, prepared by the reversible addition-fragmentation chain transfer (RAFT) polymerization. In order to obtain highly selective recognition cavities, an enhanced imprinting method based on binary functional monomers, e.g. 4-vinylpyridine (4-VP) and β-cyclodextrin (β-CD), was chosen for BPA imprinting. The morphological and magnetic properties of the Fe3O4-MIP beads were characterized by Transmission Electron Microscopy (TEM), Fourier Transform Infrared (FT-IR) Spectroscopy, Thermogravimetric Analysis (TGA), and Vibrating Sample Magnetometer (VSM). The characterization results suggested that MIP was synthesized evenly on Fe3O4-SiO2 surface. The adsorption experiments revealed that Fe3O4-MIPs showed better extraction capacity and selectivity toward BPA and its analogues than the non-imprinted polymers (NIPs). The saturation capacity of Fe3O4-MIP was 17.98mg/g. In milk samples, the present method displayed a lower the detection thresholds, down to 3.7μg/L. The recoveries of BPA in milk samples for three concentrations were found to be within 99.21%, 98.07% and 97.23%, respectively to three concentrations: 1.0μmol/L, 10.0mol/L, 100.0μmol/L. Thus, the MIPs can be used for remove BPA in milk samples.

Antibody-free ultra-high performance liquid chromatography/tandem mass spectrometry measurement of angiotensin I and II using magnetic epitope-imprinted polymers

The major challenges in measuring plasma renin activity (PRA) stem from the complexity of biological matrix, as well as from the instability and low circulating concentration of angiotensin. In this study, an ultra-high performance liquid chromatography/tandem mass spectrometry (UPLC-MS/MS) based technique has been developed for the measurement of angiotensin using magnetically imprinted polymers for simultaneous enrichment of the precursor peptide angiotensin II (Ang II) and the upstream peptide precursor angiotensin I (Ang I). This technique involved surface graft imprinting in aqueous solutions using vinyl-modified nano-iron oxide as solid supports, the specificity determinant of Ang I and Ang II as the epitope, and methacrylic acid and N-t-butylacrylamide as functional monomers. The vinyl-modified nano-iron oxide acted as a magnetic separation media, and the molecularly imprinted shell provided analyte selectivity for the recognition of Ang I and Ang II. Selective enrichment of Ang I and Ang II was accomplished by the magnetically imprinted polymers, followed by a magnetic separation procedure and subsequent quantification by UPLC-MS/MS in the positive ionization mode with multiple reaction monitoring. Through the latter protocol, a low limit of detection could be realized, viz. 0.07ng/mL and 0.06ng/mL for Ang I and II, respectively, which was thoroughly validated for accuracy and reproducibility through analyzing Ang I and Ang II in human plasma samples.