Imprinted Silica Nanoparticles Research Articles

Study on the creation of boronate affinity-based oriented imprinted silica nanoparticles and their selective recognition toward glycopeptide antibiotics in food and water.

Taking into account the drug resistance of antibiotics, teicoplanin has been banned in the veterinary field. Also, it brings threat to people's health when they eat foods containing teicoplanin residue. In addition, the abuse of teicoplanin in humans and food animals also poses a potential risk to water. Therefore, it is crucial to purify teicoplanin from food before quantifying its amount. In this study, researchers employed boronate affinity-based controlled oriented surface imprinting technique to produce molecularly imprinted polymers (MIPs) for the isolation of teicoplanin. The 3-fluoro-4-formylphenylboronic acid-functionalized silica nanoparticle substrate was first used as the supporting material for immobilizing teicoplanin. Next, the substrate surface was coated with an imprinting coating whose thickness could be controlled, produced through the self-copolymerization of dopamine and m-aminophenylboronic acid (APBA) in water. After the template was removed, 3D cavities that matched the template were created in the imprinting layer. The prepared teicoplanin-imprinted silica nanoparticles exhibited several significant satisfactory results such as good specificity, high binding capacity (46.9 ± 2.3 mg g-1), moderate binding constant ((5.46 ± 0.18) × 10-5 M-1), fast kinetics (8 min) and low binding pH (pH 5.0) toward teicoplanin. The teicoplanin-imprinted silica nanoparticles could still be reused after seven cycles of adsorption-desorption, which indicated a high chemical stability. In addition, recoveries of the proposed method for teicoplanin at three spiked levels in milk and water ranged from 91.8 to 105.6% and 92.3 to 97.4%, respectively. The teicoplanin-imprinted silica nanoparticles are capable of identifying the target teicoplanin in real samples in a simple, fast, selective and efficient manner.

High-capacity boronate affinity-based template-immobilized surface imprinted silica nanoparticles for rapid, selective, and efficient extraction and determination of lincomycin in milk and chicken

BackgroundLincomycin, a natural antibiotic, is widely used by animal and fishery husbandries to prevent infections and treat diseases. It endangers people’s health when they eat foods containing lincomycin residue, especially the frequent consumption of milk and chicken products containing lincomycin. Hence, it is extremely important to evaluate the content of lincomycin in food samples. However, a direct analysis of lincomycin in milk and chicken is quite difficult because of its very low concentration level and the presence of undesirable matrix effects. Therefore, selective and efficient extraction of lincomycin from complex food samples prior to its quantification is required.ResultsIn this study, lincomycin-imprinted silica nanoparticles were prepared according to boronate affinity-based template-immobilized surface imprinting. Silica nanoparticles and boronic acid ligands 3-fluoro-4-formylphenylboronic acid were used as supporting materials and functional monomers, respectively. The prepared lincomycin-imprinted silica nanoparticles exhibited several significant results, such as good specificity, high binding capacity (19.45 mg/g), fast kinetics (6 min), and low binding pH (pH 5.0) toward lincomycin. The reproducibility of lincomycin-imprinted silica nanoparticles was satisfactory. The lincomycin-imprinted silica nanoparticles could still be reused after seven adsorption–desorption cycles, which indicated high chemical stability. In addition, the recoveries of the proposed method for lincomycin at three spiked levels of analysis in milk and chicken were 93.3–103.3% and 90.0–100.0%, respectively.ConclusionThe prepared lincomycin-imprinted silica nanoparticles are feasible for the recognition of target lincomycin with low concentrations in real food samples such as milk and chicken. Our approach makes sample pre-preparation simple, fast, selective, and efficient.

Preparation of a Molecularly Imprinted Silica Nanoparticles Embedded Microfiltration Membrane for Selective Separation of Tetrabromobisphenol A from Water.

The ubiquitous presence of tetrabromobisphenol A (TBBPA) in aquatic environments has caused severe environmental and public health concerns; it is therefore of great significance to develop effective techniques to remove this compound from contaminated waters. Herein, a TBBPA imprinted membrane was successfully fabricated via incorporating imprinted silica nanoparticles (SiO2 NPs). The TBBPA imprinted layer was synthesized on the 3-(methacryloyloxy) propyltrimethoxysilane (KH-570) modified SiO2 NPs via surface imprinting. Eluted TBBPA molecularly imprinted nanoparticles (E-TBBPA-MINs) were incorporated onto a polyvinylidene difluoride (PVDF) microfiltration membrane via vacuum-assisted filtration. The obtained E-TBBPA-MINs embedded membrane (E-TBBPA-MIM) showed appreciable permeation selectivity toward the structurally analogous to TBBPA (i.e., 6.74, 5.24 and 6.31 of the permselectivity factors for p-tert-butylphenol (BP), bisphenol A (BPA) and 4,4'-dihydroxybiphenyl (DDBP), respectively), far superior to the non-imprinted membrane (i.e., 1.47, 1.17 and 1.56 for BP, BPA and DDBP, respectively). The permselectivity mechanism of E-TBBPA-MIM could be attributed to the specific chemical adsorption and spatial complementation of TBBPA molecules by the imprinted cavities. The resulting E-TBBPA-MIM exhibited good stability after five adsorption/desorption cycles. The findings of this study validated the feasibility of developing nanoparticles embedded molecularly imprinted membrane for efficient separation and removal of TBBPA from water.

Synthesis of surface dual-template molecularly imprinted silica nanoparticles for extraction of ciprofloxacin and norfloxacin

Synthesis of selective dual-template molecularly imprinted silica nanoparticles (MI-SiNPs) on the surface of graphene quantum dots (GQDs) for the simultaneous extraction of ciprofloxacin (CIP) and norfloxacin (NOR) from biological samples.

Controlled drug delivery for cancer cell treatment via magnetic doxorubicin imprinted silica nanoparticles.

Herein, we report a facile and rapid one-step synthetic strategy for the development of magnetic doxorubicin imprinted silica nanoparticles for drug release experiments in living cells showing a remotely triggered doxorubicin release upon applying an alternating magnetic field, without temperature elevation of the medium (local heating).

Selective separation and determination of quercetin from red wine by molecularly imprinted nanoparticles coupled with HPLC and ultraviolet detection.

In this study, a highly sensitive and selective sample pretreatment procedure using molecularly imprinted silica nanoparticles was developed for the extraction and determination of quercetin in red wine samples coupled with high-performance liquid chromatography with ultraviolet detection. The imprinted silica nanoparticles were prepared in the presence of N-acryoyl-l-aspartic acid (functional monomer), quercetin (template), azobisisobutyronitrile (initiator) and methylene bisacrylamide (cross-linker) and methanol/water (porogen) via surface-initiated reversible addition-fragmentation chain transfer polymerization. Surface characterization was performed and several imprinting parameters were investigated, and the results indicated that adsorption of quercetin on the imprinted silica nanoparticles followed a pseudo-first-order adsorption isotherm with a maximum adsorption capacity at 26.4mg/g within 60min. The imprinted silica nanoparticles also showed satisfactory selectivity towards quercetin as compared with its structural analogues. Moreover, the imprinted nanoparticles preserved their recognition ability even after five adsorption-desorption cycles. Meanwhile, the nanoparticles were successfully applied to selective extraction of quercetin from red wine with a high recovery (99.7-100.4%). The limit of detection was calculated to be 0.058μg/mL with a correlation coefficient 0.9996 in the range of 0.2-50μg/mL. As a result, the developed selective extraction method using molecular imprinting technology simplifies the sample pretreatment procedure before determination of quercetin in real samples.

Biomimetic Silica Nanoparticles Prepared by a Combination of Solid-Phase Imprinting and Ostwald Ripening

Herein we describe the preparation of molecularly imprinted silica nanoparticles by Ostwald ripening in the presence of molecular templates immobilised on glass beads (the solid-phase). To achieve this, a seed material (12 nm diameter silica nanoparticles) was incubated in phosphate buffer in the presence of the solid-phase. Phosphate ions act as a catalyst in the ripening process which is driven by differences in surface energy between particles of different size, leading to the preferential growth of larger particles. Material deposited in the vicinity of template molecules results in the formation of sol-gel molecular imprints after around 2 hours. Selective washing and elution allows the higher affinity nanoparticles to be isolated. Unlike other strategies commonly used to prepare imprinted silica nanoparticles this approach is extremely simple in nature and can be performed under physiological conditions, making it suitable for imprinting whole proteins and other biomacromolecules in their native conformations. We have demonstrated the generic nature of this method by preparing imprinted silica nanoparticles against targets of varying molecular mass (melamine, vancomycin and trypsin). Binding to the imprinted particles was demonstrated in an immunoassay (ELISA) format in buffer and complex media (milk or blood plasma) with sub-nM detection ability.

Development of dummy molecularly imprinted based on functionalized silica nanoparticles for determination of acrylamide in processed food by matrix solid phase dispersion

A novel technique was applied for the synthesis of dummy molecularly imprinted silica nanoparticles (DMISNPs). DMISNPs were characterized by Fourier transmission infrared spectrometry, scanning electron microscopy and transmission electron microscope. The material was used as dispersant for the analysis of biscuit and bread samples using matrix solid phase dispersion (MSPD). Of advantages of such approach may be counted as the simplicity of synthesis procedure, low consumption of organic solvent, mild working temperature during the synthesis, high binding capacity and affinity. The effect of various parameters such as sample-to-dispersant ratio and eluents volume on extraction recovery was investigated and optimized by central composite design under response surface methodology. It was proven that the proposed dispersant leads to high affinity toward acrylamide even in complicated matrices. Quantification of the acrylamide was carried out by high performance liquid chromatography with UV detection (HPLC-UV).

Selective determination of trace bisphenol a using molecularly imprinted silica nanoparticles containing quenchable fluorescent silver nanoclusters

We describe a kind of molecularly imprinted polymer (MIP)-based fluorescent sensor. It was obtained by anchoring a surface-imprinted MIP layer for the model analyte bisphenol A (BPA) onto the surface of fluorescent silver nanoclusters (Ag-NCs). The MIP-coated Ag-NCs were synthesized by the sol-gel technique. The hyphenation of the fluorescence of Ag-NCs with MIP technology expands the use of fluorescent nanomaterials in sensing and recognition. BPA is capable of quenching the fluorescence of the Ag-NCs, and the reduction in fluorescence intensity is related to the concentration of BPA in the 0.2 μg mL−1 to 2 mg L−1 range. The detection limit for BPA is 0.02 μg mL−1, and the recovery of BPA from spiked milk and juice samples ranged from 92.5 to 108.5 %. The MIP-coated Ag-NCs presented here are characterized by their ease of synthesis, selectivity and sensitivity. In our perception, this approach can be extended to numerous other analytes.

Imprinted silica nanoparticles coated with N-propylsilylmorpholine-4-carboxamide for the determination of m-cresol in synthetic and real samples.

m-Cresol-imprinted silica nanoparticles coated with N-propylsilylmorpholine-4-carboxamide have been developed that contain specific pockets for the selective uptake of m-cresol. Silica nanoparticles were synthesized by a sol-gel process followed by functionalization of their surface with N-propylsilylmorpholine-4-carboxamide. The formation of m-cresol-imprinted silica nanoparticles was confirmed by UV-Vis spectrophotometry, infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy and transmission electron microscopy. Electron microscopic studies revealed the formation of monodispersed imprinted silica nanoparticles with spherical shape and an average size of 83 nm. The developed nanoparticles were filled in a syringe and used for the extraction of m-cresol from aqueous samples followed by quantification using high-performance liquid chromatography with diode array detection. Various adsorption experiments showed that developed m-cresol-imprinted silica nanoparticles exhibited a high adsorption capacity and selectivity and offered a fast kinetics for rebinding m-cresol. The chromatographic quantification was achieved using mobile phase consisting of acetonitrile/water (70:30 v/v) at an isocratic flow rate of 1.0 mL/min using a reversed-phase C18 column and detection at λmax = 275 nm. The limits of detection and quantification were 1.86 and 22.32 ng/mL, respectively, for the developed method. The percent recoveries ranged from 96.66-103.33% in the spiked samples. This combination of this nanotechnique with molecular imprinting was proved as a reliable, sensitive and selective method for determining the target from synthetic and real samples.

The effectively specific recognition of bovine serum albumin imprinted silica nanoparticles by utilizing a macromolecularly functional monomer to stabilize and imprint template

Structural stability of the template is one of the most important considerations during the preparation of protein imprinting technology. To address this limitation, we propose a novel and versatile strategy of utilizing macromolecularly functional monomers to imprint biomacromolecules. Results from circular dichroism and synchronous fluorescence experiments reflect the macromolecularly functional monomers tendency to interact with the protein surface instead of permeating it and destroying the hydrogen bonds that maintain the protein’s structural stability, therefore stabilizing the template protein structure during the preparation of imprinted polymers. The imprinted polymers composed of macromolecularly functional monomers or their equivalent micromolecularly functional monomers over silica nanoparticles were characterized and carried out in batch rebinding test and competitive adsorption experiments. In batch rebinding test, the imprinted particles prepared with macromolecularly functional monomers exhibited an imprinting factor of 5.8 compared to those prepared by micromolecularly functional monomers with the imprinting factor of 3.4. The selective and competitive adsorption experiments also demonstrated the imprinted particles made by macromolecularly functional monomers possessed much better selectivity and specific recognition ability for template protein. Therefore, using macromolecularly functional monomers to imprint may overcome the mutability of biomacromolecule typically observed during the preparation of imprinted polymers, and thus promote the further development of imprinting technology.

Click synthesis of boronic acid-functionalized molecularly imprinted silica nanoparticles with polydopamine coating for enrichment of trace glycoproteins

Novel boronic acid-functionalized molecularly imprinted silica nanoparticles with polydopamine coating were prepared and applied to the recognition and enrichment of glycoproteins.

Interfacial molecular imprinting of Stöber particle surfaces: A simple approach to targeted saccharide adsorption

The use of surfactant headgroups for interfacial imprinting is established as a simple and tunable approach to create molecularly imprinted silica nanoparticles based on a modification of the Stöber method. Adsorption of d-glucose and d-xylose (initial concentrations ranging from 0.139 to 1.67mol/l) is measured on silica nanoparticles created by the addition of a glucose-based surfactant (n-octyl-β-d-glucopyranoside (C8G1)) or surfactant mixtures (C8G1 and cetyltrimethylammonium bromide (CTAB)) to Stöber particles shortly after their precipitation. Silica particles synthesized in the presence of C8G1 as an imprinting surfactant have a significantly higher affinity for glucose over xylose (as much as 3.25 times greater at 0.25M saccharide), and an enhanced affinity for glucose relative to non-imprinted silica particles (as much as 4 times greater at 0.25M), which adsorb glucose and xylose similarly. Glucose imprinting is significantly enhanced using a surfactant mixture of 1:1 C8G1/CTAB. The interfacial activity of the nonionic imprinting surfactant at the silica surface is suggested to be improved by the presence of interfacial cationic CTAB, which is driven to the silica surface through electrostatic interactions. The concept of imprinting through the interaction of surfactant headgroups with the soft surface of silica particles is supported by the importance of the time of addition of the surfactants. The greatest enhancement in glucose adsorption is observed when the surfactants are added 1min after precursor addition (at the onset of aggregated particle formation, as indicated by solution turbidity) and the silica affinity for glucose decreases with the time of surfactant addition. The versatility of the surfactant imprinting of Stöber particles is demonstrated by the enhanced adsorption of xylose relative to glucose on particles imprinted using a 1:1 mixture of n-octyl-β-d-xylopyranoside and CTAB, suggesting that the process can be customized to selectively adsorb target molecules of interest.

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.

Synthesis of boronic acid-functionalized molecularly imprinted silica nanoparticles for glycoprotein recognition and enrichment.

A novel imprinting strategy using reversible covalent complexation of glycoprotein is described for creating glycoprotein-specific recognition cavities on 3-acrylamidophenylboronic acid-immobilized silica nanoparticles (SiO2@AAPBA). Two kinds of organic silanes (3-aminopropyltriethoxysilane (APTES) and n-octyltrimethoxysilane (OTMS)) were then polymerized on the surface of SiO2@AAPBA after the template (horseradish peroxidase (HRP)) was covalently immobilized by forming cyclic boronate complexes and their influence was examined. The results showed that not only the silane composition but also the relative proportions play an important role in glycoprotein imprinting. The template recognition properties were evaluated by single-protein or competitive batch rebinding experiments, and the results showed that the HRP-imprinted silica nanoparticles (HRP-MIP silica NPs) exhibited higher recognition ability and selectivity towards the template than the nonimprinted silica NPs and their corresponding imprinted factor (a) reached 2.71. The as-prepared HRP-MIP silica NPs could not only differentiate the template from another glycoprotein, but also enrich HRP from spiked human serum. The good results demonstrated their potential in glycoproteomic analysis.

Water-compatible surface molecularly imprinted silica nanoparticles as pseudostationary phase in electrokinetic chromatography for the enantioseparation of tryptophan

A novel approach based on surface molecularly imprinted technique is demonstrated for the synthesis of surface molecularly imprinted silica nanoparticles (MI-SiNPs) in aqueous media, using l-tryptophan (l-Trp) as template molecule. The MI-SiNPs were fully characterized by transmission electron microscopy (TEM), thermo gravimetric analysis (TGA) and atomic force microscopy (AFM), and the results showed MI-SiNPs thus prepared were uniform in particle size (∼87nm) with a distinct core–shell structure with shell thickness of ∼7nm. The terminal carboxyl groups endowed the MI-SiNPs with good water-compatibility, and so good suspension stability for MI-SiNPs in water-rich buffer solutions can be easily achieved without the addition of any other reagents. When MI-SiNPs were used as pseudostationary phases (PSPs) in electrokinetic chromatography (EKC) for the enantioseparation of Trp, a resolution of 2.73 can be achieved in less than 10min with symmetric peaks. These excellent separation features are mainly attributed to the fast mass transfer and good accessibility of the interaction sites locating at the surface of the MI-SiNPs. The effects of some important separation factors, e.g., pH and concentration of buffer solution, content of MI-SiNPs added, content of organic modifier in buffer solution, on the enantioseparation of Trp were studied, and an optimum separation condition of 30% (v/v) acetonitrile in 20mmolL−1 phosphate buffer (pH 7.0), with 0.50mgmL−1 MI-SiNPs added was ultimately selected.

Facile synthesis of polydopamine-coated molecularly imprinted silica nanoparticles for protein recognition and separation

Surface imprinting over nanostructured matrices is an effective solution to overcome template removal and achieve high binding capacity. In this work, a facile method was developed for synthesis of polydopamine-coated molecularly imprinted silica nanoparticles (PDA-coated MIP silica NPs) based on self-polymerization of dopamine (DA) on the surface of silica NPs in the presence of template protein. Transmission electronic microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR) and thermogravimetric analysis (TGA) showed that PDA layers were successfully attached on the surface of silica NPs and the corresponding thickness was about 5nm, which enabled the MIP silica NPs to have fast binding kinetics and high binding capacity. Under the aqueous media, the imprinted silica NPs showed much higher binding affinity toward template than non-imprinted (NIP) silica NPs. The protein recognition properties were examined by single-protein or competitive batch rebinding experiments and rebinding kinetics study, validating that the imprinted silica NPs have high selectivity for the template. The resultant BHb–MIP silica NPs could not only selectively separate BHb from the protein mixture, but also specifically deplete high-abundance BHb from cattle whole blood. In addition, the stability and regeneration were also investigated, which indicated that the imprinted silica NPs had excellent reusability.

Synthesis of uniformly sized molecularly imprinted polymer-coated silica nanoparticles for selective recognition and enrichment of lysozyme

Combining surface imprinting with nanomaterials is an effective solution to overcome template removal and achieve large binding capacity. In this work, highly monodisperse and uniform-sized silica nanoparticles (NPs) with average diameter of ∼400 nm were synthesized by using tetraethoxysilane (TEOS) as a single precursor, and then vinyl groups were introduced onto the surface of silica NPs by chemical modification of γ-methacryloxypropyltrimethoxysilane (γ-MAPS). Subsequently, the molecularly imprinted polymer (MIP) coating was copolymerized and anchored onto the surface of vinyl modified silica NPs dispersed in aqueous media with lysozyme (Lyz) as a template. The morphology and structure property of the resultant MIP-coated silica NPs were characterized by scanning electronic microscopy (SEM), transmission electronic microscopy (TEM) and Fourier transform infrared spectroscopy (FT-IR). The polymerization and adsorption conditions were investigated in detail in order to obtain the highest selectivity and binding capacity. Under the optimized conditions, the imprinted nanoparticles showed higher binding affinity toward the template than non-imprinted (NIP) nanoparticles, and the corresponding imprinted factor (a) reached 1.68. The specificity for Lyz recognition was evaluated with competitive experiments, indicating the imprinted nanoparticles have a higher selectivity for the template. The resultant Lyz-MIP silica NPs could not only selectively extract a target protein from mixed proteins, but also specifically enrich Lyz from human serum. In addition, the stability and regeneration were also investigated, which indicated the imprinted silica NPs had excellent reusability.

Preparation and Characterization of Paclitaxel Imprinted Silica Nanoparticles

Highly selective molecularly imprinted layer-coated silica nanoparticles for paclitaxel were synthesized by molecular imprinting technique with a sol–gel process on the supporter of silica nanoparticles. The morphology of the obtained polymers was characterized by scanning electron microscopy (SEM). The binding properties of the imprinted polymers were evaluated through the equilibrium rebinding experiments. Scatchard analysis revealed that two classes of binding sites were formed in the imprinted polymers with equilibrium dissociation constants of 0.0509 g•L-1and 0.0094 g•L-1, respectively. Paclitaxel and its analogue were employed for selectivity tests. The results indicated that the imprinted polymers exhibited good selectivity and specificity toward paclitaxel.

Preparation of estriol–molecularly imprinted silica nanoparticles for determining oestrogens in milk tablets

In this paper, the molecularly imprinted polymer layer of estriol at the silica nanoparticles surface with selective recognition had been constructed. The methacryl groups of functional monomer at the silica nanoparticles surface were acted as reactive sites to induce imprinting polymerisation. The absorption capacity results showed that the molecularly imprinted polymers had an excellent combining affinity, recognition selectivity and fast kinetics. Furthermore, the molecularly imprinted polymers were successfully used as absorbent of dispersive solid-phase extraction coupled with high-performance liquid chromatography to determinate trace estriol and estradiol in milk tablets. The high recoveries yielded of 89.1–93.5% were achieved with the relative standard deviations less than 9.4%. So, the molecularly imprinted polymers are the effective absorbents for the separation and enrichment of oestrogens in the complex matrices samples.