Huijun Jiang

Tuning of the vinyl groups’ spacing at surface of modified silica in preparation of high density imprinted layer-coated silica nanoparticles: A dispersive solid-phase extraction materials for chlorpyrifos

This paper reports the preparation of high density imprinted layer-coated silica nanoparticles toward selective recognition and fast enrichment of chlorpyrifos (CP) from complicated matrices. The molecularly imprinted polymers (MIPs) were successfully coated at the surface of modified silica through using the chemical immovable vinyl groups at the nanoparticles surface, followed by the graft copolymerization of methacrylic acid (MAA) and ethylene glycol dimethacrylate (EGDMA) in the presence of templates CP. It has been demonstrated that the space of end vinyl groups at the surface of silica can be controlled by changing the condition of chemical modification, regulating the thickness of imprinted shells and the density of efficient imprinted sites. After removal of templates by solvent extraction, the recognition sites of CP were created in the polymer coating layer. The CP-imprinted nanoparticles exhibited high recognition selectivity and binding affinity to CP analyte. When the CP-imprinted nanoparticles were used as dispersive solid-phase extraction (dSPE) materials, the high recovery yields of 76.1-93.5% from various spiked samples with only 1microg/mL analyte were achieved by one-step extraction. These results reported herein provide the possibility for the separation and enrichment of CP from complicated matrices by the molecular imprinting modification at the surface of common silica nanoparticles.

Magnetic sensing film based on Fe3O4@Au-GSH molecularly imprinted polymers for the electrochemical detection of estradiol

A novel magnetic molecularly imprinted sensing film (MMISF) was fabricated for the determination of estradiol (E2) based on magnetic glassy carbon electrode (MGCE) and magnetic molecularly imprinted polymers (MMIPs). The MMIPs were synthesized by in situ polymerization of glutathione (GSH)-functionalized gold (Au)-coated Fe3O4 (Fe3O4@Au-GSH) nanocomposites and aniline. The MMISF was constructed with MMIPs via a kind of soft modification where MMIPs were assembled and immobilized on the surface of MGCE or removed from it by freely installing a magnet into MGCE or not. The E2-MMIPs were obtained by MMIPs recognizing E2 from sample, and the electrochemical detection was carried out after forming the soft modification sensing film by putting MGCE into the E2-MMIPs suspension liquid. Afterwards, the soft modification MMISF was peeled off from the electrode by removing the magnet from MGCE. The interface of the electrode could be quickly refreshed through simple treatment for the next detection. The structures and morphologies of Fe3O4@Au-GSH, MMIPs and MMISF were investigated by Fourier transform infrared spectrometer, ultraviolet and visible spectrophotometer, scanning electron microscope and atomic force microscope. In addition, the MMISF was successfully used for detecting E2 in milk powder with good sensitivity, selectivity, reproducibility and efficiency. The linear range of the MMISF for E2 was 0.025-10.0μmolL(-1) with the limit of detection of 2.76nmolL(-1) (S/N= 3).

Novel electrochemical sensing platform based on magnetic field-induced self-assembly of Fe3O4@Polyaniline nanoparticles for clinical detection of creatinine

A novel electrochemical sensing platform based on magnetic field-induced self-assembly of Fe3O4@Polyaniline nanoparticles (Fe3O4@PANI NPs) has been for the first time fabricated for the sensitive detection of creatinine in biological fluids. The template molecule, creatinine, was self-assembled on the surface of Fe3O4@PANI NPs together with the functional monomer aniline by the formation of N-H hydrogen bonds. After pre-assembled, through the magnetic-induction of the magnetic glassy carbon electrode (MGCE), the ordered structure of molecularly imprinted polymers (MIPs) were established by the electropolymerization and assembled on the surface of MGCE with the help of magnetic fields by a simple one-step approach. The structural controllability of the MIPs film established by magnetic field-induced self-assembly was further studied. The stable and hydrophilic Fe3O4@PANI can not only provide available functionalized sites with which the template molecule creatinine can form hydrogen bond by the abundant amino groups in PANI matrix, but also afford a promoting pathway for electron transfer. The as-prepared molecularly imprinted electrochemical sensor (MIES) shows good stability and reproducibility for the determination of creatinine with the detection limit reached 0.35 nmol L(-1) (S/N=3). In addition, the highly sensitive and selective MIES has been successfully used for the clinical determination of creatinine in human plasma and urine samples. The average recoveries were 90.8-104.9% with RSD lower than 2.7%.

Fe3O4@rGO doped molecularly imprinted polymer membrane based on magnetic field directed self-assembly for the determination of amaranth

Based on magnetic field directed self-assembly (MDSA) of Fe3O4@rGO composites, a novel magnetic molecularly imprinted electrochemical sensor (MIES) was fabricated and developed for the determination of the azo dye amaranth. Fe3O4@rGO composites were obtained by a one-step approach involving the initial intercalating of iron ions between the graphene oxide layers via the electrostatic interaction, followed by the reduction with hydrazine hydrate to deposit Fe3O4 nanoparticles onto the reduced oxide graphene nanosheets. In molecular imprinting, the complex including the function monomer of aniline, the template of amaranth and Fe3O4@rGO was pre-assembled through π-π stacking and hydrogen bonding interactions, and then was self-assembled on the surface of magnetic glassy carbon electrode (MGCE) with the help of magnetic field induction before electropolymerization. The structures and morphologies of Fe3O4@rGO and the doped molecularly imprinted polymers (MIPs) were investigated by Fourier transform infrared spectrometer (FT-IR), Raman spectra and scanning electron microscope (SEM). Besides, the characterization by differential pulse voltammetry (DPV) showed that Fe3O4@rGO composites promoted the electrical conductivity of the imprinted sensors when doped into the MIPs. The adsorption isotherms and adsorption kinetics were employed to evaluate the performances of MIES. The detection of amaranth was achieved via the redox probe K3[Fe(CN)6] by blocking the imprinted cavities, which avoided the interferences of oxidation products and analogs of amaranth. Furthermore, the prepared MIES exhibited good sensitivity, selectivity, reproducibility and efficiency for detecting amaranth in fruit drinks. The average recoveries were 93.15-100.81% with the RSD <3.0%.

Facile and controllable one-step fabrication of molecularly imprinted polymer membrane by magnetic field directed self-assembly for electrochemical sensing of glutathione

Based on magnetic field directed self-assembly (MDSA) of the ternary Fe3O4@PANI/rGO nanocomposites, a facile and controllable molecularly imprinted electrochemical sensor (MIES) was fabricated through a one-step approach for detection of glutathione (GSH). The ternary Fe3O4@PANI/rGO nanocomposites were obtained by chemical oxidative polymerization and intercalation of Fe3O4@PANI into the graphene oxide layers via π-π stacking interaction, followed by reduction of graphene oxide in the presence of hydrazine hydrate. In molecular imprinting process, the pre-polymers, including GSH as template molecule, Fe3O4@PANI/rGO nanocomposites as functional monomers and pyrrole as both cross-linker and co-monomer, was assembled through N-H hydrogen bonds and the electrostatic interaction, and then was rapidly oriented onto the surface of MGCE under the magnetic field induction. Subsequently, the electrochemical GSH sensor was formed by electropolymerization. In this work, the ternary Fe3O4@PANI/rGO nanocomposites could not only provide available functionalized sites in the matrix to form hydrogen bond and electrostatic interaction with GSH, but also afford a promoting network for electron transfer. Moreover, the biomimetic sensing membrane could be controlled more conveniently and effectively by adjusting the magnetic field strength. The as-prepared controllable sensor showed good stability and reproducibility for the determination of GSH with the detection limit reaching 3 nmol L(-1) (S/N = 3). In addition, the highly sensitive and selective biomimetic sensor has been successfully used for the clinical determination of GSH in biological samples.

One-step facile synthesis of novel β-amino alcohol functionalized carbon dots for the fabrication of a selective copper ion sensing interface based on the biuret reaction

In this paper, a facile and one-step hydrothermal carbonization approach has been developed for the first time to synthesize β-amino alcohol functionalized fluorescent carbon dots (CDs) with L-phenylalaninol as the sole precursor source. The present CDs with β-amino alcohol moieties attached to the surface were successfully applied to fabricate a novel, simple fluorescent sensing interface for selective detection of copper ions under basic conditions based on the biuret reaction. The added copper ions, not only lead to the specific cross-linked formation of the violet complex with the two β-amino alcohol units on the surface of the CDs, but also in turn lead to the aggregation of the functionalized CDs and induce fluorescence quenching. Such fluorescence responses can be used for monitoring copper ions in the range of 0.01–100 μmol L−1 under basic conditions with the limit of detection (LOD) as low as 3.2 nmol L−1. Moreover, the proposed fluorescent sensor can resist interferences from other metal ions and can be employed for the detection of copper ions in water samples. Due to the simplicity and effectiveness, it exhibits great promise as a practical sensing platform for copper ions especially under basic conditions.

Selective separation and determination of the synthetic colorants in beverages by magnetic solid-phase dispersion extraction based on a Fe3O4/reduced graphene oxide nanocomposite followed by high-performance liquid chromatography with diode array detection

A facile adsorbent, a nanocomposite of Fe3 O4 and reduced graphene oxide, was fabricated for the selective separation and enrichment of synthetic aromatic azo colorants by magnetic solid-phase dispersion extraction. The nanocomposite was synthesized in a one-step reduction reaction and characterized by atomic force microscopy, scanning electron microscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, X-ray diffraction and Brunauer-Emmett-Teller analysis. The colorants in beverages were quickly adsorbed onto the surface of the nanocomposite with strong π-π interactions between colorants and reduced graphene oxide, and separated with the assistance of an external magnetic field. Moreover, the four colorants in beverages were detected at different wavelengths by high performance liquid chromatography with diode array detection. A linear dependence of peak area was obtained over 0.05-10 μg/mL with the limits of detection of 10.02, 11.90, 10.41, 15.91 ng/mL for tartrazine, allure red, amaranth, and new coccine, respectively (signal to noise = 3). The recoveries for the spiked colorants were in the range of 88.95-95.89% with the relative standard deviation less than 2.66%. The results indicated that the nanocomposite of Fe3 O4 and reduced graphene oxide could be used as an excellent selective adsorbent for aromatic compounds and has potential applications in sample pretreatment.

Silver-Incorporated Mussel-Inspired Polydopamine Coatings on Mesoporous Silica as an Efficient Nanocatalyst and Antimicrobial Agent

To tackle severe environmental pollution, a search for materials by economical and eco-friendly preparations is demanding for public health. In this study, a novel in situ method to form silver nanoparticles under mild conditions was developed using biomimetic reducing agents of polydopamine coated on the rodlike mesoporous silica of SBA-15. The synthesized SBA-15/polydopamine (PDA)/Ag nanocomposites were characterized by a combination of physicochemical and electrochemical methods. 4-Nitrophenol (4-NP) and methylene blue (MB) were used as models for the evaluation of the prepared nanocatalysts of SBA-15/PDA/Ag in which the composite exhibited enhanced catalytic performance toward degrading 4-NP in solution and MB on the membrane, respectively. Additionally, compared with that of solid core-shell SiO2/PDA/Ag, tubular SBA-15/PDA/Ag showed the prolonged inhibitory effect on microbial growth as typified by Escherichia coli (60 h), Staphylococcus aureus (36 h), and Aspergillus fumigatus (60 h), which demonstrated efficient control of silver nanoparticles release from the mesopores. The constructed dual-functional SBA-15/PDA/Ag as the long-term antimicrobial agent and the catalyst of industrial products provides an integrated nanoplatform to deal with environmental concerns.

Multifunctional Bismuth Oxychloride/Mesoporous Silica Composites for Photocatalysis, Antibacterial Test, and Simultaneous Stripping Analysis of Heavy Metals

The increasing complexity of environmental pollution nowadays poses a severe threat to the public health, which attracts considerable attentions in searching for nanomaterials of multiproperty. In this study, mesoporous silica of KIT-6-encapsulated bismuth oxychloride (BiOCl), an intrinsically multifunctional material exhibiting bunched structure in the composites, are facilely prepared under hydrothermal conditions. Subsequently, the produced materials of multifunctionality were applied for photocatalysis, antibacterial test, and simultaneous determination of heavy metals including lead and cadmium. A combination of physiochemical characterizations have revealed that the BiOCl–KIT-6 composites exhibit enlarged yet refined surface morphology contributing to the improved photocatalytic ability with a band gap of 3.06 eV at a molecular ratio of 8Bi–Si. Moreover, the antibacterial activities of our BiOCl–KIT-6 composites were explored, and possible antimicrobial mechanism related to the production of reactive oxygen species was discussed. Furthermore, a sensitive electrochemical determination of heavy metals of lead and cadmium using square-wave anodic stripping voltammetry was also achieved. The composites-modified glassy carbon electrode displays a linear range of calibration curve from 0.2 to 300 μg/L with a detection limit of 0.05 μg/L (Pb2+) and 0.06 μg/L (Cd2+), respectively.

Raspberry-Like Bismuth Oxychloride on Mesoporous Siliceous Support for Sensitive Electrochemical Stripping Analysis of Cadmium

BiOCl-SiO2 KIT-6 composite materials with raspberry-like structures are facilely prepared under hydrothermal conditions. The mesoporous siliceous support of SiO2 KIT-6-incorporated BiOCl with enlarged yet refined surface morphology characterized by physiochemical methods exhibits an improved electrochemical performance. A sensitive electrochemical detection method of cadmium concentration using square wave anodic stripping voltammetry was developed based on BiOCl-SiO2 KIT-6 composite-modified glassy carbon electrodes, which displayed wide linear ranges of 0.5 to 10 μg/L and 10 to 300 μg/L and a detection limit of 65 ng/L. The sensitive, versatile and eco-friendly sensor was successfully applied for the determination of cadmium-spiked human blood samples.