Minghua Lu

Enzymatic Oxydate-Triggered Self-Illuminated Photoelectrochemical Sensing Platform for Portable Immunoassay Using Digital Multimeter

Herein a novel split-type photoelectrochemical (PEC) immunosensing platform was designed for sensitive detection of low-abundance biomarkers (prostate-specific antigen, PSA, used in this case) by coupling a peroxyoxalate chemiluminescence (PO-CL) self-illuminated system with digital multimeter (DMM) readout. The PEC detection device consisted of a capacitor/DMM-joined electronic circuit and a PO-CL-based self-illuminated cell. Initially, reduced graphene oxide-doped BiVO4 (BiVO4-rGO) photovoltaic materials with good photoelectric properties was integrated into the capacitor/DMM-joined circuit for photocurrent generation in the presence of hydrogen peroxide (H2O2, as the hole-trapping reagent). A sandwich-type immunoreaction with target PSA was carried out in capture antibody-coated microplates by using glucose oxidase/detection antibody-conjugating gold nanoparticle (pAb2-AuNP-GOx). Accompanying the sandwiched immunocomplex, the labeled GOx could oxidize glucose to produce H2O2. The as-generated H2O2 could act as the coreaction reagent to trigger the chemiluminescence of the peroxyoxalate system and the PEC reaction of the BiVO4-rGO. Meanwhile, the self-illuminated light could induce photovoltaic material (BiVO4-rGO) to produce a voltage that was utilized to charge an external capacitor. With the switch closed, the capacitor could discharge through the DMM and provide an instantaneous current. Different from conventional PEC immunoassays, the as-generated photoelectron was stored in the capacitor and released instantaneously to amplify the photocurrent. Under the optimal conditions, the transient current increased with the increasing target PSA concentration in the dynamic working range from 10 pg mL(-1) to 80 ng mL(-1) with a detection limit (LOD) of 3 pg mL(-1). This work demonstrated for the first time that the peroxyoxalate CL system could be used as a suitable substitute of physical light source to apply in PEC immunoassay. In addition, this methodology afforded good reproducibility, precision, and high specificity, and the method accuracy matched well with the commercial PSA ELISA kit. Importantly, the developed split-type photoelectrochemical immunoassay could not only avoid the interfering of the biomolecules relative to the photovoltaic materials but also eliminate the need of an exciting light source and expensive instrumentation, thus representing a user-friendly and low-cost assay protocol for practical utilization in quantitative low-abundance proteins.

Portable and quantitative monitoring of heavy metal ions using DNAzyme-capped mesoporous silica nanoparticles with a glucometer readout

A portable and quantitative monitoring protocol for sensitive detection of lead ions is designed, based on target-responsive cargo release from Pb2+-specific DNAzyme-capped mesoporous silica nanoparticles (MSNs), by coupling with a widely accessible personal glucose meter (PGM). Initially, glucose molecules are loaded into the pores of the MSNs, the pores are then capped with Pb2+-specific DNAzymes. Upon target introduction, the molecular gates open, resulting in release of the cargo from the pores. The released glucose can be quantitatively monitored using a portable PGM. Under optimal conditions, the as-prepared sensing platform presents good analytical properties for the determination of the target Pb2+ ions, and allows detection of Pb2+ at concentrations as low as 1.0 pM. Importantly, the portable sensing platform has the advantages of simple, on-site, user-friendly and low-cost assessment and has tremendous potential for quantitative detection of non-glucose targets by the public.

Mesoporous carbon-enriched palladium nanostructures with redox activity for enzyme-free electrochemical immunoassay of brevetoxin B

A new signal amplification strategy based on mesoporous carbon-enriched palladium nanostructure (MSC-PdNS) was designed for enzyme-free electrochemical immunoassay of brevetoxin B (BTB) in marine toxins. The assay was carried out on a BTB-bovine serum albumin-functionalized electrode by using monoclonal mouse anti-BTB-labeling MSC-PdNS as the signal-transduction tag. A competitive-type assay protocol was successfully introduced to develop a high-efficiency enzyme-free immunoassay accompanying the doped palladium nanostructure into MSC-PdNS toward reduction of H2O2. Under the optimal conditions, the catalytic current decreased with the increment of BTB concentration in the range from 0.01 to 10 ng mL(-1) with a detection limit (LOD) of 5.0 pg mL(-1) BTB at the 3s(blank) criterion. The selectivity and precision were acceptable. In addition, the methodology was further validated for assaying spiked seafood samples, and consistent results between the electrochemical immunoassay and the referenced enzyme immunoassay were obtained. Importantly, the enzyme-free electrochemical immunoassay provides a promising approach for rapid screening of marine toxin because of its simplicity, low cost, sensitivity, specificity and without the need of sample pretreatment.

Gold nanocatalyst-based immunosensing strategy accompanying catalytic reduction of 4-nitrophenol for sensitive monitoring of chloramphenicol residue.

A new competitive-type immunosensing system based on gold nanoparticles toward catalytic reduction of 4-nitrophenol (4-NP) was developed for sensitive monitoring of antibiotic residue (chloramphenicol, CAP, used in this case) by using ultraviolet-visible (UV-vis) spectrometry. Gold nanoparticle (AuNP) with 16 nm in diameter was initially synthesized and functionalized with CAP-bovine serum albumin (CAP-BSA) conjugate, which were used as the competitor on monoclonal anti-CAP antibody-coated polystyrene microtiter plate (MTP). In the presence of target CAP, the labeled CAP-BSA on the AuNP competed with target CAP for the immobilized antibody on the MTP. The conjugated amount of CAP-BSA-AuNP on the MTP decreased with the increase of target CAP in the sample. Upon addition of 4-NP and NaBH4 into the MTP, the carried AuNP could catalytically reduce 4-NP to 4-aminophenol (4-AP), and the as-produced 4-AP could be monitored by using UV-vis absorption spectroscopy. Experimental results indicated that the absorbance at 403 nm increased with the increment of target CAP concentration in the sample, and exhibited a dynamic range from 0.1 to 100 ng mL(-1) with a detection limit (LOD) of 0.03 ng mL(-1) at the 3s(blank) level. Intra- and inter-assay coefficients of variation were lower than 5.5% and 8.0%, respectively. In addition, the methodology was evaluated for CAP spiked honey and milk samples, respectively. The recovery was 92-112%.

Novel electrochemical sensing platform for quantitative monitoring of Hg(II) on DNA-assembled graphene oxide with target recycling.

This work designs a new electrochemical sensing platform for the quantitative monitoring of mercury ion (Hg(2+)) on poly-T(15) oligonucleotide-functionalized graphene oxide by coupling with DNase I-assisted target recycling amplification. The assay was carried out on the basis of T-Hg(2+)-T coordination chemistry by using target-induced dissociation of indicator-labeled poly-T(15) oligonucleotide from graphene oxide nanosheets. The electronic signal was amplified through DNase I-triggered target recycling. Experimental results indicated that the amperometric response of DNA-based sensing platform deceased with the increasing Hg(2+) concentration in the sample, and has a detection limit of 0.12nM with a dynamic working range of up to 50nM. Our strategy afforded exquisite selectivity for Hg(2+) against other environmentally related metal ions. More significantly, this methodology displayed high reproducibility and acceptable accuracy, thus representing an optional sensing scheme for the screening of Hg(2+) in environmental water samples.

Graphene oxide-SiO2 nanocomposite as the adsorbent for extraction and preconcentration of plant hormones for HPLC analysis

In this research, a modified Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) method based on graphene oxide@SiO2(SiO2@GO) nanocomposite as adsorbent of dispersive solid-phase extraction (dSPE) combined with high performance liquid chromatography (HPLC) for the analysis of four plant hormones in different plants was established. The as-prepared SiO2@GO was characterized by scanning electron microscopy, transmission electron microscopy and infrared spectroscopy. The experimental conditions for dSPE, including the ratio of material to liquid, pH of sample, adsorption and desorption time, desorption temperature as well as desorption solution, were investigated. The detection limits for the analysis of indole-3-acetic acid, indole-3-butyric acid, 1-naphthylacetic acid and abscisic acid were achieved below 0.05μgmL-1. The established method was applied to the analysis of the plant hormones in fruits, vegetables and other food samples. The obtained results indicated that the method was sensitive, accurate, convenient and quick, which provided an alternative analytical approach for plant hormones in complex matrices.

Analysis of flavors and fragrances by HPLC with Fe3O4@GO magnetic nanocomposite as the adsorbent

In this article, a method for the analysis of flavors and fragrances including ethyl vanillin, trans-cinnamic acid, methyl cinnamate, ethyl cinnamate, and benzyl cinnamate in foods by HPLC with Fe3O4@GO nanocomposite as the adsorbent of magnetic solid-phase extraction was developed. The magnetic Fe3O4@GO nanocomposite was prepared and characterized by transmission electron microscope, infrared spectroscopy, X-ray diffraction and vibrating sample magnetometer. The as-prepared Fe3O4@GO nanocomposite was used as adsorbent for extraction and preconcentration of flavors and fragrances in foods. The extraction and desorption conditions including amount of materials, extraction time and desorption solvents were investigated. The analytes were separated within 10min and detected with LODs ranged from 0.02 to 0.04μg/mL. The recovery obtained from the analysis of spiked juice sample was between 71.5% and 112.4% with RSDs lower than 4.14%. The developed method was successfully applied to the analysis of real samples including orange juice, chocolate and fruit sugar.

Nanomaterials as Assisted Matrix of Laser Desorption/Ionization Time-of-Flight Mass Spectrometry for the Analysis of Small Molecules

Matrix-assisted laser desorption/ionization (MALDI), a soft ionization method, coupling with time-of-flight mass spectrometry (TOF MS) has become an indispensible tool for analyzing macromolecules, such as peptides, proteins, nucleic acids and polymers. However, the application of MALDI for the analysis of small molecules (<700 Da) has become the great challenge because of the interference from the conventional matrix in low mass region. To overcome this drawback, more attention has been paid to explore interference-free methods in the past decade. The technique of applying nanomaterials as matrix of laser desorption/ionization (LDI), also called nanomaterial-assisted laser desorption/ionization (nanomaterial-assisted LDI), has attracted considerable attention in the analysis of low-molecular weight compounds in TOF MS. This review mainly summarized the applications of different types of nanomaterials including carbon-based, metal-based and metal-organic frameworks as assisted matrices for LDI in the analysis of small biological molecules, environmental pollutants and other low-molecular weight compounds.

In situ synthesis of fluorescent polydopamine nanoparticles coupled with enzyme-controlled dissolution of MnO2 nanoflakes for a sensitive immunoassay of cancer biomarkers

Herein, a novel immunosensing strategy was designed for the sensitive fluorescence/visual detection of alpha-fetoprotein (AFP), by combining the enzyme-controlled formation of polydopamine (PDA) nanoparticles with the dissolution of manganese dioxide (MnO2) nanoflakes. Initially, a sandwich-type immunoreaction was fabricated on a capture antibody-coated microplate by using detection antibody/ascorbate oxidase-conjugating gold nanoparticles (AOX-AuNP-Ab2) as the detection probe. The ascorbate oxidase, carried within the immunocomplex, oxidized ascorbic acid (AA) to dehydroascorbic acid (DAA) to inhibit the dissolution of the MnO2 nanoflakes. This resulted in an increment in fluorescent PDA nanoparticles from the oxidation of dopamine (DA) into its quinone derivative with the aid of the MnO2 nanoflakes. Under optimal conditions, the fluorescence intensity of the PDA nanoparticles increased with increasing AFP concentration within the dynamic working range of 0.05-20 ng mL-1, with a detection limit (LOD) of 17.3 pg mL-1. The sensor also showed high specificity and acceptable accuracy for the detection of target AFP against other potential cancer biomarkers. Importantly, this study demonstrated for the first time that fluorescent PDA nanoparticles could be used as signal-generation tags and applied to an enzyme immunoassay. Although this methodology focused on AFP detection, it would be suitable for the detection of other cancer biomarkers if the corresponding antibodies were employed.

Highly Efficient, Rapid, and Simultaneous Removal of Cationic Dyes from Aqueous Solution Using Monodispersed Mesoporous Silica Nanoparticles as the Adsorbent

In this work, a highly efficient and rapid method for simultaneously removing cationic dyes from aqueous solutions was developed by using monodispersed mesoporous silica nanoparticles (MSNs) as the adsorbents. The MSNs were prepared by a facile one-pot method and characterized by scanning electron microscopy, transmission electron microscopy, Fourier-transform infrared spectroscopy, and Brunauer-Emmett-Teller. Experimental results demonstrated that the as-prepared MSNs possessed a large specific surface area (about 585 m2/g), uniform particle size (about 30 nm), large pore volume (1.175 cm3/g), and narrow pore size distribution (1.68 nm). The materials showed highly efficient and rapid adsorption properties for cationic dyes including rhodamine B, methylene blue, methyl violet, malachite green, and basic fuchsin. Under the optimized conditions, the maximum adsorption capacities for the above mentioned cationic dyes were in the range of 14.70 mg/g to 34.23 mg/g, which could be achieved within 2 to 6 min. The probable adsorption mechanism of MSNs for adsorption of cationic dyes is proposed. It could be considered that the adsorption is mainly controlled by electrostatic interactions and hydrogen bonding between the cationic dyes and MSNs. As a low-cost, biocompatible, and environmentally friendly material, MSNs have a potential application in wastewater treatment for removing some environmental cationic contaminants.