Mei-Jin Li

A dual-mode nanosensor based on carbon quantum dots and gold nanoparticles for discriminative detection of glutathione in human plasma

Glutathione (GSH) plays key roles in biological systems and serves many cellular functions. Since biothiols all incorporate thiol, carboxylic and amino groups, discriminative detection of GSH over cysteine (Cys) and homocysteine (Hcy) is still challenging. We herein report a dual-mode nanosensor with both colorimetric and fluorometric readout based on carbon quantum dots and gold nanoparticles for discriminative detection of GSH over Cys/Hcy. The proposed sensing system consists of AuNPs and fluorescent carbon quantum dots (CQDs), where CQDs function as fluorometric reporter, and AuNPs serve a dual function as colorimetric reporter and fluorescence quencher. The mechanism of the nanosensor is based on two distance-dependent phenomenons, color change of AuNPs and FRET. Through controlling the surface properties of as-prepared nanoparticles, the addition of CQDs into AuNPs colloid solution might induce the aggregation of AuNPs and CQDs, leading to AuNPs color changing from red to blue and CQDs fluorescence quench. However, the presence of GSH can protect AuNPs from being aggregated and enlarge the inter-particle distance, which subsequently produces color change and fluorescent signal recovery. The nanosensor described in this report reflects on its simplicity and flexibility, where no further surface functionalization is required for the as-prepared nanoparticles, leading to less laborious and more cost-effective synthesis. The proposed dual-mode nanosensor demonstrated highly selectivity toward GSH, and allows the detection of GSH as low as 50 nM. More importantly, the nanosensor could not only function in aqueous solution for GSH detection with high sensitivity but also exhibit sensitive responses toward GSH in complicated biological environments, demonstrating its potential in bioanalysis and biodection, which might be significant in disease diagnosis in the future.

Multifunctional Ruthenium(II) Polypyridine Complex-Based Core–Shell Magnetic Silica Nanocomposites: Magnetism, Luminescence, and Electrochemiluminescence

Multifunctional nanoparticles (NPs) that consist of silica-coated magnetic cores and luminescent ruthenium(II) polypyridine complexes have been prepared. These multifunctional nanocomposites were shown to exhibit superparamagnetic behavior, high emission intensity, and electrochemiluminescence. An intense low-oxidation-potential electrochemiluminescence signal was observed by attachment of these functional NPs onto a fluorosurfactant-modified gold (Au(m)) electrode via application of an external magnetic field.

Quinoline derivative-functionalized carbon dots as a fluorescent nanosensor for sensing and intracellular imaging of Zn2+

Surface functionalization of nanomaterials with highly specific recognition elements, such as biomolecules and organic molecules, has made possible many novel nanosensors for bio/chemical analysis and target bioimaging. In this report, a fluorescent nanosensor which exhibits highly specific recognition capability towards Zn2+ over competing metal ions has been developed through covalently functionalizing carbon dots (C-dots) with the quinoline derivatives which show response to Zn2+. The nanosensor exhibits excellent water solubility, biocompatibility, and cell-membrane permeability, and demonstrates high selectivity towards Zn2+ with a detection limit as low as 6.4 nM. Additionally, the rapid response of the nanosensor towards Zn2+ can be achieved within 1 min. The large amount of recognition units on the outer surface of an individual nanoparticle enables the signal amplification, hence making the immediate and highly sensitive detection of Zn2+ possible. Therefore, a reliable and highly specific nanosensor has been demonstrated for both rapid quantitative detection of Zn2+ in aqueous solution and real-time imaging of intracellular Zn2+, suggesting its potential and significance in bioanalysis and biomedical detection in the future.

Reduced graphene oxide/BiFeO3 nanohybrids-based signal-on photoelectrochemical sensing system for prostate-specific antigen detection coupling with magnetic microfluidic device

A novel magnetic controlled photoelectrochemical (PEC) sensing system was designed for sensitive detection of prostate-specific antigen (PSA) using reduced graphene oxide-functionalized BiFeO3 (rGO-BiFeO3) as the photoactive material and target-triggered hybridization chain reaction (HCR) for signal amplification. Remarkably enhanced PEC performance could be obtained by using rGO-BiFeO3 as the photoelectrode material due to its accelerated charge transfer and improved the visible light absorption. Additionally, efficient and simple operation could be achieved by introducing magnetic controlled flow-through device. The assay mainly involved in anchor DNA-conjugated magnetic bead (MB-aDNA), PSA aptamer/trigger DNA (Apt-tDNA) and two glucose oxidase-labeled hairpins (H1-GOx and H2-GOx). Upon addition of target PSA, the analyte initially reacted with the aptamer to release the trigger DNA, which partially hybridized with the anchor DNA on the MB. Thereafter, the unpaired trigger DNA on the MB opened the hairpin DNA structures in sequence and propagated a chain reaction of hybridization events between two alternating hairpins to form a long nicked double-helix with numerous GOx enzymes on it. Subsequently, the enzymatic product (H2O2) generated and consumed the photo-excited electrons from rGO-BiFeO3 under visible light irradiation to enhance the photocurrent. Under optimal conditions, the magnetic controlled PEC sensing system exhibited good photocurrent responses toward target PSA within the linear range of 0.001 - 100ng/mL with a detection limit of 0.31pg/mL. Moreover, favorable selectivity, good stability and satisfactory accuracy were obtained. The excellent analytical performance suggested that the rGO-BiFeO3-based PEC sensing platform could be a promising tool for sensitive, efficient and low cost detection of PSA in disease diagnostics.

Bio-bar-code-based photoelectrochemical immunoassay for sensitive detection of prostate-specific antigen using rolling circle amplification and enzymatic biocatalytic precipitation

Methods based on photoelectrochemistry have been developed for immunoassay, but most involve in a low sensitivity and a relatively narrow detectable range. Herein a new bio-bar-code-based split-type photoelectrochemical (PEC) immunoassay was designed for sensitive detection of prostate-specific antigen (PSA), coupling rolling circle amplification (RCA) with enzymatic biocatalytic precipitation. The bio-bar-code-based immunoreaction was carried out on monoclonal anti-PSA antibody (mAb1)-coated microplate using primer DNA and polyclonal anti-PSA antibody-conjugated gold nanoparticle (pDNA-AuNP-pAb2) with a sandwich-type assay format. Accompanying the immunocomplex, the labeled primer DNA on gold nanoparticle readily triggered RCA reaction in the presence of padlock probe/dNTPs/ligase/polymerase. The RCA product with a long single-stranded DNA could cause the formation of numerous hemin/G-quadruplex-based DNAzyme concatamers. With the assistance of nicking endonuclease, DNAzyme concatamers were dissociated from gold nanoparticle, which catalyzed the precipitation of 4-chloro-1-naphthol in the presence of H2O2 onto CdS nanorods-coated electrode (as the photoanode for the generated holes). The formed insoluble precipitate inhibited the electron transfer from the solution to CdS nanorods-modified electrode by using ascorbic acid as the electron donor. Under the optimum conditions, the photocurrent of the modified electrode decreased with the increasing of PSA concentration. A detectable concentration for target PSA with this system could be achieved as low as 1.8pgmL-1. In addition, our strategy also showed good reproducibility, high specificity and accuracy matched well with commercial PSA ELISA kits for real sample analysis. These remarkable properties revealed that the developed PEC immunoassay has great potential as a useful tool for the detection of PSA in practical application.

Determination of iron(III) based on the fluorescence quenching of rhodamine B derivative

A new method for determination of iron(III) has been developed using a kind of rhodamine B derivative fluorescent probe, rhodamine amide (RHA), in acidic HAc-NaAc buffer solution. In this approach, the heavy atom effect of I₃(-) was applied to quench the fluorescence of RHA. When iron(III) and KI coexisted in HAc-NaAc buffer solution, iron(III) reacted with the excess KI to produce I₃(-) that quenched the fluorescence of RHA through the formation of a non-fluorescence compound. The results showed that the fluorescence intensity decrease of RHA presented a good linear relationship with the iron(III) concentrations in the range from 0.5 to 5.0 μmol L(-1) with the correlation coefficient of 0.9970, and the detection limit was 0.3 μmol L(-1) iron(III). The approach was applied to determination of iron(III) in water samples, and the recovery was found to be from 80.7% to 100. 8%.

Electrochemiluminescence of ruthenium(II) complexes functionalized with crown ether pendants and effects of cation binding

Electrochemiluminescence (ECL) of a series of ruthenium(II) diimine complexes with appended crown ethers derived from 1,10-phenanthroline was studied via either the annihilation route or the coreactant schemes, and the ECL efficiency has been determined. The effect of an FSN surfactant on the ECL properties was also studied in buffer solutions. The effect of cation binding on the ECL behavior was examined. The ECL intensity of [Ru(bpy)2(phen-2NH)](ClO4)2 has been found to be strongly enhanced upon binding with Zn2+ and alkaline-earth metal ions. The X-ray crystal structure of [Ru(bpy)2(phen-2NH)](ClO4)2 has also been determined.

Coupling gold nanoparticles to silica nanoparticles through disulfide bonds for?glutathione detection

Advances in the controlled assembly of nanoscale building blocks have resulted in functional devices which can find applications in electronics, biomedical imaging, drug delivery etc. In this study, novel covalent nanohybrid materials based upon [Ru(bpy)3](2+)-doped silica nanoparticles (SiNPs) and gold nanoparticles (AuNPs), which could be conditioned as OFF-ON probes for glutathione (GSH) detection, were designed and assembled in sequence, with the disulfide bonds as the bridging elements. The structural and optical properties of the nanohybrid architectures were characterized using transmission electron microscopy, UV-vis spectroscopy and fluorescence spectroscopy, respectively. Zeta potential measurements, x-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy were employed to monitor the reaction processes of the SiNPs-S-S-COOH and SiNPs-S-S-AuNPs synthesis. It was found that the covalent nanohybrid architectures were fluorescently dark (OFF state), indicating that SiNPs were effectively quenched by AuNPs. The fluorescence of the OFF-ON probe was resumed (ON state) when the bridge of the disulfide bond was cleaved by reducing reagents such as GSH. This work provides a new platform and strategy for GSH detection using covalent nanohybrid materials.

Synthesis, characterization, and DNA binding of a novel ligand and its Cu(II) complex

A novel naphthalene-2,3-diamine-2-salicylaldehyde (NS) ligand and its mononuclear copper(II) complex (CuNS) have been synthesized and structurally characterized. The UV–vis absorption and emission spectra of NS showed obvious changes on addition of Cu2+ solution. The interaction of the compounds with calf thymus DNA and G-quadruplex DNA were investigated by spectroscopic methods and thermal melting assay. The nucleolytic cleavage activity of the compounds was investigated on double-stranded circular pBR322 plasmid DNA and G-quadruplex DNA by electrophoretic mobility shift assay. The results show that CuNS has a greater ability to stabilize G-quadruplex DNA over calf-thymus DNA. The cytotoxicity of the compounds toward HpeG2 cancer cells was also studied, and they showed significant potential for antineoplastic effects.

Förster Resonance Energy Transfer Studies of Luminescent Gold Nanoparticles Functionalized with Ruthenium(II) and Rhenium(I) Complexes: Modulation via Esterase Hydrolysis

A number of ruthenium(II) and rhenium(I) bipyridine complexes functionalized with lipoic acid moieties have been synthesized and characterized. Functionalization of gold nanoparticles with these chromophoric ruthenium(II) and rhenium(I) complexes has resulted in interesting supramolecular assemblies with Förster resonance energy transfer (FRET) properties that could be modulated via esterase hydrolysis. The luminescence of the metal complex chromophores was turned on upon cleavage of the ester bond linkage by esterase to reduce the efficiency of FRET quenching. The prepared nanoassembly conjugates have been characterized by transmission electron microscopy (TEM), energy-dispersive X-ray analysis (EDX), Fourier transform infrared spectroscopy (FTIR), dynamic light scattering (DLS), UV-visible spectroscopy, and emission spectroscopy. The quenching mechanism has also been studied by transient absorption and time-resolved emission decay measurements. The FRET efficiencies were found to vary with the nature of the chromophores and the length of the spacer between the donor (transition metal complexes) and the acceptor (gold nanoparticles).