Flower-like self-assembly of gold nanoparticles for highly sensitive electrochemical detection of chromium(VI).
ABSTRACT: We report here the fabrication of a flower-like self-assembly of gold nanoparticles (AuNPs) on a glassy carbon electrode (GCE) as a highly sensitive platform for ultratrace Cr(VI) detection. Two AuNP layers are used in the current approach, in which the first is electroplated on the GCE surface as anchors for binding to an overcoated thiol sol-gel film derived from 3-mercaptopropyltrimethoxysilane (MPTS). The second AuNP layer is then self-assembled on the surface of the sol-gel film, forming flower-like gold nanoelectrodes enlarging the electrode surface. When functionalized by a thiol pyridinium, the fabricated electrode displays a well-defined peak for selective Cr(VI) reduction with an unusually large, linear concentration range of 10-1200 ng L(-1) and a low detection limit of 2.9 ng L(-1). In comparison to previous approaches using MPTS and AuNPs on Au electrodes, the current work expands the use of AuNPs to the GCE. Subsequent functionalization of the secondary AuNPs by a thiol pyridinium and adsorption/preconcentration of Cr(VI) lead to the unusually large detection range and high sensitivity. The stepwise preparation of the electrode has been characterized by electrochemical impedance spectroscopy (EIS), scanning electronic microscopy (SEM), and IR. The newly designed electrode exhibits good stability, and has been successfully employed to measure chromium in a pre-treated blood sample. The method demonstrates acceptable fabrication reproducibility and accuracy.
Project description:A biosensor based on a combination of cytochrome c (Cyt c), electrochemical reduced graphene oxides (ERGO), and gold nanoparticles (AuNPs) on a glassy carbon electrode (GCE) was fabricated. The proposed biosensor electrode was denoted as GCE/ERGO-Nafion/AuNPs/Cyt c/Nafion, where ERGO-Nafion was deposited by dropping graphene oxides-Nafion mixed droplet first and following electrochemical reduction, AuNPs were directly deposited on the surface of the ERGO-Nafion modified electrode by electrochemical reduction, and other components were deposited by the dropping-dry method. The effect of the deposition amount of AuNPs on direct electrochemistry of Cyt c in the proposed electrode was investigated. The hydrogen peroxide was taken to evaluate the performance of the proposed biosensor. The results showed that the biosensor has great analytical performance, including a high sensitivity, a wide linear range, a low detection limit, and good stability, reproducibility, and reliability.
Project description:In the presence of nanocatalyst, L-cysteine reduce HAuCl4 rapidly to form gold nanoparticles (AuNP), and a quick nanocatalytic preparation procedure was established for Au/AuNP sol with highly active surface enhanced Raman scattering (SERS) effect and good stability. The nanoreaction was also studied by absorption, resonance Rayleigh scattering (RRS), transmission electron microscopy (TEM) and energy spectra. In the selected conditions, the analyte heparin sodium (HS) could react with victoria blue 4?R (VB4r) to form associated complexes which have very weak SERS effect to make the SERS signals decrease. The SERS signals at 1617?cm-1 reduced linearly with HS concentration increasing. Upon addition of FeCl3, it hydrolyzed to form stable Fe(OH)3 sol platform that carried SERS active Au/AuNPs to enhance the sensitivity. Accordingly, we established a SERS quantitative analysis method in the sol substrate of Fe(OH)3-Au/AuNPs, with a linear range of 0.5-75 ng/mL HS and a detection limit of 0.2 ng/mL. HS in real samples was determined, with a relative standard deviation of 2.65-7.63% and a recovery of 99.3-101%.
Project description:In this work, we explored the formation processes of interfacial polygonal patterning via surfactant-mediated self-assembly of gold nanoparticles (AuNPs). We found that a balance between DDT-capped AuNPs and PVP-passivated AuNPs is a key to making these inorganic-organic thin films. The interfacial polygonal patterning possesses many processing advantages and flexibilities, such as controllable interfacial shape and inter-AuNP distance, tuning of particle sizes, thiol population, chain lengths, and other new properties by introducing functional groups to thiol chains. In principle, self-assembly of AuNPs via well-designed interfaces may be useful for fabrications of other complex architectures.
Project description:We report that poly(L-lysine)-graft-poly(ethylene glycol) (PLL-g-PEG) copolymers that bear multiple thiol groups on the polymer backbone are exceptional ligands for gold nanoparticles (AuNPs). In general, these graft copolymer ligands stabilize AuNPs against environments that would ordinarily lead to particle aggregation. To characterize the effect of copolymer structure on AuNP stability, we synthesized thiolated PLL-g-PEGs (PLL-g-[PEG:SH]) with different backbone lengths, PEG grafting densities, and number of thiols per polymer chain. AuNPs were then combined with these polymer ligands, and the stabilities of the resulting AuNP@PLL-g-[PEG:SH] particles against high temperature, oxidants, and competing thiol ligands were characterized using dynamic light scattering, visible absorption spectroscopy, and fluorescence spectrophotometry. Our observations indicate that thiolated PLL-g-PEG ligands combine thermodynamic stabilization via multiple Au-S bonds and steric stabilization by PEG grafts, and the best graft copolymer ligands balance these two effects. We hope that this new ligand system enables AuNPs to be applied to biotechnological applications that require harsh experimental conditions.
Project description:This study aimed to develop a novel influenza A vaccine by conjugating the highly conserved extracellular region of the matrix 2 protein (M2e) of influenza A virus to gold nanoparticles (AuNPs) and to test the vaccine in a mouse influenza challenge model.Citrate-reduced AuNPs (diameter: 12 nm) were synthesized, and characterized by transmission electron microscopy and dynamic light scattering. M2e was conjugated to AuNPs through thiol-gold interactions to form M2e-AuNP conjugates. Particle stability was confirmed by UV-visible spectra, and M2e conjugation was further characterized by x-ray photoelectron spectroscopy. Mice were immunized with M2e-AuNPs with or without CpG (cytosine-guanine rich oligonucleotide) as an adjuvant with appropriate control groups. Sera was collected and M2e-specific immunoglobulin (IgG) was measured, and immunized mice were challenged with PR8-H1N1 influenza virus.M2e-capped AuNPs could be lyophilized and stably resuspended in water. Intranasal vaccination of mice with M2e-AuNP conjugates induced M2e-specific IgG serum antibodies, which significantly increased upon addition of soluble CpG as adjuvant. Upon challenge with lethal PR8, mice vaccinated with M2e-AuNP conjugates were only partially protected, while mice that received soluble CpG as adjuvant in addition to M2e-AuNP were fully protected.Overall, this study demonstrates the potential of using the M2e-AuNP conjugates with CpG as an adjuvant as a platform for developing an influenza A vaccine.
Project description:A new supramolecular electrochemical sensor for highly sensitive detection of dopamine (DA) was fabricated based on supramolecular assemblies of mixed two surfactants, tetra-butylammonium bromide (TBABr) and sodium dodecyl sulphate (SDS), on the electrodeposition of gold nanoparticles on graphene oxide modified on glassy carbon electrode (AuNPs/GO/GCE). Self-assembled mixed surfactants (TBABr/SDS) were added into the solution to increase the sensitivity for the detection of DA. All electrodes were characterized by scanning electron microscopy (SEM), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The supramolecular electrochemical sensor (TBABr/SDS???AuNPs/GO/GCE) showed excellent electrocatalytic activity toward the oxidation of DA. Under the optimum conditions, the concentration of DA was obtained in the range from 0.02 µM to 1.00 µM, with a detection limit of 0.01 µM (3s/b). The results displayed that TBABr/SDS???AuNPs/GO/GCE exhibited excellent performance, good sensitivity, and reproducibility. In addition, the proposed supramolecular electrochemical sensor was successfully applied to determine DA in human serum samples with satisfactory recoveries (97.26% to 104.21%).
Project description:2 nm gold nanoparticles (AuNPs) have promising applications within drug and protein delivery, bioimaging, and biosensing. By performing ligand place-exchange reactions, AuNPs protected with alkanethiolate ligands can be functionalized to regulate their behaviors. In this reaction, a new ligand is incorporated by mixing a thiol with the AuNPs. To remove the excess new ligand as well as the displaced thiolate, dialysis has previously been the most widely used method. However, this purification method is time-consuming and fails to remove unwanted thiols completely. In this study, we describe a fast and efficient procedure to purify AuNP aqueous solution through liquid-liquid extraction using dichloromethane.•We demonstrate a facile way to purify AuNPs after ligand place-exchange reactions through liquid-liquid extraction.•Liquid-liquid extraction is a simple, inexpensive and efficient method for AuNP purification.•This protocol enables us to completely purify AuNPs in a few hours and can be used as a much quicker and more scaleable valid alternative to dialysis.
Project description:It has been reported that increased levels and activity of the heme oxygenase-1 (HO-1) protein ameliorate tissue injuries. In the present study, we investigated the effects and mechanisms of action of gold nanoparticles (AuNPs) on HO-1 protein expression in human vascular endothelial cells (ECs). The AuNPs induced HO-1 protein and mRNA expression in a concentration- and time-dependent manner. The induction was reduced by the thiol-containing antioxidants, including N-acetylcysteine and glutathione, but not by the non-thiol-containing antioxidants and inhibitors that block the enzymes for intracellular reactive oxygen species generation. The AuNPs enhanced Nrf2 protein levels but did not affect Nrf2 mRNA expression. In response to the AuNP treatment, the cytosolic Nrf2 translocated to the nucleus, and, concomitantly, Bach1 exited the nucleus and its tyrosine phosphorylation increased. The chromatin immunoprecipitation assay revealed that the translocated Nrf2 bound to the antioxidant-response element located in the E2 enhancer region of the HO-1 gene promoter and acted as a transcription factor. Although N-acetylcysteine inhibited the AuNP-induced Nrf2 nuclear translocation, the AuNPs did not promote intracellular reactive oxygen species production or endoplasmic reticulum stress in the ECs. Knockdown of Nrf2 expression by RNA interference significantly inhibited AuNP-induced HO-1 expression at the protein and mRNA levels. In summary, AuNPs enhance the levels and nuclear translocation of the Nrf2 protein and Bach1 export/tyrosine phosphorylation, leading to Nrf2 binding to the HO-1 E2 enhancer promoter region to drive HO-1 expression in ECs. This study, together with our parallel findings, demonstrates that AuNPs can act as an HO-1 inducer, which may partially contribute to their anti-inflammatory bioactivity in human vascular ECs.
Project description:Gold nanoparticles (AuNPs) were homogeneously electrodeposited on nitrogen-doped reduced graphene oxide (N-rGO) to modify a glassy carbon electrode (GCE/N-rGO-Au) in order to improve the simultaneous detection of dopamine (DA), ascorbic acid (AA), and uric acid (UA). N-rGO was prepared by the hydrothermal treatment of graphene oxide (GO) and urea at 180 °C for 12 h. AuNPs were subsequently electrodeposited onto the surface of GCE/N-rGO using 1 mM HAuCl4 solution. The morphology and chemical composition of the synthesized materials were characterized by field-emission scanning electron microscopy and X-ray photoelectron spectroscopy. The electrochemical performance of the modified electrodes was investigated through cyclic voltammetry and differential pulse voltammetry measurements. Compared to GCE/rGO-Au, GCE/N-rGO-Au exhibited better electrochemical performance towards the simultaneous detection of the three analytes due to the more homogeneous distribution of the metallic nanoparticles as a result of more efficient anchoring on the N-doped areas of the graphene structure. The GCE/N-rGO-Au-based sensor operated in a wide linear range of DA (3-100 µM), AA (550-1500 µM), and UA (20-1000 µM) concentrations with a detection limit of 2.4, 58, and 8.7 µM, respectively, and exhibited satisfactory peak potential separation values of 0.34 V (AA-DA), 0.20 V, (DA-UA) and 0.54 V (AA-UA). Remarkably, GCE/N-rGO-Au showed a very low detection limit of 385 nM towards DA, not being susceptible to interference, and maintained 90% of its initial electrochemical signal after one month, indicating an excellent long-term stability.
Project description:We presented the colorimetric and electrochemical methods for determination of the dipeptidyl peptidase-IV (DPP-IV) activity and screening of its inhibitor using gold nanoparticle (AuNP) as the probe. In the colorimetric assay, the substrate peptide with a sequence of Arg-Pro-Arg induced the aggregation and color change of AuNPs, whereas cleavage of the peptide by DPP-IV prevented the aggregation of AuNPs. Furthermore, the aggregation of AuNPs in the solution was easily initiated on a solid/liquid (electrode/electrolyte) surface, which induced a decrease in the electron-transfer resistance. However, once the peptide was clipped by DPP-IV, the assembly of AuNPs on electrode surface was prevented. Consequently, a higher electron-transfer resistance was observed. The colorimetric and electrochemical assays allowed for the determination of DPP-IV with the detection limits of 70 μU/mL and 0.55 μU/mL, respectively. Meanwhile, the proposed methods were used to determine DPP-IV inhibitor with satisfactory results. Both the colorimetric and electrochemical methods are simple, rapid and sufficiently sensitive for DPP-IV activity assay and inhibitor screening. The results also demonstrated that the AuNP-based colorimetric assay could be converted into an enhanced surface tethered electrochemical assay with improving sensitivity. The simple detection principle may be extended to the design of other peptidases biosensors with easy manipulation procedures.