Bimetallic Au and Pd Nanoparticles Modified WO3 Nanosheets for Enhancing the Sensitivity and Selectivity of Formaldehyde Assessment in Aquatic Products.

Formaldehyde, a common illegal additive in aquatic products, poses a threat to people's health and lives. In this study, a novel metal oxide semiconductor gas sensor based on AuPd-modified WO3 nanosheets (NSs) had been developed for the highly efficient detection of formaldehyde. WO3 NS modified with 2.0% AuPd nanoparticles showed a higher response (Ra/Rg = 94.2) to 50 ppm of formaldehyde at 210 °C, which was 36 times more than the pristine WO3 NS. In addition, the AuPd/WO3 gas sensor had a relatively short response/recovery time of 10 s/9 s for 50 ppm of formaldehyde at 210 °C, with good immunity to other interfering gases and good stability for formaldehyde. The excellent gas-sensitive performance was attributed to the chemical sensitization of Au, the electronic sensitization of Pd, and the synergistic effect of bimetallic AuPd, which facilitated the recognition and response of formaldehyde molecules. Additionally, the high sensitivity and broad application prospect of the 2.0% AuPd/WO3 NS composite-based sensor in real sample detection were also confirmed by using the above sensor for the detection of formaldehyde in aquatic products such as squid and shrimp.

Hierarchical Flower-like WO3 Nanospheres Decorated with Bimetallic Au and Pd for Highly Sensitive and Selective Detection of 3-Hydroxy-2-butanone Biomarker.

Listeria monocytogenes, which is abundant in environment, can lead to many kinds of serious illnesses and even death. Nowadays, indirectly detecting the metabolite biomarker of L. monocytogenes, 3-hydroxy-2-butanone, has been verified to be an effective way to evaluate the contamination of L. monocytogenes. However, this detection approach is still limited by sensitivity, selectivity, and ppb-level detection limit. Herein, low-cost and highly sensitive and selective 3-hydroxy-2-butanone sensors have been proposed based on the bimetallic AuPd decorated hierarchical flower-like WO3 nanospheres. Notably, the 1.0 wt % AuPd-WO3 based sensors displayed the highest sensitivity (Ra/Rg = 84 @ 1 ppm) at 250 °C. In addition, the sensors showed outstanding selectivity, rapid response/recovery (8/4 s @ 10 ppm), and low detection limit (100 ppb). Furthermore, the evaluation of L. monocytogenes with high sensitivity and specificity has been achieved using 1.0 wt % AuPd-WO3 based sensors. Such a marvelous sensing performance benefits from the synergistic effect of bimetallic AuPd nanoparticles, which lead to thicker electron depletion layer and increased adsorbed oxygen species. Meanwhile, the unique hierarchical nanostructure of the flower-like WO3 nanospheres benefits the gas-sensing performance. The AuPd-WO3 nanosphere-based sensors exhibit a particular and highly selective method to detect 3-hydroxy-2-butanone, foreseeing a feasible route for the rapid and nondestructive evaluation of foodborne pathogens.

Ternary Electrochemiluminescence Biosensor Based on DNA Walkers and AuPd Nanomaterials as a Coreaction Accelerator for the Detection of miRNA-141.

In this study, a ternary electrochemiluminescence (ECL) sensing platform coupled with a multiple signal amplification strategy was proposed for ultrasensitive detection of miRNA-141. The initial signal amplification was achieved via three-dimensional reduced graphene oxide (3D-rGO)@Au nanoparticles (NPs) to form an excellent conductive layer. Then, AuPd NPs as a coreaction accelerator was introduced into the N-(4-aminobutyl)-N-(ethylisoluminol) (ABEI)-H2O2 system to facilitate the transformation from H2O2 to excess superoxide anion radicals (O2•-), which further amplified the ECL emission of ABEI, leading to a significant increase of the ECL signal. Meanwhile, in the presence of miRNA-141 and T7 Exonuclease (T7 Exo), the self-assembled DNA swing arm can be driven to walk autonomously. The DNA walker reaction could result in the release of numerous labeled luminophores, which could react to achieve an extremely weak ECL signal. Surprisingly, the established ECL sensor platform for the detection of miRNA-141 demonstrated excellent sensitivity with a low detection limit of 31.9 aM in the concentration range from 100 aM to 1 nM. Consequently, the designed strategy greatly improves the luminous efficiency of the ternary ECL system and provides a special approach for the detection of nucleic acids and biomarkers in clinical and biochemical analysis.

Ionic liquid functionalized 3D graphene-carbon nanotubes‒AuPd nanoparticles‒molecularly imprinted copolymer based paracetamol electrochemical sensor: Preparation, characterization and application.

An innovative electrochemical sensor for paracetamol (PCM) determination was fabricated by electropolymerization imprinting on three-dimension (3D) AuPd nanoparticles‒ionic liquid (IL) functionalized graphene‒carbon nanotubes nanocomposite (AuPd/GN-CNTs-IL) modified glassy carbon electrode. The GN-CNTs supported AuPd alloy nanoparticles were prepared via one-pot hydrothermal method in the presence of IL (i.e. 1-hydroxyethyl-3-methyl imidazolium bis[(trifluoromethyl) sulfonyl] imide), which not only promoted the formation of small AuPd alloy nanoparticles, but also acted as "spacer" to prevent the π-π stacking and aggregation of graphene sheets and carbon nanotubes. The resulting composite had large surface area and high electrocatalysis. The PCM imprinted poly(carbazole-co-pyrrole) exhibited good recognition to PCM and had high stability. Based on the synergic effect of PCM imprinted copolymer and 3D AuPd/GN-CNTs-IL nanocomposite, a highly selective and sensitive electrochemical sensor was established. It presented a good linear relationship from 0.10 to 10 µM with a low limit of detection of 50 nM (S/N = 3). The sensor could be applied to the detection of PCM in biological samples, with acceptable recoveries (84.5%-102%). In addition, it was successfully used to monitor the concentration of PCM in urine from a patient with fever cold.

Paper-based closed Au-Bipolar electrode electrochemiluminescence sensing platform for the detection of miRNA-155.

This paper introduces a paper-based closed Au-bipolar electrode (BPE) biosensing system for the rapid and sensitive electrochemiluminescence (ECL) detection of miRNA-155. This microfluidic paper-based sensing platform is formed by wax-printing technology, screen printing method and in-situ Au nanoparticles (NPs) growth to form hydrophilic cells, hydrophobic boundaries, water proof electronic bridge, driving electrode regions and bipolar electrode regions. For rapid and sensitive detection, the cathode of bipolar electrode was modified with the prepared DNA (S1)-AuPd NPs by hybridization chain reaction, in which the target could initiate multiple cycles reaction to load more AuPd NPs which catalyzed H2O2 reduction. In addition, a classical ECL system tris (2,2'-bipyridine) ruthenium (II)- tripropylamine (Ru(bpy)32+/TPrA) exists at the anode of the bipolar electrode. Due to the charge balance between the anode and the cathode of BPE, the ECL signal response of Ru(bpy)32+/TPrA system was enhanced in the reporting cell. The intensity of ECL was quantitatively correlated with the concentration of miRNA-155 in the range of 1 pM-10 µM with the detection limit 0.67 pM. Moreover, this method paves a novel way for highly sensitive detection of miRNA-155 in clinical application.

Electrochemiluminescence cytosensing platform based on Ru(bpy)32+@silica-Au nanocomposite as luminophore and AuPd nanoparticles as coreaction accelerator for in situ evaluation of intracellular H2O2.

An electrochemiluminescence (ECL) cytosensor was fabricated onto a microfluidic paper-based analytical device (µ-PAD) in order to detect hydrogen peroxide (H2O2) which was released from tumor cells. The ECL probe Ru(bpy)32+@silica-Au nanocomposite (Ru@SiO2-Au) was fabricated and served as ECL reagent. The ECL of Ru@SiO2-Au nanocomposite was quenched by the ferrocene (Fc). AuPd nanoparticles (AuPd NPs), which were modified on the paper working electrode (PWE), were served as the catalyst of H2O2 to produce hydroxyl radicals (•OH) for cleaving Fc-labelled DNA to achieve "signal-on", and AuPd NPs also severed as coreaction accelerator. H2O2 was released from cells under the stimulation of phorbol myristate acetate. Fc-labelled DNA strand was cleaved via •OH. Fc molecule departed from the PWE surface, The ECL could be recovered. An ECL cytosensor on a 3D origami device was constructed. The ECL response of the Ru@SiO2-Au-Fc system was related to the number of cells. The ECL intensity was quantitatively related with the logarithm of MCF-7 cells number and H2O2 concentration, the detection limit was 30 cells mL-1. As a consequence, this work provided a really low-cost and disposable µ-PAD for sensitive detection of intracellular H2O2. What's more, this work had potential application value for studying cellular biology and pathophysiology.

Tuning the Selectivity of AuPd Nanoalloys towards Selective Dehydrogenative Alkyne Silylation.

The cross-dehydrogenative coupling of terminal alkynes and hydrosilanes catalyzed by AuPd nanoalloys is described. Metal nanoparticles are readily prepared in 15 minutes from commercially available and cheap starting materials by using a photochemical approach. The ratio of Au and Pd in the alloys heavily influences their reactivity. These cooperative nanoalloy catalysts tolerate a large number of functional groups (e.g., free amines and acids), operate at room temperature under air atmosphere at low loading (2 mol %), and the cross-dehydrogenative coupling can easily be scaled up.

Synthesis of BiVO4 nanoflakes decorated with AuPd nanoparticles as selective oxidation photocatalysts.

The ultrathin BiVO4 nanoflakes decorated with Pd and AuPd nanoparticles (NPs) were respectively synthesized and optimized for the enhanced photocatalysis towards selective oxidation of aromatic alcohols. The monometallic Pd(x)-BiVO4 samples presented hump-like variation in the photocatalytic activity with increasing Pd amount (x) from 0 to 2.0 wt%. Subsequently, coupling Au with Pd on BiVO4 nanoflakes resulted in a further improvement in the photocatalysis, with retaining the high selectivity (>99%) for aldehyde production. By tuning metal loading, the typical Au(0.5)Pd(0.5)-BiVO4 photocatalyst exhibited the highest benzaldehyde yield of 887.7 µmol·g-1·h-1, which was 6.0 times that of bare BiVO4 nanoflakes and 1.35 times that of Pd(1.0)-BiVO4 photocatalyst. A series of characterizations and DFT calculations confirmed the enhanced light harvesting and charge separation of the Au(0.5)Pd(0.5)-BiVO4 material, owing to the strong electronic couplings in AuPd NPs and its remarkable influence on the band structure of BiVO4. The photocatalytic mechanism studies indicated that the selective oxidation of aromatic alcohols was achieved by the cooperation of photogenerated holes and O2- radical, and this process was promoted by the interfacial synergism between AuPd NPs and BiVO4 nanoflakes. This work demonstrates a systematic study on optimizing photocatalysts to improve their performance in light-driven organic transformations as well as highlights the synergistic effect of metal-metal coupling and metal-semiconductor interface on photocatalysis.

Ultrasensitive electrochemiluminescence assay of tumor cells and evaluation of H2O2 on a paper-based closed-bipolar electrode by in-situ hybridization chain reaction amplification.

In this manuscript, a disposable paper-based analytical device comprised of a closed bipolar electrode (BPE) was fabricated for the ultrasensitive electrochemiluminescence (ECL) detection of intracellular H2O2 and the number of cancer cells. In this approach, wax printing was used to fabricated reaction zone, and carbon ink-based BPE and driving electrodes were screen-printed into the paper. AuPd nanoparticles (NPs), which served as a carrier of the capture aptamer and as the catalyst for the ECL reaction of luminol and H2O2, were used to modify the BPE. Luminol/Au NPs were attached to the surface of the captured cells via hybridation chain reaction with two hairpin structure DNA labelled luminol/Au NPs. In the stimulation of phorbol myristate acetate, The coreactant H2O2 was released from the target cells. The ECL response of the luminol-H2O2 system was related to the number of cancer cells in the testing buffer, which served as a quantitative signal for the determination of cancer cells and the concentration of H2O2. In order to decrease the external voltage, K3[Fe(CN)6] was introduced in the cathode resevoir of BPE because it gained electrons at the cathode more easily than oxygen. The ECL intensity was quantitatively related to the concentration of MCF-7 in the range of 1.0 × 102-1.0 × 107 cells/mL. The detection limit was 40 cells/mL and it showed good specificity for cells with high overexpression of mucin-1 receptor, it was concluded that the developed protocol could be effectively utilized for the detection of MCF-7 cells.

Fabrication of novel nitrogen-doped graphene-hollow AuPd nanoparticle hybrid films for the highly efficient electrocatalytic reduction of H2O2.

Hollow AuPd (hAuPd) alloy nanoparticles (NPs) were prepared through simultaneous reduction of HAuCl4 and Na2PdCl4 using Co NPs as sacrificial template (i.e., reductant). Then, the hAuPd NPs were assembled on nitrogen-doped graphene (NG) to prepare an NG-hAuPd hybrid film. The obtained NG-hAuPd composite showed higher electrocatalytic activity toward the reduction of H2O2, compared with graphene-hAuPd hybrid, NG-solid AuPd hybrid, and hAuPd NPs. The enhanced performance was related to the hollow structure of hAuPd NPs and the synergistic effect between NG and hAuPd NPs. Under optimum conditions, the NG-hAuPd hybrid film showed a linear response to H2O2 in the range of 0.1-20 µM, with a sensitivity of 5095.5 µA mM(-1) cm(-2)and a comparable detection limit of 0.02 µM (S/N = 3). These results demonstrated that the NG-hAuPd composite was a promising electrocatalytic material for constructing sensors, etc.

Sensitive voltammetric determination of vanillin with an AuPd nanoparticles-graphene composite modified electrode.

In this work, graphene oxide was reduced to graphene with an endogenous reducing agent from dimethylformamide, and then AuPd alloy nanoparticles were electrodeposited on the graphene film. The obtained AuPd-graphene hybrid film was characterized by scanning electron microscopy, energy dispersive X-ray spectroscopy, X-ray diffraction and voltammetry. The electrochemical behavior of vanillin was studied using the AuPd-graphene hybrid based electrode. It presented high electrocatalytic activity and vanillin could produce a sensitive oxidation peak at it. Under the optimal conditions, the peak current was linear to the concentration of vanillin in the ranges of 0.1-7 and 10-40 µM. The sensitivities were 1.60 and 0.170 mA mM(-1) cm(-2), respectively; the detection limit was 20 nM. The electrode was successfully applied to the detection of vanillin in vanilla bean, vanilla tea and biscuit samples.