Operando X-ray absorption and EPR evidence for a single electron redox process in copper catalysis

An unprecedented single electron redox process in copper catalysis is confirmed using operando X-ray absorption and EPR spectroscopies. The oxidation state of the copper species in the interaction between Cu(ii) and a sulfinic acid at room temperature, and the accurate characterization of the formed Cu(i) are clearly shown using operando X-ray absorption and EPR evidence. Further investigation of anion effects on Cu(ii) discloses that bromine ions can dramatically increase the rate of the redox process. Moreover, it is proven that the sulfinic acids are converted into sulfonyl radicals, which can be trapped by 2-arylacrylic acids and various valuable β-keto sulfones are synthesized with good to excellent yields under mild conditions.     

Rapid and ultrasensitive colorimetric detection of mercury(II) by chemically initiated aggregation of gold nanoparticles

The article describes a method for rapid and visual determination of Hg(II) ion using unmodified gold nanoparticles (Au-NPs). It involves the addition of Au-NPs to a solution containing Hg(II) ions which, however, does not induce a color change. Next, a solution of lysine is added which induces the aggregation of the Au-NPs and causes the color of the solution to change from wine-red to purple. The whole on-site detection process can be executed in less than 15 min. Other amines (ethylenediamine, arginine, and melamine) were also investigated with respect to their capability to induce aggregation. Notably, only amines containing more than one amino group were found to be effective, but a 0.4 μM and pH 8 solution of lysine was found to give the best results. The detection limits for Hg (II) are 8.4 pM (for instrumental read-out) and 10 pM (for visual read-out). To the best of our knowledge, this LOD is better than those reported for any other existing rapid screening methods. The assay is not interfered by the presence of other common metal ions even if present in 1000-fold excess over Hg(II) concentration. It was successfully applied to the determination of Hg(II) in spiked tap water samples. We perceive that this method provides an excellent tool for rapid and ultrasensitive on-site determination of Hg(II) ions at low cost, with relative ease and minimal operation.

Rapid and ultrasensitive detection of mercury ions using gold nanoparticle based label-free colorimetric method with excellent sensitivity, easy operation and low cost.

     

Clean and Efficient Synthesis of Pyrazole Derivatives in Aqueous Media

A series of 5‐aryl‐1H‐pyrazole derivatives were synthesized via the reaction of 3‐(dimethylamino)‐1‐arylprop‐2‐en‐1‐one with hydrazine in aqueous media without using any catalyst. This method has the advantages of easier work‐up, mild reaction condition, high yields, and an environmentally benign procedure.     

Functional graphene-gold nano-composite fabricated electrochemical biosensor for direct and rapid detection of bisphenol A

In this research, the graphene with excellent dispersity is prepared successfully by introducing gold nanoparticle to separate the individual sheets. Various techniques are adopted to characterize the prepared graphene and graphene-gold nanoparticle composite materials. This fabricated new composite material is used as the support material to construct a novel tyrosinase based biosensor for detection of bisphenol A (BPA). The electrochemical performances of the proposed new enzyme biosensor were investigated by differential pulse voltammetry (DPV) method. The proposed biosensor exhibited excellent performance for BPA determination with a wide linear range (2.5 × 10⁻³–3.0 μM), a highly reproducible response (RSD of 2.7%), low interferences and long-term stability. And more importantly, the calculated detection limit of the proposed biosensor was as low as 1 nM. Compared with other detection methods, this graphene-gold nanoparticle composite based tyrosinase biosensor is proved to be a promising and reliable tool for rapid detection of BPA for on-site analysis of emergency BPA related pollution affairs.     

Magnetic graphene oxide modified with choline chloride-based deep eutectic solvent for the solid-phase extraction of protein

Four kinds of green deep eutectic solvents (DESs) based on choline chloride (ChCl) have been synthesized and coated on the surface of magnetic graphene oxide (Fe₃O₄@GO) to form Fe₃O₄@GO-DES for the magnetic solid-phase extraction of protein. X-ray diffraction (XRD), vibrating sample magnetometer (VSM), Fourier transform infrared spectrometry (FTIR), field emission scanning electron microscopy (FESEM) and thermal gravimetric analysis (TGA) were employed to characterize Fe₃O₄@GO-DES, and the results indicated the successful preparation of Fe₃O₄@GO-DES. The UV–vis spectrophotometer was used to measure the concentration of protein after extraction. Single factor experiments proved that the extraction amount was influenced by the types of DESs, solution temperature, solution ionic strength, extraction time, protein concentration and the amount of Fe₃O₄@GO-DES. Comparison of Fe₃O₄@GO and Fe₃O₄@GO-DES was carried out by extracting bovine serum albumin, ovalbumin, bovine hemoglobin and lysozyme. The experimental results showed that the proposed Fe₃O₄@GO-DES performs better than Fe₃O₄@GO in the extraction of acidic protein. Desorption of protein was carried out by eluting the solid extractant with 0.005 mol L⁻¹ Na₂HPO₄ contained 1 mol L⁻¹ NaCl. The obtained elution efficiency was about 90.9%. Attributed to the convenient magnetic separation, the solid extractant could be easily recycled.     

Three-dimensional roselike α-Ni(OH)2 assembled from nanosheet building blocks for non-enzymatic glucose detection

Glucose detection plays very important roles in diagnostics and management of diabetes. The search for novel catalytic materials with appropriate architectures is the key step in the fabrication of highly sensitive glucose sensors. In this work, α-Ni(OH)₂ roselike structures (Ni(OH)₂-RS) assembled from nanosheet building blocks were successfully synthesized by a hydrothermal method through the hydrolysis of nickel chloride in the mixed solvents of water and ethanol with the assistance of polyethylene glycol (PEG). The structure and morphology of the roselike α-Ni(OH)₂ were characterized by transmission electron microscopy (TEM), field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRD) and N₂ adsorption–desorption isotherm measurement. TEM and FE-SEM images showed that the synthesized Ni(OH)₂ was roselike and the size of the leaf-shaped nanosheet was about 5 nm in thickness, which leads to larger active surface areas and faster electron transfer for the detection of glucose. Compared with the bare GCE and bulk Ni(OH)₂/GCE, the Ni(OH)₂-RS/GCE had higher catalytic activity toward the oxidation of glucose. Under the optimal conditions, the Ni(OH)₂-RS/GCE offers a variety of merits, such as a wide linear response window for glucose concentrations ranging from 0.87 μM to 10.53 mM, short response time (3 s), a lower detection limit of 0.08 μM (S/N = 3), as well as long term stability and repeatability.     

Propane σ‐Complexes on PdO(101): Spectroscopic Evidence of the Selective Coordination and Activation of Primary C?H Bonds

Achieving selective C H bond cleavage is critical for developing catalytic processes that transform small alkanes to value‐added products. The present study clarifies the molecular‐level origin for an exceptionally strong preference for propane to dissociate on the crystalline PdO(101) surface via primary C H bond cleavage. Using reflection absorption infrared spectroscopy (RAIRS) and density functional theory (DFT) calculations, we show that adsorbed propane σ‐complexes preferentially adopt geometries on PdO(101) in which only primary C H bonds datively interact with the surface Pd atoms at low propane coverages and are thus activated under typical catalytic reaction conditions. We show that a propane molecule achieves maximum stability on PdO(101) by adopting a bidentate geometry in which a H Pd dative bond forms at each CH₃ group. These results demonstrate that structural registry between the molecule and surface can strongly influence the selectivity of a metal oxide surface in activating alkane C H bonds.