Mild Synthesis of Pt/SnO2/Graphene Nanocomposites with Remarkably Enhanced Ethanol Electro‐oxidation Activity and Durability

We have designed a new Pt/SnO₂/graphene nanomaterial by using L ‐arginine as a linker; this material shows the unique Pt‐around‐SnO₂ structure. The Sn²⁺ cations reduce graphene oxide (GO), leading to the in situ formation of SnO₂/graphene hybrids. L ‐Arginine is used as a linker and protector to induce the in situ growth of Pt nanoparticles (NPs) connected with SnO₂ NPs and impede the agglomeration of Pt NPs. The obtained Pt/SnO₂/graphene composites exhibit superior electrocatalytic activity and stability for the ethanol oxidation reaction as compared with the commercial Pt/C catalyst owing to the close‐connected structure between the Pt NPs and SnO₂ NPs. This work should have a great impact on the rational design of future metal–metal oxide nanostructures with high catalytic activity and stability for fuel cell systems.     

S-nitrosocysteine and cystine from reaction of cysteine with nitrous acid. A kinetic investigation

The formation of the S-nitrosocysteine (CySNO) in aqueous solution starting from cysteine (CySH) and sodium nitrite is shown to strongly depend on the pH. Experiments conducted within the pH range 0.5-7.0 show that at pH below 3.5 the NO+ (or H2NO 2 +) is the main nitrosating species, while at higher pH (>3.5) the nitrosating species is most likely the N2O3. A kinetic study provided a general kinetic equation, V(CySNO) = k1[HNO2][CySH]eq [H+] + k2[HNO2]2. The first term of this equation is predominant at pH lower than 3.5, in agreement with the literature for the direct nitrosation of thiols with nitrous acid; the value for the third-order rate constant, k(1) = 7.9 x 10(2) L(2) mol(-2) min(-1), was calculated. For experiments at pH higher than 3.5, the second term becomes prevalent and the second-order rate constant k(2) = (3.3 +/- 0.1) x 10(3) L mol(-1) min(-1) was calculated. A competitive oxidation process leading to the direct formation of cystine (CySSCy) has been also found. Most likely also for this process two different mechanisms are involved, depending on the pH, and a general kinetic equation, V(CySSCy) = k3[CySH](eq)[HNO2][H+] + k3'[CySH]eq[HNO2], is proposed.     

Strongly Coupled Pt–Ni2GeO4 Hybrid Nanostructures as Potential Nanocatalysts for CO Oxidation

A facile and low‐cost method has been developed to successfully fabricate 3D flower‐like and sphere‐like Ni₂GeO₄ nanostructures with tunable sizes and shapes. It is found that the hard template, polymethyl methacrylate (PMMA) nanopsheres, is essential to the formation of the final products. The as‐prepared nanostructures can serve as an outstanding support for Pt nanoparticles after surface modification with L ‐lysine. In the catalytic test of CO oxidation, Pt–Ni₂GeO₄ nanoflowers exhibited much higher catalytic performance compared with Pt–Ni₂GeO₄ nanospheres, representing a typical size‐dependent catalytic property.     

Determination of thiols and disulfides in normal rat tissues and hamster pancreas treated with N-nitrosobis(2-oxopropyl)amine using 4-(aminosulfonyl)-7-fluoro-2,1,3-benzoxadiazole and ammonium 7-fluoro-2,1,3-benzoxadiazole-4-sulfonate

Biological thiols and disulfides in rat and hamster tissues were simultaneously determined by HPLC-fluorescence detection using 4-(aminosulfonyl)-7-fluoro-2,1,3-benzoxadiazole (ABD-F) and ammonium 7-fluoro-2,1,3-benzoxadiazole-4-sulfonate (SBD-F). The coefficients of variation (CV) of the method for reduced glutathione (GSH) and oxidized glutathione (GSSG) in liver and for cysteine (CySH) and cystine (CySSCy) in kidney were less than 3.1%. In 11 tissues of Wistar rats (liver, spleen, heart, lung, stomach, bladder, ovary, uterus, adrenal, kidney and pancreas), only CySH, CySSCy, GSH and/or GSSG were detected. Other thiols and disulfides were at extremely low levels in all samples. Both concentrations of CySH and CySSCy in the livers of old rats (111 weeks old, F344) were significantly higher than those of young rats (8 weeks old) (CySH, 0.246 +/- 0.099 vs 0.130 +/- 0.020 mumol/g; CySSCy, 0.051 +/- 0.027 vs 0.013 +/- 0.002 mumol/g). Administration of N-nitrosobis(2-oxopropyl)amine (BOP), a selective carcinogen of hamster pancreatic cancer, to Syrian golden hamsters (38 weeks old) resulted in the increase in the pancreas of GSH to a level 19 times as high and of GSSG to a level 14 times as high as those in untreated hamsters (GSH, 1.173 +/- 0.272 vs 0.062 +/- 0.017 mumol/g; GSSG, 0.155 +/- 0.063 vs 0.011 +/- 0.001 mumol/g).     

Sensitivity of Positive Ion Mode Electrospray Ionization Mass Spectrometry in the Analysis of Thiol Metabolites

High signal intensities of glutathione (GSH), [GSH+H]⁺ (m/z 308), cysteine (CySH), [CySH+H]⁺ (m/z 122), and homocysteine (hCySH), [hCySH+H]⁺ (m/z 136), are observed in ESI MS with on‐line electrochemistry (EC). Dimers formed by H‐bonding, which are not electrochemical products, are detected as [2GSH+H]⁺ (m/z 615), [2CySH+H]⁺ (m/z 243) and [2hCySH+H]⁺ (m/z 271) together with disulfide dimers GSSG, CySSCy and hCySSCyh, [GSSG+H]⁺ (m/z 613), [CySSCy+H]⁺ (m/z 241) and [hCySSCyh+H]⁺ (m/z 269). When dopamine is present a thiol/dopamine quinone (DAQ) adduct is observed. Formation of this adduct is proposed to occur by an electrochemical mechanism during ESI. Catalysis of thiol oxidation and analysis of thiol mixtures is addressed.     

Sputtering deposition of Pt nanoparticles on vertically aligned multiwalled carbon nanotubes for sensing L-cysteine

A highly sensitive electrochemical sensor for determination of L-cysteine (CySH) is presented. It is based on vertically aligned multiwalled carbon nanotubes modified with Pt nanoparticles by magnetron sputtering deposition. The morphology of the nanocomposite was characterized by scanning electron microscopy, transmission electron microscopy and energy-dispersive. The electrochemistry of CySH was investigated by cyclic voltammetry, differential pulse voltammetry and chronoamperometry. The mechanism for the electrochemical reaction of CySH at the modified electrode at different pH values is discussed. The electrode exhibits a higher electrocatalytic activity towards the oxidation of CySH than comparable other electrodes. It displays a linear dependence (R ²?=?0.9980) on the concentration of CySH in the range between 1 and 500 μM and at an applied potential of +0.45 V, a remarkably low detection limit of 0.5 μM (S/N?=?3), and an outstandingly high sensitivity of 1.42?×?10³ μA?mM^?1?cm^?2, which is the highest value ever reported. The electrode also is highly inert towards other amino acids, creatinine and urea. The sensor was applied to the determination of CySH in urine with satisfactory recovery, thus demonstrating its potential for practical applications.

L‐Cysteine Voltammetry at a Carbon Paste Electrode Bulk‐Modified with Ferrocenedicarboxylic Acid

The electrochemical behavior of L ‐cysteine studied at the surface of ferrocenedicarboxylic acid modified carbon paste electrode (FDCMCPE) in aqueous media using cyclic voltammetry, differential pulse voltammetry and double potential step chronoamperometry. It has been found that under optimum condition (pH 8.00) in cyclic voltammetry, the oxidation of L ‐cysteine occurs at a potential about 200 mV less positive than that of an unmodified carbon paste electrode. The kinetic parameters such as electron transfer coefficient, α, and catalytic reaction rate constant, k_h were also determined using electrochemical approaches. The electrocatalytic oxidation peak current of L ‐cysteine showed a linear dependent on the L ‐cysteine concentration and linear analytical curves were obtained in the ranges of 3.0×10^?5 M–2.2×10^?3 M and 1.5×10^?5 M–3.2×10^?3 M of L ‐cysteine concentration with cyclic voltammetry (CV) and differential pulse voltammetry (DPV) methods respectively. The detection limits (3σ) were determined as 2.6×10^?5 M and 1.4×10^?6 M by CV and DPV methods.     

One Step Fabrication of Au Nanoparticles‐Ni‐Al Layered Double Hydroxide Composite Film for the Determination of L‐Cysteine

This paper reports the fabrication of Au nanoparticles (Au NPs)‐Ni‐Al layerd double hydroxide (LDH) composite film by one step electrochemical deposition on the surface of a glass carbon electrode from the mixture solution containing HAuCl₄ and nitrate salts of Ni²⁺ and Al³⁺. Improved conductivity was obtained by Au NPs codeposited on LDH film. The synergic effect of LDHs and Au NPs dramatically improves the performance of L ‐cysteine electro‐oxidation, displaying low oxidation peak potential (0.16 V) and high current response. Thus the electrode was used to sense L ‐cysteine, showing good sensitivity and selectivity.     

Silica veils-conductive diamond powder composite as a new propitious substrate for platinum electrocatalysts

An innovative composite was obtained by a straightforward sol-gel procedure, involving boron-doped diamond powder (BDDP) incorporation into a SiO₂ veil (SiO₂V) matrix. Composite-coated glassy carbon plates were used as substrate for Pt electrochemical deposition, and the electrodes thus obtained (Pt/BDDP–SiO₂V) were compared on a relative basis with those prepared in the absence of the silica matrix (Pt/BDDP). SEM measurements have shown that a BDDP substrate promotes Pt cluster formation, whereas on BDDP–SiO₂V, particles are much smaller (ca. 45 nm to ca. 140 nm). The activity for CH₃OH oxidation was checked by cyclic voltammetry, and it was found that at Pt/BDDP–SiO₂V, the main anodic peak is shifted with ca. 0.35 V toward lower potentials, indicating a considerable improvement in the overall process kinetics. Stripping experiments together with long-term polarization measurements demonstrated that when deposited on the BDDP–SiO₂V support, Pt particles are less susceptible to CO poisoning and this behavior was tentatively ascribed to the presence of a higher relative surface concentration of more stable, oxidized platinum species, as evidenced by XPS.     

Electrochemical Behavior and Determination of L‐Tyrosine at Single‐walled Carbon Nanotubes Modified Glassy Carbon Electrode

Based on single‐walled carbon nanotubes (SWCNTs) modified glassy carbon electrode (GCE/SWCNTs), a novel method was presented for the determination of L ‐tyrosine. The GCE/SWCNTs exhibited remarkable catalytic and enhanced effects on the oxidation of L ‐tyrosine. In 0.10 mol/L citric acid‐sodium citrate buffer solution, the oxidation potential of L ‐tyrosine shifted negatively from +1.23 V at bare GCE to +0.76 V at GCE/SWCNTs. Under the optimized experimental conditions, the linear range of the modified electrode to the concentration of L ‐tyrosine was 5.0×10^?6–2.0×10^?5 mol/L (R₁=0.9952) and 2.7×10^?5–2.6×10^?4 mol/L (R₂=0.9998) with a detection limit of 9.3×10^?8 mol/L. The kinetic parameters such as α (charge transfer coefficient) and D (diffusion coefficient) were evaluated to be 0.66, 9.82×10^?5 cm² s^?1, respectively. And the electrochemical mechanism of L ‐tyrosine was also discussed.     

Electro-deposition of gold nanostructures on carbon paste electrode: a platform with signal amplification for voltammetric study and determination of pyridoxine (vitamin B<Subscript>6</Subscript>)

For the first time, the electrochemical synthesis of gold nanostructures was done at the surface of carbon paste electrode. This device was used as a simple and sensitive electrochemical sensor for measurement of pyridoxine (Vitamin B₆, VB₆). The diffusion coefficient (D) and the kinetic parameters such as electron transfer coefficient (α) and catalytic rate constant (k) for VB₆ were also determined using electrochemical approaches. The cyclic voltammetry method showed VB₆ oxidation reaction with irreversible characteristics was diffusion-controlled at low scan rates. Using differential pulse voltammetry (DPV), the peak current was linearly dependent on VB₆ concentration in the ranges of 1.9–110.8 and 110.8–257.0 μM, with detection limit of 74.0 nM, respectively. Results showed there is no interference of other vitamins in oxidation of VB₆. DPV was used to quantify of VB₆ in some real samples by the standard addition method. The modified electrode showed good sensitivity and stability.     

Electrochemical synthesis of a novel platinum nanostructure on a glassy carbon electrode, and its application to the electrooxidation of methanol

We show that the addition of white dextrin during the electrochemical deposition of platinum nanostructures (nano-Pt) on a glassy carbon electrode (GCE) results in an electrochemically active surface that is much larger than that of platinum microparticles prepared by the same procedure but in the absence of dextrin. The nano-Pt deposits are characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy, and electrochemical methods. The SEM images reveal deposits composed of mainly nanoparticles and short nanorods. The GCE was applied as a novel and cost-effective catalyst for methanol oxidation. The use of nano-Pt improves the electrocatalytic activity and the stability of the electrodes.

Fabrication of Trimetallic Pt−Pd−Co Porous Nanostructures on Reduced Graphene Oxide by Galvanic Replacement: Application to Electrocatalytic Oxidation of Ethylene Glycol

In present work, reduced graphene oxide nanosheets (rGO) decorated with trimetallic three‐dimensional (3D) Pt−Pd−Co porous nanostructures was fabricated on glassy carbon electrode (Pt−Pd−Co/rGO/GCE). First, GO suspension was drop‐casted on the electrode surface, then GO film reduction was carried out by cycling the potential in negative direction to form the rGO film modified GCE (rGO/GCE). Then, electrodeposition of the cobalt nanoparticles (CoNPs) as sacrificial seeds was performed onto the rGO/GCE by using cyclic voltammetry. Afterward, Pt−Pd−Co 3D porous nanostructures fabrication occurs through galvanic replacement (GR) method based on a spontaneous redox process between PtCl₂, PdCl_2, and CoNPs. The morphology and structure of the Pt−Pd−Co/rGO porous nanostructure film was characterized by scanning electron microscopy, energy dispersive spectroscopy and X‐ray diffraction method. The performance of the prepared electrode was investigated by various electrochemical methods including, cyclic voltammetry and electrochemical impedance spectroscopy. The electrocatalytic activity of the as‐prepared modified electrode with high surface areas was evaluated in anodic oxidation of ethylene glycol. The study on electrocatalytic performances revealed that, in comparison to various metal combinations in modified electrodes, trimetallic Pt−Pd−Co/rGO/GCE exhibit a lower onset potential, significantly higher peak current density, high durability and stability for the anodic oxidation of ethylene glycol. The excellent performances are attributed to the rGO as catalysts support and resulting synergistic effects of the trimetallic and appropriate characteristics of the resulted 3D porous nanostructures. Moreover, the influence of various concentrations of ethylene glycol, the potential scan rate and switching potential on the electrode reaction, in addition, long‐term stability have been studied by chronoamperometric and cyclic voltammetric methods.     

A General and High‐Yield Galvanic Displacement Approach to Au?M (M=Au,Pd, and Pt) Core–Shell Nanostructures with Porous Shells and Enhanced Electrocatalytic Performances

In this work, we utilize the galvanic displacement synthesis and make it a general and efficient method for the preparation of Au? M (M=Au, Pd, and Pt) core–shell nanostructures with porous shells, which consist of multilayer nanoparticles. The method is generally applicable to the preparation of Au? Au, Au? Pd, and Au? Pt core–shell nanostructures with typical porous shells. Moreover, the Au? Au isomeric core–shell nanostructure is reported for the first time. The lower oxidation states of Au^I, Pd^II, and Pt^II are supposed to contribute to the formation of porous core–shell nanostructures instead of yolk‐shell nanostructures. The electrocatalytic ethanol oxidation and oxygen reduction reaction (ORR) performance of porous Au? Pd core–shell nanostructures are assessed as a typical example for the investigation of the advantages of the obtained core–shell nanostructures. As expected, the Au? Pd core–shell nanostructure indeed exhibits a significantly reduced overpotential (the peak potential is shifted in the positive direction by 44 mV and 32 mV), a much improved CO tolerance (I_f/I_b is 3.6 and 1.63 times higher), and an enhanced catalytic stability in comparison with Pd nanoparticles and Pt/C catalysts. Thus, porous Au? M (M=Au, Pd, and Pt) core–shell nanostructures may provide many opportunities in the fields of organic catalysis, direct alcohol fuel cells, surface‐enhanced Raman scattering, and so forth.     

Electroanalytical Study of Methanol Oxidation and Oxygen Reduction at Carbon Nanohorns‐Pt Nanostructured Electrodes

This work reports a comprehensive electroanalytical study of carbon nanohorns (CNHs) in electrochemical applications. Compared to other types of carbons, the bare CNHs electrode exhibited higher peak current densities and lowest anodic peak‐to‐cathodic peak separation of less than 50 mV for the [Fe(CN)^4?]₆/[Fe(CN)^3?]₆ redox couple. Furthermore, CNHs exhibited excellent electrocatalyst supporting properties for porous Pt film towards methanol oxidation reaction reaching a peak current density of 127 mA cm^?2 or peak current mass activity 184 mA mg_Pt^?1. Regarding oxygen reduction reaction, an onset potential as positive as 0. 77 V vs. Ag/AgCl was achieved with CNHs/porous Pt film.     

A Single Biosensor for Evaluating the Levels of Copper Ion and L‐Cysteine in a Live Rat Brain with Alzheimer's Disease

Copper ion (Cu²⁺) and L ‐cysteine (CySH) are closely correlated with physiological and pathological events of Alzheimer’s Disease (AD), however the detailed mechanism is still unclear, mainly owing to a lack of accurate analytical methods in live brains. Herein, we report a single biosensor for electrochemical ratiometric detection of Cu²⁺ and CySH in live rat brains with AD. N,N‐di‐(2‐picoly)ethylenediamine (DPEA) is first synthesized for specific recognition of Cu²⁺ to form a DPEA–Cu²⁺ complex. This complex shows high selectivity for CySH owing to the release of Cu²⁺ from the complex through CySH binding to Cu²⁺ center. In parallel, 5′‐MB‐GGCGCGATTTTTTTTTTTTT‐SH‐3′ (HS‐DNA‐MB, MB=Methylene Blue) is designed as an inner‐reference for providing a built‐in correction to improve the accuracy. As a result, combined with the amplified effect of Au nanoleaves, our single ratiometric biosensor can be successfully applied in real‐time detection of Cu²⁺ and CySH in the live rat brains with AD. To our knowledge, this is the first report on the accurate concentrations of Cu²⁺ and CySH in live rat brains with AD.     

Integrating NiCo Alloys with Their Oxides as Efficient Bifunctional Cathode Catalysts for Rechargeable Zinc–Air Batteries

The lack of high‐efficient, low‐cost, and durable bifunctional electrocatalysts that act simultaneously for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) is currently one of the major obstacles to commercializing the electrical rechargeability of zinc–air batteries. A nanocomposite CoO‐NiO‐NiCo bifunctional electrocatalyst supported by nitrogen‐doped multiwall carbon nanotubes (NCNT/CoO‐NiO‐NiCo) exhibits excellent activity and stability for the ORR/OER in alkaline media. More importantly, real air cathodes made from the bifunctional NCNT/CoO‐NiO‐NiCo catalysts further demonstrated superior performance to state‐of‐the‐art Pt/C or Pt/C+IrO₂ catalysts in primary and rechargeable zinc–air batteries.     

Green synthesis of nanowire-like Pt nanostructures and their catalytic properties

We reported a simple and effective green chemistry route for facile synthesis of nanowire-like Pt nanostructures at one step. In the reaction, dextran acted as a reductive agent as well as a protective agent for the synthesis of Pt nanostructures. Simple mixing of precursor aqueous solutions of dextran and K₂PtCl₄ at 80 °C could result in spontaneous formation of the Pt nanostructures. Optimization of the experiment condition could yield nanowire-like Pt nanostructures at 23:1 molar ratio of the dextran repeat unit to K₂PtCl₄. Transmission electron microscopy results revealed that as-prepared nanowire-like Pt nanostructures consisted of individual Pt nanoparticles with the size range from 1.7 to 2.5 nm. Dynamic light scattering analysis indicated that as-prepared nanowire-like nanostructures have already formed in solution. The as-prepared nanowire-like Pt nanostructures were further characterized by UV-vis spectroscopy, X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. In addition, the ratio dependence and temperature dependence of this reaction have also been investigated. The as-prepared nanowire-like Pt nanostructures can be immobilized on glassy carbon electrodes using an electrochemical coupling strategy, and the resulting nanowire-like Pt nanostructures modified film exhibited an excellent electrocatalytic activity for the reduction of oxygen and the oxidation of NADH.     

One‐Pot Synthesis of Pt–Co Alloy Nanowire Assemblies with Tunable Composition and Enhanced Electrocatalytic Properties

Three‐dimensional (3D) Pt‐based alloy nanostructures composed of one‐dimensional (1D) nanowires/nanorods have recently attracted significant interest as electrocatalysts. In this work, we report an effective solvothermal method for the direct preparation of 3D Pt–Co nanowire assemblies (NWAs) with tunable composition. The composition‐ and structure‐dependent electrocatalytic performance is thoroughly investigated. Because of the bimetallic synergetic effect and unique structural advantage, the as‐prepared 3D Pt₃Co NWA outperforms commercial Pt/carbon and Pt black catalysts and even 3D Pt NWA. The electrochemical results demonstrate that the 3D Pt₃Co NWA is indeed a promising electrocatalyst with enhanced catalytic activity and improved durability for practical electrocatalytic applications.     

Study on the Electrochemical Behavior of Dopamine and Uric Acid at a 2‐Amino‐5‐mercapto‐[1,3,4] Triazole Self‐Assembled Monolayers Electrode

Selected from a series of structurally related heteroaromatic thiols, a newly synthesized reagent 2‐amino‐5‐mercapto‐[1,3,4] triazole (MATZ) was used to fabricate self‐assembled monolayers (SAMs) on gold electrode for the first time. The MATZ/Au SAMs was characterized by electrochemical methods and scanning electronic microscopy (SEM). In 0.04 mol/L Britton–Robinson buffer solution (pH 5), the electrochemical behavior of dopamine showed a quasireversible process at the MATZ/Au SAMs with an electrode kinetic constant 0.1049 cm/s. However, the electrochemical reaction of uric acid at the SAMs electrode showed an irreversible oxidation process, the charge‐transfer kinetics of uric acid was promoted by the SAMs. By Osteryoung square‐wave voltammetry (OSWV), the simultaneous determination of dopamine and uric acid can be accomplished with an oxidation peak separation of 0.24 V, the peak current of dopamine and uric acid were linearly to its concentration in the range of 2.5×10^?6–5.0×10^?4 mol/L for dopamine and 1×10^?6–1×10^?4 mol/L for uric acid with a detection limit of 8.0×10^?7 mol/L for dopamine and 7.0×10^?7 mol/L for uric acid. The MATZ/Au SAMs electrode was used to detect the content of uric acid in real urine and serum sample with satisfactory results.