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An alternative and efficient approach for the synthesis of N-alkylated amides from nitriles and alcohols was proposed and accomplished. By the combination of [(IPr)Au(NTf2)] (IPr = 1,3-bis(diisopropylphenyl)imidazol-2-ylidene) and [CpIrCl2]2 (Cp = eta5-pentamethylcyclopentadienyl), a series of nitriles were first hydrated to give amides, in which the resulting amides were further N-alkylated with a variety of alcohols as alkylating agents to afford N-alkylated amides with good to excellent yields. Compared with previous methods for the synthesis of N-alkylated amides from nitriles and alcohols as starting materials, this protocol could be accomplished with high atom economy under more environmentally benign conditions.

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An ultrasensitive electrochemical biosensor for detecting microRNAs is fabricated based on hollow molybdenum disulfide (MoS2) microcubes. Duplex-specific nuclease, enzyme and electrochemical?chemical?chemical redox cycling are used for signal amplification. Hollow MoS2 microcubes constructed by ultrathin nanosheets are synthesized by a facile template-assisted strategy and used as supporting substrate. For biosensor assembling, biotinylated ssDNA capture probes are first immobilized on Au nanoparticles (AuNPs)/MoS2 modified electrode in order to combine with streptavidin-conjugated alkaline phosphatase (SA-ALP). When capture probes hybridize with miRNAs, duplex-specific nuclease cleaves the formative duplexes. At the moment, the biotin group strips from the electrode surface and SA-ALP is incapacitated to attach onto electrode. Then, ascorbic acids induce the electrochemical?chemical?chemical redox cycling to produce electrochemical response in the presence of ferrocene methanol and tris (2-carboxyethyl) phosphine. Under optimum conditions, the proposed biosensor shows a good linear relationship between the current variation and logarithm of the microRNAs concentration ranging from 0.1 fM to 0.1 pM with a detection limit of 0.086 fM (S/N=3). Furthermore, the biosensor is successfully applied to detect target miRNA-21 in human serum samples.

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The electrochemical reduction of carbon dioxide is very much in the focus of interest today. Intensive research is carried out in leading laboratories trying to work out methods for making useful materials from this unwanted greenhouse gas using solar or wind power generated excess electric energy. In this work, electrochemical reduction experiments are carried out in homemade cells supplied with different metal electrodes. Electrolytes containing carbon dioxide absorbing components like monoethanolamine (MEA) or KHCO3, KOH, and K2CO3 solutions are used. Metal-containing species were noticed in the used electrolytes after being in contact with the metal working electrodes. Therefore parallel to the electrochemical measurements, the metal components in the electrolyte were checked with atomic absorption methods for getting better insight into the nature of the electrode passivation. This paper attempts to compare the behavior of different electrode materials (copper, nickel) in CO2 capturing media, and investigate of the products of the electrolysis using Scanning Electrochemical Microscopy (SECM), Atomic Absorption Spectroscopy (AAS) and gas chromatography.

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The phthalonitrile derivative chosen for the synthesis of substituted phthalocyanines [M: 2H, Zn(II), Co(II)] with four chloro and four phenyloxyacetic acid substituents on the periphery is 4-chloro-5-(4-phenyloxyacetic acid)phthalonitrile. The sodium salt of carboxyl substituted zinc phthalocyanine is good soluble in water. Further reactions of zinc and cobalt phthalocyanines bearing phenyloxyacetic acid with thionylchloride gave the corresponding acylchlorides. This functional group reacted with hydroxymethylferrocene in dry DMF to obtain ferrocenyl substituted phthalocyanines. Also chloro substituent in new phthalonitrile was substituted with hexylsulfanyl substituent and its cyclotetramerization in the presence of Zn(AcO)2·2H2O and 2-(dimethylamino)ethanol resulted with zinc phthalocyanine. The compounds have been characterized by elemental analysis, MALDI-TOF mass, FT-IR, 1H NMR, UV-Vis and fluorescence data. Aggregations properties of phthalocyanines were investigated at different concentrations in tetrahydrofuran, dimethylformamide, dimethylsulfoxide, water, and water/ethanol mixture. Also fluorescence spectral properties are reported.

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Scanning electrochemical microscopy, SECM, is proposed as a tool for the fabrication of copper nanowires. In a first step, configuration based on two electrodes, a platinum UME (cathode) and a copper substrate (anode), operating in the SECM configuration was employed. For nanowires generated in water the conductance changes stepwise and varies by integer values of the conductance quantum G0. The formation of atomic contacts is supported by the ohmic behavior of the I-V curve. It depends neither on the UME tip radius nor on the initial gap size between tip and substrate. Atomic contacts generated in aqueous solutions of sodium dodecyl sulfate (SDS) below the critical micellar concentration (CMC) have conductances below 1G0 attributed to molecular adsorption on the contact. In some cases, the nanowires have low conductance, 0.01G0. The corresponding I-V curve shows tunneling rather than ohmic behavior, suggesting that molecular junctions are formed with a few surfactant molecules trapped between the two electrodes. Finally, copper nanowires with quantized conductance have been generated using the SECM operating in a four-electrode setup. Thanks to the reference electrode, this configuration leads to better control of the potential of each working electrode; this setup will make it possible to evaluate the conductance variation and/or modulation upon electrochemical stimuli.

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The design and characterization of a lactate biosensor using a nanostructured rough gold surface as a transducer is reported. The biosensor is developed by immobilization of lactate oxidase (LOx), on a rough gold electrode modified with a self-assembled monolayer of dithiobis-N-succinimidyl propionate (DTSP). This bifunctional reagent preserves the rough gold structure and allows further covalent immobilization of the enzyme through the terminal succinimidyl groups. The rough gold electrode is characterized using field emission scanning electron microscopy (FE-SEM) and atomic force microscopy (AFM). The preferential orientation and average crystallite size are obtained by X-ray diffraction (XRD). The resulting lactate oxidase monolayers are characterized by electrochemical impedance spectroscopy (EIS). This nanostructured transducer allows higher mediated electrocatalytic activity than polycrystalline ones. The biosensor response to increasing lactate concentrations, using hydroxymethylferrocene as a redox mediator in solution, is linear up to 1.2mM with a sensitivity of 1.49muAmM-1.

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This work illustrates how polyamide nanofibrous membranes, prepared by the electrospinning process, can act as a new type of biosensor element. The sensing unit is based on a glassy carbon electrode coated with polyamide nanofibrous membranes, in which glucose oxidase is covalently tethered. The work is carried out by means of transient electrochemical techniques, such as cyclic voltammetry and amperometry, in which ferrocene methanol was employed as mediator. The results show that nanofibrous membranes are an excellent support for the development of biosensors thanks to their high-surface to volume ratio, high porosity and permeability of the cosubstrate and minimal effect on both the biocatalytic kinetics and the selectivity of the biorecognition event. The optimization, characterization, and attractive performance of the nanofibrous biosensor are reported in connection with the detection of glucose in a variety of food beverages.

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Probing the central metal with NMR can provide a wealth of information on the geometrical and electronic structure of transition-metal compounds. Accurate quantum-chemical computations of the salient metal NMR parameters can be a valuable complement to experiments, which are frequently plagued by low sensitivity, poor resolution or other fundamental problems, in particular for quadrupolar nuclei. Current computational approaches are mainly rooted in density functional theory and face different challenges, namely the proper choice of the exchange-correlation functional, and the treatment of relativistic, solvation and dynamical effects. This review summarizes the present state-of-the art of first-principles approaches for computation of transition-metal NMR parameters, calling special attention to the isotropic chemical shifts. Typical accuracies that can be reached for different classes of compounds are given, and illustrative chemical applications are highlighted. Corresponding results are also discussed for the full magnetic shielding and nuclear quadrupole coupling tensors, relevant for solid-state NMR spectroscopy, as well as for indirect spin-spin coupling constants involving transition-metal nuclei. In many cases, the computations can lead to a deeper understanding of the factors influencing the NMR parameters.

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Direct inkjet printing of a complete and working amperometric biosensor for the detection of hydrogen peroxide, based on horseradish peroxidase (HRP), has been demonstrated. The device has been realized with a commercial printer. A thin layer of PEDOT:PSS, which was in turn covered with HRP, was inkjet printed on top of an ITO-coated glass slide. The active components of the device retained their properties after the thermal inkjet printing. The whole device has been encapsulated by means of a selectively permeable cellulose acetate membrane. The successful electron transfer between the PEDOT:PSS covered electrode and the enzyme has been demonstrated, and the biosensor evidenced very good sensitivity, in line with the best devices realized with other techniques, and a remarkable operational stability. This result paves the way for an extensive application of “biopolytronics”, i.e. the utilization of conductive/semiconductive polymers and biologically active molecules to design bioelectronic devices using a common PC, and exploiting normal commercial printers to print them out.

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Metallocenyl carbinols FcCH2OH (1a) and RcCH2OH (1b) dissolved in sc-CO2 penetrate into the acidic Nafion film under 20 MPa and 80 or 35 C. After removal of pressure and leaving at room temperature, the crystals rapidly formed on the surface of the film, were identified as ethers McCH2OCH2Mc, Mc = Fc or Rc, by X-ray study. Mechanism of their formation is discussed.

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