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A label-free method that can doubly image both the physical patterns and the electrochemical information of latent fingerprints (LFPs) on nitrocellulose (NC) membrane has been achieved here by water and scanning electrochemical microscopy (SECM). In this approach, the NC membrane with LFP (LFP/NC) sample was first placed in water, where the different absorption of water onto relatively hydrophobic ridge residues of LFP versus NC membrane background resulted in a high-resolution physical ridge pattern of the fingerprint to naked eyes within just 1?3 s and could further be photographed by a digital camera. Thereafter, the LFP/NC sample was electrochemically imaged by recording the current variations of SECM tip scanning over the label-free fingerprint in the surface-interrogation (SI) mode. The methyl viologen (MV2+) was chosen as the redox mediator to react selectively with the electroactive species in the fingerprint ridge residues rather than furrow regions, which could cause the sharp contrast of the SECM tip current for imaging. Both the collected physical and electrochemical images of LFPs can provide high resolution up to level 2 and level 3 features required for personal identification. In addition, for the first time commercial NC membrane instead of adhesive forensic tape was discovered here for lifting the LFPs from various surfaces, which can then be imaged by this electrochemical approach. Taken together, this method demonstrates a powerful strategy for directly imaging the electrochemical information in LFPs without damaging the fingerprint physical ridge pattern on various substrates, so it has great potentiality in individual identity related applications.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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A new method for the hydrosilylation of alkynes controlled by a platinum catalyst with a monophosphine ligand (called TBSO-MOP) was explored. The platinum-catalyzed multicomponent and sequential silylation reaction involving alkynes, alcohols, and dihydrosilanes resulted in the highly stereoselective and high-yielding construction of functional (E)-vinylsilyl ethers. Moreover, the one-pot bis-hydrosilylation of terminal alkynes with dihydrosilanes was also achieved with the same platinum catalyst system.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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For the first time a novel, simple and facile approach is described to construct highly stable glucose oxidase (GOx) multilayer onto glassy carbon (GC) electrode using thiourea (TU) as a covalent attachment cross-linker. The layer by layer (LBL) attachment process was confirmed by cyclic voltammetry, electrochemical impedance spectroscopy and Fourier transform infrared reflection spectroscopy (FT-IR-RS) techniques. Immobilized GOx shows excellent electrocatalytic activity toward glucose oxidation using ferrocenemethanol as artificial electron transfer mediator and biosensor response was directly correlated to the number of bilayers. The surface coverage of active GOx per bilayer, heterogeneous electron transfer rate constant (ks) and Michaelis-Menten constant (KM), of immobilized GOx were 1.50 × 10-12 mol cm-2, 9.2 ± 0.5 s-1 and 3.42(±0.2) mM, respectively. The biosensor constructed with four-bilayers of TU/GOx showed good stability, high reproducibility, long life-time, fast amperometric response (5 s) with the high sensitivity of 5.73 muA mM -1 cm-2 and low detection limit of 6 muM at concentration range up to 5.5 mM.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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The inhibitive effects of alternating current-treated (AC-treated) mixed self-assembled monolayer (SAMHL/DT) with 2-(Pyridin-2-yliminomethyl)-phenol (HL) and dodecanethiol (DT) on copper corrosion have been studied by using the scanning electrochemical microscope (SECM) combined with Tafel and electrochemical impedance spectroscopy (EIS) methods When the AC-treated potential is applied in the cathodic region, the inhibition efficiency increases, and the pitting dynamic processes are inhibited. All the results reveal that the AC-treated effects are related to both the formation of complex compounds and the reduction of the oxide film on the surface of copper.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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A novel, simple and label-free multianalyte immunoassay system is presented here by integrating arrayed electrodes on a silicon chip via MEMS. The chip is consisted of six Au disk electrodes, an Au counter electrode and an Ag/AgCl reference electrode. Semi-insulating poly(o-phenylenediamine) (PoPD) was utilized to co-polymerize and immobilize antibodies at the arrayed Au electrodes, and wider linear detection range was obtained than those prepared with completely insulating PoPD. Electrochemical cyclic voltammogram (CV), AC impedance spectroscopy, AFM and fluorescence microscopy were employed to characterize the system. The arrayed electrodes offered exact control of deposition position via electrochemical operation, allowing selectively immobilization of different antibodies at desired positions on a single chip. Specific recognition of antibody (Ab) to corresponding antigen (An) was quantitatively monitored by cyclic voltammograms in the presence of electrochemical redox probe, ferrocene methanol. The proposed immunoassay chips showed sensitive response to three liver fibrosis markers, hyaluronic acid (HA), collagen type IV (IV-C) and lamin (LN) at ng/mL level simultaneously and specifically in a tiny amount of volume, usually 50 muL. The results obtained via chips were well consistent with those obtained by commercial radio immunoassays (RIA).

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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In this review, we summarize recent advances in nanoscale electrochemistry, including the use of nanoparticles, carbon nanomaterials, and nanowires. Exciting developments are reported for nanoscale redox cycling devices, which can chemically amplify signal readout. We also discuss promising high-frequency techniques such as nanocapacitive CMOS sensor arrays or heterodyning. In addition, we review electrochemical microreactors for use in (drug) synthesis, biocatalysis, water treatment, or to electrochemically degrade urea for use in a portable artificial kidney. Electrochemical microreactors are also used in combination with mass spectrometry, e.g., to study the mimicry of drug metabolism or to allow electrochemical protein digestion. The review concludes with an outlook on future perspectives in both nanoscale electrochemical sensing and electrochemical microreactors. For sensors, we see a future in wearables and the Internet of Things. In microreactors, a future goal is to monitor the electrochemical conversions more precisely or ultimately in situ by combining other spectroscopic techniques.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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The electron self-exchange rate constants for the (trimethylammonio) methylferrocene(+/2+) couple (FcTMA+/2+) have been measured in the absence and presence of the cucurbit[7]uril (CB[7]) host molecule in aqueous solution, using 1H NMR line-broadening experiments. The very strong binding of the ferrocene to CB[7] results in slow exchange of the guest on the NMR time scale, such that resonances for both the free and bound forms of the reduced ferrocene can be observed. The extents of line broadening in the resonances of the two forms of the guest in the presence of the FcTMA 2+ species can be monitored independently, allowing for the determination of the rate constants for the possible self-exchange pathways involving the bound and free forms of both the oxidized and reduced members of the redox couple. The encapsulation of both the reduced and oxidized forms of the ferrocene increases the rate constant (25C) from (2.1 ± 0.1) × 106 M-1 s-1 (for FcTMA+/2+) to (6.7 ± 0.7) × 106 M-1 s-1 (for {FcTMA-CB[7]}+/2+), whereas inclusion of the reduced form only decreases the rate constant to (6 ± 1) × 105 M -1 s-1. The changes in the exchange rate constants upon inclusion of the reactants are related to the effects of CB[7] acting as an outer, second-coordination sphere and are compared to those observed previously for the electron-exchange process in the presence of beta-cyclodextrin and p-sulfonated calix[6]arene hosts. The binding of FcTMA+ and hydroxymethylferrocene to CB[7] significantly reduces the rate constants for their oxidations by the bis(2,6-pyridinedicarboxylato)cobaltate(III) ion (which does not bind to CB[7]) as a result of reduced thermodynamic driving forces and steric hindrance to close approach of the oxidant to the encapsulated ferrocenes.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Uniform, vertically aligned multiwalled carbon nanotube arrays (VACNTs) were grown on glassy carbon-like thin films by thermal chemical vapour deposition (CVD). Thin (5 nm) aluminum and iron catalyst layers were pre-deposited by evaporation on the carbon substrates and VACNTs were grown at 750 C by water-assisted CVD using ethylene as the carbon source. The aluminum layer was shown to be essential for aligned nanotube growth. VACNT arrays adhered strongly to the carbon film with low contact resistance between the VACNTs and the substrate. The VACNT arrays grown directly on the planar conducting carbon substrate have attractive properties for use as electrodes. Excellent voltammetric characteristics are demonstrated after insulating the arrays with a dielectric material.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Ferrocenylalkyl 2-mercaptobenzimidazoles 3 (a-e) and 2-mercaptobenzo[d]thiazole-2(3H)-thiones 5 (a-e) were prepared via the reaction of the alpha-(hydroxy)alkyl ferrocenes, FcCHR(OH) (1a-e; Fc = ferrocenyl; R = H, Me, Et, i-Pr, Ph), either with thiobenzimidazole in acetone at room temperature in the presence of TFA (catalytic amounts), in yields of 55-74%, or with thiobenzothiazole in methylendicloride in presence of aqueous HBF4 (equimolar amounts) at r.t.; in yields of 41-58%. The structures, electrochemical properties and enantiomeric resolution 3a-e and 5a-e (using HPLC on modified amylose as chiral selector) were investigated. In cyclic voltammetry all studied compounds exhibited a reversible one-electron oxidation-reduction wave owing to the ferrocene-ferricenium redox couple with a positive shift (0.56-0.80 V) compared with that of ferrocene (0.50 V). X-ray determinations of molecular structures of 3-ferrocenylmethylbenzo[d]thiazole-2(3H)-thione (5a) 3-ferrocenylethylbenzo[d]thiazole-2(3H)-thione (5b) and 3-ferrocenylphenylmethylbenzo[d]thiazole-2(3H)-thione (5d) were carried out. The toxicity and antitumor activity of N-(ferrocenylethyl)-2-thiobenzimidazole (3b) were evaluated in vivo. Maximum tolerated dose (MTD) value for the compound 3b was found to be equal to 800 mg kg-1. The effectiveness of compound under investigation against murine solid tumor system, carcinoma Ca755 (Ca755), was studied in a wide range of doses and significant antitumor effects were found. The index of tumor growth inhibition (TGI) on Ca755 equaled 87% in comparison with control.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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L10-ordered FePt nanoparticles (NPs) with ultra-high coercivity were directly prepared from a new metallopolyyne using a one-step pyrolysis method. The chemical ordering, morphology and magnetic properties of the as-synthesized FePt NPs have been studied. Magnetic measurements show the coercivity of these FePt NPs is as high as 3.6 T. Comparison of NPs synthesized under the Ar and Ar/H2 atmospheres shows that the presence of H2 in the annealing environment influences the nucleation and promotes the growth of L10-FePt NPs. Application of this metallopolymer for bit-patterned media was also demonstrated using nanoimprint lithography.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion