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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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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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Ferrocene-bridged trisporphyrin (2) was synthesized by two-steps condensation of corresponding aldehydes and dipyrromethanes, and its self-assembling behavior based on the complementary coordination motif of imidazolylporphyrinatozinc(II) was investigated in conjunction with hinge-like flexibility given by freely rotating cyclopentadienyl rings of ferrocene connector. Ferrocene-bridged trisporphyrin (2) spontaneously and exclusively generated the dimeric ring (7) upon simple zinc(II) insertion, indicating that the freely rotating hinge connector favored the smallest ring formation. Taking advantage of the unique hinge-like flexibility of ferrocene, we attempted to transform the dimer ring into a mixture of porphyrin macrocycles by reorganizing the structure cleaved once by pyridine. A series of porphyrin macrocycles from trimer to decamer can be separated into its components by preparative gel permeation chromatograms. Macrocycles obtained are kept stable in the absence of coordinating solvents. On the other hand, they were easily transformed to the dimer ring in the presence of coordinating solvents such as methanol, showing that the transformation is completely reversible and can be controlled by the choice of the solvent system. A series of porphyrin macrocycles was confirmed via covalent linking of each complementary coordination dimer pair by metathesis reaction in the presence of Grubbs’s catalyst. The coordination behavior of the bidentate ligands with different spacer lengths toward the dimer ring revealed that only the bidentate ligand (15) with a spacer length that matched the facing central porphyrins was selectively accommodated inside the ring. Coordination assembled flexible rings with tunable cavities and multiple coordination sites will be used as versatile hosts for a wide variety of guest molecules.

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The complexes [(H3N)5RuII(-NC)Mn ILx]2+, prepared from [Ru(OH 2)(NH3)5]2+ and [Mn(CN)L x] {Lx = trans-(CO)2{P(OPh)3}(dppm); cis-(CO)2(PR3)(dppm), R = OEt or OPh; (PR 3)(NO)(eta-C5H4Me), R = Ph or OPh}, undergo two sequential one-electron oxidations, the first at the ruthenium centre to give [(H3N)5RuIII(-NC)MnIL x]3+; the osmium(iii) analogues [(H3N) 5OsIII(-NC)MnILx]3+ were prepared directly from [Os(NH3)5(O3SCF 3)]2+ and [Mn(CN)Lx]. Cyclic voltammetry and electronic spectroscopy show that the strong solvatochromism of the trications depends on the hydrogen-bond accepting properties of the solvent. Extensive hydrogen bonding is also observed in the crystal structures of [(H 3N)5RuIII(-NC)MnI(PPh 3)(NO)(eta-C5H4Me)][PF6] 3·2Me2CO·1.5Et2O, [(H 3N)5RuIII(-NC)MnI(CO)(dppm) 2-trans][PF6]3·5Me2CO and [(H3N)5RuIII(-NC)MnI(CO) 2{P(OEt)3}(dppm)-trans][PF6] 3·4Me2CO, between the ammine groups (the H-bond donors) at the Ru(iii) site and the oxygen atoms of solvent molecules or the fluorine atoms of the [PF6]- counterions (the H-bond acceptors). The Royal Society of Chemistry 2006.

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A cesium fluoride-promoted reductive coupling reaction of acylferrocene tosylhydrazones with arylboronic acids has been developed, producing highly substituted alpha-arylalkylferrocenes in moderate to excellent yields. The reaction employs anionic fluorine to facilitate the cleavage of C?B bond. The developed methodology demonstrates a wide substrate scope and high functional groups tolerance. Moreover, the alpha-arylalkylferrocenes compounds were also obtained on a multi-gram scale.

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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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Reaction of [IrCp?Cl2]2 with ferrocenylimines (Fc=NAr, Ar=Ph, p-MeOC6H4) results in ferrocene C-H activation and the diastereoselective synthesis of half-sandwich iridacycles of relative configuration Sp?,RIr?. Extension to (S)-2-ferrocenyl-4-(1-methylethyl)oxazoline gave highly diastereoselective control over the new elements of planar chirality and metal-based pseudo-tetrahedral chirality, to give both neutral and cationic half-sandwich iridacycles of absolute configuration Sc,Sp,RIr. Substitution reactions proceed with retention of configuration, with the planar chirality controlling the metal-centred chirality through an iron-iridium interaction in the coordinatively unsaturated cationic intermediate.

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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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The chiral 1,1?-bis-acetals, bis-1,1?-[(2S, 4S)-(hydroxymethyl)-2-dioxane1,3]-ferrocene (3) and 1,1?-bis-1,1?-[(2S, 4S)-(methoxymethyl)-2-dioxane1,3]-ferrocene (4) were synthesized. (3) was crystallographically characterised. The ortholithiation of (4) was studied in various conditions. Fair yields of monosubstituted compounds could be obtained with a complete regioselectivity in favor of the 2 position but the diastereoselectivities were moderate (up to 35%). Some disubstituted compounds can be isolated but in low yields (up to 8%). The regioselectivity is complete in favor of the 2,2?-disubstituted isomer. Only the diastereoisomer with two opposite planar chiralities is observed.

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Molecular or supramolecular level photoluminescence (PL) modulation combining chemical and photonic input/output signals together in an integrated system can provide potential high-density data memorizing and process functions intended for miniaturized devices and machines. Herein, a PL-responsive supramolecular coordination cage has been demonstrated for complex interactions with redox-active guests. PL signals of the cage can be switched and modulated by adding or retracting Fc derivatives or converting TTF into different oxidation states through chemical or photochemical pathways. As a result, reversible or stepwise PL responses are displayed by these host?guest systems because of the occurrence of photoinduced electron-transfer (PET) or fluorescence resonance energy transfer (FREnT) processes, providing unique nanodevice models bearing off/on logic gates or memristor-like sequential memory and Boolean operation functions.

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