Electrical, structural, and optical properties of sulfurized Sn-doped In2O 3 nanowires.

Sn-doped In2O3 nanowires have been grown on Si via the vapor-liquid-solid mechanism at 800 °C and then exposed to H2S between 300 to 600 °C. We observe the existence of cubic bixbyite In2O3 and hexagonal SnS2 after processing the Sn:In2O3 nanowires to H2S at 300 °C but also cubic bixbyite In2O3, which remains dominant, and the emergence of rhombohedral In2(SO4)3 at 400 °C. The resultant nanowires maintain their metallic-like conductivity, and exhibit photoluminescence at 3.4 eV corresponding to band edge emission from In2O3. In contrast, Sn:In2O3 nanowires grown on glass at 500 °C can be treated under H2S only below 200 °C which is important for the fabrication of Cu2S/Sn:In2O3 core-shell p-n junctions on low-cost transparent substrates such as glass suitable for quantum dot-sensitized solar cells.

Memristive and neuromorphic behavior in a Li(x)CoO2 nanobattery.

The phenomenon of resistive switching (RS), which was initially linked to non-volatile resistive memory applications, has recently also been associated with the concept of memristors, whose adjustable multilevel resistance characteristics open up unforeseen perspectives in cognitive computing. Herein, we demonstrate that the resistance states of Li(x)CoO2 thin film-based metal-insulator-metal (MIM) solid-state cells can be tuned by sequential programming voltage pulses, and that these resistance states are dramatically dependent on the pulses input rate, hence emulating biological synapse plasticity. In addition, we identify the underlying electrochemical processes of RS in our MIM cells, which also reveal a nanobattery-like behavior, leading to the generation of electrical signals that bring an unprecedented new dimension to the connection between memristors and neuromorphic systems. Therefore, these LixCoO2-based MIM devices allow for a combination of possibilities, offering new perspectives of usage in nanoelectronics and bio-inspired neuromorphic circuits.

Correlations of synthetic, spectroscopic, structural, and speciation studies in the biologically relevant cobalt(II)-citrate system: the tale of the first aqueous dinuclear cobalt(II)-citrate complex.

Synthetic efforts targeting soluble species of Co(II) with the low molecular mass physiological ligand citric acid led to the isolation of the first dinuclear complex [Co(2)(C(6)H(5)O(7))(2)(H(2)O)(4)](2-), at pH approximately 5, in the form of its K+ (1) and Na+ (2) salts. Both 1 and 2 were characterized analytically, spectroscopically (FT-IR, UV/visible, EPR), and magnetically. Complex 1 crystallizes in the monoclinic space group P2(1)/n, with a = 10.348(5) A, b = 11.578(6) A, c = 12.138(6) A, beta = 112.62(2) degrees, V = 1342(1) A(3), and Z = 2. Complex 2 crystallizes in the monoclinic space group P2(1)/c, with a = 9.234(4) A, b = 11.913(4) A, c = 11.728(6) A, beta = 99.93(2) degrees, V = 1271(1) A(3), and Z = 2. X-ray crystallography on 1 and 2 reveals the presence of two Co(II) ions, in a dinuclear assembly, octahedrally coordinated by two citrate ligands in a tridentate fashion. The octahedral environment around each Co(II) is complemented by another singly bonded citrate belonging to the adjacent Co(II) unit and two water molecules. Magnetic susceptibility and EPR studies on 1, in the solid state, corroborate the X-ray results, indicating a weak interaction between the two Co(II) ions. Moreover, EPR and UV/visible studies in solution suggest that 1 does not retain its dimeric structure, yielding a mononuclear octahedral Co(II)-citrate species. Detailed speciation studies suggest the presence of a number of species including the mononuclear complex [Co(C(6)H(5)O(7))](-), optimally present around pH approximately 5. In consonance with EPR and UV/visible spectroscopy, [Co(C(6)H(5)O(7))](-) is likely the scaffolding unit on the basis of which the dimer [Co(2)(C(6)H(5)O(7))(2)(H(2)O)(4)](2-) is isolated from aqueous solutions. Collectively, this comprehensive study offers significant structural insight into the Co(II)-citrate speciation and the elucidation of the role of Co(II) in biological fluids.

Synthesis and structural and spectroscopic characterization of a complex between Co(II) and imino-bis(methylphosphonic acid): gaining insight into biologically relevant metal-ion phosphonate interactions or looking at a new Co(II)-organophosphonate material?

Cobalt is an essential metal ion involved in key biomolecules, regulating processes in human physiology. As a metal ion, Co(II) assumes forms, which are dictated by the nature of organic binders in biological fluids, and the conditions under which metal ion ligand interactions arise. Among the various low molecular mass metal ion binders in biological fluids are amino acids, organic acids, as well as their variably phosphorylated forms. As a representative metal ion binder, the organophosphonate ligand H(2)O(3)P-CH(2)-NH(2)(+)-CH(2)-PO(3)H(-) was employed in aqueous reactions with Co(II), ultimately leading to the isolation of complex [Co(C(2)H(8)O(6)NP(2))(2)(H(2)O)(2)] (1) at pH 2. The complex was characterized analytically, spectroscopically (FTIR, UV-vis, EPR), and magnetically. Compound 1 crystallizes in the monoclinic space group P2(1)/n, with a = 7.361(3) A, b = 8.133(3) A, c = 14.078(5) A, beta = 104.40(1) degrees, V = 816.3(5) A(3), and Z = 2. X-ray crystallography reveals that 1 is a compound with a molecular type of lattice. In it, there exist mononuclear octahedral sites of Co(II) surrounded by oxygens, belonging to terminal phosphonates and bound water molecules. Both ends of the ligand zwitterionic form are involved in binding to adjacent Co(II) ions, thus creating tetranuclear 32-membered rings, with cavities extending in two dimensions and holes in the third dimension throughout the lattice of 1. Similar structural features were observed in other metal organophosphonate lattices of potential catalytic and chemical reactivity. The magnetic and EPR data on 1 support the presence of a high-spin octahedral Co(II) in an oxygen environment, having a ground state with an effective spin S = (1)/(2). The solution UV-vis and EPR data suggest retention of the high-spin octahedral Co(II) ion, consistent with the magnetization measurements on 1. Collectively, the data reflect the existence of a soluble Co(II)-iminodiphosphonate species not unlike those expected in biological fluids containing the specific ligand or ligands similar to that. Both biologically relevant perspectives and a synthetic outlook into Co(II)-organophosphonate materials are discussed.

Vanadium(IV)-citrate complex interconversions in aqueous solutions. A pH-dependent synthetic, structural, spectroscopic, and magnetic study.

Citrate is abundantly encountered in biological fluids as a natural metal ion chelator. Vanadium participates in biological processes as a catalyst in the active sites of metalloenzymes, as a metabolic regulator, as a mitogenic activator, and as an insulin-mimicking agent. Thus, vanadium chemistry with natural chelators, such as citrate, may have immediate implications on its role in a cellular milieu, and its action as a biological agent. In an effort to comprehend the aqueous chemistry of one of vanadium's oxidation states, namely, V(IV), implicated in its biological activity, reactions of VCl(3) and citric acid were pursued in water and led to V(IV)-citrate complexes, the nature and properties of which depend strongly on the solution pH. Analytical, FT-IR, UV/vis, EPR, and magnetic susceptibility data supported the formulation of X(4)[[VO(H(-1)Cit)](2)] x nH(2)O (H(-1)Cit = C(6)H(4)O(7)(4-); X = K(+), n = 6 (1); X = Na(+), n = 12 (2); X = NH(4)(+), n = 2 (3)) (pH approximately 8) and X(3)[[V(2)O(2)(H(-1)Cit)(Cit)]] x nH(2)O (X = K(+), n = 7 (4)) (pH approximately 5). Complex 2 crystallizes in space group P2(1)/c, a = 11.3335(9) A, b = 15.788(1) A, c = 8.6960(6) A, beta = 104.874(3) degrees, V = 1503.8(2), Z = 2. Complex 3 crystallizes in space group P one macro, a = 9.405(1) A, b = 10.007(1) A, c = 13.983(2) A, alpha = 76.358(4) degrees, beta = 84.056(4) degrees, gamma = 66.102(4) degrees, V = 1169.2(3), Z = 2. Complex 4 crystallizes in space group P2(1)nb, a = 9.679(4) A, b = 19.618(8) A, c = 28.30(1) A, V = 5374.0(4), Z = 8. The X-ray structures of 1-4 are V(2)O(2) dimers, with the citrate displaying varying coordination numbers and modes. 1 exhibits a small ferromagnetic interaction, whereas 4 exhibits an antiferromagnetic interaction between the V(IV) ions. 1 and 4 interconvert with pH, thus rendering the pH a determining factor promoting variable structural, electronic, and magnetic properties in V(IV)-citrate species. The observed aqueous behavior of 1-4 is consistent with past solution speciation studies, and contributes to the understanding of significant aspects of the biologically relevant vanadium(IV)-citrate chemistry.

Synthesis, spectroscopic, and structural characterization of the first aqueous cobalt(II)-citrate complex: toward a potentially bioavailable form of cobalt in biologically relevant fluids.

Citric acid represents a class of carboxylic acids present in biological fluids and playing key roles in biochemical processes in bacteria and humans. Its ability to promote diverse coordination chemistries in aqueous media, in the presence of metal ions known to act as trace elements in human metabolism, earmarks its involvement in a number of physiological functions. Cobalt is known to be a central element of metabolically important biomolecules, such as B12, and therefore its biospeciation in biological fluids constitutes a theme worthy of chemical and biological perusal. In an effort to unravel the aqueous chemistry of cobalt in the presence of a physiologically relevant ligand, citrate, the first aqueous, soluble, mononuclear complex has been synthesized and isolated from reaction mixtures containing Co(II) and citrate in a 1:2 molar ratio at pH approximately 8. The crystalline compound (NH4)4[Co(C6H5O7)2] (1) has been characterized spectroscopically (UV/vis, EPR) and crystallographically. Its X-ray structure consists of a distorted octahedral anion with two citrate ligands fulfilling the coordination requirements of the Co(II) ion. The magnetic susceptibility measurements of 1 in the range from 6 to 295 K are consistent with a high-spin complex containing Co(II) with a ground state S=3/2. Corroborating this result is the EPR spectrum of 1, which shows a signal consistent with the presence of a Co(II) system. The spectroscopic and structural properties of the complex signify its potential biological relevance and participation in speciation patterns arising under conditions consistent with those employed for its synthesis and isolation.

Manganese citrate chemistry: syntheses, spectroscopic studies, and structural characterizations of novel mononuclear, water-soluble manganese citrate complexes.

The first two mononuclear manganese citrate complexes, (NH4)4[MnII(C6H5O7)2] (1) and (NH4)5[MnIII(C6H4O7)2].2H2O (2) were synthesized in aqueous solutions near physiological pH values. They were isolated in their pure crystalline forms and characterized by elemental analyses and spectroscopic techniques, including UV/visible, electron paramagnetic resonance, Fourier transformed infrared, and magnetic susceptibility measurements. Compound 1 crystallizes in the monoclinic space group P2(1)/c, with a = 8.777(1) A, b = 13.656(3) A, c = 9.162(2) A, beta = 113.62(2) degrees, V = 1006.2(6) A3, and Z = 2. Compound 2 crystallizes in the triclinic space group P1, with a = 9.606(3) A, b = 9.914(3) A, c = 7.247(3) A, alpha = 91.05(1) degrees, beta = 105.60(1) degrees, gamma = 119.16(1) degrees, V = 571.3(3) A3, and Z = 1. The X-ray crystal structures of 1 and 2 revealed that, in both cases, the manganese ion is six-coordinate and is bound by two citrate ligands in a distorted octahedral fashion. In the case of complex 1, the citrate ion binds to Mn2+ as a triply deprotonated ligand, retaining the central carbon hydroxyl hydrogen, whereas, in the case of compound 2, the citrate ligand coordinates to Mn3+ as a fully deprotonated entity. Compound 2 contains water molecules of crystallization in the unit cell which, through extensive hydrogen-bonding interactions, bestow considerable stability upon the Mn(3+)-citrate assembly. There are significant contributions to the stabilities of the assembled lattices in 1 and 2 arising from the ammonium counterions neutralizing the high anionic charges of the complexes. The EPR spectra attest to the presence of paramagnetic Mn2+ and Mn3+ species in the solid state. Corroborative evidence is obtained from the magnetic susceptibility measurements in the range 5-300 K. Complexes 1 and 2 present clear cases of mononuclear manganese citrate species relevant to manganese speciation in biological media and potentially related to the beneficial as well as toxic effects of manganese on humans.