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D Mikhailova, N N Kuratieva, Y Utsumi, A A Tsirlin, A M Abakumov, M Schmidt, S Oswald, H Fuess, H Ehrenberg
The substitution of vanadium in vanadium dioxide VO2 influences the critical temperatures of structural and metal-to-insulator transitions in different ways depending on the valence of the dopant. Rhenium adopts valence states between +4 and +7 in an octahedral oxygen surrounding and is particularly interesting in this context. Structural investigation of V1-xRexO2 solid solutions (0.01 ≤ x ≤ 0.30) between 80 and 1200 K using synchrotron X-ray powder diffraction revealed only two polymorphs that resemble VO2: the low-temperature monoclinic MoO2-type form (space group P21/c), and the tetragonal rutile-like form (space group P42/mnm)...
January 16, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
Marianela Saldías, Jorge Manzur, Rodrigo E Palacios, María L Gómez, Julio De La Fuente, Germán Günther, Nancy Pizarro, Andrés Vega
Lithium diphenylphosphide unexpectedly provokes the ring-opening of tetrahydrofuran (THF) and by reaction with 3,6-dichloropyridazine leads to the formation of the ligand 3-chloro-6-(4-diphenylphosphinyl)butoxypyridazine (P⋯N), which was isolated. The reaction of this ligand with the (Re(CO)3(THF)Br)2 dimer yields the novel complex [Br(CO)3Re(μ-3-chloro-6-(4-diphenylphosphinyl)butoxypyridazine)2Re(CO)3Br] (BrRe(P⋯N)(N⋯P)ReBr), which was crystallized in the form of a chloroform solvate, (C46H40Br2Cl2N4O8P2Re2)·(CHCl3)...
January 16, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
Indranil Chakraborty, Samantha J Carrington, Graham Roseman, Pradip K Mascharak
Two manganese(I) carbonyl complexes derived from 2-(pyridyl)benzothiazole (pbt) and 1,10-phenanthroline (phen) release carbon monoxide (CO) under low-power broad-band visible-light illumination. CO photorelease from [Mn(CO)3(pbt)(PTA)]CF3SO3 (1, where PTA = 1,3,5-triaza-7-phosphaadamantane) is accompanied by an emergence of a strong fluorescence around 400 nm from almost nonfluorescent preirradiated 1. However, [Mn(CO)3(phen)(PTA)]CF3SO3 (2) showed no such phenomenon upon prolonged illumination under similar experimental conditions...
January 12, 2017: Inorganic Chemistry
Sebastian Schneider, Annette Strumpf, Johannes Schetelig, Gerd Wunderlich, Gerhard Ehninger, Jörg Kotzerke, Martin Bornhäuser
No abstract text is available yet for this article.
January 6, 2017: Biology of Blood and Marrow Transplantation
Luiz Duarte Ramos, Hugo Moreira da Cruz, Karina P Morelli Frin
fac-[Re(ampy)(CO)3(NN)](+) complexes (ampy = 2-aminomethylpyridine and NN = 1,10-phenanthroline (phen), and 2,2'-bipyridine (bpy)) were synthesized, purified and characterized by proton nuclear magnetic resonance ((1)H NMR), UV-visible and Fourier-transformed infrared (FT-IR) spectroscopies, and their photophysical properties were investigated using steady state and time-resolved emission spectroscopies. The electronic absorption spectra exhibit two main absorption bands: the higher energy band, which was assigned to intraligand transition (IL), and the lower energy band assigned to metal-to-ligand charge transfer (MLCT)...
January 5, 2017: Photochemical & Photobiological Sciences
Yudong Cui, Feifei Lu, Xueming Liu
Monolayer of transition metal dichalcogenides (TMDs), with lamellar structure as that of graphene, has attracted significant attentions in optoelectronics and photonics. Here, we focus on the optical absorption response of a new member TMDs, rhenium disulphide (ReS2) whose monolayer and bulk forms have the nearly identical band structures. The nonlinear saturable and polarization-induced absorption of ReS2 are investigated at near-infrared communication band beyond its bandgap. It is found that the ReS2-covered D-shaped fiber (RDF) displays the remarkable polarization-induced absorption, which indicates the different responses for transverse electric (TE) and transverse magnetic (TM) polarizations relative to ReS2 plane...
January 5, 2017: Scientific Reports
Eric M Pierce, Kristina Lilova, David M Missimer, Wayne W Lukens, Lili Wu, Jeffrey Fitts, Claudia Rawn, Ashfia Huq, Donovan N Leonard, Jeremy R Eskelsen, Brian F Woodfield, Carol M Jantzen, Alexandra Navrotsky
Treatment and immobilization of technetium-99 ((99)Tc) contained in reprocessed nuclear waste and present in contaminated subsurface systems represents a major environmental challenge. One potential approach to managing this highly mobile and long-lived radionuclide is immobilization into micro- and meso-porous crystalline solids, specifically sodalite. We synthesized and characterized the structure of perrhenate sodalite, Na8[AlSiO4]6(ReO4)2, and the structure of a mixed guest perrhenate/pertechnetate sodalite, Na8[AlSiO4]6(ReO4)2-x(TcO4)x...
December 27, 2016: Environmental Science & Technology
Lukasz J Raszeja, Daniel Siegmund, Anna L Cordes, Jörn Güldenhaupt, Klaus Gerwert, Stephan Hahn, Nils Metzler-Nolte
The synthesis and photophysical properties of a novel series of rhenium tricarbonyl complexes based on tridentate phenanthridinyl-containing ligands are described. Photophysical data reveal beneficial luminescence behaviour especially for compounds with an asymmetric ligand set. These advantageous properties are not limited to organic solvents, but indeed also improved in aqueous solutions. The suitability of our new rhenium complexes as potent imaging agents has been confirmed by fluorescence microscopy on living cancer cells, which also confirms superior long-time stability under fluorescence microscopy conditions...
December 23, 2016: Chemical Communications: Chem Comm
Hao Tang, Edward N Brothers, Michael B Hall
The noninnocent 2-diphenylphosphino-benzenethiolate (DPPBT) ligand containing both phosphorus and sulfur donors delocalizes the electron density in a manner reminiscent of dithiolenes. The electronic structure of the [ReL3](n) (L = DPPBT, n = 0, 1+, 2+) complexes was probed with density-functional theory (DFT) and high-level ab initio methods including complete active space self-consistent field (CASSCF and CASPT2) and coupled cluster (CCSD and CCSD(T)). DFT predicts a slight preference for a closed-shell (CS) singlet ground state for the neutral [ReL3](0) and stronger preferences for low-spin ground states for the oxidized [ReL3](+) and [ReL3](2+)...
January 3, 2017: Inorganic Chemistry
Christopher H Woodall, Gavin A Craig, Alessandro Prescimone, Martin Misek, Joan Cano, Juan Faus, Michael R Probert, Simon Parsons, Stephen Moggach, José Martínez-Lillo, Mark Murrie, Konstantin V Kamenev, Euan K Brechin
Materials that demonstrate long-range magnetic order are synonymous with information storage and the electronics industry, with the phenomenon commonly associated with metals, metal alloys or metal oxides and sulfides. A lesser known family of magnetically ordered complexes are the monometallic compounds of highly anisotropic d-block transition metals; the 'transformation' from isolated zero-dimensional molecule to ordered, spin-canted, three-dimensional lattice being the result of through-space interactions arising from the combination of large magnetic anisotropy and spin-delocalization from metal to ligand which induces important intermolecular contacts...
December 21, 2016: Nature Communications
Jonathan A Robson, Ferran Gonzàlez de Rivera, Khairil A Jantan, Margot N Wenzel, Andrew J P White, Oriol Rossell, James D E T Wilton-Ely
The disulfide ligand (SC6H4CO2H-4)2 acts as a simple but versatile linker for a range of group 8 transition metals through reaction of the oxygen donors. This leads to a range of homobimetallic ruthenium and osmium alkenyl compounds, [{M(CH═CHR)(CO)(PPh3)2(O2CC6H4S-4)}2] (M = Ru, Os; R = C6H4Me-4). Additional metal-based functionality can be added through the use of precursors incorporating rhenium bipyridine units (R = (bpy)ReCl(CO)3). The more robust diphosphine ligands in [{Ru(dppm)2(O2CC6H4S-4)}2](2+) (dppm = diphenylphosphinomethane) allow reduction of the disulfide bond with sodium borohydride to yield the thiol complex [Ru(O2CC6H4SH-4)(dppm)2](+)...
December 19, 2016: Inorganic Chemistry
Allen J Osinski, Tanner Blesener, Abed Hasheminasab, Cole Holstrom, Victor N Nemykin, Richard S Herrick, Christopher J Ziegler
Half-hemiporphyrazine macrocycles, which can be called "semihemiporphyrazines", were synthesized using the Re(CO)3 unit as a templating agent. The products of these template reactions are six-coordinate rhenium complexes, with a facial arrangement of carbonyls, a halide, and a bidentate semihemiporphyrazine chelate that tilts out of the plane of coordination. Three types of semihemiporphyrazines can be produced from these reactions, depending on the alternate heterocycle to the isoindoline unit; structures including pyridine, thiazole, and benzimidazole were formed...
December 19, 2016: Inorganic Chemistry
Genin Gary Huang, Chung-Jay Lee, Jyisy Yang, Che-Hao Chang, Malaichamy Sathiyendiran, Zong-Zhan Lu, Kuang-Lieh Lu
An evanescent wave infrared chemical sensor was developed to selectively detect volatile amines with heterocyclic or phenyl ring. To achieve this goal, a rhenium-based metallacycle with a "molecular-trap" structure was designed and synthesized as host molecules to selectively trap amines with heterocyclic or phenyl ring through Re-amine and π-π interactions. To explore the trapping properties of the material, a synthesized Re-based molecular trap was treated on an IR sensing element, and wide varieties of volatile organic compounds (VOCs) were examined to establish the selectivity for detection of amines...
December 28, 2016: ACS Applied Materials & Interfaces
Kokila Ranasinghe, Shiroma Handunnetti, Inoka C Perera, Theshini Perera
BACKGROUND: Re(I) tricarbonyl complexes exhibit immense potential as fluorescence imaging agents. However, only a handful of rhenium complexes have been utilized in biological imaging. The present study describes the synthesis of four novel rhenium complexes, their characterization and preliminary biological studies to assess their potential as biological imaging agents. RESULTS: Four facial rhenium tricarbonyl complexes containing a pyridyl triazine core, (L1 = 5,5'(3-(2-pyridyl)-1,2,4-triazine-5,6-diyl)-bis-2-furansulfonic acid disodium salt and L2 = (3-(2- pyridyl)-5,6-diphenyl-1,2,4-triazine-4',4''-disulfonic acid sodium salt) have been synthesized by utililzing two different Re metal precursors, Re(CO)5Br and [Re(CO)3(H2O)3]OTf in an organic solvent mixture and water, respectively...
2016: Chemistry Central Journal
Trevor D Lohrey, Robert G Bergman, John Arnold
We present two routes to the oxo rhenium complex OReCl2(BDI) (1) (BDI = N,N'-bis(2,6-diisopropylphenyl)-β-diketiminate) and discuss the properties and reactivity of this material. Several adducts of 1 with DMAP (1-DMAP; DMAP = 4-dimethylaminopyridine), isonitriles (1-XylNC; XylNC = 2,6-dimethylphenyl isocyanide), and phosphines (1-PEt3; PEt3 = triethylphosphine) were isolated and characterized. Additionally, to probe the ancillary limitations of the BDI framework in high-valent rhenium complexes, oxygen atom transfer (OAT) reactivity with 1 was pursued...
November 21, 2016: Inorganic Chemistry
Jorge Jimenez, Indranil Chakraborty, Pradip Mascharak
The title compound, [ReCl(pyAm)(CO)3], where pyAm is 1-[(pyridin-2-yl-methyl-idene)amino]-adamantane (C16H20N2), was synthesized from the reaction of [ReCl(CO)5] and pyAm in an equimolar ratio. The Re(I) atom resides in an octa-hedral C3ClN2 coordination sphere. The Re-C bond trans to the chloride ligand is noticeably longer compared to the other two Re-C distances. Weak C-H⋯Cl hydrogen-bonding inter-actions consoldiate the packing of the mol-ecules. In this design, the pyAm ligand was employed due to its well-known pharmacokinetic properties...
September 1, 2016: Acta Crystallographica. Section E, Crystallographic Communications
J L Wedding, H H Harris, C A Bader, S E Plush, R Mak, M Massi, D A Brooks, B Lai, S Vogt, M V Werrett, P V Simpson, B W Skelton, S Stagni
Optical epifluorescence microscopy was used in conjunction with X-ray fluorescence imaging to monitor the stability and intracellular distribution of the luminescent rhenium(i) complex fac-[Re(CO)3(phen)L], where phen = 1,10-phenathroline and L = 5-(4-iodophenyl)tetrazolato, in 22Rv1 cells. The rhenium complex showed no signs of ancillary ligand dissociation, a conclusion based on data obtained via X-ray fluorescence imaging aligning iodine and rhenium distributions. A diffuse reticular localisation was detected for the complex in the nuclear/perinuclear region of cells, by either optical or X-ray fluorescence imaging techniques...
December 2, 2016: Metallomics: Integrated Biometal Science
Thomas J Reade, Thomas S Murphy, James A Calladine, Raphael Horvath, Ian P Clark, Gregory M Greetham, Michael Towrie, William Lewis, Michael W George, Neil R Champness
The structures and photochemical behaviour of two new metal-organic frameworks (MOFs) are reported. Reaction of Re(2,2'-bipy-5,5'-dicarboxylic acid)(CO)3Cl or Mn(2,2'-bipy-5,5'-dicarboxylic acid)(CO)3Br with LiCl or LiBr, respectively, produces single crystals of {Li2(DMF)2 [(2,2'-bipy-5,5'-dicarboxylate)Re(CO)3Cl]}n ( RELI: ) or {Li2(DMF)2[(2,2'-bipy-5,5'-dicarboxylate)Mn(CO)3Br]}n ( MNLI: ). The structures formed by the two MOFs comprise one-dimensional chains of carboxylate-bridged Li(I) cations that are cross-linked by units of Re(2,2'-bipy-5,5'-dicarboxylate)(CO)3Cl ( RELI: ) or Mn(2,2'-bipy-5,5'- dicarboxylate)(CO)3Br ( MNLI: )...
January 13, 2017: Philosophical Transactions. Series A, Mathematical, Physical, and Engineering Sciences
Jackie Morton, Emma Tan, S Kim Suvarna
The aim of this study was to establish concentrations of a wide range of elements in human lung samples to allow better identification of potential exposures in subsequent cases. This study reports concentrations of 48 elements (Al, As, Au, B, Ba, Be, Bi, Br, Cd, Ce, Co, Cr, Cs, Cu, Fe, Ga, Gd, Ge, Hf, Hg, In, Li, Mn, Mo, Nb, Ni, Os, Pb, Pd, Pt, Rb, Re, Ru, Sb, Se, Sm, Sn, Sr, Ta, Te, Ti, Tl, Tm, V, W, Y, Zn and Zr) in fresh lung tissue samples from 54 hospital patients, of which 93% exhibited various forms of neoplasia...
November 19, 2016: Journal of Trace Elements in Medicine and Biology
Anita Toscani, Khairil A Jantan, Jubeda B Hena, Jonathan A Robson, Emily J Parmenter, Valentina Fiorini, Andrew J P White, Stefano Stagni, James D E T Wilton-Ely
The versatile rhenium complex [ReCl(CO)3(bpyC[triple bond, length as m-dash]CH)] (HC[triple bond, length as m-dash]Cbpy = 5-ethynyl-2,2'-bipyridine) is used to generate a series of bimetallic complexes through the hydrometallation of [MHCl(CO)(BTD)(PPh3)2] (M = Ru, Os; BTD = 2,1,3-benzothiadiazole). The ruthenium complex [Ru{CH[double bond, length as m-dash]CH-bpyReCl(CO)3}Cl(BTD)(CO)(PPh3)2] was characterised structurally. Ligand exchange reactions with bifunctional linkers bearing oxygen and sulfur donors provide access to tetra- and pentametallic complexes such as [{M{CH[double bond, length as m-dash]CH-bpyReCl(CO)3}(CO)(PPh3)2}2(S2CNC4H8NCS2)] and Fe[C5H4CO2M{CH[double bond, length as m-dash]CH-bpyReCl(CO)3}(CO)(PPh3)2]2...
November 22, 2016: Dalton Transactions: An International Journal of Inorganic Chemistry
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