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Jing-Kai Qin, Wen-Zhu Shao, Cheng-Yan Xu, Yang Li, Dan-Dan Ren, Xiao-Guo Song, Liang Zhen
Substitutional doping of transition metal dichalcogenides (TMDs) two-dimensional materials has proven to be effective in tuning their intrinsic properties, such as band gap, transport characteristics and magnetism. In this study, we realized substitutional doping of monolayer rhenium disulfide (ReS2) with Mo via chemical vapor deposition. Scanning transmission electron microscope (STEM) demonstrated that Mo atoms are successfully doped into ReS2 by substitutionally replacing Re atoms in the lattice. Electrical measurements revealed the degenerate p-type semiconductor behavior of Mo-doped ReS2 field effect transistors (FETs), in agreement with density functional theory (DFT) calculations...
April 25, 2017: ACS Applied Materials & Interfaces
Marharyta I Kharlova, Kseniia O Piletska, Kostiantyn V Domasevitch, Alexander V Shtemenko
In the title compound, [ReBr(C16H16N4O3)(CO)3]·CH3OH, the Re(I) atom adopts a distorted octa-hedral coordination sphere with a facial arrangement of the three carbonyl ligands. Two N atoms of the chelating 5-(3,4,5-tri-meth-oxy-phen-yl)-3-(pyridin-2-yl)-1H-1,2,4-triazole ligand and two carbonyl ligands define the equatorial plane of the complex, with the third carbonyl ligand and the bromide ligand in axial positions. Conventional hydrogen bonds including the methanol solvent mol-ecules assemble the complex mol-ecules through mutual N-H⋯O-H⋯Br links [N⋯O = 2...
April 1, 2017: Acta Crystallographica. Section E, Crystallographic Communications
Lisa Suntrup, Sinja Klenk, Johannes Klein, Sebastian Sobottka, Biprajit Sarkar
Bidentate ligands containing at least one triazole or triazolylidene (mesoionic carbene, MIC) unit are extremely popular in contemporary chemistry. One reason for their popularity is the similarities as well as differences in the donor/acceptor properties that these ligands display in comparison to their pyridine or other N-heterocyclic carbene counterparts. We present here seven rhenium(I) carbonyl complexes where the bidentate ligands contain combinations of pyridine/triazole/triazolylidene. These are the first examples of rhenium(I) complexes with bidentate 1,2,3-triazol-5-ylidene-containing ligands...
April 21, 2017: Inorganic Chemistry
Qaisar Nadeem, Yunjun Shen, Muhammad Farooq Warsi, Gulfam Nasar, Muhammad Abdul Qadir, Roger Alberto
The present study reports the syntheses of half-sandwich complexes of the type [M(η(5) -C5 H4 CONH-R)(CO)3 ] (M = Re,(99m) Tc;R = cyclic RGD peptide (cRGDyK) for potential imaging of αv β3 integrin expression. The (99m) Tc complex was prepared directly from the reaction of [(99m) Tc(OH2 )3 (CO)3 ](+) with cRGDyK, doubly conjugated to Thiele's acid [(C5 H5 COOH)2 ] in water. This approach extends the viability of metal-mediated retro Diels-Alder reactions for the preparation of small molecules such as linear tripeptides to a more complex cyclic peptide carrying a [(η(5) -C5 H4 )(99m) Tc(CO)3 ] tag...
April 21, 2017: Journal of Labelled Compounds & Radiopharmaceuticals
Allan R Petersen, Peter Fristrup
The deoxydehydration (DODH) reaction remains one of the most efficient methods of reducing the oxygen content of biomass while keeping important functionality in place. This reaction is traditionally catalysed by high-valent oxorhenium species. Recent research into heterogeneous rhenium-based catalysts for DODH demonstrates their ability to rival and in some cases surpass their homogeneous counterparts. Furthermore, catalysts based on the metals molybdenum and vanadium show great potential as inexpensive alternatives to rhenium catalysts...
April 17, 2017: Chemistry: a European Journal
Joyce M van Dodewaard-de Jong, John M H de Klerk, Haiko J Bloemendal, Daniela E Oprea-Lager, Otto S Hoekstra, H Pieter van den Berg, Maartje Los, Aart Beeker, Marianne A Jonker, Joe M O'Sullivan, Henk M W Verheul, Alfons J M van den Eertwegh
BACKGROUND: Rhenium-188-HEDP is a beta-emitting radiopharmaceutical used for palliation of metastatic bone pain. We investigated whether the addition of rhenium-188-HEDP to docetaxel/prednisone improved efficacy of chemotherapy in patients with CRPC. METHODS: Patients with progressive CRPC and osteoblastic bone metastases were randomised for first-line docetaxel 75 mg/m(2) 3-weekly plus prednisone with or without 2 injections of rhenium-188-HEDP after the third (40 MBq/kg) and after the sixth (20 MBq/kg) cycle of docetaxel...
April 18, 2017: European Journal of Nuclear Medicine and Molecular Imaging
Zhongkai Zhang, Bian Tian, Qiuyue Yu, Peng Shi, Qijing Lin, Na Zhao, Weixuan Jing, Zhuangde Jiang
A thermal stress range analysis of tungsten-rhenium thin film thermocouples based on ceramic substrates is presented to analyze the falling off and breakage problems caused by the mismatch of the thermal stresses in thin film thermocouples (TFTCs) and substrate, and nano-indentation experiments are done to measure and calculate the film stress to compare with the simulation results. Optimal design and fabrication of tungsten-rhenium TFTCs based on ceramic substrates is reported. Static high temperature tests are carried out, which show the optimization design can effectively reduce the damage caused by the thermal stress mismatch...
April 14, 2017: Sensors
Shaodong Zhou, Jilai Li, Marjan Firouzbakht, Maria Schlangen, Helmut Schwarz
The potential of carbonyl rhenium complexes in activating and coupling carbon dioxide and methane has been explored by using a combination of gas-phase experiments (FT-ICR mass spectrometry) and high-level quantum chemical calculations. While the complexes [Re(CO)x](+) (x = 0, 1, 3) are thermally unreactive toward CO2, [Re(CO)2](+) abstracts one oxygen atom from this substrate spontaneously at ambient conditions. Based on (13)C and (18)O labeling experiments, the newly generated CO ligand is preferentially eliminated, and two mechanistic scenarios are considered to account for this unexpected finding...
April 19, 2017: Journal of the American Chemical Society
Masahito Murai, Erika Uemura, Shunsuke Hori, Kazuhiko Takai
A regioselective cyclization of 1,n-diynes under rhenium catalysis was developed on the basis of a rare type of 1,1-difunctionalization of terminal alkynes with carbon nucleophiles, followed by sequential addition reactions of the resulting alkenylrhenium species. The reaction provides an efficient approach to the synthesis of complex cyclopentane-fused bi- and tricycles and spirocycles, which are useful building blocks for the construction of essential frameworks of biologically active compounds as well as functional materials, from simple starting materials by the formation of up to six new carbon-carbon bonds in a single step...
April 11, 2017: Angewandte Chemie
Joseph M Mannion, Charles R Shick, Glenn A Fugate, Matthew S Wellons, Brian A Powell, Scott M Husson
This communication presents findings on the effect of rhenium filament oxidation on thermal ionization mass spectrometry (TIMS) analyses of plutonium. Additionally, the roles of atmospheric humidity and carburization on the oxidation characteristics (i.e. aging) of rhenium filaments were studied. Degassed and carburized filaments were aged for up to 79 days under dry and humid conditions, and the growth of oxo-rhenium crystallites was investigated intermittently by scanning electron microscopy (SEM) to construct growth profiles...
June 1, 2017: Talanta
Jana Rohacova, Osamu Ishitani
This account looks comprehensively at the syntheses, photophysical properties and applications of structurally diverse, multinuclear coordination compounds that embed a Re(i)-diimine-carbonyl moiety. Different types of linkages in terms of configuration and proper bridging lead to several types of discrete linear or cyclic macromolecular aggregates with different sizes, which consequently have a significant effect on their properties. The Re-backbone in the multinuclear assembly may have only a structural role and mainly exhibits host-guest behaviour for encapsulation, or it may produce photofunctional properties as a direct result of the Re(i) chromophoric unit, which makes these compounds applicable in light-harvesting systems or photochemical CO2 reduction...
April 5, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
S A Chabolla, C W Machan, J Yin, E A Dellamary, S Sahu, N C Gianneschi, M K Gilson, F A Tezcan, C P Kubiak
Herein, we report a new approach to bio-inspired catalyst design. The molecular catalyst employed in these studies is based on the robust and selective Re(bpy)(CO)3Cl-type (bpy = 2,2'-bipyridine) homogeneous catalysts, which have been extensively studied for their ability to reduce CO2 electrochemically or photochemically in the presence of a photosensitizer. These catalysts can be highly active photocatalysts in their own right. In this work, the bipyridine ligand was modified with amino acids and synthetic peptides...
April 4, 2017: Faraday Discussions
Rebeca Arévalo, Lucía Riera, Julio Pérez
Intramolecular C-C coupling between N-bonded 1,2-dimethylimidazole, 2-methyloxazoline, or 2-methylpyridine and either 2,2'-bipyridine (bipy) or 1,10-phenanthroline (phen) ligands results from α-methyl group deprotonation in the coordination sphere of Re(CO)3 fragments. The nucleophilic CH2 group generated by the deprotonation attacks the 6 (bipy) or 2 (phen) positions of the diimines, dearomatizing the involved pyridine ring and generating new asymmetric, fac-capping tridentate ligands.
April 3, 2017: Inorganic Chemistry
Jing Yang, Ji-Xian Zhao, Qian Cao, Liang Hao, Danxia Zhou, Zhenji Gan, Liang-Nian Ji, Zong-Wan Mao
Mitochondrial metabolism is essential for tumorigenesis, and the development of cancer is usually accompanied by alternations of mitochondrial function. Emerging studies have demonstrated that targeting mitochondria and mitochondrial metabolism is an effective strategy for cancer therapy. In this work, eight phosphorescent organometallic rhenium(I) complexes have been synthesized and explored as mitochondria-targeted theranostic agents, capable of inducing and tracking the therapeutic effect simultaneously...
April 13, 2017: ACS Applied Materials & Interfaces
Peter V Simpson, Ilaria Casari, Silvano Paternoster, Brian W Skelton, Marco Falasca, Massimiliano Massi
Rhenium and ruthenium complexes containing N-heterocylic carbene (NHC) ligands and conjugated to indomethacin were prepared. The anticancer properties were probed against pancreatic cell lines, revealing a remarkable activity of the rhenium fragment as anticancer agent. The ruthenium complexes were found to be inactive against the same pancreatic cancer cell lines, either alone or in conjugation with indomethacin. An in depth biological study revealed the origin of the anticancer properties of the rhenium tricarbonyl fragment, of which a complete elucidation had yet to be achieved...
March 23, 2017: Chemistry: a European Journal
Marta Roqué I Figuls, Maria José Martinez-Zapata, Martin Scott-Brown, Pablo Alonso-Coello
BACKGROUND: This is an update of the review published in Issue 4, 2003. Bone metastasis cause severe pain as well as pathological fractures, hypercalcaemia and spinal cord compression. Treatment strategies currently available to relieve pain from bone metastases include analgesia, radiotherapy, surgery, chemotherapy, hormone therapy, radioisotopes and bisphosphonates. OBJECTIVES: To determine efficacy and safety of radioisotopes in patients with bone metastases to improve metastatic pain, decrease number of complications due to bone metastases and improve patient survival...
March 23, 2017: Cochrane Database of Systematic Reviews
Mitchell Ashley Klenner, Giancarlo Pascali, Bo Zhang, Tiffany Russel Sia, Lawson Kyle Spare, Anwen M Krause-Heuer, Janice Aldrich-Wright, Ivan Greguric, Adam Guastella, Massimiliano Massi, Benjamin Hugh Fraser
Azeotropic distillation is typically required to achieve fluorine-18 radiolabelling during the production of positron emission tomography (PET) imaging agents. However, this time consuming process also limits fluorine-18 incorporation, due to radioactive decay of the isotope and its adsorption to the drying vessel. In addressing these limitations, we herein report the fluorine-18 radiolabelling of one model rhenium(I) complex, which is significantly improved under conditions that do not require azeotropic drying...
March 22, 2017: Chemistry: a European Journal
Allen M Lunsford, Kristina F Goldstein, Matthew A Cohan, Jason A Denny, Nattamai Bhuvanesh, Shengda Ding, Michael B Hall, Marcetta Y Darensbourg
The bipyridine ligand is renowned as a photo- and redox-active ligand in catalysis; the latter has been particularly explored in the complex Re(bipy)(CO)3Cl for CO2 reduction. We ask whether a bidentate, redox-active MN2S2 metallodithiolate ligand in heterobimetallic complexes of Mn and Re might similarly serve as a receptor and conduit of electrons. In order to assess the electrochemical features of such designed bimetallics, a series of complexes featuring redox active MN2S2 metallodithiolates, with M = Ni(2+), {Fe(NO)}(2+), and {Co(NO)}(2+), bound to M'(CO)3X, where M' = Mn and Re, were synthesized and characterized using IR and EPR spectroscopies, X-ray diffraction, cyclic voltammetry, and density functional theory (DFT) computations...
April 19, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
Damaris E Pérez, Jessica L Smeltz, Roger D Sommer, Paul D Boyle, Elon A Ison
A series of novel cationic Re(iii) complexes [(DAAm)Re(CO)(NCCH3)2][X] [DAAm = N,N-bis(2-arylaminoethyl)methylamine; aryl = C6F5 (a), Mes (b)] [X = OTf (2), BAr(F)4 [BAr(F)4 = tetrakis[3,5-(trifluoromethyl)phenyl]borate] (3), BF4 (4), PF6 (5)], and their analogue [(DAmA)Re(CO)(Cl)2] [DAmA = N,N-bis(2-arylamineethyl)methylamino; aryl = C6F5] (6) were synthesized. The catalytic efficiency for the hydrosilylation reaction of aldehydes using 4a (0.03 mol%) has been demonstrated to be significantly more active than rhenium catalysts previously reported in the literature...
March 21, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
Alexander Wilting, Thorsten Stolper, Ricardo A Mata, Inke Siewert
Herein, we present the reduction chemistry of a dinuclear α-diimine rhenium complex, 1, [Re2(L)(CO)6Cl2], with a proton responsive ligand and its application as a catalyst in the electrochemical CO2 reduction reaction (L = 4-tert-butyl-2,6-bis(6-(1H-imidazol-2-yl)-pyridin-2-yl)phenol). The complex has a phenol group in close proximity to the active center, which may act as a proton relay during catalysis, and pyridine-NH-imidazole units as α-diimine donors. The complex is an active catalyst for the electrochemical CO2 reduction reaction...
March 20, 2017: Inorganic Chemistry
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