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Rhenium

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https://www.readbyqxmd.com/read/28521090/ultrafast-vibrational-energy-transfer-in-catalytic-monolayers-at-solid-liquid-interfaces
#1
Jan Philip Kraack, Angelo Frei, Roger Alberto, Peter Hamm
We investigate the ultrafast vibrational dynamics of monolayers from adsorbed rhenium-carbonyl CO2-reduction catalysts on a semiconductor surface (indium-tin-oxide (ITO)) with ultrafast two-dimensional attenuated total reflection infrared (2D ATR IR) spectroscopy. The complexes are partially equipped with isotope-labeled ((13)C) carbonyl ligands to generate two spectroscopically distinguishable forms of the molecules. Ultrafast vibrational energy transfer between the molecules is observed via the temporal evolution of cross-peaks between their symmetric carbonyl stretching vibrations...
May 22, 2017: Journal of Physical Chemistry Letters
https://www.readbyqxmd.com/read/28512575/new-leads-for-fragment-based-design-of-rhenium-technetium-radiopharmaceutical-agents
#2
Alice Brink, John R Helliwell
Multiple possibilities for the coordination of fac-[Re(CO)3(H2O)3](+) to a protein have been determined and include binding to Asp, Glu, Arg and His amino-acid residues as well as to the C-terminal carboxylate in the vicinity of Leu and Pro. The large number of rhenium metal complex binding sites that have been identified on specific residues thereby allow increased target identification for the design of future radiopharmaceuticals. The core experimental concept involved the use of state-of-art tuneable synchrotron radiation at the Diamond Light Source to optimize the rhenium anomalous dispersion signal to a large value (f'' of 12...
May 1, 2017: IUCrJ
https://www.readbyqxmd.com/read/28505142/mitochondria-targeting-with-luminescent-rhenium-i-complexes
#3
Joanna Skiba, Tytus Bernaś, Damian Trzybiński, Krzysztof Woźniak, Giarita Ferraro, Daniela Marasco, Antonello Merlino, Marsel Z Shafikov, Rafał Czerwieniec, Konrad Kowalski
Two new neutral fac-[Re(CO)₃(phen)L] compounds (1,2), with phen = 1,10-phenanthroline and L = O₂C(CH₂)₅CH₃ or O₂C(CH₂)₄C≡CH, were synthetized in one-pot procedures from fac-[Re(CO)₃(phen)Cl] and the corresponding carboxylic acids, and were fully characterized by IR and UV-Vis absorption spectroscopy, ¹H- and (13)C-NMR, mass spectrometry and X-ray crystallography. The compounds, which display orange luminescence, were used as probes for living cancer HeLa cell staining. Confocal microscopy revealed accumulation of both dyes in mitochondria...
May 15, 2017: Molecules: a Journal of Synthetic Chemistry and Natural Product Chemistry
https://www.readbyqxmd.com/read/28467613/charged-macromolecular-rhenium-bipyridine-catalysts-with-tunable-co2-reduction-potentials
#4
Nathan Claude Gianneschi, Swagat Sahu, Po Ling Cheung, Charles Machan, Steven Chabolla, Clifford Kubiak
A series of polymeric frameworks with functional assemblies were designed to alter the catalytic activity of covalently bound Re(I) electrocatalysts. Norbornenyl polymers containing positively charged quaternary ammonium salts, neutral phenyl, or negatively charged trifluoroborate groups were end-labelled with a Re(I) fac-tricarbonyl bipyridine electrocatalyst via cross metathesis. Electrochemical studies in acetonitrile under an inert atmosphere and with saturated CO2, indicate that the quaternary ammonium polymers exhibit a significantly lower potential for CO2 reduction to CO (ca...
May 3, 2017: Chemistry: a European Journal
https://www.readbyqxmd.com/read/28466932/co-induced-apoptotic-death-of-colorectal-cancer-cells-by-a-luminescent-photocorm-grafted-on-biocompatible-carboxymethyl-chitosan
#5
Indranil Chakraborty, Jorge Jimenez, P K Mascharak
A photo-active luminescent rhenium carbonyl complex namely, [Re(CO)3(phen)(pyAl)](CF3SO3) was grafted on a biocompatible carboxymethyl chitosan (CMC) matrix through Schiff base condensation reaction. The light-induced CO delivery from ReCMC has been shown to eradicate human colorectal adenocarcinoma cells (HT-29) very efficiently in a dose-dependent fashion. The onset of CO-induced apoptosis was realized by caspase-3,-7 detection aided by fluorescence confocal microscopy. ReCMC represents a unique example of a biocompatible and biodegradable antineoplastic agent that could find its use in cancer photopharmacology...
May 3, 2017: Chemical Communications: Chem Comm
https://www.readbyqxmd.com/read/28451117/rhenium-i-trinuclear-rings-as-highly-efficient-redox-photosensitizers-for-photocatalytic-co2-reduction
#6
Jana Rohacova, Osamu Ishitani
We developed new cyclic Re(i)-based trinuclear redox photosensitizers with both high oxidation power in the excited state and strong reduction power in the reduced form. These excellent properties were achieved by introducing electron-donating groups on the diimine ligand of the Re(i) metal centre and by connecting each Re(i) unit with polyphenyl-bisphosphine bridging ligands. These Re-rings were applied to homogenous visible light-driven photocatalytic CO2 reduction in conjunction with various mononuclear catalysts, such as Re(i), Ru(ii) and Mn(i) metal complexes, employing a relatively weak sacrificial electron donor, triethanolamine...
November 1, 2016: Chemical Science
https://www.readbyqxmd.com/read/28440614/chemical-vapor-deposition-growth-of-degenerate-p-type-mo-doped-res2-films-and-their-homojunction
#7
Jing-Kai Qin, Wen-Zhu Shao, Cheng-Yan Xu, Yang Li, Dan-Dan Ren, Xiao-Guo Song, Liang Zhen
Substitutional doping of transition metal dichalcogenide 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 microscopy 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, in agreement with density functional theory calculations...
May 1, 2017: ACS Applied Materials & Interfaces
https://www.readbyqxmd.com/read/28435703/crystal-structure-of-bromido-fac-tricarbon-yl-5-3-4-5-tri-meth-oxy-phen-yl-3-pyridin-2-yl-1h-1-2-4-triazole-%C3%AE%C2%BA-2-n-2-n-3-rhenium-i-methanol-monosolvate
#8
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
https://www.readbyqxmd.com/read/28430422/gauging-donor-acceptor-properties-and-redox-stability-of-chelating-click-derived-triazoles-and-triazolylidenes-a-case-study-with-rhenium-i-complexes
#9
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
https://www.readbyqxmd.com/read/28430366/cyclic-rgd-penta-peptides-crgdyk-derivatized-with-cyclopentadienyl-complexes-of-technetium-and-rhenium-as-radiopharmaceutical-probes
#10
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
https://www.readbyqxmd.com/read/28423204/new-motifs-in-deoxydehydration-beyond-the-realms-of-rhenium
#11
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
https://www.readbyqxmd.com/read/28421240/a-randomised-phase-ii-study-of-repeated-rhenium-188-hedp-combined-with-docetaxel-and-prednisone-versus-docetaxel-and-prednisone-alone-in-castration-resistant-prostate-cancer-crpc-metastatic-to-bone-the-taxium-ii-trial
#12
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
https://www.readbyqxmd.com/read/28420088/range-analysis-of-thermal-stress-and-optimal-design-for-tungsten-rhenium-thin-film-thermocouples-based-on-ceramic-substrates
#13
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
https://www.readbyqxmd.com/read/28403605/sequential-gas-phase-activation-of-carbon-dioxide-and-methane-by-re-co-2-the-sequence-of-events-matters
#14
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
https://www.readbyqxmd.com/read/28398619/rhenium-catalyzed-construction-of-polycyclic-hydrocarbon-frameworks-by-a-unique-cyclization-of-1-n-diynes-initiated-by-1-1-difunctionalization-with-carbon-nucleophiles
#15
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
https://www.readbyqxmd.com/read/28391840/rhenium-filament-oxidation-effect-on-tims-performance-and-the-roles-of-carburization-and-humidity
#16
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
https://www.readbyqxmd.com/read/28379240/photofunctional-multinuclear-rhenium-i-diimine-carbonyl-complexes
#17
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
https://www.readbyqxmd.com/read/28374024/bio-inspired-co2-reduction-by-a-rhenium-tricarbonyl-bipyridine-based-catalyst-appended-to-amino-acids-and-peptidic-platforms-incorporating-proton-relays-and-hydrogen-bonding-functional-groups
#18
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
https://www.readbyqxmd.com/read/28368589/interligand-c-c-coupling-between-%C3%AE-methyl-n-heterocycles-and-bipy-or-phen-at-rhenium-tricarbonyl-complexes
#19
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
https://www.readbyqxmd.com/read/28368110/simultaneously-inducing-and-tracking-cancer-cell-metabolism-repression-by-mitochondria-immobilized-rhenium-i-complex
#20
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
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