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Svetlana A Dalmatova, Anastasiya D Fedorenko, Lev N Mazalov, Igor P Asanov, Alexandra Yu Ledneva, Mariya S Tarasenko, Andrey N Enyashin, Vladimir I Zaikovskii, Vladimir E Fedorov
The synthesis, characterization, experimental X-ray photoelectron spectra (XPS) and density-functional theory (DFT) investigations on solid solutions of Mo1-xRexS2 (x = 0.05, 0.10, 0.15 and 0.20) are reported herein. It is shown that even at a low concentration of dopant Re atoms, clustering occurs. At an Re concentration of 5% the formation of dimer-like impregnations is observed. An increase in the dopant concentration leads to an increase in the amount of clustered rhenium atoms and to the formation of rhombic clusters...
May 23, 2018: Nanoscale
Andrew J Hallett, Emeline Placet, Roxane Prieux, Danielle McCafferty, James A Platts, David Lloyd, Marc Isaacs, Anthony J Hayes, Simon J Coles, Mateusz B Pitak, Sarah Marchant, Stephen N Marriott, Rudolf K Allemann, Athanasia Dervisi, Ian A Fallis
A systematic study of the cellular uptake of emissive complexes as a function of their lipophilicity is presented. Here a series of amphiphilic rhenium fac-tricarbonyl bisimine complexes bearing axial substituted imidazole or thiazole ligands, [Re(bpy)(CO)3(ImCnHm)]+ {n = 1 m = 3 (1+), n = 4 m = 9 (2+), n = 8 m = 17 (3+), n = 12 m = 25 (4+), n = 16 m = 33 (5+), n = 2 m = 3 (6+); bpy = 2,2'-bipyridine, Im = imidazole} and [Re(bpy)(CO)3(L)]+ {L = 1-mesitylimidazole, ImMes (7+), 4,5-dimethylthiazole, dmt (8+) and 4-methyl-5-thiazole-ethanol, mte (9+)} is reported...
May 23, 2018: Dalton Transactions: An International Journal of Inorganic Chemistry
Misaki Nakai, Jihne Pan, Kuo-Shyan Lin, John R Thompson, Alessio Nocentini, Claudiu T Supuran, Yasuo Nakabayashi, Tim Storr
With the aim to prepare hypoxia tumor imaging agents, technetium(I) and rhenium(I) tricarbonyl complexes with dipyridylamine (L1 = N-{[1-(2,2-dioxido-1,2-benzoxathiin-6-yl)-1H-1,2,3-triazol-4-yl]methyl}-N-(2-pyridinylmethyl)-2-pyridinemethanamine; L3 = N-{[1-[N-(4-aminosulfonylphenyl)]-1H-1,2,3-triazol-4-yl]methyl}-N-(2-pyridinyl-methyl)-2-pyridinemethanamine), and iminodiacetate (H2 L2 = N-{[1-(2,2-dioxido-1,2-benzoxathiin-6-yl)-1H-1,2,3-triazole-4-yl]methyl}-N-(carboxy-methyl)-glycine; H2 L4 = N-{[1-[N-(4-aminosulfonylphenyl)]-1H-1,2,3-triazole-4-yl]methyl}-N-(carboxymethyl)-glycine) ligands appended to sulfonamide or sulfocoumarin carbonic anhydrase inhibitors were synthesized...
April 13, 2018: Journal of Inorganic Biochemistry
Marcos Tassano, Natalia Oddone, Marcelo Fernández, Williams Porcal, María Fernanda García, Wilner Martínez, Juan Claudio Benech, Pablo Cabral
PURPOSE: Study of rhenium-188 labeling of polyamidoamine (PAMAM) generation 4 (G4) dendrimer and its evaluation on biodistribution and chromosomal aberrations in melanoma cells induced by ionizing radiation as potential treatment agent. MATERIALS AND METHODS: Dendrimers were first conjugated with Suc-HYNIC (Succinimidyl 6-hydrazinopyridine-3-carboxylic acid hydrochloride). Dendrimer-HYNIC was then incubated with 188 ReO4 - . Biodistribution were performed administrating 188 Re-dendrimer to normal (NM) or melanoma-bearing mice (MBM)...
May 18, 2018: International Journal of Radiation Biology
Maxim Bykov, Elena Bykova, Egor Koemets, Timofey Fedotenko, Georgios Aprilis, Konstantin Glazyrin, Hanns-Peter Liermann, Alena V Ponomareva, Johan Tidholm, Ferenc Tasnádi, Igor A Abrikosov, Natalia Dubrovinskaia, Leonid Dubrovinsky
A novel nitrogen-rich compound, ReN8·xN2, was synthesized via a direct reaction between rhenium and nitrogen at high pressure and high temperature in a laser-heated diamond anvil cell. Single-crystal X-ray diffraction revealed that the crystal structure, which is based on the ReN8 framework, has rectangular-shaped channels that accommodate nitrogen molecules. Thus, despite a very high synthesis pressure, exceeding 100 GPa, ReN8·xN2 is an inclusion compound. The amount of trapped nitrogen (x) depends on the synthesis conditions...
May 18, 2018: Angewandte Chemie
Mathias Glatz, Berthold Stöger, Daniel Himmelbauer, Luis F Veiros, Karl Kirchner
Several hydride Mn(I) and Re(I) PNP pincer complexes were applied as catalysts for the homogeneous chemoselective hydrogenation of aldehydes. Among these, [Mn(PNP- i Pr)(CO)2 (H)] was found to be one of the most efficient base metal catalysts for this process and represents a rare example which permits the selective hydrogenation of aldehydes in the presence of ketones and other reducible functionalities, such as C=C double bonds, esters, or nitriles. The reaction proceeds at room temperature under base-free conditions with catalyst loadings between 0...
May 4, 2018: ACS Catalysis
Ji Chen, Jimmy Wu
We report the first example of the rhenium-catalyzed allylation reaction of indolyl compounds by means of cross-coupling with propargyl ethers as non-obvious allylating reagents. Data from isotope-labeling and kinetic isotopic studies are consistent with a mechanism that proceeds by vinylidene formation as the rate determining step, followed by 1,5-hydride shift to generate a key rhenium vinylcarbenoid complex. Bond formation occurs at the vinylogous site and the reaction is conveniently carried out in air.
March 7, 2018: Chemical Science
Hirendra N Banerjee, Deidre Vaughan, Ava Boston, Gabriel Thorne, Gloria Payne, Josiah Sampson, Vinod Manglik, Pola Olczak, Brent V Powell, Angela Winstead, Roosevelt Shaw, Santosh K Mandal
Purpose: Because of the scarcity of suitable brain cancer drugs, researchers are frantically trying to discover novel and highly potent drugs free of side effects and drug-resistance. Rhenium compounds are known to be nontoxic and exhibit no drug resistance. For that reason, we have developed a series of novel rhenium acetylsalicylato (RAC or ASP) complexes to test their cytotoxicity on brain cancer cells. Also we have attempted to explore the DNAbinding properties of these compounds because many drugs either directly or indirectly bind to DNA...
2018: Journal of Cancer Science & Therapy
Andrea M Bruck, Jiefu Yin, Xiao Tong, Esther S Takeuchi, Kenneth J Takeuchi, Lisa F Szczepura, Amy C Marschilok
The cluster-based material Re6 Se8 Cl2 is a two-dimensional ternary material with cluster-cluster bonding across the a and b axes capable of multiple electron transfer accompanied by ion insertion across the c axis. The Li/Re6 Se8 Cl2 system showed reversible electron transfer from 1 to 3 electron equivalents (ee) at high current densities (88 mA/g). Upon cycling to 4 ee, there was evidence of capacity degradation over 50 cycles associated with the formation of an organic solid-electrolyte interface (between 1...
April 26, 2018: Inorganic Chemistry
Wanfu Shen, Chunguang Hu, Jin Tao, Jun Liu, Shuangqing Fan, Yaxu Wei, Chunhua An, Jiancui Chen, Sen Wu, Yanning Li, Jing Liu, Daihua Zhang, Lidong Sun, Xiaotang Hu
Optical anisotropy is one of the most fundamental physical characteristics of emerging low-symmetry two-dimensional (2D) materials. It provides abundant structural information and is crucial for creating diverse nanoscale devices. Here, we have proposed an azimuth-resolved microscopic approach to directly resolve the normalized optical difference along two orthogonal directions at normal incidence. The differential principle ensures that the approach is only sensitive to anisotropic samples and immune to isotropic materials...
April 24, 2018: Nanoscale
Sekar Prakash, Yu-Che Chang, Chien-Hong Cheng
Hydroarylation of bicyclic alkenes has been developed using low-valent Re(I)-catalyzed, directing group assisted C-H bond activation strategy. The addition of sodium acetate significantly improves the reaction efficiency, moreover, bicyclic alkenes such as 7-oxa and aza norboradienes worked efficiently under this reaction condition. Preliminary mechanistic studies suggest that after thealkene insertion, the rhenacycle preferentially undergoes protonolysis rather than reductive elimination.
April 19, 2018: Chemistry, An Asian Journal
Ivan Maisuls, Franco Cabrerizo, Pedro David Gara, Bernd Epe, Gustavo Teodosio Ruiz
Re(I)-polypyridyl complexes show quite interesting and distinctive photochemical and photosensitizing properties. This work describes the capability to induce (or photoinduce) DNA damage of three Re(I)-complexes with a naturally occurring alkaloid called norharmane (nHo) as ligand: [Re(CO)3(nHo)(L)]CF3SO3 where L = 2,2´-bipyridine (ReBpy), phenanthroline (RePhen) or dipyrido[3,2-a:2',3'-c]phenazine (ReDppz). The interaction of the complexes with DNA was investigated by steady-state and time-resolved spectroscopy...
April 19, 2018: Chemistry: a European Journal
Angelo Frei, Bernhard Spingler, Roger Alberto
Multifunctional cyclopentadiene ligands and their rhenium and 99mTc complexes were prepared along a versatile synthetic route. The properties of these Cp-ligands can be tuned on demand, either during their synthesis (variation of R1) or through post-synthetic functionalization with two equal or different vectors (V1 and V2). Variation of these groups enables a combinatorial approach in the synthesis of bioorganometallic complexes. This is demonstrated by the preparation of Cp-ligands containing both electron-donating and withdrawing groups at the R1 position and their subsequent homo- or hetero-functionalization with biovector models (benzylamine and phenylalanine) under standard amide bond formation conditions...
April 19, 2018: Chemistry: a European Journal
Jiage Jia, Pengtao Ma, Panpan Zhang, Dongdi Zhang, Chao Zhang, Jingyang Niu, Jingping Wang
A monomeric trinickel(ii)-substituted phosphotungstate [H9P2W15O62Ni3]9- ion is stabilized by grafting three {Re(CO)3} organometallic groups on the surface for the first time. Magnetic measurements manifest that the resulting complex, Na(NH4)5[P2W15O56Ni3(H2O)3(μ3-OH)3(Re(CO)3)3]·18H2O (1), displays overall ferromagnetic interactions with the presence of ZFS for Ni2+ at low temperature.
April 18, 2018: Dalton Transactions: An International Journal of Inorganic Chemistry
Fransiska Kurniawan, Rahmana E Kartasasmita, Naoki Yoshioka, Abdul Mutalib, Daryono H Tjahjono
Melanoma is the most aggressive type of skin cancer. Metastatic melanoma is extremely difficult to treat with current therapy methods such as surgery. On the other hand, it is a good opportunity to develop a radiopharmaceutical using a radionuclide such as technetium (Tc) for diagnostic and rhenium (Re) for therapeutic purposes. T3,4BCPP has been be used as a radioimaging agent for melanoma cancers experimentally. The aim of the present research was to design new imidazolylporphyrin derivatives with better selectivity and higher affinity than those of T3,4BCPP by molecular modeling...
April 16, 2018: Current Computer-aided Drug Design
Daniel A Kurtz, Kelsey R Brereton, Kevin P Ruoff, Hui Min Tang, Greg A N Felton, Alexander J M Miller, Jillian L Dempsey
A series of rhenium diimine carbonyl complexes was prepared and characterized in order to examine the influence of axial ligands on electronic structure. Systematic substitution of the axial carbonyl and acetonitrile ligands of [Re(deeb)(CO)3 (NCCH3 )]+ (deeb = 4,4'-diethylester-2,2'-bipyridine) with trimethylphosphine and chloride, respectively, gives rise to red-shifted absorbance features. These bathochromic shifts result from destabilization of the occupied d-orbitals involved in metal-to-ligand charge-transfer transitions...
April 12, 2018: Inorganic Chemistry
Madhava B Mallia, Viju Chirayil, Ashutosh Dash
Rhenium-188-N-(DEDC)2 /lipiodol (abbreviated as188 ReN-DEDC, where DEDC = monoanionic diethyldithiocarbamate) is a clinically proven radiopharmaceutical for the therapy of unresectable hepatocellular carcinoma (HCC) through trans arterial radioembolization (TARE). A two-vial freeze-dried kit for the preparation of [188 ReN(DEDC)2 ] complex using sodium perrhenate (Na188 ReO4 ) obtained from a commercial Tungsten-188/Rhenium-188 generator had been reported earlier. This method required addition of stipulated volume of glacial acetic acid into vial 1 by the user for efficient preparation of [188 ReN]2+ intermediate...
March 26, 2018: Applied Radiation and Isotopes
Andrew L Gulley, Nedal T Nassar, Sean Xun
Historically, resource conflicts have often centered on fuel minerals (particularly oil). Future resource conflicts may, however, focus more on competition for nonfuel minerals that enable emerging technologies. Whether it is rhenium in jet engines, indium in flat panel displays, or gallium in smart phones, obscure elements empower smarter, smaller, and faster technologies, and nations seek stable supplies of these and other nonfuel minerals for their industries. No nation has all of the resources it needs domestically...
April 2, 2018: Proceedings of the National Academy of Sciences of the United States of America
Maria Fumanal, Felix Plasser, Sebastian Mai, Chantal Daniel, Etienne Gindensperger
In the construction of diabatic vibronic Hamiltonians for quantum dynamics in the excited-state manifold of molecules, the coupling constants are often extracted solely from information on the excited-state energies. Here, a new protocol is applied to get access to the interstate vibronic coupling constants at the time-dependent density functional theory level through the overlap integrals between excited-state adiabatic auxiliary wavefunctions. We discuss the advantages of such method and its potential for future applications to address complex systems, in particular, those where multiple electronic states are energetically closely lying and interact...
March 28, 2018: Journal of Chemical Physics
Jingkun Lu, Xinyi Ma, Vikram Singh, Yujiao Zhang, Pengtao Ma, Chao Zhang, Jingyang Niu, Jingping Wang
A novel isotetramolybdate-supported rhenium carbonyl derivative, [(CH3)4N]4[{Re(CO)3}4(Mo4O16)]·H2O (1), has been successfully synthesized and characterized by single crystal X-ray diffraction crystallography, IR and UV spectroscopy, etc. Results showed that, compound 1 is an efficient catalyst for the oxidation of thioanisole into the corresponding sulfoxide in the presence of hydrogen peroxide with good to excellent conversion (99%) and excellent selectivity (93%). Highly efficient oxygenation of thioanisole can also be achieved with 100% selectivity of sulfone and >99% conversion...
March 22, 2018: Dalton Transactions: An International Journal of Inorganic Chemistry
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