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Dalton Transactions: An International Journal of Inorganic Chemistry

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https://www.readbyqxmd.com/read/28644503/the-first-re-i-organometallic-complex-with-an-organoimido-polyoxometalate-ligand
#1
Patricio Hermosilla-Ibáñez, Kerry Wrighton-Araneda, Gaspar Prado, Verónica Paredes-García, Nancy Pizarro, Andrés Vega, Diego Venegas-Yazigi
The spectroscopic, electrochemical and photophysical properties of the first Re(I) organometallic organoimido-polyoxometalate complex [n-Bu4N][Mo6O18NC6H4-CH2-N3C2H2-Re-phen(CO)3] compared with all fragments are reported. The UV-Vis spectra are analysed using experimental and theoretical tools. In contrast to the reported studies in the literature, our results show that a new more intense band is present in the spectra of the hybrid ligand obscuring the intra-polyanion charge transfer. The electrochemical results show that the strong acceptor character of the polyoxometalate fragment is quenched by the condensation of the phenyl-triazole molecule...
June 23, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/28644494/feco-nanoparticles-embedded-carbon-nanofibers-as-robust-peroxidase-mimics-for-sensitive-colorimetric-detection-of-l-cysteine
#2
Zezhou Yang, Yun Zhu, Guangdi Nie, Meixuan Li, Ce Wang, Xiaofeng Lu
A simple and low cost detection of l-cysteine is essential in the fields of biosensors and medical diagnosis. In this study, we have developed a simple electrospinning, followed by calcination process to prepare FeCo nanoparticles embedded in carbon nanofibers (FeCo-CNFs) as an efficient peroxidase-like mimic for the detection of l-cysteine. FeCo nanoparticles are uniformly dispersed within CNFs, and their diameters are highly influenced by the calcination temperature. The calcination temperature also influences the peroxidase-like catalytic activity, and the maximum activity is achieved at a calcination temperature of 550 °C...
June 23, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/28644489/dehydrogenation-of-cyclic-amines-by-a-coordinatively-unsaturated-cp-ir-iii-phosphoramidate-complex
#3
Marcus W Drover, Laurel L Schafer, Jennifer A Love
The reaction of a Cp*Ir(iii) phosphoramidate complex with secondary amines gives amine, imine-bound Cp*Ir(iii) hydride complexes resulting from amine dehydrogenation. These well-characterized species could serve as models of relevant intermediates that have been proposed in catalytic amine dehydrogenation using related N,O-chelated Cp*Ir(iii) pyridonate complexes.
June 23, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/28640312/speciation-in-human-blood-of-metvan-a-vanadium-based-potential-anti-tumor-drug
#4
Daniele Sanna, Valeria Ugone, Giovanni Micera, Péter Buglyó, Linda Bíró, Eugenio Garribba
The first report on the anti-cancer activity of the compound Metvan, [V(IV)O(Me2phen)2(SO4)], where Me2phen is 4,7-dimethyl-1,10-phenanthroline, dates back to 2001. Although it was immediately identified as one of the most promising multitargeted anti-cancer V compounds, no development on the medical experimentation was carried out. One of the possible reasons is the lack of information on its speciation in aqueous solution and its thermodynamic stability, factors which influence the transport in the blood and the final form which reaches the target organs...
June 22, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/28640310/spectroscopic-evidence-for-cofactor-substrate-interaction-in-the-radical-sam-enzyme-tyw1
#5
Velavan Kathirvelu, Phanélie Perche-Letuvée, Jean-Marc Latour, Mohamed Atta, Farhad Forouhar, Serge Gambarelli, Ricardo Garcia-Serres
TYW1 is a metalloenzyme involved in the modifications of guanosine 37 of Phe-tRNA of Eukaryota and Archaea. It catalyzes the second step of Wybutosine biosynthesis, which consists of the formation of the tricyclic compound imG-14 from m(1)G using pyruvate and SAM (S-adenosyl-methionine) as co-substrates. Two [4Fe-4S] clusters are needed in the catalytic process. One effects the reductive binding of SAM, which initiates the radical reaction that inserts a C-C moiety into m(1)G. The other [4Fe-4S] cluster binds the pyruvate molecule that provides the C-C motif...
June 22, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/28640302/influence-of-substituents-on-dna-and-protein-binding-of-cyclometalated-ir-iii-complexes-and-anticancer-activity
#6
Sujay Mukhopadhyay, Roop Shikha Singh, Rajendra Prasad Paitandi, Gunjan Sharma, Biplob Koch, Daya Shankar Pandey
Synthesis of terpyridyl based ligands 3-([2,2':6',2''-terpyridin]-4'-yl)-7-methoxy-2-(methylthio)-quinolone, (L1); 3-([2,2':6',2''-terpyridin]-4'-yl)-6-methoxyquinolin-2(1H)-one, (L2); 3-([2,2'-:6',2''-terpyridin]-4'-yl)-6-methylquinolin-2(1H)-one (L3) and cyclometalated iridium(iii) complexes [[Ir(ppy)2L1](+)PF6(-) (1), [Ir(ppy)2L2](+)PF6(-) (2), [Ir(ppy)2L3](+)PF6(-) (3) (2-phenylpyridine = Hppy)] involving these ligands has been described. The ligands L1-L3 and complexes 1-3 have been thoroughly characterized by elemental analyses, spectral studies (IR, (1)H, (13)C NMR, UV/vis and fluorescence) ESI-MS, and the structure of 3 has been unambiguously authenticated by single crystal X-ray analyses...
June 22, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/28640301/synthesis-of-zwitterionic-palladium-complexes-and-their-application-as-catalysts-in-cross-coupling-reactions-of-aryl-heteroaryl-and-benzyl-bromides-with-organoboron-reagents-in-neat-water
#7
V Ramakrishna, N Dastagiri Reddy
N-(3-Chloro-2-quinoxalinyl)-N'-arylimidazolium salts (aryl = 2,6-diisopropylphenyl [HL1Cl]Cl, aryl = mesityl [HL2Cl]Cl) have been synthesized by treating 2,3-dichloroquinoxaline with the corresponding N'-arylimidazole in neat water. Facile reactions of these imidazolium salts with Pd(PPh3)4 and Pd2(dba)3/PPh3 (dba = dibenzyledene acetone) at 50 °C have afforded zwitterionic palladium(ii) complexes [Pd(HL1)(PPh3)Cl2] (I) and [Pd(HL2)(PPh3)Cl2] (II) in excellent yields. I and II have been tested for their ability to catalyze Suzuki-Miyaura cross coupling (SMC) reactions in neat water/K2CO3 and are found to be highly active for carrying out these reactions between aryl bromides and organoboron reagents...
June 22, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/28640297/preparation-of-tetrazine-containing-2-1-complexes-of-99m-tc-and-in-vivo-targeting-using-bioorthogonal-inverse-electron-demand-diels-alder-chemistry
#8
Abdolreza Yazdani, Nancy Janzen, Shannon Czorny, Robert G Ungard, Tanya Miladinovic, Gurmit Singh, John F Valliant
The aim of this work was to synthesize and evaluate [2 + 1] (99m)Tc(i) polypyridine complexes containing tetrazines, which along with the corresponding Re(i) complexes, represent a new class of isostructural nuclear and turn-on luminescent probes that can be derivatized and targeted using bioorthogonal chemistry. To this end, [2 + 1] complexes of (99m)Tc(i) of the type [(99m)Tc(CO)3(N^N)(L)] (N^N = bathophenanthroline disulfonate (BPS) or 2,2'-bipyridine (bipy)), where the monodentate ligand (L) was a tetrazine linked to the metal through an imidazole derivative, were prepared...
June 22, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/28640296/synthesis-and-photophysical-and-magnetic-studies-of-ternary-lanthanide-iii-complexes-of-naphthyl-chromophore-functionalized-imidazo-4-5-f-1-10-phenanthroline-and-dibenzoylmethane
#9
A Josephine Kanimozhi, V Alexander
The luminescent ternary lanthanide(iii) complexes [Ln(DBM)3(L1)] and [Ln(DBM)3(L2)] (Ln = Eu and Tb) of dibenzoylmethane (DBM) and 2-(2-naphthyl)-1H-imidazo[4,5-f][1,10]phenanthroline (L1) and 2-(2-hydroxy-1-naphthyl)-1H-imidazo[4,5-f][1,10]phenanthroline (L2) are reported in this work. The naphthyl chromophore functionalized imidazophenanthroline ligands L1 and L2 are structurally characterized by using single crystal X-ray diffraction: (L1), a = 14.933(4) Å, b = 7.4965(13) Å, c = 15.999(4) Å, α = γ = 90°, β = 102...
June 22, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/28640294/space-confined-synthesis-of-multilayer-cu-n-doped-graphene-nanosheets-for-efficient-oxygen-electroreduction
#10
Yangyang Ni, Zhengyan Chen, Fantao Kong, Yu Qiao, Aiguo Kong, Yongkui Shan
Cu-based carbon electrocatalysts for the oxygen reduction reaction are difficult to compare with the corresponding Fe- or Co-based electrocatalytic materials, owing to their insufficient catalytic activity and stability. Herein, as an impressive Cu-based electrocatalyst, a multilayer Cu-N-doped graphene sheet (Cu-N-GR) is directly synthesized by the thermal conversion of copper(ii) 2,2'-bipyridine in the confined space of lamellar montmorillonites. The open layered morphology of Cu-N-GR materials facilitated the exposure of more active centers and enhanced the flexibility and mobility of charge carriers...
June 22, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/28640292/co-ligand-tuned-pyrimidine-2-carboxylate-mn-ii-complexes-from-a-2d-6-3-layer-to-an-interpenetrated-srs-net
#11
Rui Sun, Su-Mei Gao, Shao-Qiang Wang, Wei-Chao Song, Jiong-Peng Zhao, Fu-Chen Liu
A 6(3) 2D layer complex [Mn3Cl3(L3)]n·H2O (1) (L = pyrimidine-2-carboxylate) was obtained by assembling 2-cyanopyrimidine and manganese chloride, in which the L ligands were generated in situ. In 1 six-membered Mn rings were constructed from Mn(II) ions and L ligands, which were connected to each other by double chloride anions affording a 2D layer. When the chloride anions in 1 were substituted partly by formate, [Mn4Cl3L4(HCO2)]n (2) was obtained. In 2, the L ligands bridge Mn(II) to give a 1D chain, which was further connected by the double chloride anions and Cl/formate bridges to form a two-fold interpenetrated srs-net...
June 22, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/28640290/intrinsic-37-35-cl-and-18-16-o-isotope-shifts-in-195-pt-and-103-rh-nmr-of-purely-inorganic-pt-and-rh-complexes-as-unique-spectroscopic-fingerprints-for-unambiguous-assignment-of-structure
#12
Klaus R Koch, Leon Engelbrecht
Well-resolved intrinsic (1)ΔM((37/35)Cl) and (1)ΔM((18/16)O) isotope shifts (where M = (195)Pt or (103)Rh) are visible in the (195)Pt NMR peak profiles of relatively kinetically inert [PtCln(H2O)6-n](4-n) (n = 1-6) complexes, their corresponding hydroxido [PtCl6-n(OH)n](2-) (n = 1-5/6) anions, and [RhCln(H2O)6-n](3-n) (n = 3-6) complexes in aqueous solutions at ca. 293 K. Although some such isotope effects have been previously reported, there are very limited published data in the open literature, and the first systematic studies of such intrinsic (1)ΔM((37/35)Cl) and (1)ΔM((18/16)O) isotope effects are reviewed in this perspective...
June 22, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/28640289/consensus-structures-of-the-mo-v-sites-of-sulfite-oxidizing-enzymes-derived-from-variable-frequency-pulsed-epr-spectroscopy-isotopic-labelling-and-dft-calculations
#13
John H Enemark
Sulfite-oxidizing enzymes from eukaryotes and prokaryotes have five-coordinate distorted square-pyramidal coordination about the molybdenum atom. The paramagnetic Mo(v) state is easily generated, and over the years four distinct CW EPR spectra have been identified, depending upon enzyme source and the reaction conditions, namely high and low pH (hpH and lpH), phosphate inhibited (Pi) and sulfite (or blocked). Extensive studies of these paramagnetic forms of sulfite-oxidizing enzymes using variable frequency pulsed electron spin echo (ESE) spectroscopy, isotopic labeling and density functional theory (DFT) calculations have led to the consensus structures that are described here...
June 22, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/28639637/syntheses-structures-and-magnetic-properties-of-tetranuclear-cubane-type-and-heptanuclear-wheel-type-nickel-ii-complexes-with-3-methoxysalicylic-acid-derivatives
#14
Fumiya Kobayashi, Ryo Ohtani, Saki Teraoka, Wataru Kosaka, Hitoshi Miyasaka, Yingjie Zhang, Leonard F Lindoy, Shinya Hayami, Masaaki Nakamura
Two ferromagnetic multinuclear Ni(ii) clusters, [Ni4L(1)4(μ3-OMe)4(CH3OH)4] (1) and [Ni7(HL(2))6(μ3-OMe)6]Cl2 (2), and a mononuclear complex [NiL(3)]·2H2O (3) (HL(1) = benzyl 2-hydroxy-3-methoxybenzoate; H2L(2) = 1-(2-hydroxy-3-methoxybenzamido)-2-(benzylideneamino)ethane; H2L(3) = 1-(2-hydroxy-3-methoxybenzamido)-2-(pyridylmethyleneamino)ethane) were synthesised, and their structures and magnetic behaviours were investigated in detail. 1 has a [Ni4O4] cubane structure while 2 has a wheel-like [Ni@Ni6] arrangement...
June 22, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/28638907/ruthenium-ii-p-cymene-complexes-of-a-benzimidazole-based-ligand-capable-of-vegfr2-inhibition-hydrolysis-reactivity-and-cytotoxicity-studies
#15
Sudipta Bhattacharyya, Kallol Purkait, Arindam Mukherjee
The design of Ru or other metal-based anticancer agents may achieve better and faster optimization if the ligands used are also designed to have standalone functions. In this scenario, even after dissociation from the metal complex under adverse conditions, the ligand would have anti-cancer properties. In our work, we have generated a bispyrazole-containing benzimidazole ligand with potency against vascular endothelial growth factor receptor 2 (VEGFR2), which is known to have roles in vasculogenesis/angiogenesis...
June 22, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/28636049/neutral-mixed-metal-coordination-polymers-based-on-a-ditopic-acetylacetonate-mg-ii-and-ag-i-syntheses-characterization-and-solvent-dependent-topologies
#16
Qianqian Guo, Ulli Englert
The complex [Mg(acacCN)2(H2O)2] (acacCN = 3-cyanoacetylacetonate) has been synthesized in good yield and fully characterized. It represents a versatile labile precursor for an anionic tris(ligand) complex which is crosslinked with Ag(i) to five different neutral bimetallic networks; all of them are solvates. Four of these extended structures share the same framework stoichiometry Ag[Mg(acacCN)3] and only differ in their solvent content. The co-crystallized solvent molecules decide the topological outcome of the crosslinking: the four compounds can be classified into two isomorphous 3D networks and two non-isomorphous but related 2D layer structures...
June 21, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/28636006/copper-ion-interaction-with-the-rnase-catalytic-site-fragment-of-the-angiogenin-protein-an-experimental-and-theoretical-investigation
#17
Antonio Magrì, Giovanni Tabbì, Raffaella Breglia, Luca De Gioia, Piercarlo Fantucci, Maurizio Bruschi, Raffaele P Bonomo, Diego La Mendola
The angiogenin protein (Ang) is a member of the vertebrate-specific secreted ribonucleases and one of the most potent angiogenic factors known. Ang is a normal constituent of human plasma and its concentration increases under some physiological and pathological conditions to promote neovascularization. Ang was originally identified as an angiogenic tumour factor, but its biological activity has been found to extend from inducing angiogenesis to promoting cell survival in different neurodegenerative diseases...
June 21, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/28632276/optimising-the-relaxivities-of-mn-2-complexes-by-targeting-human-serum-albumin-hsa
#18
Attila Forgács, Lorenzo Tei, Zsolt Baranyai, David Esteban-Gómez, Carlos Platas-Iglesias, Mauro Botta
We report two novel macrocyclic ligands based on the 1,4-DO2AM platform (1,4-DO2AM = 2,2'-(1,4,7,10-tetraazacyclododecane-1,4-diyl)diacetamide) and containing two benzyl groups attached either to the nitrogen atoms of the macrocyclic unit (1,4-BzDO2AM) or to the amide pendant arms (1,4-DO2AMBz). The protonation constants of the ligands and the stability constants of their Mn(2+) complexes were determined using pH potentiometry. The introduction of benzyl groups results in a slight decrease of the stability constants of the Mn(2+) complexes and a slight increase of their acid-catalysed dissociation reactions...
June 20, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/28632261/syntheses-and-post-functionalization-of-tri-substituted-polyalkoxohexavanadates-containing-tris-alkoxo-ligands
#19
Xunliang Hu, Zicheng Xiao, Bo Huang, Xiaokang Hu, Min Cheng, Xinjun Lin, Pingfan Wu, Yongge Wei
A new synthetic approach to tri-substituted trisalkoxy-hexavanadate clusters containing different organic groups was developed in this work. Four mixed-valence or fully reduced POV hybrids were synthesized and structurally characterized, including an amino-containing derivative of hexavanadate, Na2[VVO10{NH2C(CH2O)3}3] (1). Furthermore, a novel mixed-valence POV hybrid was prepared via the amidation of 1, indicating that 1 can be used as an excellent building block for the design and synthesis of mixed-valence POV functional materials...
June 20, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/28631802/aqueous-tantalum-polyoxometalate-reactivity-with-peroxide
#20
Lauren B Fullmer, Christopher E Malmberg, Dylan B Fast, Lindsay A Wills, Paul Ha-Yeon Cheong, Michelle R Dolgos, May Nyman
Peroxide ligation of aqueous metal-oxo clusters provides rich speciation and structural diversity, radiation sensitivity for manipulation with light, and both broadens and shifts pH-range stability. Here we demonstrate peroxide ligation of the polyoxometalate (POM) [Ta6O19](8-). We study in detail solution speciation of the peroxide-substituted cluster, and benchmark it to the peroxide-ligated niobate analogue, [Nb6O10(OH)3(O2)6](5-), whose solid-state structure has been reported. Raman and electrospray ionization mass spectroscopy do not detect any significant differences between the two analogues...
June 20, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
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