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https://www.readbyqxmd.com/read/27934982/shape-electronic-structure-and-steric-effects-of-organometallic-nanocatalysts-relevant-tools-to-improve-the-synergy-between-theory-and-experiment
#1
Lucy Cusinato, Iker Del Rosal, Romuald Poteau
Working closely with experimentalists on the comprehension of the surface properties of catalytically active organometallic nanoparticles (NPs) requires the development of several computational strategies which significantly differ from the cluster domain where a precise knowledge of their optimal geometry is a mandatory prerequisite to computational modeling. Theoretical simulations can address several properties of organometallic nanoparticles: the morphology of the metal core, the surface composition under realistic thermodynamic conditions, the relationship between adsorption energies and predictive descriptors of reactivity...
December 9, 2016: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/27934460/kinetic-study-of-the-reaction-of-the-phthalimide-n-oxyl-radical-with-amides-structural-and-medium-effects-on-the-hydrogen-atom-transfer-reactivity-and-selectivity
#2
Massimo Bietti, Veronica Forcina, Osvaldo Lanzalunga, Andrea Lapi, Teo Martin, Marco Mazzonna, Michela Salamone
A kinetic study of the hydrogen atom transfer (HAT) reactions from a series of secondary N-(4-X-benzyl)acetamides and tertiary amides to the phthalimide-N-oxyl radical (PINO) has been carried out. The results indicate that HAT is strongly influenced by structural and medium effects; in particular, the addition of Brønsted and Lewis acids determines a significant deactivation of C-H bonds α to the amide nitrogen of these substrates. Thus, by changing the reaction medium, it is possible to carefully control the regioselectivity of the aerobic oxidation of amides catalyzed by N-hydroxyphthalimide, widening the synthetic versatility of this process...
December 2, 2016: Journal of Organic Chemistry
https://www.readbyqxmd.com/read/27934438/electrochemical-properties-and-co2-reduction-ability-of-m-terphenyl-isocyanide-supported-manganese-tricarbonyl-complexes
#3
Douglas W Agnew, Matthew D Sampson, Curtis E Moore, Arnold L Rheingold, Clifford P Kubiak, Joshua S Figueroa
To circumvent complications with redox-active ligands commonly encountered in the study of manganese electrocatalysts for CO2 reduction, we have studied the electrochemistry of the manganese mixed carbonyl/isocyanide complexes XMn(CO)3(CNAr(Dipp2))2 (X = counteranion), to evaluate the pairing effects of the counteranion and their influence over the potential necessary for metal-based reduction. The complexes described herein have been shown to act as functional analogues to the known homoleptic carbonyl manganese complexes [Mn(CO)5](n) (n = 1-, 0, 1+)...
December 5, 2016: Inorganic Chemistry
https://www.readbyqxmd.com/read/27934320/oxygen-atom-transfer-and-intramolecular-nitrene-transfer-in-a-rhenium-%C3%AE-diketiminate-complex
#4
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
https://www.readbyqxmd.com/read/27934303/solvent-dependent-thermochemistry-of-an-iridium-ruthenium-h2-evolution-catalyst
#5
Kelsey R Brereton, Catherine L Pitman, Thomas R Cundari, Alexander J M Miller
The hydricity of the heterobimetallic iridium/ruthenium catalyst [Cp*Ir(H)(μ-bpm)Ru(bpy)2](3+) (1, where Cp* = η(5)-pentamethylcyclopentadienyl, bpm = 2,2'-bipyrimidine, and bpy = 2,2'-bipyridine) has been determined in both acetonitrile (63.1 kcal mol(-1)) and water (29.7 kcal mol(-1)). Hydride 1 features a large increase in the hydride donor ability when the solvent is changed from acetonitrile to water. The acidity of 1, in contrast, is essentially solvent-independent because 1 remains strongly acidic in both solvents...
November 21, 2016: Inorganic Chemistry
https://www.readbyqxmd.com/read/27934299/interaction-of-the-hiv-ncp7-protein-with-platinum-ii-and-gold-iii-complexes-containing-tridentate-ligands
#6
Victor H F Bernardes, Yun Qu, Zhifeng Du, James Beaton, Maria D Vargas, Nicholas P Farrell
The human immunodeficiency virus (HIV) nucleocapsid protein (NCp7) plays significant roles in the virus life cycle and has been targeted by compounds that could lead to its denaturation or block its interaction with viral RNA. Herein, we describe the interactions of platinum(II) and gold(III) complexes with NCp7 and how the reactivity/affinity of potential inhibitors can be modulated by judicious choice of ligands. The interactions of [MCl(N3)](n+) (M = Pt(2+) (n = 1) and Au(3+) (n = 2); N3 = tridentate chelate ligands: bis(2-pyridylmethyl)methylamine (Mebpma, L(1)) and bis(2-pyridylmethyl)amine (bpma, L(2)) with the C-terminal zinc finger of NCp7 (ZF2) were investigated by electrospray ionization-mass spectroscopy (ESI-MS)...
November 7, 2016: Inorganic Chemistry
https://www.readbyqxmd.com/read/27934214/birch-type-hydrogenation-of-few-layer-graphenes-products-and-mechanistic-implications
#7
Xu Zhang, Yuan Huang, Shanshan Chen, Na Yeon Kim, Wontaek Kim, David Schilter, Mandakini Biswal, Baowen Li, Zonghoon Lee, Sunmin Ryu, Christopher W Bielawski, Wolfgang S Bacsa, Rodney S Ruoff
Few-layer graphenes, supported on Si with a superficial oxide layer, were subjected to a Birch-type reduction using Li and H2O as the electron and proton donors, respectively. The extent of hydrogenation for bilayer graphene was estimated at 1.6-24.1% according to Raman and X-ray photoelectron spectroscopic data. While single-layer graphene reacts uniformly, few-layer graphenes were hydrogenated inward from the edges and/or defects. The role of these reactive sites was reflected in the inertness of pristine few-layer graphenes whose edges were sealed...
November 16, 2016: Journal of the American Chemical Society
https://www.readbyqxmd.com/read/27934023/diphosphine-stabilized-small-gold-nanoclusters-from-crystal-structure-determination-to-ligation-driven-symmetry-breaking-and-anion-exchange-properties
#8
Liao-Yuan Yao, Vivian Wing-Wah Yam
A new class of small gold nanoclusters with molecular characteristics has been constructed using 1,1'-bis(diphenylphosphino)ferrocene (dppf) as the stabilizing ligand. The identities of the small gold nanoclusters have been fully characterized by NMR, electrospray ionization mass spectrometry, elemental analysis, and single-crystal X-ray diffraction analysis. Octa- and undecagold clusters are found to display different UV-vis absorption behavior. The ligation of the bidentate ligands and halides or pseudohalides has resulted in the symmetry breaking of these nanoclusters with C1 symmetry...
December 7, 2016: Journal of the American Chemical Society
https://www.readbyqxmd.com/read/27933670/gold-i-fluorohalides-theory-and-experiment
#9
Babil Menjón, Miguel Baya, Alberto Pérez-Bitrián, Sonia Martínez-Salvador, José María Casas, Jesús Orduna
The anionic trifluoromethyl-gold(I) derivatives [CF₃AuX]⁻, which have been prepared and isolated as their [PPh₄]⁺ salts in good yield, undergo thermally-induced difluorocarbene extrusion in the gas phase giving rise to the mixed gold(I) fluorohalide complexes [F-Au-X]⁻ (X = Cl, Br, I). These triatomic species have been detected by tandem mass spectrometry (MS2) experiments and their properties have been analyzed by DFT methods. The CF₂ extrusion mechanism from the Au-CF₃ moiety serves as a model for the CF₂ insertion into the Au-F bond, since both reactivity channels are connected by the microreversibility principle...
December 9, 2016: Chemistry: a European Journal
https://www.readbyqxmd.com/read/27932349/nadph-oxidase-2-and-atherothrombosis-insight-from-chronic-granulomatous-disease
#10
REVIEW
Francesco Violi, Roberto Carnevale, Lorenzo Loffredo, Pasquale Pignatelli, John I Gallin
The phagocytic cell enzyme NADPH oxidase-2 (Nox2) is critical for killing micro-organisms via production of reactive oxygen species and thus is a key element of the innate immune system. Nox2 is also detectable in endothelial cells and platelets where it has vasoconstrictive and aggregating properties, respectively. Patients with X-linked chronic granulomatous disease with hereditary Nox2 deficiency not only have impaired bacterial killing but, in association with loss of Nox2 function, also have enhanced carotid artery dilation, impaired platelet-related thrombosis, and reduced carotid atherosclerotic burden...
December 8, 2016: Arteriosclerosis, Thrombosis, and Vascular Biology
https://www.readbyqxmd.com/read/27931181/platelet-aggregation-and-risk-of-stent-thrombosis-or-bleeding-in-interventionally-treated-diabetic-patients-with-acute-coronary-syndrome
#11
K Kukula, M Klopotowski, P K Kunicki, J Jamiolkowski, A Debski, P Bekta, M Polanska-Skrzypczyk, Z Chmielak, A Witkowski
BACKGROUND: Platelet aggregation monitoring in diabetic patients treated with coronary interventions (PCI) for an acute coronary syndrome (ACS) is a promising way of optimizing treatment and outcomes in this high risk group. The aim of the study was to verify whether clopidogrel response measured by Multiplate analyzer (ADPtest) in diabetic ACS patients treated with PCI predicts the risk of stent thrombosis or cardiovascular mortality and bleeding. METHODS: Into this prospective, observational study 206 elective PCI patients were enrolled...
December 8, 2016: BMC Cardiovascular Disorders
https://www.readbyqxmd.com/read/27930850/elusive-antimony-centered-radical-cations-isolation-characterization-crystal-structures-and-reactivity-studies
#12
Tao Li, Houjia Wei, Yong Fang, Lei Wang, Sheng Chen, Zaichao Zhang, Yue Zhao, Gengwen Tan, Xinping Wang
One-electron oxidation of the stibines Aryl3 Sb (1, Aryl=2,6-(i) Pr2 -4-OMe-C6 H2 ; 2, Aryl=2,4,6-(i) Pr3 -C6 H2 ) with AgSbF6 and NaBAryl(F)4 (Aryl(F) =3,5-(CF3 )2 C6 H3 ) afforded the first structurally characterized examples of antimony-centered radical cations 1(.+) [BAryl(F)4 ](-) and 2(.+) [BAryl(F)4 ](-) . Their molecular and electronic structures were investigated by single-crystal X-ray diffraction, electron paramagnetic resonance spectroscopy (EPR) and UV/Vis absorption spectroscopy, in conjunction with theoretical calculations...
December 8, 2016: Angewandte Chemie
https://www.readbyqxmd.com/read/27929749/critical-role-of-x-box-binding-protein-1-in-nadph-oxidase-4-triggered-cardiac-hypertrophy-is-mediated-by-receptor-interacting-protein-kinase-1
#13
Li Chen, Mingyue Zhao, Junli Li, Yu Wang, Qinxue Bao, Siyuan Wu, Xueqin Deng, Xiaoju Tang, Wenchao Wu, Xiaojing Liu
NADPH oxidase 4 (NOX4) and the NOX4-related redox signaling are implicated in cardiac hypertrophy. NOX4 is interrelated with endoplasmic reticulum stress (ERS). Spliced X-box binding protein 1 (Xbp1s) is a key mediator of ERS while its role in cardiac hypertrophy is still poorly understood. Recently, receptor interacting protein kinase 1(RIPK1) has been increasingly reported to be associated with ERS. Therefore, we aimed to test the hypothesis that Xbp1s mediates NOX4-triggered cardiac hypertrophy via RIPK1 signaling...
December 8, 2016: Cell Cycle
https://www.readbyqxmd.com/read/27929460/the-synthesis-of-sn10-si-sime3-3-4-2-using-a-metastable-sn-i-halide-solution-synthesized-via-a-co-condensation-technique
#14
Mareike Binder, Claudio Schrenk, Andreas Schnepf
The number of well-characterized metalloid tin clusters, synthesized by applying the disproportionation of a metastable Sn(I) halide in the presence of a sterically demanding ligand, has increased in recent years. The metastable Sn(I) halide is synthesized at "outer space conditions" via the preparative co-condensation technique. Thereby, the subhalide is synthesized in an oven at high temperatures, around 1,300 °C, and at reduced pressure by the reaction of elemental tin with hydrogen halide gas (e.g., HCl)...
November 28, 2016: Journal of Visualized Experiments: JoVE
https://www.readbyqxmd.com/read/27927648/renin-angiotensin-system-transgenic-mouse-model-recapitulates-pathophysiology-similar-to-human-preeclampsia-with-renal-injury-that-may-be-mediated-through-vegf
#15
J Morgan Denney, Cynthia E Bird, Annette Gendron-Fitzpatrick, Emmanuel Sampene, Ian M Bird, Dinesh M Shah
Using a transgenic cross, we evaluated features of preeclampsia, renal injury and the sFlt1/VEGF changes. Transgenic hAGT and hREN, or wild type (WT) C57Bl/6 mice were cross-bred: ♀hAGT x ♂hREN for preeclampsia (PRE) model and ♀WT x ♂WT for pregnant controls (WTP). Samples were collected for plasma VEGF, sFlt1 and urine albumin. Blood pressures (BP) were monitored by telemetry. Vascular reactivity was investigated by wire myography. Kidneys and placenta were immunostained for sFlt1 and VEGF. Eleven PRE and 9 WTP mice were compared...
December 7, 2016: American Journal of Physiology. Renal Physiology
https://www.readbyqxmd.com/read/27922685/5%C3%A2-bromo%C3%A2-3%C3%A2-3%C3%A2-hydroxyprop%C3%A2-1%C3%A2-ynyl-%C3%A2-2h%C3%A2-pyran%C3%A2-2%C3%A2-one-induces-apoptosis-in-t24-human-bladder-cancer-cells-through-mitochondria-dependent-signaling-pathways
#16
Guo-Qiang Yu, Zhong-Ling Dou, Zhao-Hui Jia
The present study was performed to investigate the effect of 5-bromo-3-(3-hydroxyprop-1-ynyl)-2H-pyran-2-one (BHP) on the induction of apoptosis and cell cycle arrest in T24 human bladder carcinoma cells. An MTT assay was used to investigate the inhibition of cell proliferation. Flow cytometry was used to observe alterations in the cell cycle, generation of reactive oxygen species (ROS), alterations in mitochondrial membrane potential (MMP) and induction of apoptosis in the T24 cells following BHP treatment...
December 6, 2016: Molecular Medicine Reports
https://www.readbyqxmd.com/read/27920337/effect-of-epigallocatechin-3-gallate-on-acrylamide-induced-oxidative-stress-and-apoptosis-in-pc12-cells
#17
Y He, D Tan, Y Mi, B Bai, D Jiang, X Zhou, S Ji
Acrylamide (ACR) is a chemical intermediate utilized in industry. ACR is also formed during heating of foods containing carbohydrates and amino acids. Therefore, humans are widely exposed to ACR, and ACR neurotoxicity in humans is a significant public health issue attracting wide attention. In this study, we investigated the potential neuroprotective effects of epigallocatechin-3-gallate (EGCG), the most abundant polyphenolic compound in green tea, in PC12 cells treated with ACR. ACR-treated PC12 cells pretreated with various concentrations of EGCG (2...
December 5, 2016: Human & Experimental Toxicology
https://www.readbyqxmd.com/read/27918301/solvent-dependence-of-the-solid-state-structures-of-salicylaldiminate-magnesium-amide-complexes
#18
Jeffrey A Rood, Ashley M Landis, Daniel R Forster, Timothy Goldkamp, Allen G Oliver
There are challenges in using magnesium coordination complexes as reagents owing to their tendency to adopt varying aggregation states in solution and thus impacting the reactivity of the complexes. Many magnesium complexes are prone to ligand redistribution via Schlenk equilibrium due to the ionic character within the metal-ligand interactions. The role of the supporting ligand is often crucial for providing stability to the heteroleptic complex. Strategies to minimize ligand redistribution in alkaline earth metal complexes could include using a supporting ligand with tunable sterics and electronics to influence the degree of association to the metal atom...
December 1, 2016: Acta Crystallographica. Section C, Structural Chemistry
https://www.readbyqxmd.com/read/27918246/rice-leaf-transcriptional-profiling-suggests-a-functional-interplay-between-xanthomonas-oryzae-pv-oryzae-lipopolysaccharide-and-extracellular-polysaccharide-in-modulation-of-defense-responses-during-infection
#19
Anil Madhusoodana Girija, Bipin Kumar Kumar, Madhavi B Mylavarapu, Palaparthi Ramesh, Sridivya Vungarala, Hitendra Kumar Patel, Ramesh Sonti
Treatment of rice leaves with isolated Xanthomonas oryzae pv. oryzae lipopolysaccharide (LPS) induces the production of callose deposits, reactive oxygen species and enhanced resistance against subsequent bacterial infection. Expression profiling of X. oryzae pv. oryzae LPS treated rice (Oryza sativa ssp. indica) leaves showed that genes involved in the biosynthetic pathways for lignins, phenylpropanoids, chorismate, phenylalanine, salicylic acid and ethylene as well as a number of pathogenesis related proteins are up regulated...
December 5, 2016: Molecular Plant-microbe Interactions: MPMI
https://www.readbyqxmd.com/read/27917751/hbsag-may-reappear-following-reactivation-in-individuals-with-spontaneous-hbsag-seroclearance-8-years-previously
#20
Q Y Chen, X Y Wang, T J Harrison, X He, L P Hu, K W Li, H H Jia, Q L Yang, C Wang, Z L Fang
HBsAg reappearance may constitute not only a risk for liver disease but also an infectious source. We aimed to determine whether HBsAg may reappear after spontaneous HBsAg seroclearance. A cohort of 2999 HBsAg-positive subjects aged 30-55 years was recruited in Guangxi, China in 2004. HBsAg was tested every 6 months from July 2004 to June 2007, then, one more time in December 2013. The results showed that spontaneous HBsAg seroclearance occurred in 41 subjects in the first 3 years, giving a 0·54% annual seroclearance rate...
December 5, 2016: Epidemiology and Infection
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