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Long-Fei Wang, Jiang-Zhen Qiu, Jun-Yu Hong, Yan-Cong Chen, Quan-Wen Li, Jian-Hua Jia, Jesús Jover, Eliseo Ruiz, Jun-Liang Liu, Ming-Liang Tong
The dimeric molecule [Dy2(acac)6(MeOH)2(bpe)]·bpe·2MeOH (1, acac = acetylacetonate, bpe = 1,2-bis(4-pyridyl)ethylene) undergoes a solid-state ligand substitution reaction upon heating, leading to the one-dimensional chain [Dy(acac)3(bpe)]n (2). This structural transformation takes advantage of the potential coordination of the guest bpe molecules present in 1. In both complexes the Dy(III) ions adopt similar octacoordinated D4d geometries. However, the different arrangement of the negatively charged and neutral ligands alters the direction of magnetic anisotropy axis and the energy states, thus resulting in largely distinct magnetization dynamics, as revealed by the CASSCF/RASSI calculations...
July 17, 2017: Inorganic Chemistry
E Croteau, C A Castellano, M Fortier, C Bocti, T Fulop, N Paquet, S C Cunnane
INTRODUCTION: Deteriorating brain glucose metabolism precedes the clinical onset of Alzheimer's disease (AD) and appears to contribute to its etiology. Ketone bodies, mainly β-hydroxybutyrate and acetoacetate, are the primary alternative brain fuel to glucose. Some reports suggest that brain ketone metabolism is unchanged in AD but, to our knowledge, no such data are available for MCI. OBJECTIVE: To compare brain energy metabolism (glucose and acetoacetate) and some brain morphological characteristics in cognitively healthy older adult controls (CTL), mild cognitive impairment (MCI) and early AD...
July 11, 2017: Experimental Gerontology
Antonella Muscella, Carla Vetrugno, Luca Giulio Cossa, Giovanna Antonaci, Amilcare Barca, Sandra Angelica De Pascali, Francesco Paolo Fanizzi, Santo Marsigliante
Mesothelioma cancer cells have epithelioid or sarcomatoid morphology. The worst prognosis is associated with sarcomatoid phenotype and resistance to therapy is affected by cells heterogeneity. We recently showed that in ZL55 mesothelioma cell line of epithelioid origin [Pt(O,O'-acac)(γ-acac)(DMS)] (Ptac2S) has an antiproliferative effect in vitro and in vivo. Aim of this work was to extend the study on the effects of Ptac2S on ZL34 cell line, representative of sarcomatoid mesothelioma. ZL34 cells were used to assay the antitumor activity of Ptac2S in a mouse xenograft model in vivo...
2017: PloS One
U Suyasunanont, M Nakkuntod, S Mirasena
The lower northern part of Thailand contains various genetically diverse ethnic populations. The sequences of the mitochondrial DNA hypervariable region were studied in three ethnic populations inhabiting Phitsanulok Province. One hundred and nine nucleotide sequences - 53, 29, and 27 from Hmongs (Hill tribe), Lao Songs, and Thai-Siams, respectively - were collected. The haplotypes were generated from 1130 nucleotides of the entire control region. Eighty-six haplotypes were found in the three ethnic populations, and no shared haplotypes were found between populations...
July 6, 2017: Genetics and Molecular Research: GMR
Fethi Elaieb, David Sémeril, Dominique Matt, Michel Pfeffer, Pierre-Antoine Bouit, Muriel Hissler, Christophe Gourlaouen, Jack Harrowfield
An upper rim, o-(diphenylphosphinyl)phenyl-substituted calix[4]arene has been prepared and its coordinative properties investigated. When heated in the presence of palladium, the new biarylphosphine undergoes conversion into two diastereomeric, calixarene-fused phospholes. In both, the P lone pair adopts a fixed orientation with respect to the calixarene core. The more hindered phosphole (8), i.e. the one with the endo-oriented lone pair (cone angle 150°-175°), forms complexes having their metal centre positioned very near the calixarene unit but outside the cavity, thus inducing an unusual chemical shift of one of the methylenic ArCH2Ar protons owing to interactions with the metal centre...
July 6, 2017: Dalton Transactions: An International Journal of Inorganic Chemistry
João Costa Pessoa, Isabel Correia, Ielyzaveta Chorna, Isabel Cavaco, Somnath Roy, Maxim L Kuznetsov, Nádia Ribeiro, Gonçalo Justino, Fernanda Marques, Teresa Santos Silva, Marino Santos, Hugo M Santos, José L Capelo, James Doutch
[VO(acac)2] is a remarkable vanadium compound and has potential as a therapeutic drug. It is important to clarify how it is transported in blood, but the reports addressing its binding to serum proteins have been contradictory. We use several spectroscopic and mass spectrometric techniques (ESI and MALDI-TOF), small-angle X-ray scattering and size exclusion chromatography (SEC) to characterize solutions containing [VO(acac)2] and either human serum apotransferrin (apoHTF) or albumin (HSA). DFT and modeling protein calculations are carried out to disclose the type of binding to apoHTF...
June 26, 2017: Chemistry, An Asian Journal
Dong Yang, Mohammad R Momeni, Hakan Demir, Dale R Pahls, Martino Rimoldi, Timothy C Wang, Omar K Farha, Joseph T Hupp, Christopher J Cramer, Bruce C Gates, Laura Gagliardi
The metal-organic framework NU-1000, with Zr6-oxo, hydroxo, and aqua nodes, was modified by incorporation of hydroxylated Al(iii) ions by ALD-like chemistry with [Al(CH3)2(iso-propoxide)]2 followed by steam (ALD = atomic layer deposition). Al ions were installed to the extent of approximately 7 per node. Single-site iridium diethylene complexes were anchored to the nodes of the modified and unmodified MOFs by reaction with Ir(C2H4)2(acac) (acac = acetylacetonate) and converted to Ir(CO)2 complexes by treatment with CO...
June 14, 2017: Faraday Discussions
Amlan K Pal, Adam F Henwood, David B Cordes, Alexandra M Z Slawin, Ifor D W Samuel, Eli Zysman-Colman
A structure-property relationship study of neutral heteroleptic (1 and 2, [Ir(C(∧)N)2(L(∧)X)]) and homoleptic (3 and 4, fac-[Ir(C(∧)N)3]) Ir(III) complexes (where L(∧)X = anionic 2,2,6,6-tetramethylheptane-3,5-dionato-κO(3),κO(6) (thd) and C(∧)N = a cyclometalating ligand bearing a pentafluorosulfanyl (-SF5) electron-withdrawing group (EWG) at the C4 (HL1) and C3 (HL2) positions of the phenyl moiety) is presented. These complexes have been fully structurally characterized, including by single-crystal X-ray diffraction, and their electrochemical and optical properties have also been extensively studied...
July 3, 2017: Inorganic Chemistry
Mohammad A Affan, Philip G Jessop
Catalytic hydrogenation of CO2 is an efficient and selective way to prepare formic acid derivatives, but most of the highly active catalysts used for this purpose require precious metals. In this study, in situ abundant-metal complexes have been evaluated as potential catalysts for CO2 hydrogenation to prepare formamides, including N-formylmorpholine, 2-ethylhexylformamide, and dimethylformamide, from the corresponding amines. From these initial screening results, the most active catalysts for these reactions were found to be MX2/dmpe in situ catalysts (M = Fe(II), Ni(II); X = Cl(-), CH3CO2(-), acac(-); dmpe = 1,2-bis(dimethylphosphino)ethane) in DMSO...
June 6, 2017: Inorganic Chemistry
Kaai Tung Chan, Glenna So Ming Tong, Qingyun Wan, Gang Cheng, Chen Yang, Chi-Ming Che
A series of charge-neutral Au(III) complexes, which comprise a dicarbanionic C-deprotonated biphenyl ligand and bidentate ancillary ligands ([Au(C^C)(L^X)]; L^X=β-diketonate and relatives (O^O), quinolinolate and relatives (N^O), and diphosphino (P^P) ligands), were prepared. All the complexes are emissive in degassed CH2 Cl2 solutions and in thin-film samples with Φem up to 18 and 35 %, respectively, except for 5 and 6, which bear (N^O)-type ancillary ligands. Variation of the electronic characteristics of the β-diketonate ancillary ligand was demonstrated to be a viable route for tuning the emission color from blue-green (peak λem at ca...
June 6, 2017: Chemistry, An Asian Journal
Chryssoula Drouza, Anthi Dieronitou, Ioanna Hadjiadamou, Marios Stylianou
A novel dynamic method for the investigation of the phenols activity in early stage oxidation of edible oils based on the formation of α-tocopheryl radicals initiated by oil-soluble vanadium complexes is developed. Two new vanadium complexes in oxidation states V and IV were synthesized by reacting 2,2'-((2-hydroxyoctadecyl)azanediyl)bis(ethan-1-ol) (C18DEA) with [VO(acac)2] and 1-(bis(pyridin-2-ylmethyl)amino)octadecan-2-ol (C18DPA) with VOCl2. Addition of a solution of either complex in edible oils resulted in the formation of α-tocopheryl radical, which was monitored by electron paramagnetic resonance (EPR) spectroscopy...
June 21, 2017: Journal of Agricultural and Food Chemistry
Varinia Bernales, Dong Yang, Jun Yu, Gamze Gümüşlü, Christopher J Cramer, Bruce C Gates, Laura Gagliardi
Metal-organic frameworks (MOFs) with nodes consisting of zirconium oxide clusters (Zr6) offer new opportunities as supports for catalysts with well-defined, essentially molecular, structures. We used the precursor Rh(C2H4)2(acac) (acac is acetylacetonate) to anchor Rh(I) complexes to the nodes of the MOF UiO-67 and, for comparison, to the zeolite dealuminated HY (DAY). These were characterized experimentally by measurement of catalytic activities and selectivities for ethylene hydrogenation and dimerization in a once-through flow reactor at 298 K and 1 bar...
May 24, 2017: ACS Applied Materials & Interfaces
R Mac Ciarnain, D Michaelis, T Wehlus, A F Rausch, S Wehrmeister, T D Schmidt, W Brütting, N Danz, A Bräuer, A Tünnermann
The non-isotropic alignment of molecules can increase the interaction efficiency with propagating light fields. This applies to both emissive and absorptive systems and can be exploited for achieving unprecedented efficiencies of organic opto-electronic devices such as organic light-emitting diodes. Optical analysis has revealed certain phosphorescent emitters to align spontaneously in an advantageous orientation. Unfortunately, established approaches only determine an average orientation because emission patterns solely depend on the second moments of the transition dipole vector distribution...
May 12, 2017: Scientific Reports
Daniele Sanna, Valeria Ugone, Maria Serra, Eugenio Garribba
In this work the speciation in real serum samples of five V(IV)O complexes with potential application in the therapy of diabetes was studied through EPR spectroscopy as a function of V concentration (45.4, 90.9 and 454.5μM) and time (0-180min). [VO(dhp)2], [VO(ma)2], [VO(acac)2], [VO(pic)2(H2O)], and [VO(mepic)2], where Hdhp indicates 1,2-dimethyl-3-hydroxy-4(1H)-pyridinone, Hma maltol, Hacac acetylacetone, Hpic picolinic acid, and Hmepic 6-methylpicolinic acid, were examined. The distribution of V(IV)O(2+) among the serum bioligands was calculated from the thermodynamic stability constants in the literature and compared with the experimental results...
April 25, 2017: Journal of Inorganic Biochemistry
Stefanos Mourdikoudis, Thomas Altantzis, Luis M Liz-Marzán, Sara Bals, Isabel Pastoriza-Santos, Jorge Pérez-Juste
Water-soluble Pt nanoflowers (NFs) were prepared by diethylene glycol-mediated reduction of Pt acetylacetonate (Pt(acac)2) in the presence of polyethylenimine. Advanced electron microscopy analysis showed that the NFs consist of multiple branches with a truncated cubic morphology and different crystallographic orientations. We demonstrate that the nature of the solvent strongly influences the resulting morphology. The catalytic performance of the Pt NFs in 4-nitrophenol reduction was found to be superior to that of other nanoparticle-based catalysts...
May 21, 2016: CrystEngComm
Songjie Yu, Caizhi Wu, Shaozhong Ge
We report a cobalt-catalyzed asymmetric hydroboration/cyclization of 1,6-enynes with catalysts generated from Co(acac)2 and chiral bisphosphine ligands and activated in situ by reaction with pinacolborane (HBpin). A variety of oxygen-, nitrogen-, and carbon-tethered 1,6-enynes underwent this asymmetric transformation, yielding both alkyl- and vinyl-substituted boronate esters containing chiral tetrahydrofuran, cyclopentane, and pyrrolidine moieties with high to excellent enantioselectivities (86%-99% ee).
May 4, 2017: Journal of the American Chemical Society
Hans Reuter, Martin Reichelt
The redetermination of the title compound, [Sn(CH3)2(C5H7O2)2] or SnMe2(acac)2, from CCD data recorded at 100 K basically confirms the previous study based on integrated film data recorded at room temperature [Miller & Schlemper (1972 ▸). Inorg. Chem.12, 677-681], but reveals a remarkable shrinkage of the a axis [7.12 (1) > 6.7694 (4) Å]. The mol-ecule belongs to point group Ci with the Sn(IV) atom on a centre of inversion. The Sn(IV) atom shows a slightly distorted octa-hedral coordination sphere with the methyl groups in trans positions and a Sn-C bond length of 2...
April 1, 2017: Acta Crystallographica. Section E, Crystallographic Communications
David Pertuit, Mustafa Larshini, Malika Aitsidi Brahim, Mohamed Markouk, Anne-Claire Mitaine-Offer, Thomas Paululat, Stéphanie Delemasure, Patrick Dutartre, Marie-Aleth Lacaille-Dubois
Phytochemical investigations of the roots of Spergularia marginata had led to the isolation of four previously undescribed triterpenoid saponins, a known one and one spinasterol glycoside. Their structures were established by extensive NMR and mass spectroscopic techniques as 3-O-β-D-glucuronopyranosyl echinocystic acid 28-O-α-L-arabinopyranosyl-(1 → 2)-α-L-rhamnopyranosyl-(1 → 3)-β-D-xylopyranosyl-(1 → 4)-α-L-rhamnopyranosyl-(1 → 2)-α-L- arabinopyranosyl ester, 3-O-β-D-glucopyranosyl-(1 → 3)-β-D-glucuronopyranosyl echinocystic acid 28-O-α-L-arabinopyranosyl-(1 → 2)-α-L-rhamnopyranosyl-(1 → 3)-β-D-xylopyranosyl-(1 → 4)-α-L-rhamnopyranosyl-(1 → 2)- α-L-arabinopyranosyl ester, 3-O-β-D-glucopyranosyl-(1 → 4)-3-O-sulfate-β-D-glucuronopyranosyl echinocystic acid 28-O-α-L-arabinopyranosyl-(1 → 2)-α-L-rhamnopyranosyl-(1 → 3)-β-D-xylopyranosyl-(1 → 4)-α-L-rhamnopyranosyl-(1 → 2)-α-L-arabinopyranosyl ester, and 3-O-β-D-glucopyranosyl-(1 → 4)-β-D-glucuronopyranosyl 21-O-acetyl acacic acid...
July 2017: Phytochemistry
Ji-Kun Li, Jing Dong, Chuan-Ping Wei, Song Yang, Ying-Nan Chi, Yan-Qing Xu, Chang-Wen Hu
Six alkoxohexavanadate-based Cu- or Co-POVs [Cu(dpa)(acac)(H2O)]2[V6O13(OMe)6] (1), [Cu(phen)(acac)(MeOH)]2[V6O13(OMe)6] (2), [Co(dpa)(acac)2]2[V6O13(OMe)6]·2MeOH (3), [Co(phen)(acac)2]2[V6O13(OMe)6] (4), [Cu(dpa)(acac)]2[V(IV)2V(V)4O12(OMe)7] (5), and [Cu(dpa)(acac)(MeOH)]2[V(IV)2V(V)4O11(OMe)8] (6) (POV = polyoxovanadate; dpa = 2,2'-dipyridine amine; phen = 1,10-phenanthroline; acac = acetylacetone anion) have been synthesized by controlling the reaction conditions and characterized by single-crystal X-ray diffraction and powder X-ray diffraction analyses, FT-IR spectroscopy, element analyses, and X-ray photoelectron spectroscopy...
April 21, 2017: Inorganic Chemistry
Zhenzhen Zhao, Mei Zhang, Jun Ying, Xuejiao Hu, Jingya Zhang, Yanhong Zhou, Yi Zhou, Xingbo Song, Binwu Ying
Recent studies have implicated long non-coding RNA, AC079767.4, as a highly susceptible gene in tuberculosis. The aim of the study was to preliminarily explore the possible association of single nucleotide polymorphisms (SNPs) in AC079767.4 gene with clinical phenotypes and TB susceptibility in Western Chinese Han population. The improved multiplex ligation detection reaction (iMLDR) method was employed to genotype 4 SNPs in AC079767.4 in 554 tuberculosis patients and 561 healthy individuals. In subgroup analysis, only the C allele for rs12477677 was associated with the decreased susceptibility to pulmonary TB with a p-value of 0...
April 19, 2017: Scientific Reports
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