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Yao-Tang Chang, Sunil Sharma, Miao-Ken Hung, Yu-Hsuan Lee, Show-An Chen
σ-π conjugated polymer strategy is proposed for designing electroluminescent host polymers with silylene-diphenylene as the backbone repeat unit giving a high triplet energy (ET = 2.67 eV). By incorporation of high ET (3.0 eV) electron (oxadiazole, OXD) and hole (triphenyl amine, TPA) transport moieties, or TPA alone (in this case, the main chain acts as electron transport channel) as side arms on the silylene, the high ET bipolar and unipolar polymers are formed, allowing a use of iridium green phosphor (Ir(ppy)2(acac), Ir-G) (ET = 2...
December 2, 2016: Scientific Reports
Bora Karasulu, René H J Vervuurt, Wilhelmus M M Kessels, Ageeth A Bol
Integrating metals and metal oxides with graphene is key in utilizing its extraordinary material properties that are ideal for nanoelectronic and catalyst applications. Atomic layer deposition (ALD) has become a key technique for depositing ultrathin, conformal metal(oxide) films. ALD of metal(oxide) films on graphene, however, remains a genuine challenge due to the chemical inertness of graphene. In this study we address this issue by combining first-principles density functional theory (DFT) simulations with ALD experiments...
December 1, 2016: Nanoscale
Lara Hettmanczyk, Bianca Schmid, Stephan Hohloch, Biprajit Sarkar
A series of novel palladium(ii) acetylacetonato complexes bearing mesoionic carbenes (MICs) have been synthesized and characterized. The synthesis of the complexes of type (MIC)Pd(acac)I (MIC = 1-mesityl-3-methyl-4-phenyl-1,2,3-triazol-5-ylidene (1), 1,4-(2,4,6-methyl)-phenyl-3-methyl-1,2,3-triazol-5-ylidene (2), 1,4-(2,6-diisopropyl)-phenyl-3-methyl-1,2,3-triazol-5-ylidene (3); acac = acetylacetonato) via direct metalation starting from the corresponding triazolium iodides and palladium(ii) acetylacetonate is described herein...
November 17, 2016: Molecules: a Journal of Synthetic Chemistry and Natural Product Chemistry
Fei Xue, Ying Kai Loh, Xiaolu Song, Wei Jie Teo, J Y Darrence Chua, Jin Zhao, T S Andy Hor
A catalytic [2+2+2] cyclotrimerization of unactivated internal alkynes providing cyclotrimerization products in excellent yields with high regioselectivity is described. The transformation is accomplished by using a simple catalytic mixture comprising Ni(acac)2 , an imidazolium salt and a Grignard reagent at room temperature or 60 °C for 20 min or 1 h.
November 15, 2016: Chemistry, An Asian Journal
Leon Shaw, Jack Shamie, Caihong Liu, Vincent Sprenkle
In this study, a new mechanism for the reduction of vanadyl acetylacetonate, VO(acac)2, to vanadium acetylacetonate, V(acac)3, is introduced. V(acac)3 has been studied for use in redox flow batteries for some time, however contamination by moisture leads to the formation of VO(acac)2. In previous work, once this transformation occurs, it is no longer reversible because there is a requirement of extreme low potentials for the reduction to occur. Here, we propose that with the presence of excess acetylacetone (Hacac) and free protons (H+) the reduction can take place between 2...
November 15, 2016: ChemSusChem
Andreas Dominik Benischke, Grégoire Le Corre, Paul Knochel
A catalytic system consisting of InCl₃ (3 mol%) and LiCl (30 mol%) allows a convenient preparation of polyfunctional arylzinc halides via the insertion of zinc powder to various aryl iodides in THF at 50 °C in up to 95% yield. The use of a THF:DMPU (1:1) mixture shortens the reaction rates and allows the preparation of keto-substituted arylzinc reagents. In the presence of In(acac)₃ (3 mol%) and LiCl (150 mol%), the zinc insertion to various aryl and heteroaryl bromides proceeds smoothly (50 °C, 2-18 h)...
November 8, 2016: Chemistry: a European Journal
Antonella Muscella, Carla Vetrugno, Luca Giulio Cossa, Giovanna Antonaci, Francesco De Nuccio, Sandra Angelica De Pascali, Francesco Paolo Fanizzi, Santo Marsigliante
Malignant pleural mesothelioma (MPM) is an aggressive malignancy highly resistant to chemotherapy. There is an urgent need for effective therapy inasmuch as resistance, intrinsic and acquired, to conventional therapies is common. Among Pt(II) antitumor drugs, [Pt(O,O'-acac)(γ-acac)(DMS)] (Ptac2S) has recently attracted considerable attention due to its strong in vitro and in vivo antiproliferative activity and reduced toxicity. The purpose of this study was to examine the efficacy of Ptac2S treatment in MPM...
2016: PloS One
Xue Lan, Tomoyuki Mochida, Yusuke Funasako, Kazuyuki Takahashi, Takahiro Sakurai, Hitoshi Ohta
: There are various thermochromic materials, though liquid thermochromic materials are less common. To produce functional thermochromic liquids, we have designed ionic liquids based on cationic nickel complexes with ether side chains, [Ni(acac)(Me2NC2H4NR1R2)]Tf2N ([1]Tf2N: R1 = C3H6OEt, R2 = Me, [2]Tf2N: R1 = C3H6OMe, R2 = Me, [3]Tf2N: R1 = R2 = C3H6OMe), where acac = acetylacetonate and Tf2N = (F3CSO2)2N-. The side chains (R1, R2) can moderately coordinate to the metal center, enabling temperature-dependent coordination equilibrium in the liquid state...
November 2, 2016: Chemistry: a European Journal
David R Diercks, Brian P Gorman, Johannes J L Mulders
Six precursors were evaluated for use as in situ electron beam-induced deposition capping layers in the preparation of atom probe tomography specimens with a focus on near-surface features where some of the deposition is retained at the specimen apex. Specimens were prepared by deposition of each precursor onto silicon posts and shaped into sub-70-nm radii needles using a focused ion beam. The utility of the depositions was assessed using several criteria including composition and uniformity, evaporation behavior and evaporation fields, and depth of Ga+ ion penetration...
October 17, 2016: Microscopy and Microanalysis
Benjamin E Van Kuiken, Anselm W Hahn, Dimitrios Maganas, Serena DeBeer
Spectroscopic probes of the electronic structure of transition metal-containing materials are invaluable to the design of new molecular catalysts and magnetic systems. Herein, we show that 2p3d resonant inelastic X-ray scattering (RIXS) can be used to observe both spin-allowed and (in the V(III) case) spin-forbidden d-d excitation energies in molecular vanadium complexes. The spin-allowed d-d excitation energies determined by 2p3d RIXS are in good agreement with available optical data. In V(acac)3, a previously undetected spin-forbidden singlet state has been observed...
October 12, 2016: Inorganic Chemistry
Mannar R Maurya, Bithika Sarkar, Fernando Avecilla, Isabel Correia
The ONO donor ligands obtained from the condensation of 4-benzoyl-3-methyl-1-phenyl-2-pyrazoline-5-one (Hbp) with benzoylhydrazide (H2bp-bhz I), furoylhydrazide (H2bp-fah II), nicotinoylhydrazide (H2bp-nah III) and isonicotinoylhydrazide (H2bp-inh IV), upon treatment with [V(IV)O(acac)2], lead to the formation of [V(IV)O(bp-bhz)(H2O)] 1, [V(IV)O(bp-fah)(H2O)] 2, [V(IV)O(bp-nah)(H2O)] 3 and [V(IV)O(bp-inh)(H2O)] 4, respectively. At neutral pH the in situ generated aqueous K[H2V(V)O4] reacts with ligands I and II, forming potassium salts, K(H2O)2[V(V)O2(bp-bhz)] 5 and K(H2O)2[V(V)O2(bp-fah)] 6, while ligands III and IV give neutral complexes, [V(V)O2(Hbp-nah)] 9 and [V(V)O2(Hbp-inh)] 10, respectively...
October 10, 2016: Dalton Transactions: An International Journal of Inorganic Chemistry
Práxedes Sánchez, Martín Hernández-Juárez, Eleuterio Álvarez, Margarita Paneque, Nuria Rendón, Andrés Suárez
Coordination studies of new lutidine-derived hybrid NHC/phosphine ligands (CNP) to Pd and Ir have been performed. Treatment of the square-planar [Pd(CNP)Cl](AgCl2) complex 2a with KHMDS produces the selective deprotonation at the CH2P arm of the pincer to yield the pyridine-dearomatised complex 3a. A series of cationic [Ir(CNP)(cod)](+) complexes 4 has been prepared by reaction of the imidazolium salts 1 with Ir(acac)(cod). These derivatives exhibit in the solid state, and in solution, a distorted trigonal bipyramidal structure in which the CNP ligands adopt an unusual C(axial)-N(equatorial)-P(equatorial) coordination mode...
October 4, 2016: Dalton Transactions: An International Journal of Inorganic Chemistry
Minzhi Peng, Yanna Cai, Xiefan Fang, Li Liu
A novel liquid chromatography-tandem mass spectrometry (LC-MS/MS) method has been established to quantify metabolic intermediates, including lactate (Lac), pyruvate (Pyr), acetoacetate (ACAC) and 3-hydroxybutyrate (3-HB) in blood. Samples were deproteinized with methanol-acetonitrile solution, and analytes were separated on an adamantyl group-bonded reverse phase column and detected in multiple reaction monitoring mode. Total analysis time was 4 min per sample. Method validation results displayed that limits of quantification were 10...
October 26, 2016: Analytica Chimica Acta
Anne E V Gorden, Michael L McKee
The stability of Th(4+) to reduction in water is studied by DFT methods. The standard reduction potential (SRP) of homoleptic complexes including Th(H2O)9(4+), Th(H2O)10(4+), Th(NO3)4, Th(NO2)6(2-), Th(NO3)6(2-), Th(COT)2, Th(acac)4, ThCp4, ThF4, and ThCl4 have been investigated. The values vary widely (from -3.50 V for Th(OH)4 to -0.62 V for Th(NO3)4 depending on whether the ligands are redox active (noninnocent) or not. Several additional topics of thorium chemistry are explored, including the hydrolysis mechanism of ThO2(H2O)n, n = 1, 2, 4, and the solution phase nonzero dipole moment of ThCp4...
October 7, 2016: Journal of Physical Chemistry. A
Lalita B Rane, Anup N Kate, Shefali N Ramteke, Bhupendra V Shravage, Prasad P Kulkarni, Anupa A Kumbhar
Two new zinc(ii) complexes, [Zn(l-His)(NIP)](+)(1) and [Zn(acac)2(NIP)](2) (where NIP is 2-(naphthalen-1-yl)-1H-imidazo[4,5-f][1,10]phenanthroline, acac = acetyl acetone), have been synthesized and characterized by elemental analysis, UV-vis, fluorescence, IR, (1)H NMR and electron spray ionization mass spectroscopies. Gel retardation assay, atomic force microscopy and dynamic light scattering studies show that 1 and 2 can induce the condensation of circular plasmid pBR322 DNA into nanometer size particles under ambient conditions...
October 3, 2016: Dalton Transactions: An International Journal of Inorganic Chemistry
Cristina Trejo-Solis, Mayra A Alvarez-Lemus, Dolores Jiménez-Farfán, Isabel Anaya-Rubio, Rosendo López-González, Guadalupe Palencia, Dora M Frías-Márquez, Gerardo González-García, Carmen Rubio-Osornio, Minerva Calvillo-Velasco, Guadalupe Márquez-Chablé
Phenanthroline derivatives have been reported as potential bioactive compounds because of their ability to interact with DNA. In order to evaluate the antiproliferative effect of bis(acetylacetonate-k(2) O,O)(1,10-phenanthroline-k(2) N,N)Zn(II) or Zn(acac)2 (phen) complex, the compound was obtained in a simple manner and further characterized to determine crystal structure, thermal behavior, morphology and spectroscopic properties. The structure of the complex was confirmed by X-Ray single structure as well as by solution solid-state (13) C CP/MAS NMR...
October 2, 2016: Chemical Biology & Drug Design
Xiaoxia Shi, Dangdang Li, Qinghua Deng, Zhicheng Peng, Chenxu Zhao, Xiaobing Li, Zhe Wang, Xinwei Li, Guowen Liu
Dairy cows with fatty liver or ketosis exhibit hyperketonemia, oxidative stress, and a low rate of very low density lipoprotein (VLDL) assembly, and there may be a potential link among these characteristics. Therefore, the objective of this study was to determine the effect of acetoacetic acid (AcAc) on the assembly of VLDL in cow hepatocytes. Cultured cow hepatocytes were treated with different concentrations of AcAc with or without N-acetylcysteine (NAC, an antioxidant). AcAc treatment decreased the mRNA expression and activities of antioxidant enzymes superoxide dismutase (SOD), catalase (CAT), and glutathione peroxidase (GSH-Px), and significantly increased malondialdehyde (MDA) content, indicative of oxidative stress...
October 3, 2016: Journal of Dairy Research
Shanghua Xia, Lu Gan, Kailiang Wang, Zheng Li, Dawei Ma
The combination of Cu(acac)2 and N,N'-bis(4-hydroxyl-2,6-dimethylphenyl)oxalamide (BHMPO) provides a powerful catalytic system for hydroxylation of (hetero)aryl halides. A wide range of (hetero)aryl chlorides bearing either electron-donating or -withdrawing groups proceeded well at 130 °C, delivering the corresponding phenols and hydroxylated heteroarenes in good to excellent yields. When more reactive (hetero)aryl bromides and iodides were employed, the hydroxylation reactions completed at relatively low temperatures (80 and 60 °C, respectively) at low catalytic loadings (0...
October 5, 2016: Journal of the American Chemical Society
Jiahui Kong, Qiong Zhang, Mathew Savage, Minzhi Li, Xin Li, Sihai Yang, Xu Liang, Weihua Zhu, Hans Ågren, Yongshu Xie
By oxidation of an alternately N-confused bilane in CH2Cl2, a C-N fused tetrapyrrin was synthesized that bears a 5.5.5-tricyclic ring generated from an intramolecular C-N linkage. When CH3CN was used as the reaction medium, a multiply C-N-fused octapyrrolic dimer was also obtained that contained two moieties and a bipyrrole unit generated from the intramolecular C-N linkage and intermolecular C-C linkage, respectively. This could be coordinated with Ni(acac)2 to afford a mixed-ligand complex...
October 7, 2016: Organic Letters
Miika Mattinen, Jani Hämäläinen, Feng Gao, Pasi Jalkanen, Kenichiro Mizohata, Jyrki Räisänen, Riikka L Puurunen, Mikko Ritala, Markku Leskelä
Nucleation and conformality are important issues, when depositing thin films for demanding applications. In this study, iridium and iridium dioxide (IrO2) films were deposited by atomic layer deposition (ALD), using five different processes. Different reactants, namely, O2, air, consecutive O2 and H2 (O2 + H2), and consecutive O3 and H2 (O3 + H2) pulses were used with iridium acetylacetonate [Ir(acac)3] to deposit Ir, while IrO2 was deposited using Ir(acac)3 and O3. Nucleation was studied using a combination of methods for film thickness and morphology evaluation...
October 6, 2016: Langmuir: the ACS Journal of Surfaces and Colloids
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