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Dominic Schmid, Alexander Seyboldt, Klaus Eichele, Doris Kunz
The synthesis of a η5 -coordinated LiCp complex by simple addition of a Li-salt in benzene is presented. A strongly zwitterionic fulvalene serves as the Cp-precursor. Evidence for the coordination of Li+ was obtained by the characterisitic7 Li NMR chemical shifts, variable temperature experiments in solution and by X-ray structure analysis in the solid state.
December 20, 2016: Dalton Transactions: An International Journal of Inorganic Chemistry
Wen Zhou, Rachel H Platel, Thiago Teixeira Tasso, Taniyuki Furuyama, Nagao Kobayashi, Daniel B Leznoff
The synthesis and characterization of the ring-unsubstituted zirconium phthalocyanine PcZrCl2 (; Pc(x-) = phthalocyaninato(x-)) and its reduction products are described. X-ray analysis of (crystallized from hot 1-chloronaphthalene) reveals that is a chloride-bridged dimer [PcZrCl]2(μ-Cl)2 in the solid-state; was also characterized by UV-vis/MCD spectroscopy and cyclic voltammetry, which indicated reduction potentials at -0.55, -0.95 and -1.28 V. Although attempts to access these Pc-ring reduced species with KC8 led to mixtures of reduced products due to the insolubility of both starting materials, one equivalent of the reducing agent KEt3BH reacted with to generate Pc(3-)-containing species, as indicated by visible Q-band spectral changes (from λmax = 686 for to 589/611 nm), a single ESR peak (g = 2...
August 21, 2015: Dalton Transactions: An International Journal of Inorganic Chemistry
Rachel H Platel, Thiago Teixeira Tasso, Wen Zhou, Taniyuki Furuyama, Nagao Kobayashi, Daniel B Leznoff
A series of new scandium complexes supported by the phthalocyanine (Pc) ligand have been prepared and structurally characterized. Reaction of ScCl3 with phthalonitrile affords a mixture of PcScCl (1) and unreacted ScCl3, which upon addition of LiCH(SiMe3)2 yields THF-soluble PcSc(μ-Cl2)Li(THF)2 (2). Metathesis with NaCp or LiCp* generates PcSc(η(5)-C5H5) and PcSc(η(5)-C5Me5), respectively, which represent the first examples of η(5)-Cp metal phthalocyanines where the Cp fragment sandwiches the metal centre...
April 7, 2015: Chemical Communications: Chem Comm
Michio Suzuki, Toshihiro Kogure, Shohei Sakuda, Hiromichi Nagasawa
The hinge ligament of the bivalve is an important hard tissue that functions to open and close the shells. The ligament contains a fibrous structure consisting of aragonite crystals surrounded by dense organic matrices. Although many matrix proteins have been identified from various shell microstructures in previous works, ligament-specific matrix proteins have not yet been reported. In this study, in order to reveal the formation mechanism of the fibrous aragonite crystals in the ligament of Pinctada fucata, we identified a novel, small acidic peptide, named ligament intra-crystalline peptide (LICP), from the aragonite crystal of the ligament that had been pre-treated with sodium hypochlorite to remove the inter-crystalline organic matrices...
April 2015: Marine Biotechnology
Lukman S Sarker, Zerihun A Demissie, Soheil S Mahmoud
The essential oil (EO) of Lavandula is dominated by monoterpenes, but can also contain small amounts of sesquiterpenes, depending on species and environmental conditions. For example, the sesquiterpene 9-epi-caryophyllene can make up to 8 % of the EO in a few species, including those commercially propagated for EO production. Here, we report the cloning and functional characterization of 9-epi-caryophyllene synthase (LiCPS) from the glandular trichomes of Lavandula x intermedia, cv. Grosso. The 1,617 bp open reading frame of LiCPS, which did not encode a transit peptide, was expressed in Escherichia coli and the recombinant protein purified by Ni-NTA agarose affinity chromatography...
November 2013: Planta
Richard Laï, Jean-Claude Daran, Didier Nuel, Martial Sanz, Nick Summerton, Nicolas Vanthuyne, Anaïs Zaragori-Benedetti
In order to prepare a new unsymmetrical chiral ligand, C9H7CH(CH3)CH2C5H5, with an indenyl moiety connected to a cyclopentadienyl unit by a chiral ethylene bridge, we reacted the optically active tosylate 4, derived from ethyl (S)-(-) lactate, with LiCp. The only product resulting from this reaction was an optically active spirocyclopropane 6 obtained with a high diastereoselectivity (81.8% de). We also observed that, when the reduction of the ethyl indene lactate 2 was realized with an excess of LiAlH4 in Et2O under reflux, spirocyclopropane 6 was obtained in high yield with the same diastereoselectivity...
June 14, 2013: Dalton Transactions: An International Journal of Inorganic Chemistry
Masataka Oishi, Hiroharu Suzuki
New early-late heterobimetallic hydrides (L(2)ZrCl)(Cp*Ir)(mu-H)(3) (1; L = Cp derivative, Cp* = eta(5)-C(5)Me(5)) were synthesized from zirconocene derivatives (L(2)ZrCl(2)) and LiCp*IrH(3) via a salt elimination reaction and structurally characterized by NMR and X-ray analyses. Upon treatment of 1 with an alkyllithium reagent, hydride abstraction complex 4 underwent thermolytic ligand elimination at the Zr-Ir system to yield a novel planar square complex (L(2)Zr)(2)(Cp*Ir)(2)(mu(3)-H)(4) (2). When a labeling study of the reaction was conducted, it was found that the conversion of 1 to 2 involves rapid aromatic and benzylic C-H activation by a coordinatively unsaturated dinuclear complex (L(2)Zr)(Cp*Ir)(H)(2) (3)...
March 16, 2009: Inorganic Chemistry
Pier Paolo Sainaghi, Federica Alciato, Stefania Carnieletto, Luigi Castello, Luca Bergamasco, Daniele Sola, Angelo Sante Bongo, Eugenio Inglese, Riccardo Polosa, Gian Carlo Avanzi
BACKGROUND: Gas6 protein is involved in pulmonary embolism (PE) and acute inflammation in animal models. METHODS: We enrolled 82 consecutive patients with acute dyspnea and suspected PE (Geneva score with high (HCP) or low/intermediate clinical probability (LICP)+D-dimer >or=0.5microg/mL) and 29 age-matched healthy volunteers. According to clinical and instrumental evaluations the following diagnoses were obtained: heart failure (HF), pulmonary or systemic infection (I), PE, or no illness (N)...
April 2009: Respiratory Medicine
Ning He, Hong-bin Xie, Yi-hong Ding
Recently, stimulated by the unexpected synthesis and isolation of a bis-metallic sandwich compound Cp*ZnZnCp* (Cp* = eta(5)-C(5)Me(5)), many studies have focused on various dinuclear metallocenes involving a direct metal-metal (single or multiple) bond. However, we are not aware of any report on the metallocenes incorporating a "one-electron metal-metal bond". Herein, through the good steric and electronic stabilization effect of Cp and Cp*, we for the first time theoretically design a new type of sandwich-like compounds DBe-LiCp (D = Cp or Cp*) associated by an "unaided" one-electron metal-metal bond...
December 4, 2008: Journal of Physical Chemistry. A
Sebastian Burck, Dietrich Gudat, Martin Nieger, Jürgen Tirreé
P-Cyclopentadienyl-substituted 1,3,2-diazaphospholenes were prepared by salt metathesis from NaCp or LiCp* and 2-chloro-1,3,2-diazaphospholenes. Comprehensive spectroscopic and X-ray diffraction studies revealed a significant lengthening of the phosphorus-carbon bonds as compared with typical P-C bond distances, and the presence of fluxional molecular structures in solution and solid state as a consequence of circumambulatory migration of the diazaphospholene moiety around the Cp-ring. The P-C bond lengthening is accompanied by the capability to react with transition metal complexes under P-C bond activation and cyclopentadienyl transfer...
May 21, 2007: Dalton Transactions: An International Journal of Inorganic Chemistry
Richard Laï, Sandrine Martin, Renaud Touret
Interaction of lithium cyclopentadienide with a suitable partially protected alpha-D-allofuranose triflate, 4, epimer at C3 of glucose, gives as a major product, besides the expected glucose-cyclopentadiene, 5, a glucose-disubstituted cyclopentadiene, 6. This unprecedented behaviour, which does not occur with alpha-D-glucofuranose and other sugars, is tentatively explained by a complexation of LiCp and the oxygen atoms of the isopropylidene function of one molecule of 4 and one of 5, giving a termolecular structure as the result of a template effect...
July 28, 2006: Dalton Transactions: An International Journal of Inorganic Chemistry
Jeong Min Lee, Joon Koo Han, Hong Eoh, Se Hyung Kim, Jae Young Lee, Min Woo Lee, Byung Ihn Choi
OBJECTIVE: We sought to validate the efficiency of intraoperative radiofrequency ablation (RFA) using a prototype loop internally cooled-perfusion (LICP) electrode to induce coagulation in the subcapsular portion of the liver. MATERIALS AND METHODS: In in vitro experiments, 30 ablation regions were created using a 200-W generator and a LICP electrode featured simultaneous intraelectrode cooling and continuous flow of hypertonic saline along the shaft in explanted bovine liver...
April 2006: Journal of Surgical Research
Jeng-Fen Liu, Yuanyuan Liu, Hsu Chin-Ying Stephen
OBJECTIVES: The purpose of this study was to identify the optimal laser energy range of Er:YAG laser irradiation for laser-induced caries prevention (LICP). METHODS: Twenty-one human non-carious molars were selected. The teeth were covered with nail varnish, except two 4 mm x 1 mm windows on both the buccal and lingual surfaces. The windows were randomly assigned to groups A, B, C and D, receiving no irradiation, 100, 200 and 300 mJ irradiation, respectively. The pulse width 10 pps (pulse per second) with a 1...
January 2006: Journal of Dentistry
R E Dinnebier, Sander van Smaalen, F Olbrich, S Carlson
The pressure dependencies of the crystal structures of the polymeric metallocenes lithium cyclopentadienide (LiCp) and potassium cyclopentadienide (KCp) have been determined by synchrotron X-ray powder diffraction. The decrease of the volume of LiCp by 34% up to a pressure of p = 12.2 GPa and of KCp by 23% at p = 5.3 GPa as well as the bulk moduli of K = 7.7 GPa for LiCp and 4.9 GPa for KCp indicate a high compressibility for these compounds. The crystal structures of KCp have been determined up to p = 3.9 GPa...
February 21, 2005: Inorganic Chemistry
Christian Zimmermann, Christopher E Anson, Amanda L Eckermann, Markus Wunder, Gerda Fischer, Ilka Keilhauer, Erik Herrling, Bernd Pilawa, Oliver Hampe, Florian Weigend, Stefanie Dehnen
By reacting 1-aminoethylammonium (H2NCH2CH2NH3+ = enH+) salts of [Sn2E6]4- anions (E = S, Se), [enH]4[Sn2S6] (1) and [enH]4[Sn2Se6] x en (2), with FeCl2/LiCp, three novel (partly) oxidized, Cp* ligated iron chalcogenide clusters were synthesized. Two of them, [(CpFe)3(mu3-S)2] (3) and [(Cp*Fe)3(mu3-Se)2] (4), contain formally 47 valence electrons. [(Cp*Fe)3(SnCl3)(mu3-Se)4] x DME (5) represents the first known mixed metal Fe/Sn/Se heterocubane type cluster. Compounds 3-5 were structurally characterized by single-crystal X-ray diffraction, and the odd valence electron number of the [Fe3E2] clusters (E = S, Se) was confirmed by density functional (DFT) investigations, mass spectrometry, cyclic voltammetry and a susceptibility measurement of 3...
July 26, 2004: Inorganic Chemistry
G Portella, M Cormio, G Citerio
Cerebral Compliance describes the ability of cranial content to accommodate volume variations. Intracranial vascular compartment is thought to be one of the most important determinants of Compliance. Cerebral perfusion pressure (CPP) has a significant influence upon the calibre of cerebral vessels and consequently, upon blood volume. This study was designed to investigate the influence of CPP on intracranial volumes balance, described by cerebral compliance, in severe traumatic brain injured patients (TBI)...
2002: Acta Neurochirurgica. Supplement
J L Hutton, P O Pharoah
BACKGROUND: Cerebral palsy presents with a range of severity of cognitive, motor, and sensory disabilities, which might affect survival. AIMS: To quantify the effects of motor, cognitive, and sensory disabilities, year of birth, birth weight, and gestational age on survival in cerebral palsy. METHODS: A cohort of children with cerebral palsy born between 1966 and 1989 to mothers resident in a defined geographical region was subdivided into early impairment (EICP: cerebral insult prenatally or within 28 days of birth) or late impairment (LICP: insult at least 28 days after birth)...
February 2002: Archives of Disease in Childhood
Dinnebier, Schneider, van Smaalen S, Olbrich, Behrens
The crystal structure of pentamethylcyclopentadienyllithium, [Li(C(10)H(15))] (LiCp*), has been determined from a high-resolution powder pattern by modelling and the maximum entropy method (MEM). The compound crystallizes in space group R3m with lattice parameters a = b = 14.7711 (5), c = 3.82206 (6) Å and V = 722.19 (4) Å(3) (Z = 3). LiCp* forms polymeric 'multidecker' chains along the c axis. The pentamethylcyclopentadienyl anions are coplanar with each other and show threefold rotational disorder. The MEM calculations did not only confirm the structural model and the type of disorder, but also discovered additional symmetry compared with the Rietveld analysis...
February 1, 1999: Acta Crystallographica. Section B, Structural Science
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