|
| ||
|
|
||
CH
Kinds of CH Terms modified by CH Selected AbstractsDependency of Tritium Retention in Graphite on Temperature Control of Molecular DynamicsCONTRIBUTIONS TO PLASMA PHYSICS, Issue 3-5 2010A. Ito Abstract We have investigated the carbon plasma facing material and hydrogen atom interaction by the use of molecular dynamics simulation to clarify chemical erosion processes on divertor plate. The present paper is our first try at elucidation of temperature dependence by the molecular dynamics. Temperature was controlled by using Langevin thermostat method. As a result, the retention of hydrogen atom achieve steady state, and the CH4 was generated, which was not found MD simulations without a temperature control method. About 30 percent of injected hydrogen atoms are retained. CH4 yields has a peak at 600 K, which accords with experimental results. A dominant path of CH4 generation found by the present molecular dynamics simulation is as follows: a CH is detached from eroded surface and then it grows into CH4 adsorbing hydrogen atoms via CH2 and CH3. In addition, we propose the problem that the hydrogen atom retention and CH,, yields depend on the thermal relaxation time in MD simulation using temperature control methods (© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Recent time trends in levels of self-reported anxiety, mental health service use and suicidal behaviour in StockholmACTA PSYCHIATRICA SCANDINAVICA, Issue 1 2010K. Kosidou Kosidou K, Magnusson C, Mittendorfer-Rutz E, Hallqvist J, Gumpert CH, Idrizbegovic S, Dal H, Dalman C. Recent time trends in levels of self-reported anxiety, mental health service use and suicidal behaviour in Stockholm. Objective:, To investigate recent time trends in several indicators of mental ill-health and the patterning of these indicators between genders and younger vs. older individuals in Stockholm County. Method:, Several indicators were used; self-reported anxiety from the Swedish Survey of Living Conditions, information on psychiatric in-patient and out-patient care, attempted and completed suicides from national and regional registers. Gender- and age-specific trends were compared for the time period of 1997,2006. Results:, Self-reported anxiety and psychiatric service use increased among young individuals of both genders, while attempted suicides increased only among young women. By contrast, these indicators decreased or remained stable in the older age group from year 2001 and onwards. Conclusion:, Our data indicate a rising, and highly prevalent, mental ill-health among the young in Stockholm County, a region representative of urbanized, secular Western societies. [source] Electroconvulsive therapy is equally effective in unipolar and bipolar depressionACTA PSYCHIATRICA SCANDINAVICA, Issue 6 2010S. Bailine Bailine S, Fink M, Knapp R, Petrides G, Husain MM, Rasmussen K, Sampson S, Mueller M, McClintock SM, Tobias KG, Kellner CH. Electroconvulsive therapy is equally effective in unipolar and bipolar depression. Objective:, To determine the relative efficacy of electroconvulsive therapy (ECT) in the treatment of bipolar (BP) and unipolar (UP) depressive illness and clarify its role in BP depression. Method:, Patients referred for ECT with both UP and BP depressions. [classified by Structured Clinical Interview for DSM (SCID-I) criteria for history of mania] were included in a multi-site collaborative, double-masked, randomized controlled trial of three electrode placements , right unilateral, bifrontal or bitemporal , in a permutated block randomization scheme. Results:, Of 220 patients, 170 patients (77.3%) were classified as UP and 50 (22.7%) as BP depression in the intent-to-treat sample. The remission and response rates and numbers of ECT for both groups were equivalent. Conclusion:, Both UP and BP depressions remit with ECT. Polarity is not a factor in the response rate. In this sample ECT did not precipitate mania in depressed patients. Treatment algorithms for UP and BP depression warrant re-evaluation. [source] Synthesis and calcium channel modulating effects of modified Hantzsch nitrooxyalkyl 1,4-dihydro-2,6-dimethyl-3-nitro-4-(pyridinyl or 2-trifluoromethylphenyl)-5-pyridinecarboxylatesDRUG DEVELOPMENT RESEARCH, Issue 4 2000Ramin Miri Abstract A group of racemic nitrooxyalkyl 1,4-dihydro-2,6-dimethyl-3-nitro-4-(pyridinyl or 2-trifluoromethylphenyl)-5-pyridinecarboxylates 8a,o were synthesized using modified Hantzsch reactions. In vitro calcium channel antagonist activities, determined using a guinea pig ileum longitudinal smooth muscle (GPILSM) assay, showed that compounds 8a,o exhibited weaker calcium antagonist activity (10,5 to 10,7 M range) than the reference drug nifedipine (IC50 = 1.43 × 10,8 M). Compounds 8 possessing a C-4 R1 = 2-pyridyl substituent were always more potent than the approximately equiactive analogs having an R1 = 3-pyridyl, 4-pyridyl or 2-CF3 -C6H4 -substituent, within each subgroup of nitrooxyalkyl compounds [R2 = , (CH2)nONO2 (n = 2, 3, 4) or ,CH(CH2ONO2)2]. Although the length of the R2 = ,(CH2)nONO2 substituent (n = 2,4) was not a determinant of smooth muscle calcium antagonist activity when the C-4 R1 -substituent was 2-pyridyl, when R1 was a 3-pyridyl, 4-pyridyl, or 2-CF3 -C6H4 -substituent, the relative potency order with respect to the R2 = ,(CH2)nONO2 substituent was n = 3 and 4 > n = 2. Replacement of the isopropyl substituent of the ester moiety of the calcium antagonist (±)-2-pyridyl 3a by a ,(CH2)nONO2 (n = 2,4) moiety increased calcium antagonist activity on GPILSM by 8-fold. In contrast, replacement of the isopropyl substituent of the ester moiety of the calcium agonists (±)-3-pyridyl 3b, (±)-4-pyridyl 3c or the methyl substituent of the ester moiety of Bay K8644 by a R2 nitrooxyalkyl substituent resulted in abolition of their calcium agonist effects on GPILSM that is replaced by a smooth muscle calcium antagonist effect. These calcium antagonist data support the concept that incorporation of a nitrooxyalkyl ester substituent constitutes a valuable drug design strategy to enhance Hantzsch 1,4-dihydropyridine calcium antagonist and/or abolish calcium agonist effects on smooth muscle. Replacement of the isopropyl (8b,c), or the methyl (8d) group by a ,CH2CH2ONO2 moiety resulted in retention of the cardiac positive inotropic effect where the relative potency order with respect to the C-4 substituent was 2-CF3 -C6H6 - (8d) > 3-pyridyl (8b) , 4-pyridyl (8c). Model hybrid (calcium channel modulation, ·NO release) compounds, that exhibit dual cardioselective agonist / smooth muscle selective antagonist activities, represent a novel type of 1,4-dihydropyridine CC modulator that offers a potential approach to drug discovery targeted toward the treatment of congestive heart failure and for use as probes to study the structure,function relationship of calcium channels. Drug Dev. Res. 51:225,232, 2000. © 2001 Wiley-Liss, Inc. [source] Evaluation of putative hazard tests under background risk heterogeneityENVIRONMETRICS, Issue 3 2009Yuan Liu Abstract In this paper, an evaluation of some tests for adverse health effects around fixed locations (putative hazard sites) is made. We address the situation where a heterogeneous background is included both in terms of correlated and uncorrelated heterogeneity (UH). In addition, we examine a set of tests for case event data (residential case addresses) including both distance and directional effects. The tests include distance and directional score tests (DIR), integrated intensity tests, the Besag & Newell (BES) test, and Kulldorff's focus clustering scan test. Monte Carlo power of the tests is evaluated and power curves are finally presented. Interesting results from this work include the lack of power found when correlated heterogeneity (CH) is present. This is not found with UH. The BES and Scan tests have lower power than the integrated intensity tests and score tests in general. The integrated intensity test demonstrates its omnibus ability to detect either distance or directional effects. Copyright © 2008 John Wiley & Sons, Ltd. [source] Dual Luminescent Dinuclear Gold(I) Complexes of Terpyridyl-Functionalized Alkyne Ligands and Their Efficient Sensitization of EuIII and YbIII LuminescenceEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 22 2010Xiu-Ling Li Abstract Reaction of (tpyC6H4C,CAu)n {tpyC6H4C,CH = 4,-(4-ethynylphenyl)-2,2,:6,,2,-terpyridine} with diphosphane ligands Ph2P(CH2)xPPh2 (x = 2 dppe, 3 dppp, 4 dppb, 5 dpppen, 6 dpph) in CH2Cl2 afforded the corresponding dual luminescent binuclear gold(I) complexes [(tpyC6H4C,CAu)2(,-dppe)] (1), [(tpyC6H4C,CAu)2(, - dppp)] (2), [(tpyC6H4C,CAu)2(,-dppb)] (3), [(tpyC6H4C,CAu)2(,-dpppen)] (4), [(tpyC6H4C,CAu)2(,-dpph)] (5). Crystal structural analysis of complexes 1·2CH2Cl2 and 2·2CH2Cl2 show that the terpyridine moieties are free of coordination in these gold(I)-acetylide-phosphane complexes. Spectrophotometric titration between complex 1 and [Eu(tta)3] (Htta = 2-thenoyltrifluoroacetone) or [Yb(hfac)3(H2O)2] (Hhfac = hexafluoroacetylacetone) gave a 2:1 ratio between Ln(,-diketonate)3 (Ln = Eu, Yb) units and the complex 1 moiety, indicating the formation of Au2Ln2 complexes. Both the luminescence titrations and the luminescence quantum yields of Au2Ln2 (Ln = Eu, Yb) solutions show that the energy transfer occurs efficiently from the binuclear gold(I) antennas 1,5 to EuIII and YbIII centers, and all complexes 1,5 are good energy donors for sensitization of visible and NIR luminescence of EuIII and YbIII ions. [source] Hydrido-Osmium(II), -Osmium(IV) and-Osmium(VI) Complexes with Functionalized Phosphanes as Ligands,EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 35 2009Birgit Richter Abstract Reaction of five-coordinate [OsHCl(CO)(PiPr3)2] (1) with the chelating phosphane iPr2PCH2CO2Me gave six-coordinate [OsHCl(CO)(PiPr3){,2(P,O)- iPr2PCH2C(=O)OMe}] (2), which upon treatment with CO and O2 afforded the 1:1 adducts [OsHCl(CO)(L)(PiPr3){,(P)- iPr2PCH2CO2Me}] (3, 4) by partial opening of the chelate ring. The vinyl complex [OsCl(CH=CHPh)(CO)(PiPr3){,2(P,O)- iPr2PCH2C(=O)OMe}] (5) was obtained from 2 and PhC,CH by insertion of the alkyne into the Os,H bond. Reaction of 2 with sodium acetate led to metathesis of the anionic ligands and formation of [OsH(,2 -O2CCH3)(CO)(PiPr3){,(P)- iPr2PCH2CO2Me}] (6). Osmium(VI) compounds [OsH6(PiPr2R)2] with R = CH2CH2OMe (12), CH2CO2Me (13) and CH2CO2Et (14), and [OsH6(PiPr3){,(P)- iPr2PCH2CH2NMe2}] (16) were prepared from osmium(IV) precursors and shown to rapidly react with O2 and primary alcohols. Exploratory studies revealed that the catalytic activity of the hexahydrido complexes in the hydrogen transfer reaction from 2-propanol to cyclohexanone and acetophenone depends on the type of the functionalized phosphane and is best for R = CH2CH2OMe. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] vic -Dichlorodiphosphapropenes , Synthesis and Coordination AbilityEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 5 2009Raluca Septelean Abstract New substituted 2,3-dichloro-1-,3,2 -P,3-,3,3 -P-diphosphapropenes Mes*P=C(Cl)-P(Cl)tBu (1) (Mes* = 2,4,6-tri- tert -butylphenyl) and the oxidation compounds Mes*P=C(Cl),P(=E)(Cl)R [R = tBu, E = S (2), O (3); R = Mes, E = O (4)] are reported. From the reaction of 2 with W(CO)5(thf) the chelate compound W(CO)4[Mes*P=C(Cl),P(S)(Cl)tBu] (5) was obtained. Reaction of 1 or 2 with PdCl2(cod) led to PdCl2[cyMes*PC(H)(Cl),P(Cl)tBu] (cyMes*P = 5,7-di- tert -butyl-3,3-dimethyl-1-phosphaindane) (6) or PdCl2[cyMes*PC(H)(Cl),P(S)(Cl)tBu] (7), in which the coordination to the Pd atoms is accompanied by intramolecular addition of CH(tBu) of Mes* to the P=C bond of the dichlorodiphosphapropene. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Aluminium Complexes of a Phenoxyimine Ligand with a Pendant Imidazolium Moiety: Synthesis, Characterisation and Evidence for Hydrogen Bonding in SolutionEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 35 2008Stefano Milione Abstract Novel alkylaluminium complexes (phim)AlMe2 (1) and(phimid)AlR2+Br, [R = Me (2), R = iBu (3)] bearing the Schiff base ligands 3,5- tBu2 -2-(OH)C6H2CH=NiPr (phim -H) and3,5- tBu2 -2-(OH)C6H2CH=NCH2CH2[CH(NCHCHNiPr)]Br(phimid -H·Br) have been prepared and fully characterised. Complexes 1,3 each have a tetrahedral structure, with the aluminium atom surrounded by the oxygen and nitrogen atoms of the chelating ligand and two alkyl groups. The structures of phimid -H·Br and of complex 1 have been determined by X-ray diffraction studies. Investigation of the solution structures of 1,3 by 1H NMR spectroscopy revealed that the coordinated phimid ligand is involved in hydrogen bonding with bromide anion. Treatment of 1 with B(C6F5)3 led smoothly to (phim)Al(C6F5)Me (4) by transfer of a C6F5 group from MeB(C6F5)3, to the initially formed coordinatively unsaturated cationic intermediate. In contrast, treatment of 2 with one equiv. of B(C6F5)3 afforded the cationic monomethyl species (phimid)AlMeBr+,MeB(C6F5)3, (5), stabilised by the coordination of the bromide anion acting as a Lewis base.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Using Chiral Ligand Substituents To Promote the Formation of Dinuclear, Double-Stranded Iron, Manganese, and Zinc MesocatesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 33 2007Stuart D. Reid Abstract The synthesis and structures of dinuclear manganese, iron, and zinc complexes of chiral di-iminodipyrromethane ligands (L) are reported. Schiff base condensation reactions between 5,5,-diformyl-2,2,-dipyrromethane and the chiral amines (,)-(R)-CH(Me)tBu and (+)-(R)-CH(Me)Ph result in the straightforward synthesis of the new, chiral ligands H2L2 and H2L3, respectively. Salt elimination reactions between K2L and divalent Mn and Fe halides, and protonolysis reactions between ZnMe2 and H2L result in the formation of the new dinuclear complexes [M2(L)2]. Investigation of the structures of these compounds in solution and in the solid state reveal that chiral mesocates are formed for L = L2, whereas for L = L3, a racemic mixture of helicates is present.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Aiding Factors in the Formation of Azaplatinacyclobutane Rings , X-ray and Crystal Structure of [Pt{CH(Ph)CH2NEt2 -,C,,N}(N,N,N,,N, -tetramethylethylenediamine)]+ and of Its Open-Chain PrecursorEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 15 2007Giuseppe Lorusso Abstract The addition products 2 of a secondary amine to a coordinated olefin, in the cationic complexes [PtCl(,2 -CH2=CHR)(tmeda)]+ (tmeda = N,N,N,,N, -tetramethylethylenediamine; R = Me, 1a; Ph, 1b, H, 1c), undergo in basic medium an intramolecular nucleophilic substitution with elimination of the chlorido ligand and formation of an azaplatinacyclobutane ring 3. The ring-closing process occurs notwithstanding the absence of a labilizing ligand trans to the leaving chlorido ligand and of bulky substituents on the amino,ethanide chain. If the addition product 2 is a mixture of Markovnikov and anti-Markovnikov isomers, the ring-closing reaction is faster for the anti-Markovnikov form, and this leads to an increase of the relative amount of the anti-Markovnikov isomer in the cyclized species 3. The difference in the rate of formation of the azaplatinacyclobutane ring between the two isomers has been interpreted on the basis of a more favorable stereochemistry in the case of the anti-Markovnikov form. The X-ray crystal structures of [Pt{CH(Ph)CH2NEt2 -,C,,N}(tmeda)]+ (3bn) and of its open-chain precursor, [PtCl{CH(Ph)CH2NHEt2}(tmeda)]+ (2bn) fully support this hypothesis.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Bis(phosphinimino)methanides as Ligands in Divalent Samarium Chemistry: Synthesis, Structures and CatalysisEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 6 2007Michal Wiecko Abstract The reaction of K{CH(PPh2NSiMe3)2} with samarium diiodide in a 1:1 molar ratio in thf affords the corresponding divalent samarium complex [{(Me3SiNPPh2)2CH}Sm(,-I)(thf)]2 (1), whereas treatment of K{CH(PPh2NSiMe3)2} with samarium diiodide in a 2:1 molar ratio in thf gives the homoleptic complex [{(Me3SiNPPh2)2CH}2Sm] (2). When 1 is treated with KNPh2 in toluene in a 2:1 molar ratio the mixed dimeric compound [({(Me3SiNPPh2)CH}2Sm)2(,-I)(,-NPh2)] (3) is obtained. The single-crystal X-ray structures of all these complexes have been determined. [{(Me3SiNPPh2)2CH}Sm(,-I)(thf)]2 has also been successfully used as a catalyst for the polymerization of ,-caprolactone. Good activities and molecular masses are observed with this catalyst.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Syntheses, Spectroscopic Studies, and Crystal Structures of Chiral [Rh(aminocarboxylato)(,4 -cod)] and Chiral [Rh(amino alcohol)(,4 -cod)](acetate) Complexes with an Example of a Spontaneous Resolution of a Racemic Mixture into Homochiral Helix-EnantiomersEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 11 2006Mohammed Enamullah Abstract The dimeric complex acetato(,4 -cycloocta-1,5-diene)rhodium(I), [Rh(O2CMe)(,4 -cod)]2 (cod = cycloocta-1,5-diene), reacts with amino acids [HAA = L -alanine, (S)-2-amino-2-phenylacetic acid (L -phenylglycine), N -methylglycine, and N -phenylglycine] and with the amino alcohol (S)-2-amino-2-phenylethanol to afford the aminocarboxylato(,4 -cycloocta-1,5-diene)rhodium(I) complexes [Rh(AA)(,4 -cod)] (AA = deprotonated amino acid = aminocarboxylato ligand) and [(S)-2-amino-2-phenylethanol](,4 -cycloocta-1,5-diene)rhodium(I) acetate, [Rh{(S)-HOCH2,CH(Ph)-NH2}(,4 -cod)](O2CMe) (V). The complexes are characterized by IR, UV/Vis, 1H/13C NMR and mass spectroscopy. The achiral N -phenylglycine ligand gives a chiral N -phenylglycinato complex [Rh(O2C,CH2,NHPh)(,4 -cod)] (IV) with the amine nitrogen atom becoming the stereogenic center upon metal coordination. Complex IV crystallizes in the tetragonal, chiral space group P43 and the crystal structure reveals twofold spontaneous resolution of a racemic mixture into homochiral helix-enantiomers. The investigated crystal contained only one type of helix, namely (left-handed or M- ) 43 -helical chains. This is traced first to an intermolecular N,H···O hydrogen bonding from the stereogenic amino group to a neighboring unligated carboxyl oxygen atom that connects only molecules of the same (R)-configuration into (left-handed or M- ) 43 -helical chains. This intrachain homochirality is supplemented, secondly, by the interlocking of adjacent chains with their corrugated van der Waals surface to allow for an interchain transmission of the sense of helicity, building the single crystal from the same homochiral helix-enantiomer. The enantiomeric amino alcohol complex V crystallizes in the monoclinic, noncentrosymmetric (Sohncke) space group P21. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] A Terephthalato-Bridged NiII Complex Capped with a Nonchelating Ligand Displays a Three-Dimensional Supramolecular Network Constructed by Coordination and Multi-Intermolecular ForcesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 23 2005Chang Seop Hong Abstract A new tp-bridged complex [Ni(pyrazole)4(tp)]n (1; tp = terephthalate) coordinated with a nonchelating pyrazole ligand has been synthesized and characterized using X-ray structure determination and magnetic studies. The crystal structure reveals that the capping ligand functions as a source of hydrogen bonding and intermolecular contacts, such as ,,, and CH,, interactions, that result in a three-dimensional supramolecular assembly. Weak antiferromagnetic couplings are transmitted between NiII centers through the tp linkage. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] A Facile One-Step Synthesis of a Lipophilic Gold(I) Carbene Complex ,X-ray Crystal Structures of LAuCl and LAuC,CH (L = 1,3-di- tert- Butylimidazol-2-ylidene)EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 15 2005Sanjay Singh Abstract The reaction of Au(CO)Cl with 1,3-di- tert -butylimidazol-2-ylidene and 1,3-dimesitylimidazol-2-ylidene in toluene at room temperature results in CO evolution and readily affords in high yield the adducts 1a and 1b, respectively. The reaction of 1a and 1b with ethynylmagnesium chloride in THF yields 2a and 2b, respectively. The crystal structures of 1a, 1b, and 2a were determined. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Pyrazolate-Based Dinucleating Ligands in L2M2 Scaffolds: Effects of Bulky Substituents and Coligands on Structures and M···H,C InteractionsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 8 2004Jens C. Röder Abstract A series of nickel(II) and palladium(II) complexes [L2M2]2+ have been prepared and structurally characterized, where L is a pyrazolate ligand with bulky 2,6-dimethyl- or 2,6-di(isopropyl)anilinomethyl side arms. Coordinating counter anions such as chloride can bind to axial sites of the dinickel species in a solvent-dependent process, giving rise to five-coordinate high-spin metal ions. In the case of weakly coordinating anions, the metal ions are found in roughly square-planar environments, and the structures are governed by the tendency of the bulky aryl groups to avoid each other, which forces the methyl or isopropyl substituents in the aryl 2- and 6-positions to approach the metal ions from the axial directions. This leads to drastic low-field shifts of the respective 1H NMR signals, e.g. , = 7.86 ppm for the isopropyl ,CH which comes in close proximity to the low-spin nickel(II) center. The relevance of such low-field NMR resonances of protons close to the axial sites of d8 metal ions for possible three-center four-electron M···H,C hydrogen bonds involving the filled d orbital of the metal ion is discussed. In the present case, attractive M···H interactions are assumed to be of no major significance. This was corroborated by the structure of a further [L2Ni2]2+ type complex where the anilinomethyl side arms bear only a single 2-isopropyl group, which was found rotated away from the metal. Additional spectroscopic and electrochemical properties of the various complexes are reported. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Synthesis, Structure and Chemical Transformations of EthynylgermatranesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 17 2003Edmunds Lukevics Abstract Ethynylgermatranes have been prepared from monosubstituted acetylenes by a three-step synthesis without isolation of the hydrolytically unstable intermediate chlorogermanes and ethoxygermanes. Boiling an equimolar mixture of tetrachlorogermane Cl4Ge, acetylene RC,CH and triethylamine in hexane leads to germylation of the Csp,H bond and the formation of ethynyl-substituted trichlorogermanes. Subsequent alkoxylation of chlorogermanes by ethanol in the presence of triethylamine affords triethoxygermanes that then take part in transalkoxylation with triethanolamine to give ethynylgermatranes. The molecular structures of all ethynylgermatranes and the hexacarbonyldicobalt complex of 1-heptynylgermatrane have been determined by X-ray crystallography. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] Synthesis and Dynamic Features of (Chloro)zirconocene Cations Stabilised by Pendant (Diarylphosphanyl)alkyl and (Dimethylamino)alkyl Substituents at Their Cyclopentadienyl Ring SystemsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 8 2003Steve Döring Abstract Treatment of the substituted (diarylphosphanyl)methyl group-4 metallocene complexes [(C5H4,CR1R2,PAr2)2ZrCl2] (2: R1/R2 = CH3/CH3, H/CH3, H/aryl) with Li[B(C6F5)4] in dichloromethane solution results in chloride ligand abstraction (with LiCl precipitation) to yield the complexes [(C5H4,CR1R2,PAr2)2Zr,Cl+] (5), with both phosphanyl groups internally coordinated to the metal centre. Three possible diastereoisomers are observed in the case of 5c (R1 = H; R2 = CH3), while bulkier R2 substituents give higher selectivities. The thermally induced (reversible) cleavage of the Zr,phosphane linkage results in dynamic NMR behaviour. Gibbs activation energies of ,G,(298 K) = 14.8 ± 0.5 and 14.5 ± 0.5 kcal/mol were obtained for these intramolecular equilibration processes in the complexes trans - 5d (R1 = H; R2 = Ph) and trans - 5e (R1 = H; R2 = ferrocenyl), respectively. Treatment of the substituted (dimethylamino)methyl metallocene complexes [(C5H4,CR1R2,NMe2)2ZrCl2] (6a, 6b) with Li[B(C6F5)4] proceeds analogously to yield the cation systems [{C5H4,C(CH3)2,NMe2}2ZrCl+] (12a) and [{C5H4,CH(CH3),NMe2}2ZrCl+] (12b, three possible diastereoisomers). Both complexes have their pairs of amino groups coordinated to the metal centre. The complexes exhibit dynamic NMR spectra. Selective equilibration of the diastereotopic N(CH3)A(CH3)B resonances of complex 12a is observed [,G,(233 K) = 11.5 ± 0.2 kcal/mol], whereas the adjacent C(CH3)A(CH3)B methyl groups remain diastereotopic. The dynamic equilibration of the latter was observed at a markedly higher temperature [,G,(333 K) = 17.3 ± 0.2 kcal/mol]. Treatment of [{C5H4,C(CH3)2,NMe2}CpZrCl2] (10) with Li[B(C6F5)4] resulted in the formation of complex [{C5H4,C(CH3)2,NMe2}CpZr,Cl+] (11), which shows the internal ,N(CH3)A(CH)B equilibration proceeding with a markedly higher activation barrier [,G,(333 K) = 17.6 ± 0.2 kcal/mol] than in 12a, and a stereochemical memory effect indicative of solvent coordination to the metal centre of the resulting highly electrophilic chlorozirconocene cation intermediate. Complex 11 was characterised by an X-ray crystal structure analysis, which shows the internal Zr,amine coordination. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] Synthesis of a Hexadentate Hexameric Aluminum Imide and Its Metathesis ReactionsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 3 2003N. Dastagiri Reddy Abstract The reaction of AlH3·NMe3 with one equivalent of 2-cyanothiophene in toluene afforded [HAlNCH2(C4H3S)]6 (2) in good yield. Treatment of 2 with SiMe3Br and SiMe3Cl in toluene under refluxing conditions resulted in the formation of compounds [BrAlNCH2(C4H3S)]6 (3) and [ClAlNCH2(C4H3S)]6 (4), respectively. In a similar way [PhC,CAlNCH2(C4H3S)]6 (5) was readily obtained from the reaction between 2 and PhC,CH. When 2 was treated with PhSH the Al-N cluster core dissociated and a four-membered ring compound [(PhS)2AlNHCH2(C4H3S)]2 (6) was formed. In contrast, a similar hexameric aluminum imide (HAlNCH2Ph)6 (1) retains its Al-N network when treated with PhSH to yield (PhSAlNCH2Ph)6 (7). An exchange of ethyl groups and hydrides occurred when 2 was treated with excess of ZnEt2, forming [EtAlNCH2(C4H3S)]68. Compounds 2,4 and 6,8 were characterized by X-ray single-crystal analysis. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] Effect of deep brain stimulation of the posterior hypothalamic area on the cardiovascular system in chronic cluster headache patientsEUROPEAN JOURNAL OF NEUROLOGY, Issue 9 2007P. Cortelli The objective of this study was to determine the cardiovascular effects of chronic stimulation of the posterior hypothalamic area (PHA) in cluster headache (CH) patients. Systolic and diastolic blood pressure (SBP, DBP), cardiac output, total peripheral resistance (TPR), heart rate (HR) and breathing were monitored at supine rest and during head-up tilt test (HUTT), Valsalva manoeuvre, deep breathing, cold face test and isometric handgrip in eight drug-resistant chronic CH patients who underwent monolateral electrode implantation in the PHA for therapeutic purposes. Autoregressive power spectral analysis (PSA) of HR variability (HRV) was calculated at rest and during HUTT. Each subject was studied before surgery (condition A) and after chronic deep brain stimulation (DBS) of PHA (condition B). Baseline SBP, DBP, HR and cardiovascular reflexes were normal and similar in both conditions. With respect to condition A, DBP, TPR and the LF/HF obtained from the PSA of HRV were significantly (P < 0.05) increased during HUTT in condition B. In conclusion, chronic DBS of the PHA in chronic CH patients is associated with an enhanced sympathoexcitatory drive on the cardiovascular system during HUTT. [source] Reorganization of cortical hand representation in congenital hemiplegiaEUROPEAN JOURNAL OF NEUROSCIENCE, Issue 4 2009Yves Vandermeeren Abstract When damaged perinatally, as in congenital hemiplegia (CH), the corticospinal tract usually undergoes an extensive reorganization, such as the stabilization of normally transient projections to the ipsilateral spinal cord. Whether the reorganization of the corticospinal projections occurring in CH patients is also accompanied by a topographical rearrangement of the hand representations in the primary motor cortex (M1) remains unclear. To address this issue, we mapped, for both hands, the representation of the first dorsal interosseous muscle (1DI) in 12 CH patients by using transcranial magnetic stimulation co-registered onto individual three-dimensional magnetic resonance imaging; these maps were compared with those gathered in age-matched controls (n = 11). In the damaged hemisphere of CH patients, the representation of the paretic 1DI was either found in the hand knob of M1 (n = 5), shifted caudally (n = 5), or missing (n = 2). In the intact hemisphere of six CH patients, an additional, ipsilateral, representation of the paretic 1DI was found in the hand knob, where it overlapped exactly the representation of the non-paretic 1DI. In the other six CH patients, the ipsilateral representation of the paretic 1DI was either shifted caudally (n = 2) or was lacking (n = 4). Surprisingly, in these two subgroups of patients, the representation of the contralateral non-paretic 1DI was found in a more medio-dorsal position than in controls. The present study demonstrates that, besides the well-known reorganization of the corticospinal projections, early brain injuries may also lead to a topographical rearrangement of the representations of both the paretic and non-paretic hands in M1. [source] Color stability of resin matrix restorative materials as a function of the method of light activationEUROPEAN JOURNAL OF ORAL SCIENCES, Issue 3 2004Ralf Janda The purpose was to investigate the influence of curing devices and curing times on the yellow value (b-value) of composites, ormocers and compomers after performing a suntest (EN ISO 7491). Eight samples of Charisma (CH), Durafill (DU), Definite (DE), and Dyract AP (DY) each were light cured with Translux Energy (tungsten halogen light) for 20, 40 or 60 s and with Apollo 95-E (plasma light) for 3, 10 or 20 s. All samples were subjected to a suntest. Before and after the suntest the yellow values (b-values) were determined and the change (,b) was calculated. When cured with Translux Energy for 20 and 40 s DU, CH, and DY revealed significantly negative ,b-values. The b-value of DE remained nearly constant. When cured for 60 s, DU and DE shifted to more yellow while CH and DY still bleached a little. When cured with Apollo 95-E, a dramatic bleaching process of all materials investigated occurred after the suntest (significant negative ,b). It may be concluded that the bleaching of composites, ormocers and compomers depends on (i) the used light curing device and (ii) the chosen curing times. The tungsten halogen light provided highly significantly superior results. [source] 3-Tocopherylisoxazolines by [2+3] CycloadditionEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 6 2004Thomas Rosenau Abstract New isoxazoline derivatives of ,-tocopherol (1), the main component of vitamin E, were synthesized in a facile, two-step sequence consisting of nitration followed by 1,3-dipolar cycloaddition. 5-Nitromethyl-,-tocopheryl acetate (3), obtained from the cheap ,-tocopheryl acetate (2) by direct nitration in one step, acted as the nitrile oxide precursor in the reaction with various alkenes. The facile conversion proceeded in the presence of equimolar amounts of PhNCO and catalytic amounts of triethylamine. The NMR spectra of the product isoxazolines 5,13, showing strongly temperature-dependent resonances of the 4,,-CH, 4-CH2 and the acetyl group, are discussed, and the crystal structures of model compounds containing a methyl group instead of the isoprenoid side chain are presented. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Undergraduate teaching in gerodontology in Austria, Switzerland and GermanyGERODONTOLOGY, Issue 3 2004Ina Nitschke Objective:, To survey the present state of undergraduate teaching in the domain of gerodontology in Germany, Switzerland and Austria. Study participants:, All universities of Austria (A), Germany (D) and Switzerland (CH). Protocol:, A questionnaire on undergraduate teaching in gerodontology was mailed to all Deans (A: n = 3; CH: n = 4; D: n = 31) and all independent departments except paediatric dentistry and orthodontics (A: n = 11; CH: n = 15; D: n = 111). Results:, The questionnaires were completed and returned by 29 Deans (A: n = 2; CH: n = 4; D: n = 23) and 102 departments (A: n = 7; CH: n = 8; D: n = 87). In Austria, gerodontology is a very small component of the dental curriculum and the Deans did not want this to be increased. Most German universities claimed to teach some aspects of gerodontology to undergraduate students and 87.4% of the Deans voted for separate lectures in gerodontology. In Switzerland, gerodontology seems well established. The results of questionnaires from the independent departments revealed that in all three countries lectures were more prevalent (A: n = 0; CH: n = 4; D: n = 6) than practical training in nursing homes (A: n = 0; CH: n = 3; D: n = 6). Conclusion:, Considering the demographical shift which is leading to an increasing proportion of elderly in the population, the weighting of gerodontology in the undergraduate dental curriculum should be considered for revision in Austria and Germany. [source] Electrical Stimulation of Sphenopalatine Ganglion for Acute Treatment of Cluster HeadachesHEADACHE, Issue 7 2010Mehdi Ansarinia MD (Headache 2010;50:1164-1174) Introduction., Cluster headaches (CH) are primary headaches marked by repeated short-lasting attacks of severe, unilateral head pain and associated autonomic symptoms. Despite aggressive management with medications, oxygen therapy, nerve blocks, as well as various lesioning and neurostimulation therapies, a number of patients are incapacitated and suffering. The sphenopalatine ganglion (SPG) has been implicated in the pathophysiology of CH and has been a target for blocks, lesioning, and other surgical approaches. For this reason, it was selected as a target for an acute neurostimulation study. Methods., Six patients with refractory chronic CH were treated with short-term (up to 1 hour) electrical stimulation of the SPG during an acute CH. Headaches were spontaneously present at the time of stimulation or were triggered with agents known to trigger clusters headache in each patient. A standard percutaneous infrazygomatic approach was used to place a needle at the ipsilateral SPG in the pterygopalatine fossa under fluoroscopic guidance. Electrical stimulation was performed using a temporary stimulating electrode. Stimulation was performed at various settings during maximal headache intensity. Results., Five patients had CH during the initial evaluation. Three returned 3 months later for a second evaluation. There were 18 acute and distinct CH attacks with clinically maximal visual analog scale (VAS) intensity of 8 (out of 10) and above. SPG stimulation resulted in complete resolution of the headache in 11 attacks, partial resolution (>50% VAS reduction) in 3, and minimal to no relief in 4 attacks. Associated autonomic features of CH were resolved in each responder. Pain relief was noted within several minutes of stimulation. Conclusion., Sphenopalatine ganglion stimulation can be effective in relieving acute severe CH pain and associated autonomic features. Chronic long-term outcome studies are needed to determine the utility of SPG stimulation for management and prevention of CH. [source] Haplotype Analysis Confirms the Association Between the HCRTR2 Gene and Cluster HeadacheHEADACHE, Issue 7 2008Innocenzo Rainero MD Background., Several studies suggested that genetic factors play a role in cluster headache (CH) susceptibility. We found a significant association between the 1246 G>A polymorphism of the hypocretin receptor-2 (HCRTR2) gene and the disease. This association was confirmed in a large study from Germany but was not replicated in a dataset of CH patients from Northern Europe. Objective., The purpose of this study was to further evaluate the association between CH and the HCRTR2 gene using new polymorphisms, estimating the frequency of different gene haplotypes, searching for gene mutations, and evaluating the effects of the examined polymorphisms on hypocretin binding sites. Methods., We genotyped 109 CH patients and 211 healthy controls for 5 new polymorphisms of the HCRTR2 gene and we inferred different gene haplotypes. Complete HCRTR2 sequencing was undertaken for 11 independent CH patients, 5 of whom had a positive family history. The effects of the 1246 G>A polymorphism on the hypocretin binding sites were evaluated using different computer-assisted analyses. Results., Three new polymorphisms of the HCRTR2 gene resulted significantly associated with CH. The GTAAGG haplotype resulted more frequent in cases than in controls (OR: 3.68; 95% CI: 1.85-7.67). No point mutation of the HCRTR2 gene was found. Binding analyses showed that the 1246 G>A polymorphism (substitution of valine at position 308 by isoleucine) has no effect on the hypocretin binding sites but could influence the dimerization process of the receptor. Conclusion., Our data confirm previous studies suggesting that the HCRTR2 gene or a linked locus significantly modulates the risk for CH. In addition, we suggest that the V308I substitution of the HCRTR2 may interfere with the dimerization process of the receptor, thereby influencing its functional activity. [source] Effect on Sleep of Posterior Hypothalamus Stimulation in Cluster HeadacheHEADACHE, Issue 7 2007Roberto Vetrugno MD Objective.,To evaluate the structure and quality of sleep and the circadian rhythm of body core temperature (BcT°) in patients with drug-resistant chronic cluster headache (CH) before and during deep brain stimulation (DBS) of the posterior hypothalamus. Background.,Chronic CH is a severe primary headache and frequently associated with disturbances in sleep. Posterior hypothalamus DBS is performed as an effective treatment of drug-resistant chronic CH. The effects of posterior hypothalamus DBS on sleep and the circadian rhythm of BcT° are unknown. Methods.,Three male patients with chronic drug-resistant CH underwent 48-hour consecutive polysomnography (PSG) by means of the VITAPORT® system with determination of BcT° by means of a rectal probe. Recordings were done before electrode implantation in the posterior hypothalamus and after optimized DBS of posterior hypothalamus. Results.,Before electrode implantation PSG showed nocturnal CH attacks, reduced sleep efficiency, fragmented sleep and increased periodic limb movements in sleep (PLMS). During DBS nocturnal CH attacks were abolished and sleep efficiency and PLMS improved. BcT° circadian rhythm was normal both before and during DBS. Conclusions.,Our data show that DBS of posterior hypothalamus in drug-resistant chronic CH is effective in curtailing nocturnal CH attacks, and is associated with improved sleep structure and quality. Chronic CH displays a normal circadian rhythm of BcT°, unchanged during hypothalamic DBS. [source] Gene Expression Profiling in Cluster Headache: A Pilot Microarray StudyHEADACHE, Issue 10 2006Christina Sjöstrand MD Background.,Cluster headache (CH) is a primary neurovascular headache disorder characterized by attacks of excruciating pain accompanied by ipsilateral autonomic symptoms. CH pathophysiology is presumed to involve an activation of hypothalamic and trigeminovascular systems, but inflammation and immunological mechanisms have also been hypothesized to be of importance. Objective.,To identify differentially expressed genes during different clinical phases of CH, assuming that changes of pathophysiological importance would also be seen in peripheral venous blood. Methods.,Blood samples were drawn at 3 consecutive occasions from 3 episodic CH patients: during attacks, between attacks and in remission, and at 1 occasion from 3 matched controls. Global gene expression was analyzed with microarray tehnology using the Affymetrix Human Genome U133 2.0 Plus GeneChip® Set, covering more than 54,000 gene transcripts, corresponding to almost 22,000 genes. Quantitative RT-PCR on S100P gene expression was analyzed in 6 patients and 14 controls. Results.,Overall, quite small differences were seen intraindividually and large differences interindividually. However, pairwise comparisons of signal values showed upregulation of several S100 calcium binding proteins; S100A8 (calgranulin A), S100A12 (calgranulin C), and S100P during active phase of the disease compared to remission. Also, annexin A3 (calcium-binding) and ICAM3 showed upregulation. BIRC1 (neuronal apoptosis inhibitory protein), CREB5, HLA-DQA1, and HLA-DQB1 were upregulated in patients compared to controls. The upregulation of S100P during attack versus remission was confirmed by quantitative RT-PCR analysis. Conclusions.,The S100A8 and S100A12 proteins are considered markers of non-infectious inflammatory disease, while the function of S100P is still largely unknown. Furthermore, upregulation of HLA-DQ genes in CH patients may also indicate an inflammatory response. Upregulation of these pro-inflammatory genes during the active phase of CH has not formerly been reported. Data from this pilot microarray study provide a basis for further studies in CH. [source] Substituent Effects on Crosslike Packing of 2,,7,-Diaryl- spiro(cyclopropane-1,9,-fluorene) Derivatives: Synthesis and Crystallographic, Optical, and Thermal Properties,ADVANCED FUNCTIONAL MATERIALS, Issue 2 2007Z. Wang Abstract A series of 2,,7,-diarylspiro(cyclopropane-1,9,-fluorene) derivatives are efficiently synthesized and characterized to determine the reason for the "green-light" emission of these compounds. These compounds exhibit bright-violet to blue photoluminescence (PL) (,PLmax,=,353,419,nm) with excellent PL quantum efficiencies (,PL,=,83,100,%) in solution and show high thermal stabilities (Td,=,267,474,°C). The variation of the optical properties of these molecules in the solid state depends on the different stacking modes of these compounds containing different substituents, which are revealed by crystallographic analysis. CH,, hydrogen bonds instead of intermolecular ,,, interactions act as the driving force between adjacent fluorenes, even though a very small dialkyl group (cyclopropane) is introduced at the C-9 position of fluorene. The crosslike molecular stacking efficiently reduces the energy transfer between the herring-like aggregates and therefore results in the absence of a "green-light" emission tail. In order to determine the cause of the "green-light" emission tails, the fluorescence spectra of the films annealed in N2 or in air are recorded. Broad green-light emission tails were observed for the films annealed in air, which might be caused by fluorenone defects generated during processing or during the course of the photophysical analysis by reaction with residual oxygen. [source] Prevalence and incidence of cluster headache in the Republic of San Marino.HEADACHE, Issue 3 2003C Tonon Neurology. 2002 May 14;58(9):1407-1409 Based on a preceding survey performed in 1985, the authors estimated the prevalence and incidence of cluster headache (CH) in the Republic of San Marino (26 628 inhabitants at 31 December 1999). All cases were diagnosed by direct interview according to International Headache Society criteria. The prevalence rate was 56/100 000 (95% CI 31.3 to 92.4), and the incidence rate was 2.5/100 000/year (95% CI 1.14 to 4.75). Most cases showed rare clusters. This is the first prospective study on the incidence of CH. Comment: There continues to be debate on the prevalence of cluster in the general population. Since San Marino is small, the entire cluster population, with a smaller denominator for the general population, could be estimated, making this a very important study. SJT [source] | ||||||||||||||||||||||||||||||||||||||||