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  • General Chemistry  (59)
  • Life and Medical Sciences  (50)
  • ASTROPHYSICS
  • Alpha-scintillation; DEPTH, sediment/rock; Description; Dredge; DRG; Event label; Identification; Kara Sea; Lake_Uksh_K; Lake Uksh, Karelia, Russia; Mass; NOAA and MMS Marine Minerals Geochemical Database; NOAA-MMS; Radium; Sedov (1909); Sedov-1934; SEDOV34_74; Width
  • Inorganic Chemistry
  • 1995-1999  (127)
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  • 1996  (127)
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  • 1995-1999  (127)
  • 1940-1944
  • 1935-1939
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  • 1
    Electronic Resource
    Electronic Resource
    Bone tissue-specific transcription of the osteocalcin gene: Role of an activator osteoblast-specific complex and suppressor hox proteins that bind the OC box (1996)
    New York, N.Y. : Wiley-Blackwell
    Journal of Cellular Biochemistry 61 (1996), S. 310-324 
    Details
    ISSN: 0730-2312
    Keywords: osteocalcin ; transcriptional regulation ; homeodomain protein ; Msx ; bone-specific ; OC box ; Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Bone-specific expression of the osteocalcin gene is transcriptionally controlled. Deletion analysis of osteocalcin promoter sequences by transient transfection of osseous (ROS 17/2.8) and nonosseous (R2 fibroblast) cells revealed that the most proximal 108 nucleotides are sufficient to confer tissue-specific expression. By gel mobility shift assays with wild-type and mutated oligonucleotides and nuclear extracts from several different cell lines we identified a novel transcription factor complex which exhibits sequence-specific interactions with the primary transcriptional element, the OC box (nt -99 to -76). This OC box binding protein (OCBP) is present only in osteoblast-like cells. Methylation interference demonstrated association of the factor with OC box sequences overlapping the Msx homeodomain consensus binding site. By assaying several mutations of the OC box, both in gel shift and transient transfection studies using ROS 17/2.8, we show the following. First, binding of OCBP correlates with osteocalcin promoter activity in ROS 17/2.8 cells. Increased binding leads to a 2-3-fold increase in transcription, while decreased binding results in transcription 30-40% of control. Second, homeodomain protein binding suppresses transcription. However, Msx expression is critical for full development of the bone phenotype as determined by antisense studies. Last, we show that one of the mutations of the OC box permits expression of osteocalcin in non-osseous cell lines. In summary, we demonstrate association of at least two classes of tissue-restricted transcription factors with the OC box element, the OCBP and Msx proteins, supporting the concept that these sequences contribute to defining tissue specificity. © 1996 Wiley-Liss, Inc.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New Ruthenium(II) Complexes of Functionalized Monoanionic Aryldiamine N,C,N'-Terdentate Ligands: Syntheses of [RuII{2,6-(Me2NCH2)2-4-R-C6H2}-(terpy)]+Cl-; X-ray Structure of a Dimeric Organolithium Compound, [Li{2,6-(Me2NCH2)2-4-Ph-C6H2}]2 (1996)
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 1440-1445 
    Details
    ISSN: 0947-6539
    Keywords: aryldiamines ; chelate ligands ; organometallic compounds ; ruthenium complexes ; structure elucidation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The new anionic functionalized aryldiamine ligands [2,6-(Me2NCH2)2-4-R-C6H2]- (R = Me3SiC≡C, C6H5, Me3-Si), formally derived from [2,6-(Me2-NCH2)2C6H3]-, have been prepared as their lithium compounds. The compound [Li{2,6-(Me2NCH2)2-4-Ph-C6H2}]2 crystallizes in the monoclinic space group C2/c (no. 15) with a = 13.1225(5), b = 13.5844(7), c = 18.9859(12) Å, β = 105.329(5)°, V = 3264.0(3) Å3. Z = 4. The structure refinement converged to R1 = 0.0374 for 2037 observed reflections [Fo〉4σ(Fo)] and wR2 = 0.0922 for 2560 unique data. The organolithium compounds have been used in transmetalation reactions to give the corresponding functionalized organoruthenium(II) complexes [RuII{2,6-(Me2NCH2)2-4-R-C6H2}-(terpy)]+Cl- (terpy = 2,2′;6′,2′-terpyridine). The RuII species with R = HC°C has also been synthesized.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/chem.19960021117
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  • 3
    Electronic Resource
    Electronic Resource
    Thermally Stable Self-assembling Open-Frameworks: Isostructural Cs+ and (CH3)4N+ Iron Germanium Sulfides (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 283-287 
    Details
    ISSN: 0009-2940
    Keywords: Self-assembling frameworks ; Thermal stability ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Here we report on investigations that have revealed for the first time that the Cs+ ion templates the same metal germanium sulfide open-framework as (CH3)4N+ (TMA+), and that metal complexing agents enhance crystal size by at least two orders of magnitude. The synthesis, structures and thermal properties of Cs2FeGe4S10 ·× H2O and TMA2FeGe4S10 are also described. Both have 3D zinc blende-type open-framework structures. These materials have the same connectivity as TMA2MnGe4S10. The tetrahedral sites in the lattice are alternately substituted by pseudo-tetrahedral Fe2+ and adamantanoid Ge4S104- building blocks, covalently linked together by Fe(μ-S)Ge bridge bonds, to give a tetragonal unit cell. The charge-balance of the anionic framework [Fe-Ge4S10]2- is maintained by either Cs+ or TMA+ ions in the cavity spaces. Synthesis of these materials demonstrates an interesting example of a self-assembly process in which a 3D framework is built from molecular precursors. Water adsorption-desorption cycling from room temperature to 200 °C reveals framework flexibility between larger and smaller tetragonal unit cell 14 isotypes. The compound TMA2FeGe4S10 is stable in nitrogen at 350 °C and under vacuum at 450 °C. The corresponding temperatures for Cs2FeGe4S10 are 530 °C and 630°C; it is stable on cooling to room temperature under vacuum, and after subsequent exposure to air. Six hundred thirty degrees celsius is the highest recorded temperature at which the integrity of a non-oxide framework has been maintained. The framework stability and flexibility of “all-inorganic” Cs2FeGe4S10 provides an encouraging example for researchers interested in developing sulfide-based framework materials with practical applications.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19961290307
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  • 4
    Electronic Resource
    Electronic Resource
    A Synthetic and Theoretical Study of the Aggregation of Amidoaluminium Hydrides: Solid-State Structure of the Trimethylamine Adduct [(Me3Si)2NA1(Cl)(H) · NMe3] (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 545-549 
    Details
    ISSN: 0009-2940
    Keywords: Alane ; Association ; Hydride ; Amido ; Amide ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The amidoaluminium hydride complexes [(Me3Si)2NA1(X)(H) · NMe3], X = H (1), Cl (2), were prepared by the metallation of bis(trimethylsilyl)amine by Al(X)(H)2 · NMe3 (X = H and Cl). The molecular structure of 2 as a monomeric Lewis base adduct with four-coordinate aluminium centres and terminal amido groups was confirmed by X-ray crystal structure determination. We also find that bis(trimethylsilyl)amine forms a thermally stable adduct of alane, (Me3Si)2N(H) · AlH3 (3). Ab initio molecular orbital calculations on the possible products arising from these reactions yielding 1 and 2 revealed that the amido-bridged species, {(μ-H2N)Al(X)H}2 (X = H and Cl), are favoured over nitrogen donor Lewis base adduct formation, H2NAl(X)(H) · NH3 (X = H and Cl), and then chloro-bridged, {H2NAl(μ-X)(H)}2, (X = Cl only), and hydrido-bridged species, {H2NAl(X)(μ-H)}2 (X = H and Cl).
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19961290511
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  • 5
    Electronic Resource
    Electronic Resource
    The Catalytic Ring-opening Cyclooligomerization (ROC) of Thietane by the Complexes M(CO)5L (M = Cr and W; L = CO, thietane and 1,5,9-Trithiacyclododecane) (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 313-318 
    Details
    ISSN: 0009-2940
    Keywords: Thietane ; Catalysis ; Tungsten ; Macrocycle ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The following four compounds have been synthesized: M(CO)5L (3 and 4, where M = Cr and W, and L = H2), W(CO)5(12S3) (5, where 12S3 = 1,5,9-trithia-cyclododecane), and [W(CO)5]2(12S3) (6). The molecular structures of 4 and 5 were established by single-crystal X-ray diffraction analyses. Both compounds contain a W(CO)5 group coordinated to one of the sulfur atoms of the hetero-cycle. The ability of the compounds M(CO)6, 1 and 2 (M = Cr and W), and 3 - 5 to catalytically produce ring opening cyclooligomerization (ROC) of thietane into 12S3 and 24S6, (24S6 = 1,5,9,13,17,21-hexathiacyclotetracosane) has been investigated. Compounds 1 - 3 have relatively low activity. Compounds 4 and 5 have the highest activity and selectivity for 12S3 formation. Crystal Data for 4: space group = P212121, a = 12.906(2) Å, b = 13.730(4) Å, c = 6.427(1) Å, Z = 4, 1306 reflections, R = 0.033; for 5: space group = P1¯, a = 12.703(1) Å, b = 13.510(2) Å, c = 5.833(1) Å, α = 101.75(1)°, β = 97.54(1)°, γ = 101.70(1)°, Z = 2, 2225 reflections, R = 0.023.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19961290311
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  • 6
    Electronic Resource
    Electronic Resource
    Solvent Effect on the NMR Chemical Shieldings in Water Calculated by a Combination of Molecular Dynamics and Density Functional Theory (1996)
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 452-457 
    Details
    ISSN: 0947-6539
    Keywords: density-functional theory ; liquid water ; molecular dynamics simulations ; NMR chemical shifts ; solvent effects ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The solvent effect on the NMR chemical shielding in liquid water is calculated from a combination of molecular dynamics simulations and quantum chemical calculations for protons and 17O. The simulations are performed with three different potentials, ab initio as well as empirical ones, to study the influence of the force field. From the liquid configurations obtained in these simulations, molecules are randomly chosen together with neighbouring molecules to give clusters of water typical for the liquid at the selected temperature and density. Different cluster sizes are studied. The clusters are treated as supermolecules in quantum chemical calculations of chemical shifts by sum-over-states density functional perturbation theory with individual gauge for localised orbitals. The influence of the quantum chemical method is studied with an ab initio coupled Hartree-Fock gauge including atomic orbitals calculations with different basis sets for a selected cluster. An average over clusters yields the chemical shielding in the liquid at the selected temperature and density. The calculated values for the gas-liquid shift, which are in best agreement with experiment, are -3.2 ppm (exp. -4.26 ppm) for the proton and -37.6 ppm (exp. -36.1 ppm) for 17O, but the results depend strongly on the chosen interatomic potential.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/chem.19960020415
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  • 7
    Electronic Resource
    Electronic Resource
    Ruthenium(II)-Catalyzed Oppenauer-Type Oxidation of Secondary Alcohols (1996)
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 1533-1536 
    Details
    ISSN: 0947-6539
    Keywords: catalysis ; dehydrogenations ; oxidations ; ruthenium complexes ; secondary alcohols ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Highly efficient ruthenium-catalyzed Oppenauer-type oxidations of secondary alcohols to ketones have been developed. The catalytic system consists of [(PPh3)3RuCl2] (1) and K2CO3 or [(C4Ph4COHOCC4Ph4)(μ-H)(CO)4Ru2] (2) in refluxing acetone. The catalytic reaction is of high efficiency and permits a catalyst: substrate ratio of 1:1000 at 56 °C. In some cases the initial turnover rate exceeds 1500 h-1. The reaction was found to be general and compatible with double bonds and oxidation-sensitive aromatics. With some allylic alcohols, isomerization to saturated ketones took place. The reaction proceeds by ruthenium-catalyzed dehydrogenation of the alcohol and subsequent hydrogen transfer to acetone. No primary kinetic isotope effect was observed for the catalytic reaction when α-deuterated 1-phenylethanol was employed as substrate (kH/kD=1.1); this shows that β-hydride elimination from a ruthenium alkoxide intermediate is not the rate-limiting step.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/chem.19960021210
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  • 8
    Electronic Resource
    Electronic Resource
    Synthetic Cyclic Oligosaccharides-Syntheses and Structural Properties of a Cyclo[(1 → 4)-α-L-rhamnopyranosyl-(1 → 4)-α-D-mannopyranosyl]trioside and -tetraosideSynthetic Cyclic Oligosaccharides, Part 1. (1996)
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 580-591 
    Details
    ISSN: 0947-6539
    Keywords: carbohydrates ; cyclodextrin analogues ; cyclooligomerizations ; glycosylations ; nanotubes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An efficient polycondensation-cyclization approach to the synthesis of cyclodextrin analogues is demonstrated by the preparation of cyclohexaoside 1 and cyclooctaoside 2. The key intermediate, disaccharide 3, bearing the cyanoethylidene group as a glycosyl donor function and the trityloxy group as a glycosyl acceptor function was prepared in 15 steps starting from L-rhamnose and D-mannose. The crucial cyclooligomerization of the disaccharide monomer 3 was carried out in the presence of TrClO4 as a promoter with the use of ultra-dry conditions at normal concentrations. This reaction led to formation of the cyclic oligosaccharides 28 and 29 (in 34 and 31% yield, respectively), which were deprotected to afford 1 and 2, respectively. The X-ray crystal structural analysis of the cyclooctaoside 2 reveals a cylindrical shape for the cyclic oligosaccharide with C4 symmetry. Individual molecules of 2 are arranged perfectly in stacks that form nanotubes in the solid state.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/chem.19960020518
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  • 9
    Electronic Resource
    Electronic Resource
    First Observation of a [1,7] Boron Shift - Three Independent Fluxional Processes in the Tricarbonyliron Complex of Cycloheptatrienyl(dipropyl)borane (1996)
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 1483-1488 
    Details
    ISSN: 0947-6539
    Keywords: boron compounds ; fluxionality ; iron complexes ; NMR spectroscopy ; rearrangements ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The fluxional behavior of [1-4-η4 - exo - 7 - dipropylborylcyclohepta - 1,3,5-triene]tricarbonyliron (14) has been studied by dynamic NMR. The 2 D 1H and 13C EXSY NMR experiments carried out at various temperatures revealed that three independent fluxional processes occur in 14. The fastest rearrangement is a [1,7] B sigmatropic shift accompanied by [1,2] Fe migration (EA = 71.2±2.3 kJ mol-1, ln A = 32±1). Two other rearrangements also take place: [1,3] B sigmatropic and [1,3] Fe haptotropic migrations. The analysis of the observed selectivity towards [1,j] B sigmatropic shifts ([1,3] and [1,7] B shifts are observed, but [1,5] B shifts are not) in terms of theoretical predictions gives reason to assume that the [1,j] boron migrations occur with inversion of configuration at the migrating atom.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/chem.19960021122
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  • 10
    Electronic Resource
    Electronic Resource
    Ab Initio ECP/DFT Calculation and Interpretation of Carbon and Oxygen NMR Chemical Shift Tensors in Transition-Metal Carbonyl ComplexesDedicated to Professor Paul von Ragué Schleyer on the occasion of his 65th birthday (1996)
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 24-30 
    Details
    ISSN: 0947-6539
    Keywords: density-functional theory ; NMR chemical shifts ; pseudopotentials ; relativistic effects ; transition-metal complexes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Carbon and oxygen NMR chemical shift tensors for Group 6 hexacarbonyl complexes M(CO)6 (M = Cr, Mo, W) have been calculated by using a combination of quasirelativistic metal effective-core potentials and density-functional theory. Comparison with high-resolution solid-state shift tensors indicates excellent agreement between theory and experiment. The sensitivity of the shifts to the W-C distance in W(CO)6 is discussed. A breakdown of the shielding tensor components into contributions from localized molecular orbitals allows the detailed interpretation of the trends on going down Group 6, and of differences to free CO. Group trends in the carbon shielding tensors are related largely to contributions from M-C σ-bonding orbitals. The presence of occupied metal (n-1)p and (n-1)d orbitals is partly responsible for the changes on going from free to metalbound CO. The origin of the less pronounced trends in the oxygen shielding tensors is more complicated. The influence of scalar relativistic effects on the shift tensors has been studied for W(CO)6 and is found to be relatively small, in spite of considerable changes in the W-C distance.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/chem.19960020108
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