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  • 1995-1999  (660)
  • 1999  (660)
  • Industrial Chemistry  (469)
  • apoptosis  (112)
  • crystal structure  (79)
  • Inorganic Chemistry
  • Nuclear reactions
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  • 1995-1999  (660)
Year
Keywords
  • 1
    ISSN: 1436-2813
    Keywords: thyroid tumor ; apoptosis ; TUNEL ; MIB-1
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract To clarify the growth mechanisms of thyroid tumors, we examined apoptotic cells in 61 thyroid tumors, consiting of 14 adenomas, 35 papillary carcinomas, 4 follicular carcinomas, and 8 undifferentiated carcinomas, using terminal deoxynucleotidyl transferase mediated deoxyuridine triphosphate digoxigenin-nick end labeling (TUNEL). The proliferative activity was also evaluated immunohistochemically using the monoclonal antibody to Ki-67 antigen (MIB-1) in the same tumors. The apoptotic index (AI) was expressed as a percentage of the TUNEL-positive cells in the tumor cells, and a proliferation index (PI), being the percentage of Ki-67 positive cells, was calculated for each tumor. The overall level of AI was very low in all histotypes of the thyroid tumors analyzed, the mean AI being 0.5±0.4 in adenoma, 0.4±0.3 in differentiated carcinoma, and 1.8±1.5 in undifferentiated carcinoma. The PI in the thyroid tumor subtypes was significantly lower in adenoma and differentiated carcinoma, at 0.5 ±0.7 and 1.1±0.7, respectively, than that in undifferentiated carcinoma at 14.5±3.7 (P〈0.05). There was no correlation between clinicopathological factors and AI or PI in differentiated thyroid carcinoma. Our findings suggest that apoptosis occurs infrequently in thyroid tumors, and that proliferative activity markedly differs according to the thyroid tumor subtypes. Moreover, the ratio between proliferating cells and apoptotic cells may reflect thyroid tumor progression.
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  • 2
    ISSN: 1436-2813
    Keywords: Key Words: thyroid tumor ; apoptosis ; TUNEL ; MIB-1
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: P 〈 0.05). There was no correlation between clinicopathological factors and AI or PI in differentiated thyroid carcinoma. Our findings suggest that apoptosis occurs infrequently in thyroid tumors, and that proliferative activity markedly differs according to the thyroid tumor subtypes. Moreover, the ratio between proliferating cells and apoptotic cells may reflect thyroid tumor progression.
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Journal of chemical crystallography 29 (1999), S. 203-206 
    ISSN: 1572-8854
    Keywords: Manganese(III) ; Schiff base ; hydrogen bonding ; crystal structure ; Jahn-Teller distortion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The manganese complex, (Mn2(III)(salpa)2Cl2(H2O)2], has been prepared and its structure determined using x-ray crystallography. The dimer is a di-μ2-alkoxo complex which is a six-coordinate manganese dimer with unsupported alkoxide bridges and a rare example of a chloride- and water-containing manganese dimer. The complex crystallizes in the monoclinic space group P21/c with a = 9.315(5), b = 11.130(4), c = 11.637(5) Å, β = 104.33(3)°, V = 1169.0(9) Å3, and Z = 2. The structure comprises discrete binuclear clusters in which the metal atoms are bridged by two alkoxo oxygens of the salpa2− ligands. The Mn—O and Mn—N distances are in good agreement with those found for other manganese(III) Schiff base complexes. The Mn—Cl and Mn—O3 distances are 2.585(2) and 2.371(2) Å, respectively, and the Mn ··· Mn distance is 3.001(1) Å. In the crystal, there are two types of hydrogen bonding between the H2O molecule and the Cl atom with Cl ··· H(H2O) distance of 2.33(6) (intramolecule: −1 + x, y, −1 + z) and 2.68(6) Å (intermolecule: −1 + x, 0.5−y, −0.5 + z).
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Journal of chemical crystallography 29 (1999), S. 243-246 
    ISSN: 1572-8854
    Keywords: Thorium ; dimethoxyethane ; crystal structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The molecular structure of ThBr4(DME)2 (DME = 1,2-dimethoxyethane), the first structurally characterized thorium complex containing a simple bidentate ether ligand, is described. The eight-coordinate complex presents a distorted dodecahedral geometry, with Th—Br and Th—O bond lengths in the ranges 2.8516(13)–2.8712(13) Å and 2.564(8)–2.620(8) Å, respectively. ThBr4(DME)2 is monoclinic, space group P21/n, a = 7.672(1), b = 14.581(1), c = 15.847(2) Å, β = 102.24(1)°, V = 1732.4(3) Å3, and Z = 4.
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Journal of chemical crystallography 29 (1999), S. 295-298 
    ISSN: 1572-8854
    Keywords: Copper ; crystal structure ; synthesis ; Schiff base ligand
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The title complex Cu(C8H7O2N)2(OH2) crystallized in the orthorhombic space group, Pbca with unit cell parameters: a = 15.242(2), b = 11.782(4), c = 17.946(4) Å, and Z = 8. Two nitrogen atoms, two phenolic oxygen atoms of the ligand, and one water molecule are coordinated with copper to form a distorted tetragonal pyramidal polyhedron.
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  • 6
    ISSN: 1572-8854
    Keywords: Europium ; terbium ; betaine ; crystal structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract Three dimeric lanthanide(III) complexes, [Eu2(bet)8(H2O)4](CIO4)6 (1), [Tb2(bet)8(H2O)4](ClO4)6 (2), and [Eu2(bet)4(H2O)8] Cl6·6H2O (3) (bet = Me3N+CH2COO−, trimethyl-aminoacetate), have been prepared and structurally characterized by X-ray crystallography. Complex 1 crystallizes in the monoclinic space group P21/c, with a = 11.7807(8), b = 27.757(5), c = 11.7980(8) Å, β = 99.500(4)°, V = 3805.1(8) Å3, and Z = 2. Complex 2 is isomorphous to complex 1, crystallizing in the monoclinic space group P21/c, with a = 11.7769(14), b = 27.725(3), c = 11.795(5) Å, β = 99.668(14)°, V = 3797(2) Å3, and Z = 2. Complex 3 crystallizes in the orthorhombic space group Pbca, with a = 12.5664(8), b = 17.8645(9), c = 22.2573(8) Å, V = 4996.6(4) Å3 and Z = 4. Both complexes 1 and 2 comprise quadruply carboxylate-O,O′-bridged [M2(bet)4]6+ dimeric cores (M = Eu, Tb), and each metal ion is further coordinated by two terminal aqua ligands and two monodentate bet carboxylates to form a distorted square-antiprismatic coordination geometry. Complex 3 also has a [Eu2(bet)4]6+ core, in which two bet ligands act in the η1:η1:μ2 bridging fashion, and the other two bet ligands in the less common η2:η1:μ2 bridging fashion, namely bridging-chelate mode. Each europium(III) ion in complex 3 is further coordinated by four water molecules to complete a monocapped square antiprism.
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  • 7
    ISSN: 1572-8854
    Keywords: crystal structure ; copper(II) complexes ; dinuclear complexes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract A chemical Janus, binuclear copper(II) complexes, {[Cu(TPA)Cl][Cu(BPA)Cl]}(ClO4)2 (TPA = Tris(2-pyridylmethyl) amine, BPA = bis-(2-pyridylmethyl)amine) containing two different ligands has been synthesized and characterized by X-ray single crystal analysis. Crystal data: triclinic, space group P1$sm, a = 12.529(3), b = 12.655(3), c = 13.458(3) Å, α = 70.48(3), β = 67.40(3), γ = 75.81(3)°, D x = 1.648 mg m−3, and Z = 2. The molecular structure shows that the binuclear copper complex consists of two positive cation and two perchlorate anions. The positive cations moieties have different ligands. Cu(1) is coordinated by four nitrogen atoms from TPA and one chloride atom, forming a square-pyramidal geometry, whereas the coordinate number of Cu(2) is four, three of which are from BPA, one from chloride. There are two weak bonds between the Cl(2a) ion and the Cu(2) ion (2.844 Å) and the distance of Cu(2)=O(13) is 2.750(9) Å.
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Journal of chemical crystallography 29 (1999), S. 513-521 
    ISSN: 1572-8854
    Keywords: nanotechnology ; molecular devices ; triptycene ; crown ether ; crystal structure ; thallium
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The incorporation of 9,10-triptycene unit in a crown ether is examined from a structural perspective. Insertion of a triptycene group into 18-crown-6 stretches the crown into an ellipse, as seen in structures presented here of 9,10-triptyceno-22-crown-6 and its thallium complex. Symmetric addition of two triptycene groups into 18-crown-6 results in the sterically congested bis(9,10-triptyceno)-26-crown-6, whose crown cavity is filled with the π-clouds of two arene groups. The larger bis(9,10-triptyceno)-32-crown-8 is more sterically relaxed. The structures of these bis(triptyceno)crown ether molecules are the first with two triptycene groups simultaneously linked through their 9 and 10 positions, thereby forming a simple molecular gearing mechanism. The compound 9,10-triptyceno-22-crown-6 (1) crystallizes in the orthorhombic space group Pbca with a = 10.7962(7), b = 15.826(3), c = 31.147(5) Å, V = 5321.8(12) Å3, and Z = 8; its complex with TlNO3 (Tl-1) crystallizes in the monoclinic space group P21/c with a = 8.1884(14), b = 19.552(2), c = 20.575(4) Å, β = 97.062(8)°, V = 3269.2(9) Å3, and Z = 4; bis(9,10-triptyceno)-26-crown-6 (2) crystallizes in the triclinic space group P $$\bar 1$$ with a = 8.6488(11), b = 10.7718(12), c = 12.3324(12) Å, α = 111.58(1), β = 100.55(1), γ = 106.43(1)°, V = 970.3(5) Å3, and Z = 1; and bis(9,10-triptyceno)-32-crown-8 (3) crystallizes in the orthorhombic space group Pna21 with a = 20.186(3), b = 8.558(2), c = 25.623(2) Å, V = 4426.2(14) Å3, and Z = 4.
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Journal of chemical crystallography 29 (1999), S. 555-560 
    ISSN: 1572-8854
    Keywords: alkylammonium chloroantimonates(III) ; hydrogen bonds ; disorder ; lone electron pair ; crystal structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The structure of [(CH3)3NH]2Sb3Cl11 (space group P21/n; a = 10.374(2), b = 23.723(5), c = 11.884(2) Å, β = 113.46(3)°; V = 2682.9(9) Å3) consists of a structurally novel [Sb3Cl2− 11] anion and two crystallographically nonequivalent trimethylammonium cations. The anion is composed of three deformed octahedra in the asymmetric part of the unit cell. The octahedra are connected with each other by edges and corners forming a characteristic polyanionic layer. Trimethylammonium cations, one ordered and one disordered, are connected to the inorganic sublattice by N—H· · ·Cl hydrogen bonds.
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  • 10
    ISSN: 1572-8854
    Keywords: crystal structure ; complexes ; pteridine ; lumazine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract Single-crystal X-ray diffraction studies have been performed on the complex cis-diaqua-bis(1,3-dimethylpteridine-2,4(1H,3H)-dione-O4,N5) copper(II) perchlorate monohydrate, [Cu(DLM)2(H2O)2](ClO4)2 · H2O. This compound crystallizes in the orthorhombic system, P212121 space group, Z = 4 with a = 8.749(1) Å, b = 14.213(1) Å, c = 21.200(2) Å, and V = 2636.2(4) Å3. The metal ion is surrounded in octahedral geometry by two mutually quasi-perpendicular N5,O4-coordinated lumazine chelators with the O4 atoms trans and the N5 atoms cis. The polyhedron is completed by two cis-coordinated water molecules. The absolute configuration of the complex can be described, following Bailar's nomenclature, as the enantiomer Λ of the stereoisomer 4M. A three-dimensional hydrogen-bond network is defined by water molecules, perchlorate anions, and the O2 of the pteridine A.
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  • 11
    ISSN: 1572-8854
    Keywords: dodecanuclear heterobimetallic ; molybdenum-copper cluster ; cage ; μ6-S ; crystal structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The complex (Ph4P)2[Mo2S2O2(S2)(S4)] reacts with CuBr to give the dodecanuclear heterobimetallic Mo—Cu—S cage cluster: (Ph4P)2[{Mo2Cu2O2S2(S2)2}3(μ6-S)] (1), which crystallizes in the triclinic space group P1¯, a = 14.445(5), b = 15.396(5), c = 18.858(5) Å, α = 103.12(3), β = 101.93(2), γ = 113.92(3)°, and V = 3517(2) Å3 for Z = 2. The anion 1 can be described as a cage with S2− at the center binding to six Cu atoms; the cage has two big windows each composed of a puckered Cu3S6 9-membered ring.
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  • 12
    ISSN: 1572-8854
    Keywords: copper(II) complexes ; 2,6-diacetylpyridine derivative ; open-chain ligand ; crystal structure ; trigonal-bipyramidal geometry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The title compound was obtained by a template synthesis from 2,6-diacetylpyridine, ethylhydrazinoacetate and CuCl2·2H2O (molar ratio 1:2:1, in methanol), and its structure has been determined by single-crystal X-ray diffraction: monoclinic space group P21/c, a = 13.906(5), b = 18.199(6), c = 16.641(6) Å, β = 107.18(3)°, and z = 4. The ligand was found to be tridentate in a trigonal-bipyramidal coordination geometry with two chloride ligands. There are two independent complex molecules, one of which is hydrogen bonded to the water of crystallization.
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  • 13
    Electronic Resource
    Electronic Resource
    Springer
    Journal of chemical crystallography 29 (1999), S. 629-633 
    ISSN: 1572-8854
    Keywords: heterometallic polymeric cluster ; polythiometalate ; synthesis ; crystal structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The complex (NH4)2 WS4 reacts with AgNO3 and La(NO3)3 · 6H2O in a mixture of DEF/DMF (DEF—N,N′-diethylformamide), to give a new heterometallic square-chain polythiometalate {[W4Ag5S16]2 · [La(DEF)2(DMF)6] · [La(DEF)4(DMF)4]}n (1). 1 crystallizes in the monoclinic space group P2/c, a = 19.5534(8), b = 16.9552(6), c = 22.3479(9) Å, β = 106.053(1)°, V = 7120.1(5) Å3, and Z = 2. The anion polymeric chain of 1 can be regarded as an octanuclear cyclic cluster of [W4Ag4S16]4− fragments linked through Ag+ ions. The polymeric chain is extended through the parallel edges of the square unit. The mean W—Ag distance is 2.963(16) Å. The La3+ cations are coordinated by different solvent molecules, the average La—O bond of these large trivalent cations is 2.47(1) Å.
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  • 14
    ISSN: 1572-8854
    Keywords: oxabicyclo[3.2.1]octadiene ; absolute configuration ; asymmetric synthesis ; crystal structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The compound under investigation crystallizes in the noncentrosymmetric orthorhombic space group P212121 with a = 7.9358(11), b = 11.0532(13), c = 29.2425(43) Å, volume = 2565.0(6) Å3, and Z = 4. The C23H34O8Si molecule contains three chiral centers (one of which is of known configuration, based upon an (R)-pantolactone auxillary group). We have determined the absolute configuration of this species (via the anomalous dispersion of Si relative to C and O) and show that it is consistent with the known configuration of the (R)-pantolactone moiety.
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  • 15
    ISSN: 1572-8854
    Keywords: oxabicyclo[3.2.1]octadiene ; absolute configuration ; asymmetric synthesis ; crystal structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The compound under investigation crystallizes in the noncentrosymmetric monoclinic space group P21 with a = 9.1798(23), b = 6.6606(18), c = 17.6591(41) Å, β = 94.342(20)° and Z = 2. The C20H30O6Si molecule contains three chiral centers (one of which is of known configuration, based upon an (R)-pantolactone auxiliary group). We have determined the absolute configuration of this species (via the anomalous dispersion of Si relative to C and O) and show that it is consistent with the known configuration of the (R)-pantolactone moiety
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  • 16
    ISSN: 1572-8854
    Keywords: 2,2′-biimidazole ; diester ; crystal structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract 1,1,′-Di(ethylpropionato)-2,2′-biimidazole, C16H22N4O4, crystallizes from ice-cold ethanol in the space group P $$\bar 1$$ , with a = 4.6742(9), b = 9.1119(13), c = 10.175(2) Å, α = 96.22(1), β = 96.29(2), γ = 97.53(1)°, and Z = 1. The molecule crystallizes with coplanar rings and the substituents assume a trans conformation with a center of inversion between the bridging carbon atoms.
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  • 17
    ISSN: 1572-8854
    Keywords: Hg coordination ; crystal structure ; organomercury derivatives
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The crystal structure of the title compound, Hg[S2P(OPri)2]2, has been determined by single-crystal X-ray diffraction. The compound crystallizes in the centrosymmetric P21/c space group with a = 11.800(1), b = 8.925(2), c = 22.167(2) Å, β = 94.988(7)°, and Z = 4. The same compound has been previously reported but the structure is described there in the space group C2/c. In both cases, one phosphorodithioate moiety acts as a chelating group and the other as a bridging group between neighboring mercury atoms (related to one another by the twofold screw axis), giving rise to an infinite polymer along the direction of the b axis. It turns out that in spite of the difference in space group symmetry, the structures are remarkable similar in that they are formed from infinite polymers of similar geometry. The coordination around the Hg ion shows, however, significant differences, mainly for the bridging Hg—S(4) bond length, which is 0.16 Å smaller than that previously reported.
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  • 18
    Electronic Resource
    Electronic Resource
    Springer
    Journal of chemical crystallography 29 (1999), S. 329-333 
    ISSN: 1572-8854
    Keywords: Carbene ; crystal structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract Base-promoted reaction of 11-methylenepentacyclo[5.4.0.02,6.03,10.05, 9]undecan-8-one (5) with diethyl diazomethylphosphonate when performed in the presence of excess cyclohexene, resulted in the formation of the corresponding cycloalkylidenecarbene, 6, which subsequently was trapped in situ to afford 8-methylene-11-(7′-bicyclo[4.1.0]heptylidene)pentacyclo-[5.4.0.02, 6.03, 10.05, 9]undecane (7, obtained in 44% yield as a mixture of exo, endo isomers). Subsequent reaction of 7 with dichlorocarbene (generated under phase transfer catalytic conditions) produced the corresponding mono- and di-:CCl2 adducts [i.e., 8 (64% yield) and 9 (5% yield), respectively]. The structure of 9 was established unequivocally via application of single crystal X-ray analysis: Triclinic, P1¯, a = 6.276(2), b = 8.700(2), c = 18.550(3) Å, α = 76.52(3), β = 87.59(3), γ = 70.88(4)° Z = 2; D calc 1.486 g cm−3.
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  • 19
    ISSN: 1572-8854
    Keywords: crystal structure ; manganese complex ; disubsituted oxamide ; addition compound
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The structure of the addition compound, Mn(phen)3(PMoxdH2)(ClO4)2 was established by X-ray crystallography, where PMoxdH2 is N,N′-bi(2-pyridylmethyl)-oxamide. Six nitrogen atoms of the three 1,10-phenanthroline bind to the manganese ion and the oxygen atom of PMoxdH2 is uncoordinated. The addition compound crystallizes in the monoclinic space group C2/c, with lattice parameters a = 23.780(6), b = 11.948(5), c = 18.466(6) Å, β = 117.38(3)°, V = 4659(3) Å3, and Z = 4.
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  • 20
    ISSN: 1572-8854
    Keywords: pyrazolyl derivative ; substituted cyclopentane ; substituted cyclohexane ; crystal structure ; bidentate ligand
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The species 1,1-di(pyrazol-1-yl)cyclohexane, C12H16N4, crystallizes in the monoclinic space group P21/c with a = 8.340(2), b = 14.281(5), c = 10.153(3) Å, β = 106.86(2)°, and Z = 4. The cyclohexane moiety has the chair conformation. The congener, 1,1-di(pyrazol-1-yl)cyclopentane, C11H14N4, while not isomorphous, also crystallizes in space group P21/c with a = 14.350(2), b = 6.776(1), c = 11.043(2) Å, β = 100.68(1)°, and Z = 4. The cyclopentane ring has a conformation in which four carbon atoms are essentially coplanar, while the fifth (that with the two pyrazolyl substituents) lies 0.63 Å from this plane, resulting in a bend of 41.3° across the C(2)···C(5) vector. The hydrogen atoms in each structure were located directly and their coordinates refined.
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  • 21
    Electronic Resource
    Electronic Resource
    Springer
    Journal of chemical crystallography 29 (1999), S. 719-723 
    ISSN: 1572-8854
    Keywords: synthesis ; crystal structure ; independent molecules
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The x-ray crystal structure of 4,5-(cis-cyclohexylenedithio)-1,3-dithiole-2-one has been determined. Yellow block shaped crystals of C9H10OS4 crystallize in the space group P $${\bar 1}$$ with cell dimensions a = 8.872(4), b = 9.330(8), c = 14.333(12) Å, α = 95.23(7), β = 91.09(5), γ = 107.60(5)°, V = 1124.8(14) Å3, and Z = 4. This compound has two S---S contacts [3.574, 3.610 Å] shorter than 3.70 Å and the usual disordered ethylene moiety [C(3)—C(8)] of the six-membered ring is fixed by the cis-cyclohexylene subsitituent. This means that it may be a new precursor for conducting and strong near-IR absorbing nickel-dithiolenes. Also, it provides the first example of polymorphism of the dmit derivatives and contains two independent molecules I and II in the asymmetric unit.
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  • 22
    Electronic Resource
    Electronic Resource
    Springer
    Journal of chemical crystallography 29 (1999), S. 725-727 
    ISSN: 1572-8854
    Keywords: 2-thiouracil derivatives ; crystal structure ; S-methyl-thiouracil ; hydrogen bonding ; structural methylation and metallation effects
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract 2-S-Methylthiouracil crystallizes in the triclinic space group P $${\bar 1}$$ with unit cell dimensions a = 5.508(4), b = 7.175(3), c = 8.522(2) Å, α = 80.83(2), β = 80.43(3), γ = 76.86(3)°, and Z = 2. The molecule exists in the crystal in the lactam form and is essentially planar. The molecular packing consists of molecules linked in centrosymmetric hydrogen-bonded pairs. The effects of methylation and subsequent metallation on the 2-thiouracil structure are discussed.
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  • 23
    Electronic Resource
    Electronic Resource
    Springer
    Journal of chemical crystallography 29 (1999), S. 797-802 
    ISSN: 1572-8854
    Keywords: synthesis ; crystal structure ; Cu(I) complex ; μ-oxo-bis(2,9-dimethyl-1,10-phenanthroline) ; luminescence
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The synthesis and crystal structure of a luminescent dinuclear Cu(I) complex as the BF− 4 salt from toluene and methanol containing triphenylphosphine and μ-oxo-bis(2,9-dimethyl-1,10-phenanthroline) is described. The coordination geometry about the Cu(I) center is distorted tetrahedral. An unusual feature of the structure is a pseudo-inversion center located near the oxygen atom at approximately 0.51, 0.26, 0.25, such that all of the atoms except for the oxygen are related by a pseudo-inversion center to another atom in the same molecule, as well as by crystallographic inversion to the other molecule in the unit cell. The complex displays luminescence from an MLCT band in fluid solution and emission from both a metal-centered charge-transfer and intraligand (phenanthroline) state at 77K in a chloroform snow. Crystal data: triclinic, P $$\bar 1$$ , a = 15.163(2), b = 16.985(2), c = 18.731(2) Å, α = 106.458(9), β = 91.416(8), γ = 102.557(9)°, V = 4496(1) Å3, and Z = 2.
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  • 24
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    Journal of chemical crystallography 29 (1999), S. 729-733 
    ISSN: 1572-8854
    Keywords: crystal structure ; yttrium complexes ; isothiocyanate complexes ; octahedral coordination
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The structural analysis of [(n-C4H9)4N]3[Y(NCS)6] (I) using single-crystal diffraction data and full-matrix least squares refinement has been carried out. The hexaisothiocyanate complex crystallizes in the centrosymmetric triclinic space group P $${\bar 1}$$ (No. 2) with unit cell constants of a = 12.431(1), b = 12.866(1), c = 22.750(2) Å, α = 90.78(1), β = 92.05(1), γ = 96.67(1)°, and Z = 2. The molecular unit consists of three separate cationic tetra-n-butylammonium groups and an independent hexakisisothiocyanatoyttrate anionic group in which the six thiocyanate ligands are octahedrally coordinated through the N atom to the Y central ion. Selected bond distances and angles are presented as well as the synthesis and peripheral studies of (I).
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  • 25
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    Journal of chemical crystallography 29 (1999), S. 793-796 
    ISSN: 1572-8854
    Keywords: copper complex ; crystal structure ; dibenzoylmethane complex
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract Bis(dibenzoylmethane)copper Cu(dbm)2 has been synthesized and its structure determined by x-ray diffraction. It crystallizes in the monoclinic system, space group C2/c, with a = 25.936(3), b = 5.9806(8), c = 16.4908(16) Å, β = 114.998(8)°, Z = 4, and V = 2318.3(4) Å3. The Cu atom is located at a symmetry center and surrounded by four O atoms from two dbm molecules to form a plane square coordination environment. On the a–c plane the molecules are orderly arranged to result in a layered structure, and parallel to crystallographic b-axis they form a molecular column due to the effect of aromatic stacking.
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  • 26
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    Journal of chemical crystallography 29 (1999), S. 809-812 
    ISSN: 1572-8854
    Keywords: tungsten(II) ; dibromo ; carbonyl ; diphenylcyclohexylphosphine ; but-2-yne ; crystal structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract [WBr2(Co)(PPh2Cy)2(η2-MeC2Me)]·CH2Cl2 (Cy = cyclohexyl) crystallizes in the monoclinic space group, P21/n, with a = 10.606(12), b = 23.11(3), c = 18.19(2) Å, β = 106.070(10) Dcalc = 1.610g cm−3 for Z = 4. The tungsten coordination geometry can best be considered as a distorted octahedron, with the but-2-yne ligand occupying one coordination site, which has a trans-Br(2) group. The equatorial plane is made up of trans-PPh2Cy groups, with the bromo and carbonyl ligands occupying the other two sites.
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  • 27
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    Journal of chemical crystallography 29 (1999), S. 837-839 
    ISSN: 1572-8854
    Keywords: acyclonucleoside analog ; 6-(phenyl selenyl) uracil derivative ; crystal structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The compound, 1-(ethoxymethyl)-6-(phenylselenyl)-5-ethyl uracil, crystallizes in the monoclinic space group P21/n with unit cell parameters a = 5.304(1), b = 21.261(4), c = 13.996(4) Å, β = 94.30(2)°, and Z = 4. The acyclic chain C1′, O4′, C4′, C5′ is in fully extended form and nearly perpendicular to the uracil base. The molecules are held together by van der Waal's forces.
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  • 28
    ISSN: 1572-8854
    Keywords: mercury halides ; crystal structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The synthesis, characterization and single crystal X-ray structure of three compounds of general formula HgI2R (R = phen[1], dmph [2] and bpy[3]) are presented. The crystal data for the three compounds are: [1], triclinic, space group P $$\bar 1$$ (#2) a = 7.902(2), b = 9.479(2), c = 10.002(2) Å, α = 91.45(2), β = 111.34(2), γ = 100.82(2)° [2]: monoclinic, space group C2/c (#15) a = 15.670(3), b = 11.640(2), c = 9.730(2) Å, β = 114.57(3)° [3]: triclinic, space group P1¯ (#2) a = 9.472(1), b = 9.507(1), c = 9.023(1) Å, α = 98.46(1), β = 102.89(1), γ = 119.62(1)°. Compounds [1] and [2] are monomers, with highly distorted tetrahedral environments around Hg. In [3], instead, there is a significant intermolecular I···Hg interaction leading to the formation of softly bound dimers linking two pentacoordinated cations. The structure is compared with related ones in the literature.
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  • 29
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    Journal of chemical crystallography 29 (1999), S. 907-911 
    ISSN: 1572-8854
    Keywords: tungsten(II) ; Iodo ; carbonyl ; cis-bis(diphenylphosphino)ethene ; but-2-yne ; cationic ; crystal structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The complex [WI(CO)(cis-dppen)(η2-MeC2Me)2]I·CH2Cl2(1) is prepared as a by-product from the reaction of equimolar quantities of [WI2(CO)(NCMe)(η2-MeC2Me)2] and cisdppen {dppen = bis(diphenylphosphino)ethene}. Complex 1, [WI(CO)(cis-dppen)(η2-MeC2Me)2]I·CH2Cl2 crystallizes in the triclinic space group $${\text{P}}\bar 1$$ with a = 11.189(13), b = 12.331(14), c = 15.395(17) Å, α = 83.61(1), β = 86.06(1), γ = 64.48(1)°, U = 1904 Å3, and Z = 2. The metal environment in the cation can best be considered as a distorted octahedron with the two but-2-yne groups taking up individual sites trans to phosphorus atoms of the dppen ligand. The coordination sphere is completed by mutually trans-carbonyl and iodide groups.
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  • 30
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    Journal of chemical crystallography 29 (1999), S. 955-959 
    ISSN: 1572-8854
    Keywords: crystal structure ; intramolecular hydrogen bond ; 4-(1,4-dimethoxy-2-naphthyl)-4-hydroxycyclohexanone
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract Intramolecular hydrogen bonding in the solid state is reported for the title compound and its ethylene ketal. The title compound crystallizes in the triclinic space group, $$P\bar 1$$ with a = 9.590(3), b = 9.620(3), c = 9.844(2) Å, α = 97.67(2), β = 105.25(2), γ = 115.47(2), and Z = 2. The ethylene ketal crystallizes in the monoclinic space group, P21/c, with a = 7.230(2), b = 22.639(3), c = 10.839(2) Å, β = 101.47(2), and Z = 4. The intramolecular hydrogen bond length of 1.79 Å is the same for the ketone and ketal, but the O—H---O valence angle is 144° for the ketone and 165° for the ketal.
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  • 31
    ISSN: 1572-8854
    Keywords: neotame ; crystal structure ; methanol solvate ; thermal analysis ; powder X-ray diffractometry ; 13C solid-state nuclear magnetic resonance spectroscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The crystal structure of the methanol solvate (empirical formula: 2C20H30N2O5·3CH3OH) of a new dipeptide sweetener, neotame (N-(3,3-dimethylbutyl)-L-α-aspartyl-L-phenylalanine 1-methyl ester), has been determined. Crystal data: a = 9.8989(1), b = 18.1331(1), c = 27.5725(1) Å, orthorhombic, space group P212121, with Z = 4. Each unit cell includes 8 neotame and 12 methanol molecules. Disorder exists in one neotame molecule and one methanol molecule. The crystals were characterized by the following techniques: hot-stage microscopy (HSM), Karl-Fischer titrimetry (KFT), powder X-ray diffractometry (PXRD), differential scanning calorimetry (DSC), thermogravimetry (TGA), 13C solid-state nuclear magnetic resonance (SSNMR) spectroscopy. Under HSM at a heating rate of 10°C/min in silicone oil, the sample melts at 64–84°C and liberates bubbles at 71–86°C. DSC in open pans shows two overlapping endotherms at 56 and 71°C, probably due to melting and desolvation, respectively. TGA in open pans shows 5.9% weight loss due to desolvation below 70°C. Under house vacuum (23 mm Hg) over phosphorus pentoxide at 23°C, the methanol solvate produces pure amorphous anhydrate, which converts to crystalline neotame monohydrate in the presence of moisture.
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  • 32
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    Journal of chemical crystallography 29 (1999), S. 977-982 
    ISSN: 1572-8854
    Keywords: cyano allyl radical ; thermal arrangement ; crystal structure ; isomer ; NMR, MM2
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The preparation, separation, crystal structure and 1H NMR spectra are reported for the two geometrical isomers of 1,1′-bi-3-cyanocyclohex-2-enylidene. The E-isomer crystallized as thin plates in the monoclinic space group P21/n with a = 5.3980(5), b = 7.0757(7), c = 15.300(2) Å, β = 94.571(2)°, and Z = 2. The structure has symmetry C2h. The Z-isomer crystallized as needles in the triclinic space group P1¯ with a = 7.0790(6), b = 11.3155(9),c = 15.386(1) Å, α = 104.943° β = 90.164(2)°, γ = 99.494(2)°, and Z = 4. The compound crystallized with two molecules per asymmetric unit. In C6D6, 1H NMR signals of the 2-vinyl protons appear almost identical. However, in a mixture of C6D6 and pyridine-d 5, the 2-vinyl protons can be distinguished. The structures compare favorably with MM2 calculations.
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  • 33
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    Journal of chemical crystallography 29 (1999), S. 1009-1013 
    ISSN: 1572-8854
    Keywords: crystal structure ; nickel complex ; xanthosine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The complex [Ni(XsH−1)2(H2O)4]·6H2O (XsH−1: xanthosinate) was isolated from the reaction of nickel carbonate with xanthosine in aqueous solution. The octahedral coordination is supported by the reflectance measurements. Single-crystal X-ray diffraction studies show that the crystals belong to the triclinic P1 space group, with a = 7.152(1), b = 8.830(1),c = 13.783(1) Å, α = 82.024(1)°, β = 86.155(1)°, γ = 70.900(1)°, and D = 1.643 mg/m3, forZ = 1. Nickel is six coordinate with four water molecules, and two N7 atoms from xanthosinato ligands. A complicated hydrogen-bonding network is present, all possible donors taking part in it.
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  • 34
    ISSN: 1572-8854
    Keywords: manganese ; pyridine-2-thiolate ; bis(diphenylphosphino)methane ; carbonyl ; crystal structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The dimeric complex [Mn2(μ-pyS)2(CO)6] (1) reacted with 2 M equivalents of both PPh3 and PHPh2 to give the respective monomeric phosphine complexes [Mn(pyS)(L)(CO)3][L = PPh3 (2) and PHPh2 (3)]; with 4 M equivalents of dppm, it yielded the complex [Mn(pyS)(η1-dppm)2(CO)2](4). An X-ray structure determination of 4 shows that it crystallizes in the monoclinic space group P21/n with a = 11.027(3), b = 24.984(7), c = 18.379(5) Å, β = 99.870(8)°, V = 4988(2) Å3, and Z = 4. The complex has an octahedral geometry with the chelating pyS ligand and two CO groups occupying the equatorial sites and the two monodentate dppm ligands lying in the trans positions.
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  • 35
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    Journal of chemical crystallography 29 (1999), S. 1037-1041 
    ISSN: 1572-8854
    Keywords: crystal structure ; imidazolidine ; triazene ; bis-triazene ; methoxy substituent ; π-π stacking
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The crystal and molecular structure of 1,3-di-2-[(4-methoxyphenyl)-1-diazenyl]imidazolidine (1) has been determined by single crystal X-ray diffraction analysis. This novel bis-triazene assumes a close-to planar structure with the aryltriazene moieties aligned in diametrically opposed directions, unlike many other previously reported bis-triazenes, which assume a folded structure. The structure of 1 is compared with the closely related, non-cyclic bis-triazene analogue (2), and also compared with the structure of the simple mono-triazene (3). Crystal data: 1 C17H20N6O2, monoclinic, space group C2/c, a = 34.948(3), b = 5.925(5), c = 8.1225(6) Å, β = 100.8420(10)°, and V = 1652.0(2) Å3, for Z = 4.
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  • 36
    ISSN: 1572-8854
    Keywords: crystal structure ; tritylaziridine ; acrylate ; spectroscopic features
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The crystal and molecular structure of 2-{(R)-1-Hydroxy-1-[(2S)-1-tritylaziridin-2-y1] methy1}acrylate is described. Crystal data: C26H25NO3, orthorhombic, space group P212121, a = 9.6954(5), b = 13.1458(5), c = 16.7885(7) Å, V = 2139.8(2) Å3, Z = 4. The (R,S) diastereomer shows an intramolecular hydrogen bonding N···H—O under formation of a five-membered ring with N···O distance of 2.664 Å. IR, 1H NMR and 13C NMR data are discussed. The 1H NMR of the (R,S) diastereomer shows a singlet- whereas the (S,S) diastereomer exhibits a doublet-pattern for the hydroxyl proton.
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  • 37
    ISSN: 1572-8854
    Keywords: absolute configuration ; asymmetric synthesis ; azabicyclo[3.2.1]octadiene ; crystal structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The title compound crystallized in space group P21 with a = 12.647(8), b = 14.542(4), c = 17.077(16) Å, β = 97.51(6)°, and D calc = 1.143 mg/m3 for Z = 4. There are two chemically-equivalent C27H41NO8Si molecules in the crystallographic asymmetric unit. Each contains three chiral centers, one of known absolute configuration based upon the (R)-pantolactone,—CH*—CMe2—CH2—O—CO—, moiety. The structural study was greatly complicated by disorder of an —OSiMe2(t-Bu) group in one molecule.
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  • 38
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    Journal of chemical crystallography 29 (1999), S. 1081-1084 
    ISSN: 1572-8854
    Keywords: cobalt(II) ; bipyridine ; maleato ; crystal structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract Preparation of the mononuclear cobalt(II) complex, [Co(bipy)(maleato) (H2O)3]·H2O (1) where bipy = 2,2′-bipyridine, were accomplished by reaction of an aqueous solution containing sodium maleate and an ethanolic solution of Co(NO3)2·6H2O and bipy. The crystal structure of complex (1) was determined by X-ray crystallography. The complex crystallizes in the monoclinic space group P21/n with a = 9.477(3), b = 7.660(2), c =23.526 (3) Å, β = 97.64(2)°, V = 1692.6(6) Å3, and Z = 4. The structure consists of discrete mononuclear cobalt molecules. The cobalt atom is six-coordinate and presents a slightly distorted octahedral geometry, which consists of the two imine N atoms of bipy, a terminal carboxylate O atom from maleato ligand, and a water O atom in the basal plane with Co—N bond distances of 2.116(2) and 2.124(3) Å and Co—O distances of 2.075(2) and 2.088(2) Å, respectively. The relatively shorter Co—O distances are due to the trans effect of the bipy ligand. The octahedral coordination is completed the other two water molecules. The coordinate and the lattice water molecules were identified by TG study.
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  • 39
    ISSN: 1572-8854
    Keywords: Rubidium nitroprusside monohydrate ; crystal structure ; properties
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The crystal structure of rubidium nitroprusside monohydrate, Rb2[Fe(CN)5NO] · H2O, has been determined from X-ray diffraction data and refined using direct and Fourier methods to R = 0.066 and Rw = 0.075, employing 1894 independent reflections with I 〉 3 (I). The substance crystallizes in the monoclinic space group C2/c (C 6 2h), with a = 13.987(2), b = 10.241(1), c = 18.151(1) Å, β = 110.94°, and Z = 8. Anions are located at C 1 sites, one per asymmetric unit, and are slightly distorted octahedra. TGA, DTA, FTIR, and FTIR Raman results were interpreted on the basis of the formula of the compound, its crystal structure, and the behavior of other nitroprussides.
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  • 40
    ISSN: 1572-8854
    Keywords: crystal structure ; methyl propiolate ; sulfenic acid ; vinyl sulfoxide ; leinamycin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract Evidence for the formation of unstable sulfenic acids (RSOH) as reaction intermediates is commonly provided by trapping these compounds with methyl propiolate. The crystal structure of a vinyl sulfoxide derived from the trapping of a sulfenic acid with methyl propiolate is reported here. The title compound C12H12O5S crystallized in the triclinic space group,P1¯ with unit cell parameters: a = 6.1600(4), b = 9.7286(7), c = 11.3698(8) Å, α = 112.024(1), β = 94.662(1), γ = 95.429(1)°, and Z = 2.
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  • 41
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    Journal of chemical crystallography 29 (1999), S. 1137-1139 
    ISSN: 1572-8854
    Keywords: acyclic nucleoside analog ; acyclovir ; crystal structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The compound 9[1-(2-hydroxy ethoxy)-3-hydroxy propyl] guanine crystalizes in the tetragonal system, space group P41212 with a = 11.106 (1), c = 20.558 (2) Å, and Z = 8. The acyclic chain C1′¯O1′¯C4′¯C5′¯O5′ is in the extended configuration and the glycosidic torsion angle (C4¯N9¯C1′¯O1′) is 125.1 (8)°. The molecules are held together by Van der Waal's forces.
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  • 42
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    Journal of chemical crystallography 29 (1999), S. 1205-1210 
    ISSN: 1572-8854
    Keywords: organic sulfate ; crystal structure ; DTA/TG/DSC ; vibrational spectra
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract [1-(2-ammoniumethyl) piperazinium] sulfate denoted PIPS has a monoclinic unit cell. The parameters are: a = 6.6521(3), b = 7.8756(5), c = 19.197(1) Å, β = 94.43(1)° and the space group is P21/n. The preparation, thermal analysis, and IR spectrometric investigation are described. The PIPS structure exhibits a complex three-dimensional network of H-bonds connecting all its components.
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  • 43
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    Journal of chemical crystallography 29 (1999), S. 1265-1269 
    ISSN: 1572-8854
    Keywords: crystal structure ; corticosteroid ; de-oxy corticosterone-21-hemisuccinate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract Synthetic glucocorticoid de-oxy corticosterone-21-hemisuccinate crystallizes in the monoclinic space group C2, with a = 21.896(2), b = 7.596(3) and c = 14.291(3) Å, Z = 4. Ring A is a distorted half chair, ring B and C are in the chair configuration and ring D is in the 14α-half chair configuration. The ring junctions B/C and C/D are both trans. The molecule as a whole is slightly convex towards the β-side, with an angle of 18.4(2)° between the C(10)--C(19) and C(13)--C(18) vectors. In addition to packing and stacking interaction, intermolecular hydrogen bonding plays an important role in structural association. The X-ray structure determination of the title compound was undertaken to study its high binding affinity to serum protein like globulin.
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  • 44
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    Journal of chemical crystallography 29 (1999), S. 1291-1293 
    ISSN: 1572-8854
    Keywords: crystal structure ; pyrazolo[3,4-d]pyrimidine ; fungicidal activity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The title compound 1-phenyl-3-methylthio-4-imino-5-allyl-pyrazolo[3,4-d]pyrimidine, C15H15N5S, has been synthesized and characterized by x-ray diffraction: orthorhombic, space group Pbca, with a = 17.3480(9), b = 8.5022(5), c = 19.8132(11) Å. Z = 8, V = 2922.4(3) Å3. The compound shows a fully delocalized pyrazolo[3,4-d]pyrimidine system with a sp2 hybridization of the N(4) atom.
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  • 45
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    Journal of chemical crystallography 29 (1999), S. 199-201 
    ISSN: 1572-8854
    Keywords: Manganese (II) ; phenanthroline ; polymeric complex ; crystal structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract A new polymeric manganese(II) complex, [Mn(II)(phen)(ClCH2COO)2]n, was obtained from the reaction of Mn(ClCH2COO)2 with phen and its structure was determined by x-ray crystallography. The complex crystallizes in the monoclinic system, space group C2/c with a = 19.706(4), b = 11.381(3), c = 7.482(3) Å, β = 94.01(3)°, V = 1674.0(8) Å3, and Z = 4. The structure consists of an infinite chain. The manganese atom is located on a twofold axis and presents a distorted octahedral coordination sphere, which consists of the two N atoms of a phen ligand (Mn—N = 2.304(2) Å) and four carboxylato ligands. The Mn···Mn distance within the chain is 4.53 Å, and the carboxylato bridges present a syn-anti conformation.
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  • 46
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    Journal of chemical crystallography 29 (1999), S. 1255-1259 
    ISSN: 1572-8854
    Keywords: crown ether ; crystal structure ; lariat ; sodium
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract A dibenzo-14-crown-4 ether with a novel monooxyacetone sidearm is prepared and its structure with sodium perrhenate is determined. The structure crystallizes in P21/c with cell dimensions: a = 8.107(2) Å, b = 28.138(3) Å, c = 10.293(2) Å, and β = 104.173(9)°; giving a volume of 2276.6(7) Å3. This structure is compared to other sodium complexes of dibenzo-14-crown-4 lariat ethers and is found to be the only one with intramolecular bonding between the sidearm and the cation. Possible reasons for this observation are discussed.
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  • 47
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    Journal of chemical crystallography 29 (1999), S. 1271-1275 
    ISSN: 1572-8854
    Keywords: crystal structure ; pregnen ; progestin ; 4-pregnen-21-ol-3,20-dione
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract Synthetic steroid de-oxy corticosterone (4-pregnen-21-ol-3,20-dione) crystallizes in the monoclinic space group P21, with a = 11.706(2); b = 11.171(3), c = 13.966(3) Å, and β = 100.94(2)°, Z = 4. Ring A tends to acquire the conformation of a half-boat, rings B and C are in the chair configuration, and ring D is a 13β, 14α-half-chair. The ring junctions B/C and C/D are both trans, whereas the ring junction A/B is quasi-trans. The molecule as a whole is slightly convex toward the β-side, with an angle of 16.01(0.36)° between the C10--C19 and C13--C18 vectors. Molecular packing and stacking interactions play the major role in structural association. Cohesion of the crystal is due to van der Waals interactions.
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  • 48
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    Journal of chemical crystallography 29 (1999), S. 565-569 
    ISSN: 1572-8854
    Keywords: orotic acid complex ; crystal structure ; copper(II) complex
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The compound [(C5H2N2O4)Cu(H2O)2]n has been synthesized and its structure determined at room temperature. The primary coordination sphere at the Cu ion is square planar with the orotate dianion coordinating at the metal through heterocyclic nitrogen atom and adjacent oxygen of the carboxylate group, the remaining coordination sites are occupied by two water molecules. The orotate dianion is tricoordinated to one copper via N1 and one oxygen of the carboxylato group and to another copper atom via the other oxygen of the carboxylato group. The coordination at copper is extended to five by the other oxygen of the carboxylate group of another orotate molecule. Thus, the molecules are associated to form chains, the carboxylato group acting as a bridge between the metal ions, the orotato-group being tridentate. The title compound crystallizes in the monoclinic space group. P21/n1 with a = 9.515(5), b = 6.925(2), c = 11.861(6) Å, β = 95.285(9)°, D calc = 2.17 g cm−3, and z = 4.
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  • 49
    ISSN: 1572-8854
    Keywords: pseudo-square pyramidal Cu(II) complex ; trans-4-styrylpyridine ; crystal structure ; IR, electronic, and EPR spectra
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract Single crystals of the title Cu(II) complex, [Cu(stpy)4(ONO2)(ONO2)′] [stpy = trans-4-styryl-pyridine] have been prepared and characterized by elemental and thermal analyses, IR, electronic and EPR spectral measurements, and X-ray crystal structure determination. The complex crystallizes in the monoclinic space group P21/c with unit-cell parameters, a = 12.985(2), b = 22.865(8), c = 17.024(10) Å, β = 112.29(3)°, and Z = 4. The structure consists of discrete monomeric units of [Cu(stpy)4(ONO2)(ONO2)′]. The equatorial positions of the Cu(II) polyhedron are occupied by nitrogen atoms of the four stpy ligands and the axial positions by the oxygens of two unidentate nitrate anions. One of these oxygens is at rather longer distance [2.609(3) Å] and may be considered to be semicoordinated. If this semibond is ignored, the coordination geometry lies closer to an idealized square pyramid than to the trigonal bipyramid geometry. IR spectra reveal nitrogen coordination from stpy and asymmetry in the monodentate oxygen binding of the two nitrate ligands. The optical reflectance band at 600 nm suggests pseudo-square-based pyramidal geometry around Cu(II). Well-resolved Cu(II) hyperfine features in the EPR spectra reveal the absence of exchange interactions between adjacent copper centers. Optical and EPR spectra of a methanolic solution of the complex indicate solvent interactions. Thermogravimetric analysis shows the complex to be stable up to 175°C.
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  • 50
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    Journal of chemical crystallography 29 (1999), S. 475-480 
    ISSN: 1572-8854
    Keywords: crystal structure ; ab initio calculations ; conjugation ; phosphabutadienes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The crystal and molecular structure of 1-phenyl-1-dimethylamino-4,4-bis(trimethylsilyl)-2-aza-3λ3-phosphabutadiene-1,3, Me2N(Ph)C=N—P=C(SiMe3)2 (1), has been determined. Crystal data: triclinic, P1¯, a = 8.975(4), b = 10.001(5), c = 12.440(6) Å, α = 79.04(4), β = 77.98(4), γ = 73.07(4)°, V = 1034.7 Å3, Z = 2, and D c = 1.08 g cm−3. The main geometrical parameters of 1 as well as ab initio (HF/6-31+G**) calculations of the model systems show no clear evidence of high efficiency of the π(C=N)—π (P=C) conjugation.
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  • 51
    ISSN: 1572-8854
    Keywords: contrast agents ; crystal structure ; ortho ester
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract 1-(4-Bromobenzyl)-4-methyl-2,6,7-trioxabicyclo[2.2.2]octane, C13H15BrO3, has been synthesized from 4-bromophenylacetic acid chloride via the oxetan ester (3-methyl-3-oxetanyl)methyl-2-(4-bromophenyl)acetate. The crystal structure of the title compound has been determined at low temperature (120 K), by X-ray diffraction methods. This compound crystallizes in the monoclinic space group P21/n (No. 14), Z = 4, with lattice parametersa = 6.019(5), b = 20.990(5), c = 9.915(2) Å, and β = 101.29(1)°.
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  • 52
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    Journal of chemical crystallography 29 (1999), S. 561-564 
    ISSN: 1572-8854
    Keywords: crystal structure ; Raman spectrum ; silver azide ; azide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract Silver nitrate reacts with sodium azide to give white powdery silver azide, which can be crystallized in aqueous ammonia. The compound belongs to orthorhombic space group Ibam with a = 5.600(1), b = 5.980(6), c = 5.998(1) Å, and Z = 4. The layer-type structure is constructed from edge-sharing regular rectangles, each composed of silver atoms at its vertices with an enclosed azide anion in a tilted orientation. The linear and asymmetrical structure of the azide anion in crystalline silver azide has been confirmed by its Raman spectrum.
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  • 53
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    Journal of chemical crystallography 29 (1999), S. 845-848 
    ISSN: 1572-8854
    Keywords: crystal structure ; centrosymmetric ; aminoadamantane derivative ; antiviral ; dispiro compound
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract Adamantan-1-ammonium 1-adamantanecarboxylate, C21H33NO2 (I) is a novel dispiro-type compound. Aminoadamantane derivatives, in which the spiro carbon atoms are part of heterocyclic rings, are of potential interest as biological active substances and antiviral agents. Complex (I) crystallizes in the centrosymmetric space group C2/c (No. 15) with eight molecules in the unit cell with a = 25.227(4), b = 6.527(1), c = 22.489(4) Å, and β = 90.75(1)°. The two spiro units are a 1-adamantylammonium cation and a 1-adamantane carbonyloxy anion. The complex units are stabilized by a network of intermolecular carbonyloxy-to-amine hydrogen bonding and van der Waals cohesive forces. Germane bond lengths are: C—N = 1.479(9) and C—O (mean) = 1.25(2) Å.
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  • 54
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    Journal of chemical crystallography 29 (1999), S. 891-899 
    ISSN: 1572-8854
    Keywords: cyclohexaphosphates ; organometallic compound ; crystal growth ; X-ray diffraction ; crystal structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract Three new cyclohexaphosphates with general formula M0.5((C6H5CH2)2NH2)5P6O18·H2O (M=Co, Cu, Cd) are reported. They crystallize with monoclinic unit-cells and are isotropic. We have determined their structure from the salt M=Co. This later exhibits the following unit-cell parameters: a = 22.739(5), b = 17.682(3), c = 18.342(3) Å, β = 91.22(1)°, Z = 4,P21/n, V = 7373 Å3, and Dx = 1.373 g cm−3. The atomic arrangement can be described as layers containing P6O18 ring anions and CoO6 octahedra spreading in the (101) planes and intercalated by the dibenzylammonium groups and the water molecules. Synthesis and characterization by X-ray diffraction, IR absorption, and TA are described.
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  • 55
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    Journal of chemical crystallography 29 (1999), S. 1107-1110 
    ISSN: 1572-8854
    Keywords: crystal structure ; ytterbium ; lanthanide ; coordination complex
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The preparation and structural characterization of [YbI2(DME)2] are reported. The complex crystallizes in the triclinic space group P 1¯: a = 13.0094 (10), b=14.504(3), c = 14.668 (3) Å, α = 115.281(10) β = 106.74(2), γ = 105.97(2)°. The metal center of the complex exhibits a distorted pentagonal bipyramidal coordination geometry which involves a rare example of a monodentate DME ligand.
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  • 56
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    Journal of chemical crystallography 29 (1999), S. 1127-1132 
    ISSN: 1572-8854
    Keywords: crystal structure ; phenyl-substituted cyclopentenes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The crystal structures of two stereoisomers of tetraphenyl- and pentaphenyl-substituted cyclopentenes 1 and 2 have been determined by X-ray analysis. An envelope conformation 1E has been ascertained for the cis isomer 1a, whereas the cis, cis isomer 2a, which crystallizes in two different space groups, P1¯ and P21/n, displays a twisted 2T1 conformation. The phenyl substituents are all tilted with respect to the cyclopentene ring in both structures. Compound 1a crystallizes in the space group P21/a with a = 18.553(3), b = 6.006(2), c = 19.355(5), β = 102.67(4)°, and V = 2104.2(g) Å3 for Z = 4; compound 2a I crystallizes in P21/n with a = 10.064(2), b = 20.756(5), c = 12.245(3) Å, β = 95.21(2)°, and V = 2547(1) Å3 for Z = 4; compound 2aII crystallizes in P1¯ with a = 10.117(3), b = 11.750(2), c = 12.359(2) Å, α = 111.25(2), β = 94.84(2), γ = 108.78(2)°, and V = 1262.3(6) Å3 for Z = 2.
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  • 57
    ISSN: 1572-8854
    Keywords: copper (II) ; histamine ; self-assembly ; crystal structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract A new monomeric copper (II) complex with histamine (him), [Cu(II)(him)2(No3)2], has been prepared by the reaction of Cu(NO3)2 with histaminium dichloride and its structure was determined by x-ray crystallography. The complex crystallizes in the triclinic system, space group $$P\bar 1$$ with a = 5.7238(4), b = 8.7094(7), c = 9.2481(11) Å, α = 69.693(8), β = 73.242(7), γ = 71.050(7)°, V = 400.84(6) Å3, and Z = 1. The structure consists of discrete [Cu(II)(him)2(NO3)2] molecules in which the metal atom is centrosymmetrically coordinated by two histamine ligands forming an equatorial plane with Cu–N(imidazole ring) being 2.032(2) and Cu–N(NH2 group) being 2.023(2) Å. Two O atoms from nitrate anions coordinate on the elongated axial positions with Cu–O being 2.549(2) Å. In the crystal structure, the molecules are organized by hydrogen bonds forming a two-dimensional network.
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  • 58
    ISSN: 1572-8854
    Keywords: xanthenol ; complex ; crystal structure ; H-bonding
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The title compound 14-hydroxy-14-phenyldibenzo[a,j]xanthene 1 formed a (1:1) complex with diethyl ether. 1,4-Dioxane was also enclathrated, but with a variable stoichiometric ratio. Single crystal X-ray crystallography was used to elucidate the crystal structure of the 1·diethyl ether complex. Crystals are orthorhombic with space group P212121, a = 8.532(3), b = 15.040(4), c = 18.491(5) Å, V = 2373(1) Å3, d c = 1.256 g/cm3, and Z = 4. Host and guest molecules were found to associate via hydrogen bonds, with the guest molecules residing in undulating channels lined by host molecules.
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  • 59
    ISSN: 1572-8854
    Keywords: copper(II) ; Schiff base ; polymidazole ; crystal structure ; properties
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The square-planar complex [Cu(MIMH)(CH3CO2)](ClO4) (1) (MIMH = [(4-methylimidazol-5-yl)methylene]histamine) was prepared and structurally characterized. Complex 1 crystallizes in the monoclinic space group P21/n with a = 10.5331(10), b = 12.6177(10), c = 12.9773(10) Å, β = 107.710(10)°, V = 1643.0(2) Å3, and Z = 4. Single-crystal X-ray analysis reveals that the copper(II) atom in 1 has a distorted square-planar environment defined by three nitrogen atoms from the Schiff base ligand and one oxygen atom from the acetate group. The Cu—N bond lengths range from 1.950(3) to 2.015(3) Å and the Cu—O(1) bond length is 1.952(2) Å. The electronic spectra of 1 in aqueous solutions indicates that 1 forms adducts of square-pyramidal geometry with H2O. Cyclic voltammetry of 1 in DMF solution shows that there is some degradation of 1 upon reduction.
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  • 60
    ISSN: 1572-8854
    Keywords: pyrazolyl derivative ; substituted pentane ; crystal structure ; bidentate ligand
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The title compound crystallizes in the centrosymmetric space group C2/c with a = 14.4005(23), b = 7.0494(12), c = 11.2462(20) Å, β = 101.572(13)° and Z = 4; the molecule lies on a crystallographic C 2 axis. Hydrogen atoms were both located and refined.
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  • 61
    ISSN: 1572-8854
    Keywords: crystal structure ; Frentizole ; immunomodulator ; structure-function relationship
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract Crystals of Frentizole (from ethanol/water) are monoclinic, space group P21/c, with a = 11.187(4), b = 7.392(2), c = 32.727(6) Å, β = 92.77(2)°, Z = 8, D o = 1.47 g/cm3, and D c = 1.472 g/cm3. There are two independent molecules in the crystallographic asymmetric unit with very different conformations. In molecule A the urea group is in the plane of the benzothiazole ring (0.9°) whereas in molecule B the dihedral angle between them is 4.4°. The dihedral angle between the planes of the phenyl group and the benzothiazole ring are ±157° and ±12°, respectively, in the two molecules. The molecules are linked by a pair of N–H···N hydrogen bonds involving the urea nitrogen and two other N–H···N bonds involving the urea nitrogen and the nitrogen of the benzothiazole group.
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  • 62
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    Journal of chemical crystallography 29 (1999), S. 355-358 
    ISSN: 1572-8854
    Keywords: Quinestrol ; sex steroid ; alkyne ; crystal structure ; solvent inclusion ; hydrogen bonding
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The X-ray crystal structure of the synthetic sex steroid quinestrol (3-O-cyclopentyl-17α-ethynylestradiol) as crystallized from ethanolic solution is determined. The asymmetric unit contains two steroid and one ethanol molecules. The conformation of the two steroid molecules differs in the orientation of the cyclopentane ring. The cocrystallized ethanol molecule facilitates formation of cooperative O—H···O hydrogen bonding. The title compound crystallizes in the monoclinic space group P21, with a = 13.950(6), b = 6.5945(8), c = 25.403(8) Å, β = 104.78(4)°, and D calc = 1.136 g cm−1 for Z = 4.
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  • 63
    ISSN: 1572-8862
    Keywords: Cluster core M6E8 ; structural characteristics ; crystal structure ; hexacobalt cluster complex ; phosphine ; sulfide bridging
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract Two new members of the hexanuclear series [Co6S8(PR3)6] n+, complexes [Co6S8(PMe2Ph)6](ClO4) (1) and [Co6S8P(OMe)3 6] (2), have been synthesizes and characterized by X-ray diffraction analyses. Their formation process was postulated to go through trinuclear μ3--S bridged moieties. The structural characteristics of the M6E8P6 skeleton of a whole series of [M6E8(PR3)6] n+ (M=Co, Cr, Fe, Mo; E=S, Se, Te) complexes are presented in terms of atomic distances and core volumes.
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  • 64
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    Journal of neural transmission 106 (1999), S. 1-21 
    ISSN: 1435-1463
    Keywords: Keywords: Paraquat ; Parkinson's disease ; transcription factor ; AP-1 ; apoptosis ; cycloheximide ; genistein ; SOD ; catalase ; oxidative stress.
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary. Drugs and certain environmental toxins may be responsible for the pathogenesis of Parkinson's disease. We have used paraquat as a model toxin for this study since paraquat has been shown to make its way to the nerve terminals and cause cell death of dopamine neurons by oxidative injury. We have shown by the electrophoretic mobility shift assay that paraquat, together with low concentrations of chelated iron (Fe++/DETAPAC), induced the activation of transcription factor AP-1 binding activity to DNA. Under similar conditions we also found by both a DNA laddering assay procedure and by terminal deoxynucleotidyl transferase assay (TUNEL assay) that paraquat also induces apoptotic cell death. Interestingly, both apoptotic cell death and AP-1/DNA binding activity induced by paraquat were blocked by cyclohexamide and genistein, indicating that both the AP-1/DNA binding activation and apoptosis induced by paraquat are closely related. Moreover, cells were also protected from paraquat toxicity in the presence of antioxidant defense enzymes SOD and catalase. The results support the hypothesis that oxidative stress may be contributing to the apoptotic cell death of dopaminergic neurons, leading to the manifestation of Parkinson's disease. Since paraquat was an important herbicide in the mid 20th Century, our results have the important implication that exposure to environmental toxins such as paraquat may induce Parkinson's disease.
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  • 65
    ISSN: 1572-8773
    Keywords: cadmium ; apoptosis ; RT-PCR ; p53 gene expression ; testes ; rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract Reverse transcription (RT) PCR technique was used to investigate the mechanism of apoptosis induced by Cd and the change of its related genes in testes and prostate of rats. Adult male rats were given a single (s.c.) injection of CdC l2 0, 2.5, 5.0, 10 μmol/kg. 48 h and 72 h after administration of Cd, animals were sacrificed. The results indicated that Cd can induce apoptosis in testes via p53-independent pathway. No apoptosis occurred in prostate in any of the Cd-exposed groups. There was a clearly negative relationship in testes between p53 gene expression and Cd exposure and this dose-response relationship was observed both at 48 h and 72 h. There was a very small increase of this gene expression in the dorsolateral lobe of the prostate in Cd exposed groups. The other apoptosis related gene, bcl-x, was not detectable in either control or Cd-exposed group in testes and dorsal prostate. Although the MT-I gene was expressed in testes or dorsal prostate both in control and exposed groups, no overexpression of MT-I gene was found after administration of Cd . The expression of MT-I in the ventral prostate was not detected in the control group, but a weak expression was found after Cd exposure. Since p53 is a tumo r suppressor gene which can inhibit tumorigenesis, the consequence of a Cd-induced decrease of p53 in testes may have a relation to the known risk of Cd tumorigenesis in this tissue.
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  • 66
    ISSN: 1569-8041
    Keywords: AML ; apoptosis ; etoposide ; γ-GCS ; glutathione ; oxidative stress
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Background: Etoposide mediates its cytotoxicity by inducing apoptosis. Thus, mechanisms which regulate apoptosis should also affect drug resistance. Oxidants and antioxidants have been shown to participate in the regulation of apoptosis. We were interested in studying whether responsiveness of acute myeloblastic leukemia (AML) cells to etoposide is mediated by oxidative stress and glutathione levels. Patients and methods: Two subclones of the OCI/AML-2 cell line which are etoposide-sensitive (ES), and etoposide-resistant (ER), were established by the authors at the University of Oulu, and used as models. Assays for apoptosis included externalization of phosphatidylserine (as evidenced by annexin V binding), and caspase activation as indicated by cleavage of poly(ADP-ribose)polymerase (Western blotting). Peroxide formation was analyzed by flow cytometry. Glutathione and gamma-glutamylcysteine synthetase (γ-GCS) levels were determined spectrophotometrically and by Western blotting, respectively. Results: Etoposide-induced apoptosis was evident 12 hours after treatment in the ES subclone, but was apparent in the ER subclone only after 24 hours. The basal glutathione and γ-GCS levels were higher in the ER than the ES subclone. Etoposide increased peroxide formation in both subclones after 12-hour exposure. Significant depletion of glutathione was observed in the ES subclone during etoposide exposure, while glutathione levels were maintained in the ER subclone. In neither of the subclones was induction of γ-GCS observed during 24-hour exposure to etoposide. Furthermore, the catalytic subunit of γ-GCS was cleaved during apoptosis, concurrent with depletion of intracellular glutathione. When glutathione was depleted by treatment with buthionine sulfoximine, a direct inhibitor of γ-GCS, the sensitivity to etoposide was increased, particularly in the ER subclone. Conclusions: The results underline the significance of glutathione biosynthesis in the responsiveness of AML cells to etoposide. The molecular mechanisms mediating glutathione depletion during etoposide exposure might include the cleavage of the catalytic subunit of γ-GCS.
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  • 67
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    Annals of oncology 10 (1999), S. 495-503 
    ISSN: 1569-8041
    Keywords: antisense ; apoptosis ; bcl-2 ; lymphoma ; leukaemia ; phase I
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
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  • 68
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    Annals of oncology 10 (1999), S. 1011-1021 
    ISSN: 1569-8041
    Keywords: apoptosis ; chemosensitivity ; cytotoxicity ; p53
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Background: Although hematologic malignancies and some solid tumors such as germ cell tumors and pediatric malignancies can be cured by cytotoxic treatment, the most prevalent solid tumors are relatively resistant to these interventions. Apoptosis is involved in the cell kill of anticancer drugs and p53 is believed to be of principal importance in this process. However p53 also plays a role in cell cycle arrest and DNA repair, cellular processes that can decrease the sensitivity to chemotherapy. Therefore, p53 may play a dual role after exposure to cytotoxic treatment, activating either mechanisms that lead to apoptosis or launching processes directing to DNA repair and survival of the cell. Design: In this article, we review in details the p53functions involved in the mediation of chemosensitivity. The preclinical and clinical data published in the recent years about the relation between p53 and chemosensitivity are discussed and the potential pitfalls associated to most of these studies, and that may account for the contradictory results produced so far are also mentioned.
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  • 69
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    Annals of oncology 10 (1999), S. 31-38 
    ISSN: 1569-8041
    Keywords: apoptosis ; lanreotide treatment ; neuroendocrine gastrointestinal tumors ; octreotide ; somatostatin analogs
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Neuroendocrine gastrointestinal tumors express somatostatin receptors (ssts) in 80%–90% of cases and somatostatin analogs have become increasingly important in the management of these patients. Most of the presently available somatostatin analogs (octreotide, RC-160, and lanreotide) bind to the sst2 and sst5, and in higher doses to sst3 of the ssts 1–5 described. Clinical improvement during somatostatin analog therapy is mainly mediated via a direct inhibitory effect on hormone production from the tumors, seen in 30%–70% of the patients. Also indirect non-tumor mediated effects on peripheral target organs contribute to the subjective improvement, achieved in 30%–70% of patients. Recently, significant improvement of quality of life has been demonstrated with long-acting depot formulations. There is little or no effect on tumor growth during octreotide therapy; tumor shrinkage has been reported in 10%–20% of patients, but stabilization of tumor growth can be achieved in about half of the patients with a duration of 8–16 months. Recently, induction of apoptosis has been described with high doses of lanreotide (12 mg/d). Eventually, however, all patients escape from somatostatin analog therapy with regard both to hormonal production and tumor growth, and the mechanism behind the tachyphylaxis is not yet known. Studies of optimal dosage and modes of administration, development of new slow release formulations, the potential value of high-dose somatostatin analog therapy and novel somatostatin receptor subtype specific analogs are important directions for the use of somatostatin analogs in the future. In addition, assessment of somatostatin receptor status for each patient and studies of tumor biology, e.g., inhibition of exocytosis, antiproliferative effects and induction of apoptosis during treatment will help to optimize treatment and provide new insights into mechanisms of action of somatostatin analogs.
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  • 70
    ISSN: 1436-2813
    Keywords: Key Words: nitric oxide ; DNA damage ; apoptosis ; tumor necrosis factor-α ; mitochondrial respiration
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: S -nitroso-N-acetylpenicillamine protected cul-tured L929 cells from apoptosis induced by tumor necrosis factor-α (TNF-α) plus actinomycin D, as determined by the detection of DNA fragmentation and morphological changes. NO also prevented an enhancement of the production of reactive oxygen intermediates by TNF-α plus actinomycin D, as assessed by the oxidation of dihydrorhodamine 123 and hydroethidine. Because the inhibition of mitochondrial respiration by rotenone or antimycin A suppressed the increased oxidation of both dihydrorhodamine 123 and hydroethidine, it was suggested that TNF-α accelerated the leakage of reactive oxygen intermediates from the mitochondrial electron transport system. Polarography showed that NO reversibly inhibited mitochondrial respiration at either complexes I–III, II–III, or IV, thus suggesting the inhibition of cytochrome oxidase. Taken together, these findings indicate that the decreased mitochondrial formation of reactive oxygen intermediates in the presence of NO might have a protective effect against TNF-α plus actinomycin D-induced apoptosis.
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  • 71
    ISSN: 1436-2813
    Keywords: angiogenesis ; p53 ; apoptosis ; lung adenocarcinoma ; hematogenous metastasis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The purpose of this study was to clarify which factors are important as predictors not only of patient survival but also of hematogenic metastasis in 15 patients with stage I lung adenocarcinoma who underwent curative operation. The relationship between tumor angiogenesis, apoptosis, and p53 oncogene was also studied. A total of 15 patients were divided into two groups: surviving group (n=7) and nonsurviving (metastasis) group (n=8). We studied the medical charts, operative records, pathologic reports, and tumor specimens taken at surgical resection. We measured the apoptotic index using the ApopTag kit and the intratumoral microvessel count using an anti-CD34 monoclonal antibody. In addition, immunohistochemical staining for the expression of p53 was conducted simultaneously. The clinicopathological characteristics, including age, sex, tumor size (pT), and histological differentiation, were not significantly different between the surviving and the nonsurviving group. The microvessel count was significantly higher in nonsurviving group than in the surviving group. The apoptotic index and the expression of p53 was not significantly different between the two groups. An inverse correlation between the apoptotic index and microvessel count, and a positive correlation between the expression of p53 and microvessel count, were observed. Angiogenesis may be an important prognostic factor in patients with stage I lung adenocarcinoma.
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  • 72
    ISSN: 1436-2813
    Keywords: Key Words: angiogenesis ; p53 ; apoptosis ; lung adenocarcinoma ; hematogenous metastasis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: n = 7) and nonsurviving (metastasis) group (n = 8). We studied the medical charts, operative records, pathologic reports, and tumor specimens taken at surgical resection. We measured the apoptotic index using the ApopTag kit and the intratumoral microvessel count using an anti-CD34 monoclonal antibody. In addition, immunohistochemical staining for the expression of p53 was conducted simultaneously. The clinicopathological characteristics, including age, sex, tumor size (pT), and histological differentiation, were not significantly different between the surviving and the nonsurviving group. The microvessel count was significantly higher in nonsurviving group than in the surviving group. The apoptotic index and the expression of p53 was not significantly different between the two groups. An inverse correlation between the apoptotic index and microvessel count, and a positive correlation between the expression of p53 and microvessel count, were observed. Angiogenesis may be an important prognostic factor in patients with stage I lung adenocarcinoma.
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  • 73
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    Diabetologia 42 (1999), S. 711-718 
    ISSN: 1432-0428
    Keywords: Keywords Malnutrition ; ageing ; beta-cell mass ; apoptosis ; glucose tolerance.
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Aims/hypothesis. In a recently developed rat model, maternal food restriction from day 15 of pregnancy until weaning induced low birth weight and a 70 % reduction of beta-cell mass in the offspring at day 21 after birth. Subsequent renutrition from weaning was insufficient to fully restore beta-cell mass in young adult rats. The aim of this study is to investigate the long-term consequences of early malnutrition on beta-cell mass and function. Methods. Oral glucose tolerance tests were done in 3- and 12-month-old animals and beta-cell mass and apoptosis were determined by morphometrical measurements on pancreatic sections. The specific impact of postnatal malnutrition was studied by comparing control animals (C group) with animals malnourished during their fetal life only (R/C group), and animals malnourished during fetal life and until weaning (R group). Results. In 3-month-old R/C animals beta-cell mass reached 8.0 ± 1.5 mg with no further increase until 12 months (8.1 ± 1.5 mg), compared with 9.3 ± 1.9 mg in control rats. Twelve-month-old R/C animals showed normal plasma insulin responses and borderline glucose tolerance. In R animals, apoptosis reached 1.9 ± 0.4 % of the beta cells at 3 months, compared with 0.7 ± 0.5 % in control rats, and beta-cell mass did not increase between 3 and 12 months (4.7 ± 0.8 mg at 12 months). In aged control and R animals, apoptosis affected 8 % of the beta cells. At 12 months only, R animals showed profound insulinopenia and marked glucose intolerance. Conclusion/interpretation. In conclusion, perinatal malnutrition profoundly impairs the programming of beta-cell development. In animals with decreased beta-cell mass the additional demand placed by ageing on the beta cells entails glucose intolerance since beta-cell mass does not expand and apoptosis is increased. [Diabetologia (1999) 42: 711–718]
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  • 74
    ISSN: 1432-0428
    Keywords: Keywords Type I diabetes ; interferon-γ ; transgenic mice ; apoptosis ; insulin secretion ; tumour necrosis factor.
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Aims/hypothesis. To examine whether interferon-γ destroys islet beta cells directly or indirectly through lymphocyte activation, or whether direct action of interferon-γ on beta cells by itself induces diabetes without insulitis. Methods. To avoid possible nonspecific breakdown of beta cells by transgenic overexpression of interferon-γ by the insulin promoter, we generated transgenic mice expressing interferon-γ under the control of rat glucagon promoter (RGP-IFN-γ-Tg mice). Results. The absence of insulitis in RGP-IFN-γ-Tg mice enabled us to investigate the direct effects of paracrine interferon-γ. In RGP-IFN-γ-Tg mice, serum concentrations of interferon-γ and tumour necrosis factor-α (TNF-α) were 50 and 6 times higher than those in their littermates, respectively, and glucose-responsive insulin secretion decreased to one-half the level of that in the littermates. Transgenic interferon-γ induced remodelling of beta cells where apoptosis of many beta cells was compensated by their vigorous regeneration and diabetes did not occur in most of the RGP-IFN-γ-Tg mice. Conclusion/interpretation. Interferon-γ alone is insufficient for the complete destruction of beta cells in vivo, and factors other than interferon-γ including activated lymphocytes or other cytokines, are necessary in addition to interferon-γ for the development of Type I (insulin-dependent) diabetes mellitus. [Diabetologia (1999) 42: 566–573]
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  • 75
    ISSN: 1432-0428
    Keywords: Keywords Nicotinamide ; cytokine ; islet ; insulin ; apoptosis ; diabetes.
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Nicotinamide intervention trials are presently undertaken to prevent Type I (insulin-dependent) diabetes in high risk subjects. They are based on studies in rodents reporting nicotinamide protection against beta-cell injury in vitro and in vivo. This study examines whether nicotinamide can protect human beta cells in vitro. At concentrations (2 and 5 mmol/l) to protect rat beta cells against necrosis by streptozotocin or hydrogen peroxide, nicotinamide prevents hydrogen peroxide-induced necrosis of human beta cells. As with rat beta cells, nicotinamide fails to protect human beta cells against apoptosis induced by a combination of the cytokines interleukin-1β , interferon-γ and tumour necrosis factor-α. In rat beta cells, nicotinamide (2 to 20 mmol/l) was also found to induce apoptosis, in particular during the days following its protection against necrosis; this cytotoxic effect was not observed with human beta cells. These data demonstrate that nicotinamide can protect human beta cells against radical-induced necrosis, but not against cytokine-induced apoptosis. This effect is not associated with a delayed apoptosis as in rat beta cells. [Diabetologia (1999) 42: 55–59]
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  • 76
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    Annals of oncology 10 (1999), S. 139-150 
    ISSN: 1569-8041
    Keywords: apoptosis ; chemotherapy ; clinical trials ; gene therapy ; p53
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Nearly twenty years after the initial discovery of p53, we are now in an ideal position to exploit our vast knowledge of p53 biology in the creation of novel cancer therapies. Disruption of p53 function through mutation, or other means, occurs very frequently in human cancer. Loss of p53 function has been linked with unfavourable prognosis in a large number of tumour types, as indicated by more aggressive tumours, early metastasis and decreased survival rates. Many different avenues of research have converged upon p53 to highlight this protein as being one of the foremost cellular responders to stress, in particular to DNA damage. Huge advances have been made in understanding the complex role p53 plays in the regulation of apoptosis and cell cycle arrest. This review is not meant to be a comprehensive description of p53 biology, but rather serves to highlight current progress in the development of p53- oriented cancer therapies. These may be categorised into three basic strategies: gene replacement therapy using wild-type p53, restoration of p53 function by other means and, finally, targeting of the p53 dysfunction itself. Rapid progress is expected to be made regarding the identification of conventional pharmaceutical agents which either work in a p53-independent manner or act preferentially in p53 defective cells. Gene replacement therapy with wild-type p53 also holds considerable potential for obtaining clinically relevant results quickly. The other forms of cancer therapies based around p53 are much further behind in the developmental process, but may prove to more efficacious in the long run, especially in terms of specificity. As with many other fields, the innovation of successful p53-oriented cancer therapies is only limited by our understanding of p53 biology and the creative use of such knowledge.
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  • 77
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    Annals of oncology 10 (1999), S. 122-126 
    ISSN: 1569-8041
    Keywords: apoptosis ; biliary carcinogenesis ; cholangiocarcinoma ; genotoxicity ; risk factors ; therapeutic strategies
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Carcinomas of the biliary tract are rare cancers developing from the epithelial or blast-like cells lining the bile ducts. A variety of known predisposing factors and recent experimental models of biliary carcinogenesis (e.g., infection with the liver fluke Opisthorchis viverrini, models of chemically induced carcinogenesis and experimental models of pancreaticobiliary maljunction) have elucidated different stages of this complex system of biliary tumorigenesis. Chronic inflammatory processes, generation of active oxygen radicals, altered cellular detoxification mechanisms, activation of oncogenes, functional loss of tumor-suppressor genes and dysregulation of cell proliferation and cell apoptotic mechanisms have been identified as important contributors in the development of cholangiocarcinomas. In this review, the known mechanisms involved in the carcinogenesis of biliary epithelium are addressed. We will divide the topic into four stages: 1) Predisposition and risk factors of biliary cancer, 2) Genotoxic events and alterations leading to specific DNA damage and mutation patterns. 3) Dysregulation of DNA repair mechanisms and apoptosis, permitting survival of mutated cells and 4) Morphological evolution from premalignant biliary lesions to cholangiocarcinoma. Finally, established and hypothetical future therapeutic strategies directed towards specific pathogenetic events during biliary carcinogenesis will be addressed.
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  • 78
    ISSN: 1569-8041
    Keywords: acute myelogenous leukemia ; apoptosis ; ara-CTP ; cytosine arabinoside ; HL-60 ; retinoic acid
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Background: Accumulation of the cytosine arabinoside (ara-C) metabolite ara-C-triphosphate (ara-CTP) in leukemic blast cells is considered to be the main determinant of ara-C cytotoxicity in vitro and in vivo. Retinoids such as all-trans-retinoic acid (ATRA) have been shown to increase the sensitivity of acute myelogenous leukemic (AML) blast cells to ara-C. To investigate the mechanism of this sensitisation, the hypothesis was tested that ATRA augments cellular ara-CTP levels in human-derived myelogenous leukemia HL-60 cells. Materials and methods: The effect of ATRA and 13-cis-retinoic acid on ara-CTP accumulation and ara-C-induced apoptosis was studied. Ara-CTP levels were measured by high-performance liquid chromatography (HPLC), cytotoxicity by the tetrazolium (MTT) assay, and apoptosis by occurrence of DNA fragmentation (gel electrophoresis), cell shrinkage and DNA loss (flow cytometry). Results: Pretreatment of HL-60 cells with ATRA (0.01–1 µM) caused a significant decrease in intracellular ara-CTP levels; e.g., incubation for 72 hours with ATRA 1 µM prior to one hour ara-C 10 µM reduced ara-CTP levels to 41% ± 4% of control. Similar results were obtained after preincubation with 13-cis-retinoic acid. In spite of decreased ara-CTP levels, the cytotoxicity of the combination was supraadditive and ATRA augmented ara-C-induced apoptosis. Conclusions: At therapeutically relevant concentrations ATRA increased ara-C cytotoxicity and ara-C induced apoptosis but this augmentation is not the corollary of elevated ara-CTP levels. The feasibility of ara-C treatment optimisation via strategies other than those involving elevation of ara-CTP levels should be investigated further.
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  • 79
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    Journal of thermal analysis and calorimetry 55 (1999), S. 797-806 
    ISSN: 1572-8943
    Keywords: cadmium coordination ; crystal structure ; enthalpy of solution ; lattice energy ; lattice enthalpy ; NTO salt ; preparation ; standard enthalpy of dehydration ; standard enthalpy of formation ; thermal decomposition mechanism
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract [Cd(NTO)4Cd(H2O)6]·4H2O was prepared by mixing the aqueous solution of 3-nitro-1,2,4-triazol-5-one and cadmium carbonate in excess. The single crystal structure was determined by a four-circle X-ray diffractometer. The crystal is monoclinic, space group C2/c with crystal parameters of a=2.1229(3) nm, b=0.6261(8) nm, c=2.1165(3) nm, β=90.602(7)°, V=2.977(6) nm3, Z=4, Dc=2.055 g·cm−3, μ=15.45 cm−1, F(000)=1824, λ(MoKα)=0.071073 nm. The final R is 0.0282. Based on the results of thermal analysis, the thermal decomposition mechanism of [Cd(NTO)4Cd(H2O)6]·4H2O was derived. From measurements of the enthalpy of solution of [Cd(NTO)4Cd(H2O)6]·4H2O in water at 298.15 K, the standard enthalpy of formation, lattice energy, lattice enthalpy and standard enthalpy of dehydration have been determined as -(1747.8±4.8), -2394, -2414 and 313.6 kJ mol−1 respectively.
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  • 80
    ISSN: 1572-9001
    Keywords: Tetrahydrotetrol ; polycyclic aromatic hydrocarbon derivative ; carcinogen ; crystal structure ; structure-activity relationship
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The molecular structures of two racemic trans-tetrahydrotetrols formed by hydrolysis of the (±)anti-7,8-dihydroxy-9,10-epoxy-7,8,9,10-tetrahydro derivatives of the strong carcinogen benzo[a]pyrene and the weak carcinogen chrysene have been determined by X-ray crystallographic methods.3 Focusing on the (+)isomers, the stereochemical features of the two tetrols are discussed in detail to determine structural differences, which can be related to the different biological activity of their parent hydrocarbons, since they provide a model for the hydrocarbon moiety in the major PAH-DNA adduct. As a result of this study, a tentative correlation can be stated between biological activity of quasi-planar bay-region PAHs and the presence of structural features, which can decrease the steric hindrance of the aromatic skeleton and the other hydroxy groups on the pseudo-axial O4, which mimics the position of the covalent bond to DNA. The significant structural features seem to be an out-of-plane distortion with a negative torsion angle at the bay region and a half chair conformation of the saturated ring distorted toward the envelope with C8 at the tip as in BPT, in addition to the axial and pseudo-axial conformations of the hydroxy groups at C9 and C10 due to the near bay region. They may be considered generated by trans-opening of the oxirane ring in an anti-diol epoxide biologically active because it is highly strained. The strains, derived from the activation of bay-region PAHs with a negative torsion angle, seem greater in an anti-diol epoxide relative to the syn-isomer. Thus, when the strains are released, the derived trans-tetrol occurs with structural features, which seem to better fit the target. As a consequence, the presence of a methyl group at a bay region should increase the biological activity of a PAH, imposing greater strains to the structure of the anti-diol epoxide.
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  • 81
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    Journal of thermal analysis and calorimetry 57 (1999), S. 807-821 
    ISSN: 1572-8943
    Keywords: bibliography ; critical temperature ; crystal structure ; CuRh2S4 ; CuRh2Se4 ; survey of chalcogenide superconductors
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The thread that runs through all research in the field of superconductivity is new physics through discovery of new materials. The knowledge of superconducting materials has become voluminous and complex. The comprehensive review of the superconducting materials is of particular importance. The main purpose of this report is to present the results of classification for chalcogenide superconductors. Superconducting critical temperature Tc, crystal-structure type and the references proper to these compounds are summarized. Brief survey of the superconductivity in chalcogen elements is also given. Furthermore, as representative sulfide and selenide, superconducting characteristics of CuRh2S4 and CuRh2Se4 will be shown.
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  • 82
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    Journal of thermal analysis and calorimetry 58 (1999), S. 257-267 
    ISSN: 1572-8943
    Keywords: crystal structure ; lattice energy ; lattice enthalpy ; lead salt of NTO ; preparation ; quantum chemical calculation ; thermal decomposition mechanism
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The single crystal of lead salt of 3-nitro-1,2,4-triazol-5-one (NTO), [Pb(NTO)2(H2O)] was prepared and its structure was determined by a four-circle X-ray diffractometer. The crystal is monoclinic, its space group is P21/n with crystal parameters of a=0.7262(1) nm, b=1.2129(2) nm, c=1.2268(3) nm, β=90.38(2)°, V=1.0806(2) nm3, Z=4, Dc=2.97 g cm−3, µ=157.83cm−1, F(000)=888. The final R is 0.027. By using SCF-PM3-MO method we obtained optimized geometry for [Pb(NTO)2⋅H2O] and particularly positions for hydrogen atoms. Through the analyses of MO levels and bond orders it is found that Pb atom bond to ligands mainly with its 6pz and 6py AOs. The thermal decomposition experiments are elucidated when [Pb(NTO)2⋅H2O] is heated, ligand water is dissociated first and NO2 group has priority of leaving. Based on the thermal analysis, the thermal decomposition mechanism of [Pb(NTO)2⋅H2O] has been derived. The lattice enthalpy and its lattice energy were also estimated.
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  • 83
    ISSN: 1572-9001
    Keywords: Nickel complex ; dithiocarbimate ; sulfonamide ; crystal structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Potassium N-4-methylphenylsulfonyldithiocarbimate, K2(4-CH3C6H4SO2N=CS2), reacted with nickel(II) chloride hexahydrate and tetrabutylammonium bromide to form the bis(N-4-methylphenylsulfonyldithiocarbimate)nickelate(II) tetrabutylammonium salt (Bu4N)2[Ni(4-CH3C6H4S2C=NSO2)2]. The elemental analyses, IR and UV-Vis data obtained were consistent with the formation of a $${\text{nickel}}{\kern 1pt} - {\kern 1pt} {\text{sulfur}}$$ diamagnetic planar complex. The 1H NMR and the 13C NMR spectra showed the expected signals for the dithiocarbimate moiety and the tetrabutylammonium cation. The single-crystal structure analysis showed that this substance crystallizes in the triclinic $${P\bar 1}$$ space group with a = 10.474(3) Å, b = 10.767(3) Å, c = 13.657(3) Å and α = 81.54(2)°, β = 80.44(2)°, γ = 67.63(2)°, V = 1398.5(8) Å3, and Z = 2. The nickel atom is coordinated to four sulfur atoms.
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  • 84
    ISSN: 1572-9001
    Keywords: Nicotine-derived nitrosaminoketone ; nitrosamine ; crystal structure ; molecular dimensions
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The three-dimensional structure of the carcinogenic nicotine-derived nitrosaminoketone, 4-(methyl-nitrosamino)-l-(3-pyridyl)-l-butanone, has been determined by X-ray crystallographic techniques. The molecule is essentially planar except for the methylnitrosamine group which is oriented at a dihedral angle of 68.7° to the pyridine ring. Molecules pack by way of —H⋯O interactions that involve the —NNO group.
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  • 85
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    Molecular and cellular biochemistry 196 (1999), S. 13-21 
    ISSN: 1573-4919
    Keywords: apoptosis ; DNA fragmentation ; GSHPx-1 knockout mice ; GSHPx-1 transgenic mice ; ischemia/repurfusion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract Apoptosis, a genetically controlled programmed cell death, has been found to play a role in ischemic reperfusion injury in several animal species including rats and rabbits. To examine whether this is also true for other animals, an isolated perfused mouse heart was subjected to 30 min of ischemia followed by 2 h of reperfusion. Experiments were terminated before ischemia (baseline), after ischemia, and at 30, 60, 90 and 120 min of reperfusion. At the end of each experiment, hearts were processed for the evaluation of apoptosis and DNA laddering. The in situ end labeling (ISEL) technique was used to detect apoptotic cardiomyocyte nuclei while DNA laddering was evaluated by subjecting the DNA obtained from the cardiomyocytes to 1.8% agarose gel electrophoresis followed by photographing under UV illumination. The results of our study revealed that apoptotic cells appear only after 60 min of reperfusion as demonstrated by the intense fluorescence of the immunostained genomic DNA when observed under fluorescence microscopy. None of the ischemic hearts showed any evidence of apoptosis. These results were corroborated with the findings of DNA fragmentation showing increased ladders of DNA bands in the same reperfused hearts representing integer multiples of the internucleosomal DNA length (about 180 bp). Since our previous studies showed a role of glutathione peroxidase (GSHPx) in apoptotic cell death, we performed identical experiments using isolated hearts from GSHPx-l knockout mice and transgenic mice overexpressing GSHPx-l. GSHPx-l knockout mice showed evidence of apoptotic cell death even after 30 min of reperfusion. Significant number of apoptotic cells were found in the cardiomyocytes as compared to non-transgenic control animals. To the contrary, very few apoptotic cells were found in the hearts of the transgenic mice overexpressing GSHPx-l. Hearts of GSHPx-l knockout mice were more susceptible to ischemia/reperfusion injury while transgenic mice overexpressing GSHPx- 1 were less susceptible to ischemia reperfusion injury compared to non-transgenic control animals. The results of this study clearly demonstrate a role of GSHPx in ischemia/reperfusion-induced apoptosis in mouse heart.
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  • 86
    ISSN: 1573-4919
    Keywords: MKP-1 ; Fas ligand ; Fas ; apoptosis ; prostate cancer
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract Recent studies have suggested that MAP kinase phosphatase 1 (MKP-1) is overexpressed in prostate cancer. To evaluate the role of MKP-1 in regulating cell death and tumor growth in prostate cancer, MKP-1 was conditionally overexpressed in the human prostate cancer cell line DU145. Overexpression of MKP-1 in DU145 cells blocked activation of stress-activated protein kinase (SAPK/JNK). MKP-1 overexpression in DU-145 cells was also found to inhibit Fas ligand (FasL)-induced apoptosis, as well as block the activation of caspases by Fas engagement. In addition, MKP-1 blocked the activation of apoptosis by transfected MEKK-1 and ASK-1, presumably through its inhibition of the SAPK/JNK family of enzymes. MKP-1 blocked the ability of FasL to induce loss of mitochondrial transmembrane potential (Δγm), suggesting that MKP-1 acts upstream of mitochondrial pro-apoptotic events induced by FasL and that the SAPK/JNK pathway may form the signaling link between Fas receptor and mitochondrial dysfunction. Thus, MKP-1 overexpression in prostate cancer may play a role in promoting prostate carcinogenesis by inhibiting FasL-induced cell death.
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  • 87
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    Molecular and cellular biochemistry 199 (1999), S. 125-137 
    ISSN: 1573-4919
    Keywords: apoptosis ; ADP-ribosylation ; caspases ; PARP ; PARG
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract Poly(ADP-ribosylation) is a post-translational modification playing a relevant role in DNA damage recovery, DNA replication and viral integration. Several reports also suggest a modulation of this process during cell death by apoptosis. The aim of this review is to discuss the possible involvement of poly(ADP-ribosylation) during apoptosis, by dealing with general considerations on apoptosis, and further examining the correlation between NAD consumption and cell death, the regulation of poly(ADP-ribose) metabolism in apoptotic cells, the effect of poly(ADP-ribose) polymerase inhibition on cell death occurrence and the use of enzyme cleavage as a marker of apoptosis. Finally, the future prospects of the research in this area will be addressed.
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  • 88
    ISSN: 1573-4919
    Keywords: DNA binding protein ; NAD metabolism ; cellular response to DNA damage ; γ-rays ; alkylating agents ; genomic instability ; apoptosis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract A dual approach to the study of poly (ADP-ribose)polymerase (PARP) in terms of its structure and function has been developed in our laboratory. Random mutagenesis of the DNA binding domain and catalytic domain of the human PARP, has allowed us to identify residues that are crucial for its enzymatic activity. In parallel PARP knock-out mice were generated by inactivation of both alleles by gene targeting. We showed that: (i) they are exquisitely sensitive to γ-irradiation, (ii) they died rapidly from acute radiation toxicity to the small intestine, (iii) they displayed a high genomic instability to γ-irradiation and MNU injection and, (iv) bone marrow cells rapidly underwent apoptosis following MNU treatment, demonstrating that PARP is a survival factor playing an essential and positive role during DNA damage recovery and survival.
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  • 89
    ISSN: 1573-4919
    Keywords: PARP ; poly(ADP-ribosyl)ation ; apoptosis ; DNA replication
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract We have focused on the roles of PARP and poly(ADP-ribosyl)ation early in apoptosis, as well as during the early stages of differentiation-linked DNA replication. In both nuclear processes, a transient burst of PAR synthesis and PARP expression occurs early, prior to internucleosomal DNA cleavage before commitment to apoptosis as well as at the round of DNA replication prior to the onset of terminal differentiation. In intact human osteosarcoma cells undergoing spontaneous apoptosis, both PARP and PAR decreased after this early peak, concomitant with the inactivation and cleavage of PARP by caspase-3 and the onset of substantial DNA and nuclear fragmentation. Whereas 3T3-L1, osteosarcoma cells, and immortalized PARP +/+ fibroblasts exhibited this early burst of PAR synthesis during Fas-mediated apoptosis, neither PARP-depleted 3T3-L1 PARP-antisense cells nor PARP -/- fibroblasts showed this response. Consequently, whereas control cells progressed into apoptosis, as indicated by induction of caspase-3-like PARP-cleavage activity, PARP-antisense cells and PARP -/- fibroblasts did not, indicating a requirement for PARP and poly(ADP-ribosyl)ation of nuclear proteins at an early reversible stage of apoptosis. In parallel experiments, a transient increase in PARP expression and activity were also noted in 3T3-L1 preadipocytes 24 h after induction of differentiation, a stage at which ~95% of the cells were in S-phase, but not in PARP-depleted antisense cells, which were consequently unable to complete the round of DNA replication required for differentiation. PARP, a component of the multiprotein DNA replication complex (MRC) that catalyzes viral DNA replication in vitro, poly(ADP-ribosyl)ates 15 of ~40 MRC proteins, including DNA pol α, DNA topo I, and PCNA. Depletion of endogenous PARP by antisense RNA expression in 3T3-L1 cells results in MRCs devoid of any DNA pol α and DNA pol δ activities. Surprisingly, there was no new expression of PCNA and DNA pol α, as well as the transcription factor E2F-1 in PARP-antisense cells during entry into S-phase, suggesting that PARP may play a role in the expression of these proteins, perhaps by interacting with a site in the promoters for these genes.
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  • 90
    ISSN: 1573-4919
    Keywords: breast cancer cells ; anti-apoptotic genes ; apoptosis ; progesterone
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract Progesterone inhibits the proliferation of normal breast epithelial cells in vivo, as well as breast cancer cells in vitro. But the biologic mechanism of this inhibition remains to be determined. We explored the possibility that an antiproliferative activity of progesterone in breast cancer cell lines is due to its ability to induce apoptosis. Since p53, bcl-2 and survivin genetically control the apoptotic process, we investigated whether or not these genes could be involved in the progesterone-induced apoptosis. We found a maximal 90% inhibition of cell proliferation with T47-D breast cancer cells after exposure to 10 μM progesterone for 72 h. Control progesterone receptor negative MDA-231 cancer cells were unresponsive to 10 μM progesterone. The earliest sign of apoptosis is translocation of phosphatidylserine from the inner to the outer leaflet of the plasma membrane and can be monitored by the calcium-dependent binding of annexin V in conjunction with flow cytometry. After 24 h of exposure to 10 μM progesterone, cytofluorometric analysis of T47-D breast cancer cells indicated 43% were annexin V-positive and had undergone apoptosis and no cells showed signs of cellular necrosis (propidium iodide negative). After 72 h of exposure to 10 μM progesterone, 48% of the cells had undergone apoptosis and 40% were annexin V positive/propidium iodide positive indicating signs of necrosis. Control untreated cancer cells did not undergo apoptosis. Evidence proving apoptosis was also demonstrated by fragmentation of nuclear DNA into multiples of oligonucleosomal fragments. After 24 h of exposure of T47-D cells to either 1 or 10 μM progesterone, we observed a marked down-regulation of protooncogene bcl-2 protein and mRNA levels. mRNA levels of survivin and the metastatic variant CD44 v7-v10 were also downregulated. Progesterone increased p53 mRNA levels. These results demonstrate that progesterone at relative high physiological concentrations, but comparable to those seen in plasma during the third trimester of human pregnancy, exhibited a strong antiproliferative effect on breast cancer cells and induced apoptosis.
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  • 91
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    Molecular and cellular biochemistry 200 (1999), S. 51-57 
    ISSN: 1573-4919
    Keywords: smokeless tobacco ; apoptosis ; nitric oxide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract Smokeless tobacco usage is, a growing public health concern in the United States. Lesions of the oral cavity have been clearly linked to smokeless tobacco use. The objective of this study was to determine the biochemical effects of smokeless tobacco extract (STE) exposure upon hamster cheek pouch cell (HCPC-1) cultures. HCPC-1 cells were exposed to a 5 -fold dose-range of STE (0.5, 1.0 and 2.5%) over a time-course of 24-96 h. Following each exposure we measured various biochemical parameters of cell proliferation and cell death. Cell viability, cell cycle progression and S-phase DNA synthesis were measured as markers of cell proliferation. We measured lactate dehydrogenase leakage as a marker of cell membrane damage and cell death due to necrosis. No significant alterations were observed in cell cycle progression and cell proliferation as a result of exposure to STE. LDH measured colorimetrically indicated no significant effect with the lower doses (0.5, 1.0 and 2.5% STE). Apoptosis measured as the A0 peak and by the TUNEL procedure revealed that STE caused significant rates of apoptosis. Maximal apoptosis was noted between 48-96 h. In order to probe the mechanism further we measured the levels of nitrites as an indicator of nitric oxide (NO) in the media. NO levels were significantly elevated at the doses that caused an induction of apoptosis. The results from this study indicate that STE causes a dose-dependent induction of apoptosis and that this is mediated by nitric oxide.
    Type of Medium: Electronic Resource
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  • 92
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    Molecular and cellular biochemistry 193 (1999), S. 37-42 
    ISSN: 1573-4919
    Keywords: Rho ; GTPase ; toxins ; Clostridium ; signal transduction ; apoptosis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract The Rho family small GTPases are members of the Ras superfamily of small GTPases. Rho proteins were first determined to act as key regulators of many types of actin cytoskeletal-dependent cellular functions. Recent work by several investigators indicates that Rho GTPases are also critical modulators of several important intracellular and nuclear signal transduction pathways. Certain clostridial toxins and exoenzymes covalently modify, and thereby inactivate, specific types of Rho family GTPases. As such, these microbial enzymes have proven invaluable in helping to identify structural and functional attributes of Rho GTPases.
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  • 93
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    Molecular and cellular biochemistry 193 (1999), S. 103-108 
    ISSN: 1573-4919
    Keywords: Poly(ADP-ribose) polymerase ; Drosophila melanogaster ; alternative splicing ; apoptosis ; DNA repair ; development
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract Poly(ADP-ribose) polymerase (PARP) is conserved in eukaryotes. To analyze the function of PARP, we isolated and characterized the gene for PARP in Drosophila melanogaster. The PARP gene consisted of six translatable exons and spanned more than 50 kb. The DNA binding domain is encoded by exons 1-4. Although the consensus cleavage site of CED-3 like protease during apoptosis is conserved from human to Xenopus laevis PARPs, it is neither conserved in the corresponding region of Drosophila nor Sarcophaga peregrina. There are two cDNAs species in Drosophila. One cDNA could encode the full length PARP protein (PARP I), while the other is a truncated cDNA which could encode a partial-length PARP protein (PARP II), which lacks the automodification domain and is possibly produced by alternative splicing. The expression of these two forms of PARP in E. coli demonstrated that while PARP II has the catalytic NAD-binding domain and DNA-binding domain it is enzymatically inactive. On the other hand PARP I is active. A deletion mutant of PARP gene could grow to the end of embryogenesis but did not grow to the adult fly. These results suggest that the PARP gene plays an important function during the development of Drosophila.
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  • 94
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    Molecular and cellular biochemistry 193 (1999), S. 119-125 
    ISSN: 1573-4919
    Keywords: benzamides ; nicotinamides ; apoptosis ; inflammation ; NF-kB ; DNA repair
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract Our laboratory has concentrated on the possible regulation the benzamides and nicotinamides may have on the processes of DNA repair and apoptosis. Recent reports [14-16] have suggested that both apoptosis and inflammation are regulated by the transcription factor NF-kB. We have initiated studies regarding the hypothesis that the benzamides and nicotinamides could inhibit the production of tumor necrosis factor alpha (TNFalpha) and the inflammatory response as well as induce apoptosis via inhibition of NF-kB. Our data have shown that nicotinamide and two N-substituted benzamides, metoclopramide (MCA) and 3-chloroprocainamide (3-CPA), gave dose dependent inhibition of lipopolysacharide induced TNFalpha in the mouse within the dose range of 10-500 mg/kg. Moreover, lung edema was prevented in the rat by 3 ï 50 mg/kg doses of 3-CPA or MCA, and 100-200 μM doses of MCA could also inhibit NF-kB in Hela cells. Taken together these data strongly support the notion that benzamides and nicotinamides have potent anti-inflammatory and antitumor properties, because their primary mechanism of action is regulated by inhibition at the gene transcription level of NF-kB, which in turn inhibits TNFalpha and induces apoptosis.
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  • 95
    ISSN: 1573-4919
    Keywords: antisense oligonucleotide ; apoptosis ; cAMP-dependent protein kinase ; cancer cells ; growth inhibition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract The enhanced expression of the RIα subunit of cyclic AMP-dependent protein kinase type 1 (PKA-I) has been correlated with cancer cell growth. We have investigated the effects of sequence-specific inhibition of RIα gene expression on the growth of MCF-7 human breast cancer cells. We report that RIα antisense treatment results in a reduction in RIα expression at both mRNA and protein levels and inhibition of cell growth. The growth inhibition was accompanied by changes in cell morphology, cleavage of poly(ADP-ribose) polymerase (PARP) and appearance of apoptotic nuclei. In addition, bcl-2 protein level was reduced and p53 expression increased in growth arrested cells. Interestingly, RIα antisense inhibited cell viability and induced apoptosis in the absence of p53, suggesting that these actions of RIα antisense are exerted independent of p53. In contrast, two- and four-base mismatched control oligonucleotides had no effect on either cell growth or morphology. These results demonstrate that the RIα antisense, which efficiently depletes the growth stimulatory molecule RIα, induces cell differentiation and apoptosis, providing a new approach to combat breast cancer cell growth.
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  • 96
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    Molecular and cellular biochemistry 197 (1999), S. 97-108 
    ISSN: 1573-4919
    Keywords: neutrophil ; PKC ; TNF-α ; apoptosis ; DNA fragmentation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract In the present study we investigated the TNF-α induced signal transduction mechanism in human neutrophil. Exogenously added TNF-α affects both PKC activity and its translocation from cytosol to the membrane. Endogenous protein phosphorylation pattern is inhibited in TNF-α induced neutrophil in Ca-dependent and Ca-independent manner, including a major 47 and 66 kDa cytosolic proteins, which may be implicated in superoxide anion generation. However TNF-α dose dependently enhances the expression of ζ-PKC isotype but not the β-PKC. Morphology and cell cytotoxicity are studied in TNF-α treated neutrophil to understand the TNF-α induced cell death or apoptosis and these experiment is further confirmed by DNA fragmentation analysis. These results clearly demonstrate that TNF-α induces cellular death of human neutrophil at least in part by enhanced expression of Ca-independent ζ-PKC. These observations provide an insight towards understanding the function of ζ-PKC in apoptotic pathway.
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  • 97
    ISSN: 1573-4919
    Keywords: rotenone ; apoptosis ; oncogenes ; liver cancer
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract Rotenone decreases the incidence of hepatocellular carcinoma and lowers rates of hepatocellular proliferation. In an effort to delineate mechanisms involved, the in vivo effect of rotenone on liver mitochondrial metabolism, apoptotic machinery as well as elements of the hepatic signal transduction pathways were investigated. Mitochondria from livers of male B6C3F1 mice fed a standard diet containing 600 ppm rotenone for 7 days were uncoupled or inhibited when succinate or glutamate plus malate were used as the substrate, respectively. These livers also showed a significant increase in apoptosis compared with control livers. Furthermore, rotenone increased the expression of c-myc mRNA to 5-fold of control values within 3 days, an effect which was still observed (3-fold) after 7 days. Levels of p53 mRNA were also increased 3-fold after 1 day, but declined to control levels by 7 days. Rotenone also caused a transient, yet marked increase in liver particulate glyceraldehyde phosphate dehydrogenase (GAPDH) protein expression, while it did not alter the expression of the cytosolic form of the enzyme. Conversely, mRNA of the proto-oncogene H-ras showed a decline of 35% after 3 days of rotenone treatment, and remained diminished for the duration of the experiment. These data suggest that rotenone may act as an anticancer agent by diminishing mitochondrial bioenergetics which prevents basal hepatocyte proliferation and lowers the threshold for liver cells with DNA damage to undergo apoptosis.
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  • 98
    ISSN: 1573-4943
    Keywords: Two-dimensional electrophoresis ; MALDI-MS ; apoptosis ; RNA polymerase B transcription factor 3
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Apoptosis or programmed cell death is essential in the process of controlling lymphocyte growth and selection. We identified RNA polymerase B transcription factor 3 (BTF3), which is associated with anti-IgM antibody-mediated apoptosis, using a subclone of the human Burkitt lymphoma cell line BL60. To identify the transcription factor BTF3, which is expressed only in minor amounts, we used preparative high-resolution two-dimensional gel electrophoresis (2DE) employing carrier ampholytes for isoelectric focusing. Comparison of the 2DE protein patterns from apoptotic and nonapoptotic cells showed BTF3 as a predominantly altered protein spot. The characterization of the differentially expressed transcription factor and 13 marker proteins described in this study were performed by internal Edman microsequencing and/or by peptide mass fingerprinting using matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS). The proteome analysis was significantly improved by performing the newly developed preparative high-resolution two-dimensional gels employing high protein concentrations.
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  • 99
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    Investigational new drugs 17 (1999), S. 227-240 
    ISSN: 1573-0646
    Keywords: apoptosis ; protein kinase C ; sphingoid bases ; safingol ; diglyceride ; bryostatin 1 ; staurosporine ; 7-hydroxy staurosporine (UCN-01) ; 4′-N-benzoyl staurosporine (CGP-41251) ; calphostin C (UCN-1028c)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Abstract Neoplastic cell survival is governed by a balance between pro-apoptotic and anti-apoptotic signals. Noteworthy among several anti-apoptotic signaling elements is the protein kinase C (PKC) isoenzyme family, which mediates a central cytoprotective effect in the regulation of cell survival. Activation of PKC, and subsequent recruitment of numerous downstream elements such as the mitogen-activated protein kinase (MAPK) cascade, opposes initiation of the apoptotic cell death program by diverse cytotoxic stimuli. The understanding that the lethal actions of numerous antineoplastic agents are, in many instances, antagonized by cytoprotective signaling systems has been an important stimulus for the development of novel antineoplastic strategies. In this regard, inhibition of PKC, which has been shown to initiate apoptosis in a variety of malignant cell types, has recently been the focus of intense interest. Furthermore, there is accumulating evidence that selective targeting of PKC may prove useful in improving the therapeutic efficacy of established antineoplastic agents. Such chemosensitizing strategies can involve either (a) direct inhibition of PKC (e.g., following acute treatment with relatively specific inhibitors such as the synthetic sphingoid base analog safingol, or the novel staurosporine derivatives UCN-01 and CGP-41251) or (b) down-regulation (e.g., following chronic treatment with the non-tumor-promoting PKC activator bryostatin 1). In preclinical model systems, suppression of the cytoprotective function(s) of PKC potentiates the activity of cytotoxic agents (e.g., cytarabine) as well as ionizing radiation, and efforts to translate these findings into the clinical arena in humans are currently underway. Although the PKC-driven cytoprotective signaling systems affected by these treatments have not been definitively characterized, interference with PKC activity has been associated with loss of the mitogen-activated protein kinase (MAPK) response. Accordingly, recent pre-clinical studies have demonstrated that pharmacological disruption of the primary MEK-ERK module can mimic the chemopotentiating and radiopotentiating actions of PKC inhibition and/or down-regulation.
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  • 100
    ISSN: 1573-0646
    Keywords: UCN-01 ; IL-2 receptor ; Fas ; Fas-ligand ; apoptosis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Abstract 7-hydroxystaurosporine (UCN-01) is a new anticancer agentwhich exerts an inhibitory effect on cell cycle check points andis currently under phase I clinical trials in US and Japan.Preliminary clinical data indicated that UCN-01 remained inplasma at high concentrations for long periods of time. Thisunavoidable high plasma drug exposure is likely to lead tohematological toxicities in patients. In the present study,cultured human peripheral blood lymphocytes (PBLs) were used toevaluate the possible hematological toxicities of UCN-01treatment. UCN-01 induces apoptosis, and the induction ofapoptosis-related surface markers were also examined toinvestigate the involvement of these molecules in UCN-01-inducedapoptosis in PBLs. in vitroviability of PBLs wasdecreased by high dose of UCN-01 (25 μM, 3-day exposure). Thiseffect of UCN-01 was significantly suppressed by the presence ofhuman serum, suggesting that some specific inhibitory factor(s)in human serum may antagonize the lympholytic effect of UCN-01.The percentage of annexin V-positive PI-negative cells increasedwith exposure to UCN-01 in a time- and dose-dependent manner; byup to 30.3% after exposure to 25 μM UCN-01 for 3 days.At the same time, the expression of both interleukin-2 receptor(IL-2R, CD25) and Fas (CD95), analyzed by flow cytometry, wasinduced. Con A-stimulated PBLs were more sensitive toUCN-01-induced apoptosis than non-stimulated lymphocytes andUCN-01 increased the sFas-L released into culture medium from conA-stimulated PBLs. Therefore, lymphocyte depletion mediated byactivation-induced apoptosis is likely to occur in patientstreated with UCN-01 at high doses.
    Type of Medium: Electronic Resource
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