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  • 1995-1999  (667)
  • 1999  (667)
  • Industrial Chemistry  (469)
  • Human  (119)
  • crystal structure  (79)
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  • 1995-1999  (667)
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  • 1
    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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  • 2
    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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  • 3
    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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  • 4
    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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  • 5
    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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  • 6
    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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  • 7
    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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  • 8
    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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  • 9
    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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  • 10
    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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  • 11
    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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  • 12
    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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  • 13
    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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  • 14
    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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  • 15
    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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  • 16
    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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  • 17
    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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  • 18
    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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  • 19
    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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  • 20
    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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  • 21
    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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  • 22
    Electronic Resource
    Electronic Resource
    Springer
    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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  • 23
    Electronic Resource
    Electronic Resource
    Springer
    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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  • 24
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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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  • 25
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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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  • 26
    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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  • 27
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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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  • 28
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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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  • 29
    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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  • 30
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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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  • 31
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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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  • 32
    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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  • 33
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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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  • 34
    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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  • 35
    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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  • 36
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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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  • 37
    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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  • 38
    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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  • 39
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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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  • 40
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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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  • 41
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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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  • 42
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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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  • 43
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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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  • 44
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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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  • 45
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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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  • 46
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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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  • 47
    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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  • 48
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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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  • 49
    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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  • 50
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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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  • 51
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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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  • 52
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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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  • 53
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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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  • 54
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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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  • 55
    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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  • 56
    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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  • 57
    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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  • 58
    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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  • 59
    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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  • 60
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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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  • 61
    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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  • 62
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    Surgical and radiologic anatomy 21 (1999), S. 139-141 
    ISSN: 1279-8517
    Keywords: Anatomy ; Human ; Cross-section ; Computer-assisted instruction ; Education ; Medical
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The NPAC visible human viewer (NPAC VHV), graphical interface written in JAVA, freely accessible by the Web, allows the display of anatomic cross-sections of the Visible Human Project developed by the National Library of Medicine. In April 1997, the Medical Media Library of Lyons undertook the construction of a French-language mirror site of the NPAC VHV. The aim of this work is to evaluate first year utilisation of this site. From May 1st, 1997 to April 30th, 1998, the mirror site was consulted 34,752 times. In 45.14% of cases, the request came from France, in 4.42% of cases from Belgium, in 3.98% from Canada and in 2.12% from Switzerland. Other connections came either from a country responsible for fewer than 1% of connections or from unidentified computers. Data analysis showed a peak of connections between 15:00 and 17:00, and an increased number of connections from September to March 1998. The NPAC VHV is housed in 5 sites in the world. It is a software very simple to use. As the figures have no legends, it is more appropriate for group teaching than for self-teaching.
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  • 63
    ISSN: 1437-1596
    Keywords: Key words Poisoning ; Benfuracarb ; Carbofuran ; Human ; Blood ; Urine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine , Law
    Notes: Abstract We describe here three cases involving acute fatalities due to benfuracarb ingestion and the forensic toxicological implications. Benfuracarb, a carbamate insecticide and its main metabolite carbofuran, were detected using thin layer chromatography (TLC) and gas chromatography/mass spectrophotometry (GC/MS) after extraction with ethyl acetate and then quantified using gas chromatography (GC) equipped with NPD. The blood levels of benfuracarb and carbofuran were in the range of 0.30∼2.32 μg/ml and 1.45∼1.47 μg/ml, respectively. Benfuracarb was not detected in urine, but carbofuran was detected in the range of 0.53∼2.66 μg/ml.
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  • 64
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    Experimental brain research 125 (1999), S. 389-396 
    ISSN: 1432-1106
    Keywords: Key words Neck muscles ; Vibration ; Proprioception ; Sound localization ; Space perception ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  The effect of transcutaneous vibration of the posterior neck muscles on the lateralization of dichotic sound was investigated in human subjects. Two-alternative forced-choice (left/right) judgements were made on acoustic stimuli presented with different interaural level differences via headphones during neck-muscle vibration. A shift of the subjective auditory median plane toward the side contralateral of vibration was found, indicating that the sound was perceived as shifted toward the side of vibration. The mean magnitude of the vibration-induced intracranial shift was 1.5 dB. The results demonstrate a neck-proprioceptive influence on sound lateralization and suggest that this proprioceptive input is used for a central-nervous transformation of auditory spatial coordinates onto a body-centered frame of reference.
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  • 65
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    Experimental brain research 125 (1999), S. 435-439 
    ISSN: 1432-1106
    Keywords: Key words Transcranial magnetic stimulation ; Plasticity ; Synchronization ; Motor system ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  We used focal transcranial magnetic stimulation to examine the effects of 120 synchronized thumb and foot movements on the motor output map of the right abductor pollicis brevis muscle (APB) (experiment 1). To evaluate the performance, the latencies between the onset of the electromyographic activity (EMG) of the two muscles were measured. As control, 120 asynchronous thumb and foot movements were performed (experiment 2). Exclusively in experiment 1, the center of gravity (CoG) of the output map moved medially in the direction of the foot representation area (mean 7 mm, P〈0.05) and returned into its original location within 1 h. In experiment 2, the CoG remained unchanged (mean displacement, 0.68 mm into a lateral direction; not significant). The effect in experiment 1 was independent of an improvement in performance. We conclude that a short-lasting training of synchronous movements induces modulations of motor output maps which probably occur due to interactions between hand and foot representation areas in the motor cortex.
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  • 66
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    Journal of comparative physiology 185 (1999), S. 297-304 
    ISSN: 1432-1351
    Keywords: Key words Odor coding ; Learning ; Enhanced sensitivity ; Rabbit ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract The olfactory system is faced with a particular problem – the high dimensionality and inherent unpredictability of the chemical world. Most natural odorants encountered in everyday life are complex mixtures of many different volatiles. This means that from the outset the olfactory system has to contend with a great and often unpredictable diversity of molecules, making it difficult for stable primary features of the chemical world to be mapped onto the sensory surface. One solution to such unpredictability is provided by learning. Learning confers flexibility, enabling individuals of a given species to acquire and make use of the most appropriate information in a particular environment. Two examples of this are presented: learning of maternal odors in neonatal rabbits, including evidence that the sensory surface itself may be influenced by environmental conditions so as to enhance sensitivity to molecules of particular ecological relevance, and cross-cultural human studies suggesting that experience with everyday odors influences not only the way these are evaluated, but also their perceived intensity. It is concluded that an adequate understanding of odor coding and olfactory function will not be possible without taking such experience-dependent factors into account.
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  • 67
    ISSN: 1432-2307
    Keywords: Key words Peroxisomes ; Hepatocellular tumors ; Immunocytochemistry ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  A significant reduction of catalase activity, a peroxisomal marker enzyme, occurs in human hepatic neoplasias, but no information is available on other peroxisomal proteins. We have studied by means of immunohistochemistry four specific proteins of peroxisomes (catalase and three enzymes of lipid β-oxidation) in human hepatocellular tumors of various differentiation grades from adenoma to anaplastic carcinoma. In all tumors, except the adenomas, the tumor cells contained fewer peroxisomes than extrafocal hepatocytes and the reduction of antigenic sites in the tumor types generally correlated with the degree of tumor dedifferentiation as assessed by classical histopathological criteria. Two poorly differentiated tumors had no detectable peroxisomes at all. There were no major differences in the intensities of the immunocytochemical staining for all four studied peroxisomal antigens in different tumors, suggesting that the neoplastic transformation affects the biogenesis of the entire organelle and not merely the individual peroxisomal enzyme proteins. Some tumors exhibited a distinct peripheral distribution of peroxisomes. In cases with associated liver cirrhosis, the hepatocytes in the adjacent liver showed marked peroxisome proliferation, forming large perinuclear aggregates, occupying occasionally the entire cytoplasm. Taken together, our observations indicate that peroxisomes are significantly altered in both hepatocellular tumors and liver cirrhosis and, thus, could be responsible for some of the metabolic derangements observed in those disease processes.
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  • 68
    ISSN: 1432-2307
    Keywords: Key words p21 ; p53 ; Colon ; Immunohistochemistry ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  The WAF1/CIP1 gene product, p21, an inhibitor of cyclin-dependent kinases, is a critical downstream effector in the p53 pathway. The expression of p21 in human neoplasms is heterogeneous, and may be related to p53 functional status. We evaluated p21 immunoreactivity in 103 colorectal carcinomas (CC) in relation to the p53 gene and protein alterations and clinico-pathologic parameters. High p21 expression (more than 10% reactive cells) was seen in 39% of cases. p21 staining was heterogeneous and often detected in clusters of tumour cells; in some tumours p21 staining was more pronounced in superficial areas. No relation was seen between p21 immunoreactivity and site of the tumours (right vs left), TNM stage and grade. p21 expression was related to p53 status as evaluated with IHC or with SSCP analyses, low p21 expression usually being associated with p53 protein overexpression (P=0.048) and p53 gene alteration (P=0.005). The strongest associations were seen when the combined p53/p21 immunophenotype was compared with p53 gene alterations (P=0.0002). These data support the hypothesis that p21 expression in CC is mainly related to p53 functional status, suggesting that p21 expression could be an interesting adjunct in the evaluation of the functional status of the p53 pathway in CC.
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  • 69
    ISSN: 1434-0879
    Keywords: Key words Alpha-1-microglobulin ; Calcium oxalate ; Crystallization ; ELISA ; Human ; Urine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract In the past few years, alpha-1-microglobulin (α1m) has been copurified from human urine with bikunin, a potent inhibitor of calcium oxalate (CaOx) crystallization in vitro. In this study, we have purified α1m without bikunin contamination and investigated its possible role in CaOx crystallization by in vitro and in vivo studies. Alpha-1m was purified with an anti-α1m antibodies CNBr-activated sepharose column. Two molecular species of α1m of respectively 30 and 60 kDa were purified. For each protein, two blots of 30 and 60 kDa cross-reacted with anti-α1m antibodies, suggesting that these two forms were derived one from the other. Both protein species inhibited CaOx crystallization in a dose-dependent manner in two in vitro tests. In the first test, the presence of α1m of 30 kDa (8 μg/ml) in a medium containing 0.76 mM CaCl2 (with 45Ca) and 0.76 mM Ox(NH4)2 inhibited CaOx crystallization by 38% as estimated by supernatant radioactivity after 1 h of agitation. In the second test, CaOx kinetics were examined for 3 to 10 min in a turbidimetric model at 620 nm. The presence of α1m of 30 kDa in a medium containing 4 mM CaCl2 and 0.5 mM Na2Ox inhibited CaOx crystallization by 41.5%, as estimated by the slope modification of turbidimetric curve. Alpha-1m can be considered as another inhibitor of urinary CaOx crystal formation, as shown by the present in vitro studies. Using an ELISA assay, we found that urinary α1m concentration was significantly lower in 31 CaOx stone formers than in 18 healthy subjects (2.95 ± 0.29 vs 5.34 ± 1.08 mg/l respectively, P = 0.01). The decreased concentration of α1m in CaOx stone formers could be responsible in these patients, at least in part, for an increased risk of CaOx crystalluria.
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    Anatomy and embryology 199 (1999), S. 45-56 
    ISSN: 1432-0568
    Keywords: Key words Skin ; Proteoglycan ; Development ; Human ; Fetal
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  The extracellular matrix of human fetal skin differs substantially from that of adult skin. Fetal skin contains sparse amounts of fibrillar collagen enmeshed in a highly hydrated amorphous matrix composed of hyaluronan and sulfated proteoglycans. Both fetal and adult skin contain two major interstitial proteoglycans that are extracted by chaotrophic agents and detergents. These are the large chondroitin sulfate proteoglycan versican and the small dermatan sulfate proteoglycan decorin. For this study, proteoglycans extracted from fetal and adult skin were compared on Western blots to determine the relative amounts of versican. Decorin present in the same samples provided an internal standard for these studies. Fetal skin differed from adult skin in that it contained a significantly higher proportion of versican than did adult skin. Immunohistochemical studies compared early-fetal with mid-fetal skin and found that versican was a significant component of the interstitial extracellular matrix at both of these stages of skin development. However, by the mid-fetal period, interstitial versican became restricted to the upper half of the dermis, although versican also continued to be highly expressed around hair follicles, glands, and vasculature in the lower half of the dermis. Fetal skin extracts differed from an adult skin extract by the presence of a 66-kDa protein immunologically related to versican and by the absence of a 17-kDa core protein of a proteoglycan related to decorin. Both of these molecular species may represent degradation products of their respective proteoglycans. Monoclonal antibodies which detect epitopes in native chondroitin sulfate glycosaminoglycan chains recognized versican extracted from fetal skin. However, the tissue distribution of these antigens did not entirely conform to that for versican core protein, suggesting that versican in different regions of the skin may be substituted with glycosaminoglycan chains with different microchemistries. The results of these studies indicate that human fetal skin is structurally different from adult skin in terms of both the distribution and the composition of the large, aggregating chondroitin sulfate proteoglycan versican.
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  • 71
    ISSN: 1432-0533
    Keywords: Key words Amantadine ; Human ; N-methyl-d-aspartate ; Phencyclidine ; Postmortem brain
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Low doses of N-methyl-d-aspartate (NMDA)-type glutamate receptor antagonists induce morphological alterations in neurons of the cingulate gyrus and retrosplenial cortex of the rat. Neuronal cell death may result at higher doses. These effects are a major concern with regard to the introduction of new NMDA receptor antagonists into clinical trials. Amantadine is an uncompetitive NMDA receptor antagonist, which has been in clinical use for many years. In the present study we have looked for possible morphological alterations like necrosis in postmortem human brain tissue of patients previously treated with amantadine. Formalin-fixed tissue samples were taken from the hippocampus, cingulate gyrus, and retrosplenial cortex of 8 patients on previous amantadine medication and of 11 controls. Histopathological examination of sections was performed blind. All brains except one revealed either nonspecific age-related or cerebrovascular changes or other neurodegenerative disorders including Alzheimer’s, Parkinson’s or Lewy body disease. In conclusion, histopathological examination of the hippocampus, retrosplenial cortex, and cingulate gyrus of human brain did not reveal changes suggested to be specific for previous amantadine treatment.
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  • 72
    ISSN: 1432-0533
    Keywords: Key words Purkinje cell ; Cerebellum ; Development ; Inositol 1 ; 4 ; 5-triphosphate type 1 receptor ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Immunohistochemical analyses were carried out on the Purkinje cells from 21 autopsied fetal and early postnatal normal cerebella using a monoclonal antibody against the inositol 1, 4, 5-triphosphate type 1 receptor (IP3R1) as a cytochemical marker of Purkinje cells. In normal adult cerebella used as positive controls, the cell bodies, axons, and dendrites, including spiny branchlets of the Purkinje cells, were specifically stained by the antibody. In the fetal cerebella examined, the IP3R1 immunoreactivity was first detected in the soma of multilayered cells just beneath the molecular layer at 16 weeks of gestation. The IP3R1 immunoreactivity gradually increased in area of positive staining from soma to dendrites and spiny branchlets, and the dendritic outgrowth rapidly progressed during 6 months after birth. The Purkinje cell maturation was more advanced in the vermis than in the hemisphere, more in the posterior lobe than in the anterior lobe, and more at the bottom of the folia than at the top. Partial absence of the Purkinje cells in the cerebellar cortex was observed in three cases. Heterotopias including Purkinje cells were often noted in the cerebellar white matter in five cases.
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  • 73
    ISSN: 1432-069X
    Keywords: Key words Chronic diabetic wounds ; Human ; fibroblasts ; Wound healing ; Cell culture ; Proliferation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Patients with diabetes mellitus experience impaired wound healing often resulting in chronic foot ulcers. Hospital discharge data indicate that 6–20% of all diabetic individuals hospitalized (mostly with type 2 diabetes) have a lower extremity ulcer. Maintaining glucose levels at acceptable levels (below 10 mmol/l) is considered to be an important part of the clinical treatment, but the exact mechanism by which diabetes delays wound repair is not yet known. We studied this phenomenon by determining the potential of fibroblasts isolated from the ulcer sites of four patients with non-insulin-dependent diabetes mellitus to proliferate in vitro. Controls were fibroblasts isolated from normal skin of the upper leg of five healthy age-matched volunteers and of six non-insulin-dependent diabetes patients. Proliferative capacity was analysed by evaluation of plates after trypsinization and [3H]thymidine incorporation. Fibroblast morphology was studied by light and transmission electron microscopy. Diabetic ulcer fibroblasts, measured by [3H]thymidine incorporation, proliferated significantly more slowly than the nonlesional control fibroblasts (P 〈 0.00047) and age-matched control fibroblasts (P 〈 0.00003). After culturing the fibroblasts for a prolonged period in high-glucose (27.5 mM) and low-glucose (5.5 mM, i.e. physiological) medium, this difference in proliferation rate between diabetic ulcer fibroblasts and nonlesional diabetic fibroblasts remained (P 〈 0.0001 for high-glucose and P 〈 0.0009 for low-glucose on day 7). Fibroblast proliferation in all three groups was slightly lower in high-glucose than in low-glucose medium, although not significantly at any time-point. Light microscopy showed diabetic ulcer fibroblasts to be large and widely spread. Transmission electron microscopy of cultured diabetic ulcer fibroblasts and nonlesional diabetic skin fibroblasts revealed a large dilated endoplasmic reticulum, a lack of microtubular structures and multiple lamellar and vesicular bodies. These results show a diminished proliferative capacity and abnormal morphology of fibroblasts derived from diabetic ulcers of non-insulin-dependent diabetes patients.
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  • 74
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    Archives of dermatological research 291 (1999), S. 247-252 
    ISSN: 1432-069X
    Keywords: Key words T cell activation ; Nickel ; Human ; Interferon-gamma
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Contact hypersensitivity to nickel is the most common form of allergic contact dermatitis. To gain insight into the induction of this frequent disease, T cell reactivity towards nickel was investigated in “nonallergic” individuals defined as those with no skin manifestations and a negative patch test towards NiSO4. Surprisingly, we found that nickel induced proliferation of peripheral blood mononuclear cells (PBMC) from 16 of 18 adult individuals tested. This activation was specific, and no stimulation of PBMC was observed using control stimulants at equimolar concentrations. Furthermore, the NiSO4-induced activation required the presence of professional antigen-presenting cells. To describe the functional capacity of the nickel-inducible T cells, cytokine release was investigated in both nickel-allergic and nonallergic individuals. The T cells from both groups released interferon-γ but no interleukin-4 upon stimulation with nickel, suggesting that the functional capacities of these cell populations were similar in nickel-allergic and nonallergic individuals. Thus, at this level, no qualitative differences could be demonstrated between T cells obtained from nickel-allergic and nonallergic individuals.
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  • 75
    ISSN: 1432-069X
    Keywords: Key words ORS cells ; Melanocytes ; Human ; Organotypic cultures ; Melanosomes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Because outer root sheath (ORS) cells are valuable substitutes for interfollicular epidermal keratinocytes, we wanted to determine whether epidermal equivalents generated from ORS cells and containing cultured melanocytes can serve as an in vitro model for skin pigmentation. In such epidermal equivalents prepared with ORS cells and melanocytes from donors of phototypes II, III and VI, a stratified epithelium resembling normal epidermis developed within 14 days, as documented by histological, ultrastructural (e.g. basement membrane-like structure, keratohyalin granules, keratinosomes) and immunohistochemical (e.g. keratins, integrins, gp80, involucrin, filaggrin) criteria. The melanocytes were localized in the basal layer and accounted for 10% of the total cell number. Heavily pigmented melanocytes from black donors contained regular melanosomes in all stages of maturation, whereas melanocytes derived from white donors contained predominantly melanosomes of stages I and II. Melanosome-laden dendrites were readily detected extending from the heavily pigmented melanocytes, while they were less conspicuous in melanocytes from white donors. The extent of melanosome transfer was independent of the racial origin of the ORS cells. Melanosomes could also be transferred “through racial barriers”. Melanosomes, mainly of stages III and IV, were detected in the ORS cells, being distributed either as single or compound melanosomes, again irrespective of the racial origin of the ORS cells. In conclusion, pigmented epidermal equivalents generated from ORS cells offer practical advantages over other in vitro pigmentation models: (1) the ORS cells are easily and repeatedly available from any donor regardless of age; (2) primary cultures of ORS cells are free of contaminating melanocytes, a bias if using interfollicular epidermal keratinocytes; (3) a high degree of epidermal differentiation is maintained for 3 weeks in fully defined medium, enabling labelling and stimulation experiments to be performed and compounds interfering with melanin pigmentation to be tested.
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  • 76
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    Immunogenetics 49 (1999), S. 438-445 
    ISSN: 1432-1211
    Keywords: Key words PA28 ; Proteasome ; Gene structure ; Evolution ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract  Two proteasome activators PA28α and β, which have been implicated in antigen processing for loading class I MHC molecules, are synthesized in response to Ifn-γ. The human genes encoding these activators (PSME1 and PSME2, respectively) were analyzed by sequencing. Each gene comprised 11 exons, consistent with gene duplication during vertebrate evolution. The intron/exon organization of both genes was highly conserved, the major difference being the absence of the exon encoding the lysine and glutamic acid-rich 'KEKE' motif in PA28β. Two other genes of relevance to the immune system were located close to those for PA28 at 14q11.2 including ISGF3G, a protein involved in transcription after IFNα signalling. These sequences were also characterized.
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  • 77
    ISSN: 1432-1211
    Keywords: Key words NK cells ; Human ; Surface molecule ; Lectin superfamily ; NK gene complex
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract  Natural killer (NK) cells constitute the third major population of lymphocytes. They possess the inherent capacity to kill various tumor and virally infected cells and mediate the rejection of bone-marrow grafts in lethally irradiated animals. A large family of NK cell receptors belong to the C-type lectin superfamily and are localized to the NK gene complex on Chromosome (Chr) 6 in the mouse and Chr 12 in the human. Genes in the NK gene complex encode type II receptors and examples include the families of NKR-P1, Ly-49, and NKG2 receptors. Examples of other C-type lectin-like NK cell receptors that occur as individual genes are CD94, CD69, and AICL. Here we report the molecular characterization and chromosomal mapping of a human lectin-like transcript (LLT1) expressed on NK, T, and B cells and localized to the NK gene complex within 100 kilobases of CD69. The cDNA encodes a predicted protein of 191 amino acid residues with a transmembrane domain near the N-terminus and an extracellular domain of 132 amino acid residues with similarity to the carbohydrate recognition domain of C-type lectins. The predicted protein of LLT1 shows 59 and 56% similarity to AICL and CD69, respectively. The predicted protein does not contain any intracellular ITIM motifs, suggesting that LLT1 may be involved in mediating activation signals.
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  • 78
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    Experimental brain research 128 (1999), S. 539-542 
    ISSN: 1432-1106
    Keywords: Key words Silent period ; Transcranial magnetic stimulation ; Motor cortex ; Epidural recordings ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  We investigated the nature of the silent period (SP) following transcranial magnetic stimulation by recording corticospinal volleys in a patient with implanted cervical epidural electrodes. Single suprathreshold test stimuli and paired stimuli at interstimulus intervals (ISIs) of 50–200 ms were delivered while the subject maintained a constant background contraction. The silent period duration from a single test stimulus was 357±62 ms. The test motor-evoked potentials were markedly reduced at all the ISIs tested. The I (indirect) waves induced by the test stimulus were largely unchanged at an ISI of 50 ms, suggesting that there was little change in motor cortex excitability. However, the corticospinal volleys, especially the late I waves, were substantially reduced at ISIs of 100 ms, 150 ms, and 200 ms. Our findings suggest that the early part of the SP is mainly due to spinal mechanisms, while the late part of the SP is related to reduced motor cortex excitability.
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  • 79
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    Experimental brain research 128 (1999), S. 550-556 
    ISSN: 1432-1106
    Keywords: Key words Selective attention ; Kinematics ; Human ; Visual pathways
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  In solving the selection-for-action problem, it is believed that attentional mechanisms enable dominance of target over non-target objects. However, under some conditions, information from non-target objects ”interferes” with the action to a relevant target. We investigated the possibility that this interference may result when the irrelevant object activates a specific subset of visuomotor pathways. Participants reached to grasp three-dimensional stimuli while actively attending to a nearby flanker object. The means by which the flanker was presented was manipulated. This relevant object was illuminated either abruptly or gradually. The parvocellular pathway in early visual processing is equally activated in both conditions. The magnocellular pathway is strongly activated by abrupt presentation and weakly activated with gradual presentation of the flanker object. Kinematics of the reach-to-grasp action to the target showed signs of interference only in the sudden illumination condition. This suggests a dissociation between dorsal and ventral cortical streams in terms of relevance for action. Our data suggests that this effect is not due to early visual-pathway differences, but instead reveals a property of a transient object-based visual attention mechanism.
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  • 80
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    Experimental brain research 124 (1999), S. 1-7 
    ISSN: 1432-1106
    Keywords: Key words Temporal cortex ; Connectivity ; Human ; Interhemispheric transfer ; Talairach coordinates
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  The human anterior commissure is believed, by extrapolation from data obtained in macaque monkeys, to convey axons from the temporal and orbitofrontal cortex. Reports of interhemispheric transfer and sexual dimorphism related to the anterior commissure, however, make more precise data on the human anterior commissure desirable. We investigated the connectivity of the human anterior commissure in six adults (male and female) that had circumscribed hemispheric lesions in temporal, frontal, parietal or occipital cortices or in infrapallidal white matter using the Nauta for anterogradely degenerating axons. Axons originating in the inferior part of temporal or occipital lobes, occipital convexity and possibly central fissure and prefrontal convexity were found to cross the midsagittal plane in the anterior commissure. The largest contigent of commissural axons originated in the inferior part of the temporal lobe; it displayed a roughly topographic organization, preferentially running through the inferior part of the commissure. The inferior temporal contigent seemed to reach homotopic and heterotopic targets in the opposite hemisphere. Among the latter were the amygdala and possibly the orbitofrontal cortex. The present data suggest that the human anterior commissure conveys axons from much larger territories than expected from work on non-human primates. Similarly to the human and non-human primate corpus callosum, the anterior commissure is roughly topographically organized and participates in heterotopic connectivity.
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  • 81
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    Experimental brain research 126 (1999), S. 200-204 
    ISSN: 1432-1106
    Keywords: Key words Motor development ; Anticipatory postural adjustments ; Bimanual coordination ; Children ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  Anticipatory postural adjustments (APA) are needed to perform a movement without perturbing posture. We investigated the development of APA in 3- to 4-year-old children during a bimanual load-lifting task. The task required maintaining a stable elbow position despite imposed or voluntary unloading of the forearm. Although children can compensate the consequences of unloading by using APA, their performance did not reach an adults’ level. In addition, children showed high intra-individual variability in the voluntary situation, revealed by the coexistence of both adult-like and immature patterns in kinematic and electromyographic data. In conclusion, the present study reports that APA, associated with a bimanual load-lifting task, are still being set up in 3- to 4-year-old-children. The intra-individual variability should decrease with age and be associated with a progressive mastering of the timing parameters characterizing APA.
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  • 82
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    Experimental brain research 124 (1999), S. 273-280 
    ISSN: 1432-1106
    Keywords: Key words Vestibular system ; Posture control ; Balance ; Cross-spectral analysis ; Coherency ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  Galvanic vestibular stimulation serves to modulate the continuous firing level of the peripheral vestibular afferents. It has been shown that the application of sinusoidally varying, bipolar galvanic currents to the vestibular system can lead to sinusoidally varying postural sway. Our objective was to test the hypothesis that stochastic galvanic vestibular stimulation can lead to coherent stochastic postural sway. Bipolar binaural stochastic galvanic vestibular stimulation was applied to nine healthy young subjects. Three different stochastic vestibular stimulation signals, each with a different frequency content (0–1 Hz, 1–2 Hz, and 0–2 Hz), were used. The stimulation level (range 0.4–1.5 mA, peak to peak) was determined on an individual basis. Twenty 60-s trials were conducted on each subject – 15 stimulation trials (5 trials with each stimulation signal) and 5 control (no stimulation) trials. During the trials, subjects stood in a relaxed, upright position with their head facing forward. Postural sway was evaluated by using a force platform to measure the displacements of the center of pressure (COP) under each subject’s feet. Cross-spectral measures were used to quantify the relationship between the applied stimulus and the resulting COP time series. We found significant coherency between the stochastic vestibular stimulation signal and the resulting mediolateral COP time series in the majority of trials in 8 of the 9 subjects tested. The coherency results for each stimulation signal were reproducible from trial to trial, and the highest degree of coherency was found for the 1- to 2-Hz stochastic vestibular stimulation signal. In general, for the nine subjects tested, we did not find consistent significant coherency between the stochastic vestibular stimulation signals and the anteroposterior COP time series. This work demonstrates that, in subjects who are facing forward, bipolar binaural stochastic galvanic stimulation of the vestibular system leads to coherent stochastic mediolateral postural sway, but it does not lead to coherent stochastic anteroposterior postural sway. Our finding that the coherency was highest for the 1- to 2-Hz stochastic vestibular stimulation signal may be due to the intrinsic dynamics of the quasi-static postural control system. In particular, it may result from the effects of the vestibular stimulus simply being superimposed upon the quiet-standing COP displacements. By utilizing stochastic stimulation signals, we ensured that the subjects could not predict a change in the vestibular stimulus. Thus, our findings indicate that subjects can act as ”responders” to galvanic vestibular stimulation.
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  • 83
    ISSN: 1432-1106
    Keywords: Key words Locomotion ; Load ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  Prior work from mammals suggests that load experienced by extensor muscles of the hindlimbs (i.e. Duysens and Pearson 1980; Pearson and Collins 1993; Fouad and Pearson 1997) or cutaneous afferents from the plantar surface of the foot (Duysens and Pearson 1976; Guertin et al. 1995) enhances activity in extensor muscles during the stance phase, and delays the onset of flexor activity associated with the swing phase. The presumed functional significance of this phenomenon is that extensor activity of the supporting limb during walking can: (a) reinforce the supporting function in proportion to the load experienced, and (b) prolong the stance phase until unloading of the limb has occurred. Whether a similar functional role exists for load-sensitive afferents during walking in the human is unknown. In this study, the effect of adding or removing a substantial load (30% of body weight) at the centre of mass was studied in healthy adult human subjects. Loads were applied near the centre of mass to avoid the need for postural adjustments which might confound the interpretation of the results. Subjects walked on a treadmill with either: (a) a sustained increase or decrease in load, or (b) a sudden unexpected increase or decrease in load. In general, subjects responded to the changes in load by changing the amplitude of the extensor electromyographic (EMG) bursts. For example, with sudden unexpected additions in load, the average increase in amplitude was 40% for the soleus across the stance phase, and 134% for the quadriceps during the early part of the stance phase. Extensor EMGs increased with both sustained and sudden increases in load. Extensor EMG durations also increased (average increase in duration of 4% for soleus with sudden loading, and 7% for sustained loading). Cycle duration hardly changed (average increase of 0.5% with both sudden and sustained loading). These results differ from those of infants subjected to a similar perturbation during supported walking. A large change in timing (i.e. an increase in the duration of the stance phase by 30% and the step cycle by 28%) was seen in the infants, with no change in the amplitude of the EMG burst (Yang et al. 1998). These results suggest that the central nervous system can control the timing and amplitude of extensor EMG activity in response to loading independently. Maturation of the two components most likely occurs independently. In the adult, independent control of the two components may provide greater flexibility of the response.
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  • 84
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    Experimental brain research 126 (1999), S. 235-251 
    ISSN: 1432-1106
    Keywords: Key words Motor learning and memory ; Perseveration ; Prefrontal cortex ; Reversal learning ; Basal ganglia ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  The ability to inhibit previously learned visuomotor associations is essential for efficient learning of novel behaviors. While the neural basis of the system that might control interactions between competing motor memories is not known, it has been demonstrated that animals with ventral and orbital prefrontal cortex (PFC) deficits have particular difficulties in learning to withhold responses to previously conditioned sensory stimuli. Here we measured regional cerebral blood flow (rCBF), using positron emission tomography, during learning of a novel motor task that required inhibition of a previously learned motor memory. Subjects (n=24) learned reaching movements in a force field (field A). After a variable time interval, some subjects (n=15) learned to reach in a field with a reversed pattern of forces (field B). When the time interval was short (10 min), learning in field B was coincident with a reactivation of regions that had become initially activated during learning in field A: the left putamen and bilaterally in the dorsolateral PFC. Behaviorally, this was accompanied with perseveration that lasted for hundreds of movements, suggesting an instantiation of the internal model for field A during learning in field B. Neither the reactivation nor the perseveration were observed in a different group of subjects that learned field B at 5.5 h. We found that the regions which significantly differentiated the two groups during learning of B were in the ventrolateral PFC (bilaterally): there were sharp decreases in rCBF here in the 5.5 group but not in the 10-min group. At 5.5 h motor learning again involved the striatum, but this time in the left caudate. Neither the caudate nor the ventral PFC had exhibited learning-related activity in field A. Instead, they showed changes in rCBF during the reversal of the learning problem when the previously acquired motor memory was successfully gated. The results demonstrate that: (1) perseveration of a competing motor memory may be linked to reactivation of the neural circuit that participated in acquiring that memory, and (2) the ventral PFC may play an important role in the inhibitory control of the competing motor memory.
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  • 85
    ISSN: 1432-1106
    Keywords: Key words Corpus callosum ; Interhemispheric transfer ; Positron emission tomography ; Split brain ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  We studied with PET the intra- and interhemispheric pathways subserving a simple, speeded-up visuomotor task. Six normal subjects and one patient with a complete section of the corpus callosum (M.E.) underwent regional cerebral blood flow (rCBF) measurements under conditions of lateralized tachistoscopic visual presentations in a simple manual reaction time paradigm. Confirming previous behavioural findings, we found that on average crossed hand and/or hemifield conditions, i.e. those requiring an interhemispheric transfer of information, yielded a longer RT than uncrossed conditions. This difference (0.7 ms) was dramatically larger (45.6 ms) in the callosum-sectioned patient M.E. In normal subjects the cortical areas selectively activated in uncrossed and crossed conditions were different. In the former condition, most activation foci were anterior to the ventral anterior commissure (VAC) plane, whereas in the latter there was a prevalent parietal and occipital activation. This shows that a simple model in which the cortical visuo-motor pathways are similar in the intra- and the interhemispheric condition, with an extra callosal route for the latter, is too simplistic. Furthermore, these results suggest that the bulk of visuomotor interhemispheric transfer takes place through the widespread callosal fibres interconnecting the parietal cortices of the two hemispheres. The pattern of activation in the two crossing conditions was markedly different in M.E., in whom interhemispheric transfer might take place via his intact anterior commissure or subcortical commissures.
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  • 86
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    Experimental brain research 125 (1999), S. 43-49 
    ISSN: 1432-1106
    Keywords: Key words Proprioception ; Visual localization ; Visual context ; Multisensory integration ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  In a previous study we investigated how the CNS combines simultaneous visual and proprioceptive information about the position of the finger. We found that localization of the index finger of a seen hand was more precise (a smaller variance) than could reasonably be expected from the precision of localization on the basis of vision only and proprioception only. This suggests that, in localizing the tip of the index finger of a seen hand, the CNS may make use of more information than proprioceptive information and visual information about the fingertip. In the present study we investigate whether this additional information stems from additional sources of sensory information. In experiment 1 we tested whether seeing an entire arm instead of only the fingertip gives rise to a more precise proprioceptive and/or visual localization of that fingertip. In experiment 2 we checked whether the presence of a structured visual environment leads to a more precise proprioceptive localization of the index finger of an unseen hand. In experiment 3 we investigated whether looking in the direction of the index finger of an unseen hand improves proprioceptive localization of that finger. We found no significant effect in any of the experiments. The results refute the hypothesis that the investigated effects can explain the previously reported very precise localization of a seen hand. This suggests that localization of a seen finger is based exclusively on proprioception and on vision of the finger. The results suggest that these sensory signals may contain more information than is described by the magnitude of their variances.
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  • 87
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    Experimental brain research 125 (1999), S. 139-152 
    ISSN: 1432-1106
    Keywords: Key words Reaching movements ; Direction ; Amplitude ; Initial kinematics ; Spatial variability ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  The accuracy of reaching movements to memorized visual target locations is presumed to be determined largely by central planning processes before movement onset. If so, then the initial kinematics of a pointing movement should predict its endpoint. Our study examined this hypothesis by testing the correlation between peak acceleration, peak velocity, and movement amplitude and the correspondence between the respective spatial positions of these kinematic landmarks. Subjects made planar horizontal reaching movements to targets located at five different distances and along five radially arrayed directions without visual feedback during the movements.The spatial dispersion of the positions of peak acceleration, peak velocity, and endpoint all tended to form ellipses oriented along the movement trajectory. However, whereas the peaks of acceleration and velocity scaled strongly with movement amplitude for all of the movements made at the five target distances in any one direction, the correlations with movement amplitude were more modest for trajectories aimed at each target separately. Furthermore, the spatial variability in direction and extent of the distribution of positions of peak acceleration and peak velocity did not scale differently with target distance, whereas they did for endpoint distributions. Therefore, certain features of the final kinematics are evident in the early kinematics of the movements as predicted by the hypothesis that they reflect planning processes. However, endpoint distributions were not completely predetermined by the Initial kinematics. In contrast, multivariate analysis suggests that adjustments to movement duration help compensate for the variability of the initial kinematics to achieve desired movement amplitude. These compensatory adjustments do not contradict the general conclusion that the systematic patterns in the spatial variability observed in this study reflect planning processes. On the contrary, and consistent with that conclusion, our results provide further evidence that direction and extent of reaching movements are planned and determined in parallel over time.
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  • 88
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    Keywords: Key words Three-dimensional pointing ; Human ; Remembered targets
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  The accuracy of visually guided pointing movements decreases with speed. We have shown that for movements to a visually defined remembered target, the variability of the final arm endpoint position does not depend on movement speed. We put forward a hypothesis that this observation can be explained by suggesting that movements directed at remembered targets are produced without ongoing corrections. In the present study, this hypothesis was tested for pointing movements in 3D space to kinesthetically defined remembered targets. Passive versus active acquisition of kinesthetic information was contrasted. Pointing errors, movement kinematics, and joint-angle coordination were analyzed. The movements were performed at a slow speed (average peak tangential velocity of about 1.2 m/s) and at a fast speed (2.7 m/s). No visual feedback was allowed during the target presentation or the movement. Variability in the final position of the arm endpoint did not increase with speed in either the active or the passive condition. Variability in the final values of the arm-orientation angles determining the position of the forearm and of the upper arm in space was also speed invariant. This invariance occurred despite the fact that angular velocities increased by a factor of two for all the angles involved. The speed-invariant variability supports the hypothesis that there is an absence of ongoing corrections for movements to remembered targets: in the case of a slower movement, where there is more time for movement correction, the final arm endpoint variability did not decrease. In contrast to variability in the final endpoint position, the variability in the peak tangential acceleration increased significantly with movement speed. This may imply that the nervous system adopts one of two strategies: either the final endpoint position is not encoded in terms of muscle torques or there is a special on-line mechanism that adjusts movement deceleration according to the muscle-torque variability at the initial stage of the movement. The final endpoint position was on average farther from the shoulder than the target. Constant radial-distance errors were speed dependent in both the active and the passive conditions. In the fast speed conditions, the radial distance overshoots of the targets increased. This increase in radial-distance overshoot with movement speed can be explained by the hypothesis that the final arm position is not predetermined in these experimental conditions, but is defined during the movement by a feedforward or feedback mechanism with an internal delay.
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  • 89
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    Experimental brain research 125 (1999), S. 265-270 
    ISSN: 1432-1106
    Keywords: Key words Tendon reflexes ; Biceps femoris ; Gait ; Ia afferents ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  During gait it is generally accepted that there is a reduction in amplitude of H-reflexes as compared to standing. For short-latency stretch reflexes, however, it is less clear whether a similar reduction in reflex gain is present during locomotion. Stretches of constant amplitude are hard to produce under these circumstances and for this reason some previous studies on the biceps femoris (BF) have used ”reduced gait” in which the stimulated leg is stepping on the spot while the contralateral leg is walking on a treadmill. With this method it was possible to show that BF tendon jerk reflexes are larger at end swing and therefore are likely to contribute to the EMG burst normally occurring in that part of the step cycle when the BF is rapidly stretched. In the present study two questions were addressed: first, whether the reflex is different in size during gait compared to standing and, second, whether it is modulated in size during the gait cycle not only during reduced but also during normal gait. It was found that during both types of gait there was a general reflex depression with regard to the respective control values obtained during standing at similar EMG activity levels. In previous studies on soleus and quadriceps, discrepancies between EMG activity and reflex amplitude have been ascribed to changes in presynaptic inhibition of Ia terminals mediating the afferent volley of the reflex. Based on the data presented, this may also be true for the BF. In both normal and reduced gait the reflex was similarly modulated in size, showing a maximum at the end of swing. This similarity implies that reduced gait may be useful as an acceptable alternative for normal gait in studies on phase-dependent reflex modulation during locomotion.
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  • 90
    ISSN: 1432-1106
    Keywords: Key words Hyperventilation ; Magnetoencephalography ; Somatosensory cortex ; Auditory cortex ; Somatosensory evoked response ; Auditory evoked response ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  It is well established that voluntary hyperventilation (HV) slows down electroencephalographic (EEG) rhythms. Little information is available, however, on the effects of HV on cortical responses elicited by sensory stimulation. In the present study, we recorded auditory evoked potentials (AEPs) and magnetic fields (AEFs), and somatosensory evoked magnetic fields (SEFs) from healthy subjects before, during, and after a 3- to 5-min period of voluntary HV. The effectiveness of HV was verified by measuring the end-tidal CO2 levels. Long-latency (100–200 ms) AEPs and long-latency AEFs originating at the supratemporal auditory cortex, as well as long-latency SEFs from the primary somatosensory cortex (SI) and from the opercular somatosensory cortex (OC), were all reduced during HV. The short-latency SEFs from SI were clearly less modified, there being, however, a slight reduction of the earliest cortical excitatory response, the N20m deflection. A middle-latency SEF deflection from SI at about 60 ms (P60 m) was slightly increased. For AEFs and SEFs, the center-of-gravity locations of the activated neuronal populations were not changed during HV. All amplitude changes returned to baseline levels within 10 min after the end of HV. The AEPs were not altered when the subjects breathed 5% CO2 in air in a hyperventilation-like manner, which prevented the development of hypocapnia. We conclude that moderate HV suppresses long-latency evoked responses from the primary projection cortices, while the early responses are less reduced. The reduction of long-latency responses is probably mediated by hypocapnia rather than by other nonspecific effects of HV. It is suggested that increased neuronal excitability caused by HV-induced hypocapnia leads to spontaneous and/or asynchronous firing of cortical neurones, which in turn reduces stimulus-locked synaptic events.
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  • 91
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    Experimental brain research 124 (1999), S. 42-52 
    ISSN: 1432-1106
    Keywords: Key words Ocular tracking ; Oculomanual coordination ; Electromyography ; Internal model ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  When the eyes and arm are involved in a tracking task, the characteristics of each system differ from those observed when they act alone: smooth pursuit (SP) latency decreases from 130 ms in external target tracking tasks to 0 ms in self-moved target tracking tasks. Two models have been proposed to explain this coordination. The common command model suggests that the same command be addressed to the two sensorimotor systems, which are otherwise organized in parallel, while the coordination control model proposes that coordination is due to a mutual exchange of information between the motor systems. In both cases, the interaction should take into account the dynamic differences between the two systems. However, the nature of the adaptation depends on the model. During self-moved target tracking a perturbation was applied to the arm through the use of an electromagnetic brake. A randomized perturbation of the arm increased the arm motor reaction time without affecting SP. In contrast, a constant perturbation produced an adaptation of the coordination control characterized by a decrease in arm latency and an increase in SP latency relative to motor command. This brought the arm-to-SP latency back to 0 ms. These results support the coordination control model.
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  • 92
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    Experimental brain research 124 (1999), S. 287-294 
    ISSN: 1432-1106
    Keywords: Key words Magnetoencephalography ; V1 cortex ; V2 cortex ; V6 complex ; Horizontal meridian ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  We recorded whole-scalp magnetoencephalographic (MEG) responses to black-and-white checkerboards to study whether the human cortical responses are quantitatively similar to stimulation of the lower and upper visual field at small, 0–6°, eccentricities. All stimuli evoked strongoccipital responses peaking at 50–100 ms (mean 75 ms). The activation was modeled with a single equivalent current dipole in the contralateral occipital cortex, close to the calcarine fissure, agreeing with an activation of the V1/V2 cortex. The dipole was, on average, twice as strong to lower than to upper field stimuli. Responses to hemifield stimuli that extended to both lower and upper fields resembled the responses to lower field stimuli in source current direction and strength. These results agree with psychophysical data, which indicate lower visual field advantage in complex visual processing. Parieto-occipital responses in the putative V6 complex were similar to lower and upper field stimuli.
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  • 93
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    Experimental brain research 126 (1999), S. 289-306 
    ISSN: 1432-1106
    Keywords: Key words Motor control ; Trajectory formation ; Coordination ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  The degrees of freedom problem is often posed by asking which of the many possible degrees of freedom does the nervous system control? By implication, other degrees of freedom are not controlled. We give an operational meaning to ”controlled” and ”uncontrolled” and describe a method of analysis through which hypotheses about controlled and uncontrolled degrees of freedom can be tested. In this conception, control refers to stabilization, so that lack of control implies reduced stability. The method was used to analyze an experiment on the sit-to-stand transition. By testing different hypotheses about the controlled variables, we systematically approximated the structure of control in joint space. We found that, for the task of sit-to-stand, the position of the center of mass in the sagittal plane was controlled. The horizontal head position and the position of the hand were controlled less stably, while vertical head position appears to be no more controlled than joint motions.
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  • 94
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    Experimental brain research 124 (1999), S. 469-473 
    ISSN: 1432-1106
    Keywords: Key words Form from motion ; Visual development ; Visual acuity ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  The development of dynamic vision was investigated in 400 healthy subjects (200 females and 200 males) aged between 4 and 24 years. The test consisted of a computer-generated random-dot kinematogram in which a Landolt ring was briefly presented as a form-from-motion stimulus. Motion contrast between the ring and background was varied in terms of the percentage of dots moving coherently within the ring in four levels (100%, 50%, 30%, and 20%). The subject’s task was to indicate the position of a gap in the ring (left, right, top, bottom). Results show a clear increase in performance with age for all motion contrast levels, with the greatest changes for the lowest levels. Adult performance was reached at the age of 15 years. Luminance-based static acuity measured with the Landolt test was poorly correlated with acuity for its form-from-motion analogue.
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  • 95
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    Experimental brain research 124 (1999), S. 503-512 
    ISSN: 1432-1106
    Keywords: Key words Reaching movements ; Memory for positions ; Laterality ; Posture copying ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  Many recent studies indicate that memory for final position is superior to memory for movement. There is ambiguity about what is meant by the term final position, however. Is it final spatial location or final posture? According to a recently proposed theory by Rosenbaum et al., which maintains that stored postures form the basis for movement planning, when people try to return to recently reached positions, they should try to adopt the postures they just occupied. An alternative view, which holds that movements are primarily planned with respect to spatial locations, predicts that subjects should tend to return to places in external space. We describe an experiment that tested these opposing predictions. The experiment relied on the notion that if people store and use postures, they should ”copy” the posture adopted with one arm to the other arm when possible. The results support this hypothesis.
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  • 96
    ISSN: 1432-1106
    Keywords: Key words Optokinetic nystagmus ; Positron emission tomography ; Visual motion ; Area V5 ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  Positron emission tomography (PET) was used to address the issue of physiological changes in the cerebral cortex associated to optokinetic nystagmus (OKN) in humans. We studied regional cerebral blood flow in eight volunteers during reflexive induction of OKN by a pattern of dots moving unidirectionally (toward the left side). We used two control conditions, with subjects passively viewing either stationary or incoherently moving dots. This paradigm was designed in order to differentiate the OKN-related activations from blood flow changes related to visual motion. When compared with the stationary condition, OKN activated a set of occipital areas known to be sensitive to visual motion. Bilateral activation was found in the striate cortex (V1) and the parieto-occipital fissure, while area V5, the intraparietal sulcus, and the pulvinar were activated only in the left hemisphere. When compared with incoherent motion, OKN activated the V1 and the parieto-occipital fissure bilaterally and the right lingual gyrus, while a signal decrease was observed in the V5 region in both hemispheres. No significant signal changes were found in areas implicated in saccades or in processing vestibular information. These results indicate that processing of OKN-related information is associated with neural activity in a specific set of visual motion areas and suggest that this network can be asymmetrically activated by a strictly unidirectional stimulation. Results are also discussed in terms of the specific kinds of OKN-related information processing subserved by each area in this network.
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  • 97
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    Experimental brain research 126 (1999), S. 175-186 
    ISSN: 1432-1106
    Keywords: Key words Listing’s plane ; Vergence ; Binocular ; Eye movements ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  Earlier studies have reported temporal rotation of Listing’s plane with convergence of the eyes causing torsion, which is dependent on eye elevation. The amount by which the planes rotate differs from study to study. To gain insight into the functional significance of the temporal tilt of Listing’s plane for vision, we examined whether the rotation of the plane depends on the visual conditions, namely on the stimuli driving vergence. In different conditions, accommodative vergence, disparity-vergence, combinations of disparity with accommodation or depth perception were used and the resulting rotation of Listing’s plane was measured. Our findings show, for the first time, that the relationship between convergence and Listing’s-plane temporal rotation depends on the stimuli driving vergence. When the stimulus contains only disparity cues, vergence and Listing’s plane rotate immediately and consistently among subjects. Accommodative vergence, the mutual couplings between vergence and accommodation, can influence the orientation of Listing’s plane, but they do so in a idiosyncratic way. The largest rotation was elicited by stereograms combining disparity-vergence with depth perception. These findings support the idea of a functional role of Listing’s plane rotation for binocular vision, perhaps for depth perception.
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  • 98
    ISSN: 1432-1106
    Keywords: Key words Grip force ; Force control ; Parabolic flight ; Microgravity ; Hypergravity ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  In the present study, grip forces exerted against a stationary held object were recorded during parabolic flights. Such flight maneuvers induce changes of gravity with two periods of hypergravity, associated with a doubling of normal terrestrial gravity, and a 20 s period of microgravity. Accordingly, the object’s weight changed from being twice as heavy as normally experienced and weightless. Grip-force recordings demonstrated that force control was seriously disturbed only during the first experience of hyper- and microgravity, with the grip forces being exceedingly high and yielding irregular fluctuations. Thereafter, however, grip force traces were smooth, the force level was scaled to the object’s weight under normal and high-G conditions, and the grip force changed in parallel with the weight during the transitions between hyper- and microgravity. In addition, during weightlessness, when virtually no force was necessary to stabilize the object, a low force was established, which obviously represented a reasonable safety margin for preventing possible perturbations. Thus, all relevant aspects of grip-force control observed under normal gravity conditions were preserved during gravity changes induced by parabolic flights. Hence, grip-force control mechanisms were able to cope with hyper- and microgravity, either by incorporating relevant receptor signals, such as those originating from cutaneous mechanoreceptors, or by adequately including perceived gravity signals into control programs. However, the adaptation to the uncommon gravity conditions was not complete following the first experience; finer tuning of the control system to both hyper- and microgravity continued over the measurement interval, presumably with a longer observation period being necessary before a stable performance can be reached.
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  • 99
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    Experimental brain research 129 (1999), S. 156-160 
    ISSN: 1432-1106
    Keywords: Key words Optokinetic nystagmus ; Depth-from-motion ; Transparent motion ; Ambiguous ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  When two visual patterns moving in opposite directions are superimposed, they appear to be at different depths and to slide over each other. Because the stimulus does not specify the depth-order between the surfaces, this transparent motion perception is essentially ambiguous. With prolonged observation, the perceived depth-order of the two moving surfaces reverses spontaneously. In the present study, the correlation between the perceived direction of transparent motion and optokinetic nystagmus (OKN) was examined. While viewing superimposed random-dot patterns moving in opposite horizontal or vertical directions, subjects attempted to fixate the center of the stimulus, while paying attention to either the near or far depth plane, and reported any changes of the direction of surface-motion at the attended depth. Even with attention focused on a particular depth, the spontaneous reversal of transparent motion perception still occurred. This indicates that the perceptual reversal may reflect a preattentive mechanism for depth-from-motion. Furthermore, the OKN slow-phase tended to be in the same direction as the perceived motion of the surface at the attended depth. These results support the idea that the mechanisms for OKN maintenance are sensitive to perception of depth-from-motion and, therefore, cortically mediated.
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  • 100
    ISSN: 1432-1106
    Keywords: Key words Reaching movements ; Grasping movements ; Prehension ; Manual control ; Computational model ; Human
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  Reaching and grasping an object can be viewed as the solution of a multiple-constraint satisfaction problem. The constraints include contact with the object with the appropriate effectors in the correct positions as well as generation of a collision-free trajectory. We have developed a computational model that simulates reaching and grasping based on these notions. The model, rendered as an animation program, reproduces many basic features of the kinematics of human reaching and grasping behavior. The core assumptions of the model are: (1) tasks are defined by flexibly organized constraint hierarchies; (2) manual positioning acts, including prehension acts, are first specified with respect to goal postures and then are specified with respect to movements towards those goal postures; (3) goal postures are found by identifying the stored posture that is most promising for the task, as determined by the constraint hierarchy, and then by generating postures that are more and more dissimilar to the most-promising stored posture until a deadline is reached, at which time the best posture that was found during the search is defined as the goal posture; (4) depending on when the best posture was encountered in the search, the deadline for the search in the next trial is either increased or decreased; (5) specification of a movement to the goal posture begins with straight-line interpolation in joint space between the starting posture and goal posture; (6) if an internal simulation of this default movement suggests that it will result in collision with an obstacle, the movement can be reshaped until an acceptable movement is found or until time runs out; (7) movement reshaping occurs by identifying a via posture that serves as a body position to which the actor moves from the starting posture and then back to the starting posture, while simultaneously making the main movement from the starting posture to the goal posture; (8) the via posture is identified using the same posture-generating algorithm as used to identify the goal posture. These processes are used both for arm positioning and, with some elaboration, for prehension. The model solves a number of problems with an earlier model, although it leaves some other problems unresolved.
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