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  • Inorganic Chemistry  (47)
  • Life and Medical Sciences  (8)
  • Chemical Engineering
  • Wiley-Blackwell  (57)
  • Nature Publishing Group
  • Oxford University Press
  • 1995-1999  (57)
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  • Wiley-Blackwell  (57)
  • Nature Publishing Group
  • Oxford University Press
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  • 1
    Electronic Resource
    Electronic Resource
    [Gd4(C2)](Cl, I)6, an Interstitially Stabilized Heteroleptic Gadolinium SesquihalideDedicated to Professor John D. Corbett on the Occasion of his 70th Birthday (1996)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 622 (1996), S. 494-500 
    Details
    ISSN: 0044-2313
    Keywords: Gadolinium sesquihalide ; interstitial carbon units ; crystal structure ; electronic structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: [Gd4(C2)](Cl, I)6, ein interstitiell stabilisiertes, heteroleptisches Gadoliniumsesquihalogenid[Gd4(C2)](Cl, I)6 erhält man aus CsI, Gd, GdCl3 und C2I4 in verschweißten Niob-Ampullen bei 1000/800°C in Form von schwarzen, glänzenden Nadeln. Die Kristallstruktur (tetragonal; P4/mbm; Z = 2; a = 1347,5(1); c = 1212,5(1) pm) ist ähnlich wie jene von Na[Mo4]O6 bzw. [Sc4B]Cl6. Trans-kantenverknüpfte [Gd6]-Oktaeder verlaufen parallel [001]. Sie enthalten interstitielle C2-Einheiten, Jedes dritte Oktaeder enthält fehlgeordnete C2-Einheiten, senkrecht zu jenen in den benachbarten [Gd6(C2)]-Oktaedern. Diese sind daher entlang der (pseudo)-C4-Achse gestaucht. Rechnungen zur elektronischen Struktur zeigen, daß insgesamt 13 Elektronen zur Auffüllung aller Metall-Metall-bindenden Zustände für eine „leere“ [Gd4]Cl6-Struktur nötig wären. Die Einlagerung der C2-Dimeren verändert die Bindungsverhältnisse in [Gd4(C2)]X6 (X = Cl, I) erheblich. Die formale Ladung von -6 der C2-Einheit wird durch das Aufsplitten der πg-Zustände reduziert, Gd—Gd und Gd—C-bindende Zustände werden besetzt und bindende dx2-y2-Orbitale kombinieren zu den am niedrigsten liegenden nicht besetzten Zuständen.
    Notes: [Gd4(C2)](Cl, I)6 is obtained from CsI, Gd, GdCl3 and C2I4 in sealed niobium containers at 1000/800°C as black, shiny needles. The crystal structure (tetragonal, P4/mbm, Z = 2, a = 1347.5(1), c = 1212.5(1) pm) is similar to that of Na[Mo4]O6 and [Sc4B]Cl6. It may be regarded as being built from octahedra sharing common trans edges running in the [001] direction. The octahedra contain C2 units as interstitials. Every third octahedron contains a disordered C2 unit perpendicular to those in the two neighboring [Gd6(C2)] octahedra and is therefore compressed in the direction of the (pseudo) C4 axis. Calculations of the electronic structure of an “empty” [Gd4]Cl6 structure reveals a total of 13 electrons necessary to occupy all metal-metal bonding states. The incorporation of a carbon dimer substantially alters the bonding conditions for [Gd4(C2)]X6 (X = Cl, I). The formal charge of -6 of the C2 unit is significantly reduced as πg states split up, Gd—Gd and Gd—C bonding states are occupied and bonding dx2—y2 orbitals combine to form the lowest unoccupied energy states.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19966220318
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  • 2
    Electronic Resource
    Electronic Resource
    Dimeric Silver(I) Complexes of Some Isothiazole-Based LigandsDedicated to Prof. Dr. Rolf Gleiter on the occasion of this 60th birthday. (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 95-100 
    Details
    ISSN: 0009-2940
    Keywords: Isothiazole complexes ; Dinuclear silver(I) complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of isothiazole-based potential ligands bearing substituents with additional donor sites in the 5-position of the heterocycle was synthesized [3-Me-5-R-C3HNS; R = CH=N(CH2)2py (1), CH=NCH2py (2), CH2N(CH2CH2NEt2)2 (4), (CH2)2SMe (5)]. Upon reaction with AgO3SCF3 they formed complexes [(1)AgOSO2CF3]2 (6), [(2)AgOSO2CF3]2 (7), [(4)Ag]2+2(O3SCF-3)2 (8) and [(5)AgOSO2CF3]2 (9), respectively. 6, 8 and 9 were shown by X-ray structural analyses to consist of dimeric units L2Ag2+2, either discrete (8), coordinated by terminal CF3SO-3 units (6). In 8 and 9 the isothiazole moiety is bonded to the metal center via the ring-N. The coordination potential of the isothiazole heterocycle is discussed.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300115
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  • 3
    Electronic Resource
    Electronic Resource
    Pyrazolate-Based Oligonuclear Copper and Silver Complexes with N/S Coordination SpheresDedicated to Prof. Dr. Gottfried Huttner on the occasion of his 60th birthday. (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1441-1447 
    Details
    ISSN: 0009-2940
    Keywords: Pyrazolate complexes ; Bridging ligands ; Copper ; Silver ; N,S-Donor Ligands ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of pyrazole-based potential ligands bearing thioether substituents in 3- and 5-positions of the heterocycle was synthesized [3,5-bis(RSCH2)-pyzH R=Ph (1aH), PhCH2 (1bH), iPr (1cH), tBu (1dH)]. These ligands afford oligonuclear Cu1 and Ag1 coordination compounds [LCu]x (2a-c, L = 1a - c) and [LAg]x (3a-d, L = 1a-d), respectively. The single crystal X-ray analysis of 3c shows the presence of trimeric planar arrays of N,N′-bridging pyrazolates and linear coordinated silver ions, with each two of the trinuclear moieties being linked by two unsupported short intermolecular Ag…Ag contacts [3.041(1) Å]. Molecular-weight determinations for 2a (THF) and 3c (toluene) indicate that hexanuclear entities are preserved in solution. Starting from 1bH the CuII complex [(1b)2Cu2](BF4)2 (4) was synthesized. According to an X-ray crystal structure analysis it consists of dinuclear molecules with two bridging pyrazolates, distorted square planar N2S2 coordination spheres for Cu11 and an axially bridging tetrafluoroborate. Magnetic susceptibility data reveal an antiferromagnetic exchange (J = -206 cm-1) that is among the highest found for doubly pyrazolate bridged dicopper(II) complexes, which is rationalized on the basis of the rather symmetric dinuclear core of 4. The irreversibility of the electrochemical reduction and oxidation processes for the CuII and CuI compounds, respectively, is explained by the inability of the respective coordination framework to adapt to different geometric preferences.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971301014
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  • 4
    Electronic Resource
    Electronic Resource
    Dinuclear Cobalt(II) Complexes of Pyrazole Ligands with Chelating Side ArmsDedicated to Prof. Dr. Walter Siebert on the occasion of his 60th birthday. (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 605-613 
    Details
    ISSN: 0009-2940
    Keywords: Pyrazolate complexes ; Dinuclear complexes ; Bridging ligands ; Cobalt ; Conformational analysis ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of pyrazole-based potential ligands bearing polydentate amine substituents in the 3- and 5-positions of the heterocycle has been synthesized [3,5-bis(R2NCH2)-pyzH R2N = Me2N(CH2)3NMe (2aH), [Me2N(CH2)3]2N (2bH), (Et2NCH2CH2)2N (2cH)]. Upon reaction with two equivalents of CoCl2 they form complexes LCo2Cl3 (3a-c; L = 2a-c, respectively) which are shown crystallographically to contain a dinuclear metal core bridged by both the pyrazolate unit and a chlorine atom, with each cobalt center carrying a further terminal chlorine atom. Two of the ligand side arms in 3b, c are dangling, thus leading to five-coordination of the cobalt(II) centers in all cases. Addition of two equivalents of NaBPh4 to solutions of 3b, c induced coordination of the formerly dangling side arms to the metal centers by substitution of the terminal chlorine atoms. The resulting compounds [LCo2Cl](BPh4)2 (4b, c, respectively) were characterized by X-ray structure analyses. They can be viewed as dinuclear linked versions of tran-type complexes [(tran = tris(aminoalkyl)amine] with distorted trigonal-bipyramidal coordination spheres around cobalt(II). Conformational analyses employing force-field calculations were carried out for 4b, c in order to rationalize the conformations observed in the solid state with regard to the accessible conformational space.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300511
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  • 5
    Electronic Resource
    Electronic Resource
    1,1-Hydroborierung von Alkinen mit 6-Aza-nido-decaboranen (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 947-951 
    Details
    ISSN: 0009-2940
    Keywords: 6-Aza-nido-decaborane ; 9-(1-Alkenyl)-6-phenyl-6-aza-nido-decaborane ; 1,1-Hydroboration of alkynes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1,1-Hydroboration of Alkynes with 6-Aza-nido-decaboranes[1]Alkynes AC≡CR′ (R′ = Me, Bu, tBu, SiMe3), that contain a mobile group A, like H or SiMe3, undergo hydroboration by 6-aza-nido-decaboranes RNB9H11 (1a-c, R = H, Ph, PhCH2) and 1,2-migration of the group A, to give the corresponding 9-(1-alkenyl)-6-aza-nido-decaboranes RNB9H10(CH=CR′A) (2a-h). Ethenes AHC=CH2 (A = SiMe3, SnBu3) are hydroborated by 1a, b as well to form products of the type RNB9H10(CH2CH2A) (3a-c). The alkyne Me3SiC=CH undergoes a hydroboration with 1b twice; the formation of (PhNB9H10)2CHCH2SiMe3 (4) proceeds by a 1,1- and a 1,2-hydroboration step, apparently. The crystal structure analysis of (PhCH2)NB9H10[CH=CMe(SiMe3)] (2e; space group Pl) reveals a (Z configuration of the ethene moiety.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19951280916
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  • 6
    Electronic Resource
    Electronic Resource
    Öffnung des Aza-closo-dodecaboran-Gerüsts durch Basen (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 1225-1229 
    Details
    ISSN: 0009-2940
    Keywords: 1-Organo-1-aza-closo-dodecaborane(12) ; Trialkylamine-1-organo-1-aza-nido-dodecaborane(12) (1/1) ; Undecahydro-1-organo-1-aza-nido-dodecaborate(1-), 2-hydro-, 2-halogeno-, 2-alkoxy-, 2-amino-, 2-alkyl- ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Opening of the Aza-clso-dodecaborane Skeleton by BasesThe aza-closo-borane PhNB11H11 (1a) is opened by the amines NR3 (R = Me, Et) to give the novel aza-nido-dodecaboranes PhNB11H11(NR3) (2a, b). The non-planar open pentagonal face of 2a, b accomodates the N atom, a BHB bridge, and the base-bound B atom, according to NMR spectra and the crystal structure analysis of monoclinic 2b. A similar but more symmetric structure is found when closo-RNB11H11 (1a-c, R = Ph, Me, H) is attacked by anionic bases X- to give nido-RNB11H11X- (3a-j; R/X = Me/H, Me/F, Me/Cl, Ph/OH, H/OMe, Me/OMe, Me/OtBu, Me/NEt2, Me/Me, Me/Bu). The anions are precipitated with cations [K([18]crown-6)], [S(NMe2)3], [N(PPh3)2], [Et2NH2], or [Li(tmeda)2]. The nido-structures of type 2 and 3 are derived from the hypothetical closo-NB12H13.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19951281214
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  • 7
    Electronic Resource
    Electronic Resource
    Prenatal development of the integument in Delphinidae (Cetacea: Odontoceti) (1995)
    New York, NY : Wiley-Blackwell
    Journal of Morphology 223 (1995), S. 269-287 
    Details
    ISSN: 0362-2525
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: The prenatal development of epidermis, dermis, and hypodermis was studied in embryos of different ago of two delphinid species (Stenella attenuata, Delphinus delphis), using light and transmission electron microscopical methods. The delphinid embryo is covered by a multilayered tissue formed by four different epidermal generations (periderm, stratum intermedium-I, str. intermedium-II, str. spinosum) produced by the str. basale. The first layer appears at about 40-50 mm of body length, the second type (s.i.-I) about 60-160 mm, and the third type (s.i.-II) is present at 160-500 mm. The first spinosal cells are produced at 225-260 mm body length; thenceforth, the epidermis increases continuously in thickness. Epidermal ridge formation begins about 400-mm body length. The development of the dermis is characterized by the early production of thin connective tissue fibers (40- 70-mm body length) and simultaneously the cutaneuous muscle matures in structure. Vascular development intensifies between embryos of 150-225 mm, and collagen production increases markedly in fetuses of 225-260-mm length. These events are paralledled by an increase in dermal thickness. The first elastic fibers can be recognized in the skin from the abdomen at about 600-mm body length. The development of the hypodermis is marked by very rapid and constantly progressing growth, beginning about 60-mm body length. The first typical fat cells appear in animals of 360-400 mm. Regional differences are obvious for all skin layers with regard to the flippers, where structural maturation proceeds more rapidly than in dorsal or abdominal regions. © 1995 Wiley-Liss, Inc.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/jmor.1052230305
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  • 8
    Electronic Resource
    Electronic Resource
    Tubulin gene expression during growth and maturation of leaves with different developmental patterns (1995)
    New York, NY : Wiley-Blackwell
    Cell Motility and the Cytoskeleton 30 (1995), S. 67-72 
    Details
    ISSN: 0886-1544
    Keywords: Nicotiana ; Hordeum ; microtubule ; cell differentiation ; Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: Changes in the tubulin-protein and -poly(A)+RNA contents were monitored by means of Western and Northern blot analyses, respectively, during growth and maturation of leaves of a dicotyledonous (tobacco) and monocotyledonous (barley) plant. It was recently argued from immunofluorescence and preliminary biochemical data that the density of microtubular networks and concomitantly the tubulin content are distinctly reduced after cessation of cell growth in leaves [Jung et al., 1993]. The results presented now confirm and extend this view. There appeared to be clear differences between the monocot and the dicot: (1) the loss of tubulin during leaf development was much slower in the dicot than in the monocot leaves (within months instead of days); (2) the degree of loss was more dramatic in the monocot leaf and only very low threshold levels of tubulin were retained in fully differentiated tissues; and (3) the loss of tubulin in the monocot leaf tissue appeared to be correlated with the decrease in the mRNA content, whereas the high level of tubulin-RNA in fully differentiated or even almost senescent dicot leaves indicated a gene expression control at the posttranscriptional level.The comparatively rapid and very distinct tubulin-protein and -RNA disappearance during development of the monocot leaf tissues confirm at the molecular level that differentiation proceeds much faster and is much more determinative in these leaves, as was postulated from histological and physiological data. The differences in the behaviour of the microtubular cytoskeleton perhaps even reflect the differences in the ability of the differentiated leaf cells to dedifferentiate, i.e., to establish new sets of microtubules and to reenter the mitotic cell cycle, e.g., during would response, tumour induction or in vitro culture. © 1995 Wiley-Liss, Inc.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cm.970300108
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  • 9
    Electronic Resource
    Electronic Resource
    Glucose hydrolysis and oxidation in supercritical water (1995)
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 637-648 
    Details
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Glucose hydrolysis and oxidation occurred rapidly in supercritical water at 246 bar and at 425 to 600°C. A diverse set of products, present in the liquid-phase reactor effluent and also subject to hydrolysis, was formed. At 600°C and a 6-s reactor residence time, glucose is completely gasified, even in the absence of oxygen. In the presence of oxygen, destruction of liquid-phase products is enhanced, with none found above 550°C at a 6-s reactor residence time. Major products formed wee acetic acid, acetonylacetone, propenoic acid, and acetaldehyde in the liquid phase, and carbon monoxide, carbon dioxide, methane, ethane, ethylene, and hydrogen in the gas phase. Methane and hydrogen were present among the products at temperatures up to 600°C for reactor residence times of 6 s.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/aic.690410320
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  • 10
    Electronic Resource
    Electronic Resource
    Acetic acid oxidation and hydrolysis in supercritical water (1995)
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 2108-2121 
    Details
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Acetic acid (CH3COOH) hydrolysis and oxidation in supercritical water were examined from 425 - 600°C and 246 bar at reactor residence times of 4.4 to 9.8 s. Over the range of conditions studied, acetic acid oxidation was globally 0.72 ± 0.15 order in acetic acid and 0.27 ± 0.15 order in oxygen to a 95% confidence level, with an activation energy of 168 ± 21 kJ/mol, a preexponential factor of 109.9 ± 1.7 and an induction time of about 1.5 s at 525°C. Isothermal kinetic measurements at 550°C over the range 160 to 263 bar indicated that pressure or density did not affect the rate of acetic acid oxidation as much as was previously observed in the oxidation of hydrogen or carbon monoxide in supercritical water. Major products of acetic acid oxidation in (upercriuical water are carbon dioxide, carbon monoxide, methaite, and hydrogen. Trace amounts of propenoic acid were occasionally detected. Hydrolysis or hydrothermolysis in the absence of oxygen resulted in approximately 35% conversion of acetic acid at 600°C, 246 bar, and 8-s reactor residence time. Regression of the limited hydrolysis runs assuming a reaction rate first-order in organic gave a global rate expression with a preexponential factor of 104.4 ± 1.1 and an activation energy of 94 ± 17 kJ/moL.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/aic.690410910
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