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  • Chemistry  (29)
  • 42.20  (2)
  • 74.70.Vy  (2)
  • Biochemistry and Biotechnology  (2)
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  • 1
    ISSN: 1434-6079
    Keywords: 74.30.Gn ; 74.70.Vy ; 76.60.Es
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract 13C and31P solid state NMR measurements on the organic ligands in ligated Au55, Ni8, Pt309, Cu36 and Cu70 clusters are reported. The ligands behave like diamagnetic organic molecules, giving rise to relatively narrow lines with excellent cross-polarization efficiency. The resonance lines of the nuclei directly bound to the metal core are systematically broadened in the conducting compounds. No pronounced Knight shifts or evidence of metallic-like relaxation were observed. These results support a model for the electrical conduction involving tunneling between metal cores with the ligands playing the role of a tunneling barrier.
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 33 (1989), S. 1445-1460 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A previously isolated cellodextrin glucohydrolase (β-glucosidase) from Trichoderma reesei QM 9414 is characterized using β-1,4-glucose oligomers with defined degrees of polymerization as soluble substrates. The enzyme splits off glucose units from the nonreducing chain ends of cellooligomers. Besides this hydrolytic activity there is also evidence for transfer activity depending on the concentration and degree of polymerization of substrates. Concentration-time-course data have been gathered for the degradation of cellobiose, cellotriose, cellotetraose, cellopentaose, and cellohexaose covering a wide range of enzyme and substrate concentrations. A Michaelis-Menten type kinetic model has been developed, which is able to satisfactorily describe the complex system of parallel and series reactions during the conversion of oligomers to glucose. The only kind of inhibition considered is competitive inhibition by the final product glucose. The model takes into account the formation of multiple enzyme-substrate complexes and is limited to those conditions, in which no transglucosylation products are observed. Cellodextrins with higher degrees of polymerization are found to be better substrates for this enzyme than is the dimer cellobiose.
    Additional Material: 12 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 30 (1987), S. 571-585 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A β-glucosidase (E.C. 3.2.1.21) was isolated from the culture filtrate of fungus Trichoderma reesei QM 9414 grown in continuous culture with biomass retention. The crude extracellular enzyme preparation was fractionated by a three-step purification procedure [chromatography on Fractogel HW-55 (S) and Bio-Gel A 0.5 plus final preparative isoelectric focusing] to yield three β-glucosidases with isoelectric points at pH 8.4, 8.0, and 7.4. Only one enzyme (pi 8.4) met the stringent criterion of being homogeneous according to titration curve analysis. This enzyme was then characterized not to be a glycoprotein, although the native protein contained 35% carbohydrate (as glucose). It was found to have an apparent molar mass of 7 × 104 g/mol (SDS-PAGE), exhibited its optimum activity towards cellobiose at pH 4.5 and 70°C (30 min test), and lost less than 3% activity at 50°C over a period of 7 h. The KM values towards cellobiose and p-nitrophenyl-β-D-glucopyranoside were determined to be 0.5mM and 0.3mM, respectively. The enzyme hydrolyzed cellodextrins (cellotriose to cellooctaose) by sequentially splitting off glucose units from the nonreducing end of the oligomers. The extent of the observed transfer reactions varied with the initial substrate concentration. No enzyme activity towards microcrystalline cellulose or carboxymethylcellulose could be detected. The classification of the enzyme as β-glucosidase or exo-β-1,4-glucan glucohydrolase is discussed with respect to the exhibited hydrolytic activities.
    Additional Material: 11 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    The European physical journal 20 (1991), S. 297-300 
    ISSN: 1434-6079
    Keywords: 33.20.K ; 36.40 ; 42.20 ; 78.40 ; 82.70
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract Au55 cluster compounds are investigated by optical spectroscopy and TEM. The optical spectra appear to be rather structureless, neither showing a collective excitation resonance nor exhibiting distinct absorption bands known from lower nuclearity clusters. We discuss changes of the electronic properties compared to larger Au clusters affecting both, 6sp electrons and5d-6sp interband transitions, the cluster-ligand-interaction being considered as a charge transfer process. We additionally report on a low temperature instability of the cluster compound, which results in changed optical extinction spectra. A characteristic absorption feature at λ=400 nm is attributed to small, ligand-free Au cluster fragments.
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  • 5
    ISSN: 1434-6079
    Keywords: 74.30.Gn ; 74.70.Vy ; 76.60.Es
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract 195Pt NMR on the organic ligand stabilized metal cluster compound Pt309Phen 36 * O30 reveals two separate peaks in the lineshape. Ligand-bonded platinum atoms at the surface of the core are thought to be responsible for the peak that does not show any Knight shift. The corresponding spin-lattice relaxation timeT 1 is of the order of seconds. The second peak is Knight shifted and is attributed to the other Pt atoms, for which metallic behavior is inferred from the temperature dependence ofT 1. The Korringa relation holds down to 65 K. Below 65 K the relaxation of the magnetization becomes increasingly non-exponential with decreasing temperature. The relaxation process can be successfully modelled under the assumption of a Poisson distribution of the energy levels around the Fermi energy (the electronic quantum size effect).
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    The European physical journal 12 (1989), S. 515-520 
    ISSN: 1434-6079
    Keywords: 33.20.K ; 36.40 ; 42.20 ; 78.40 ; 82.70
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract Gold cluster compounds were investigated which contain clusters of 55 gold atoms in each unit. The ligands stabilize these clusters and, hence, many-cluster systems can be prepared which mainly show the properties of the single dressed cluster. Experimental results of optical and electron-microscopical investigations are presented and shortly discussed in view of the question whether the clusters are molecular or solid-state like.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 418 (1975), S. 243-246 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: P2J3 - a New Complex LigandP2J4 and Na2Cr(CO)5 react in benzene to the monomeric diamagnetic complex (CO)4CrP2J3. The 31P-nmr spectrum shows the presence of different bonded phosphorus atoms. The exchange of one iodine atom between the P atoms leads to a temperature dependent equilibrium with a symmetrical transition state. Triphenyl- and tricyclohexylphosphine react with (CO)4CrP2J3 to (CO)4CrPJ2 · P(C6H5)3 resp. (CO)4CrPJ2 · P(C6H11)3, probably of dimeric nature.
    Notes: P2J4 und Na2Cr(CO)5 reagieren in Benzol zu dem monomeren, diamagnetischen Komplex (CO)4CrP2J3. Das 31P-NMR-Spektrum zeigt die Anwesenheit unterschiedlich gebundener Phosphoratome. Der Austausch eines Jodatoms zwischen den P-Atomen führt zu einem temperaturabhängigen Gleichgewicht, in dem ein symmetrischer Übergangszustand auftritt. Triphenyl- und Tricyclohexylphosphin reagieren mit (CO)4CrP2J3 zu (CO)4 · P(C6H5)3 bzw. (CO)4 CrPJ2 · P(C6H11)3, wahrscheinlich dimerer Natur.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 415 (1975), S. 97-103 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Experiments on the Oxidative Addition of Thionylhalides to Transition Metal ComplexesThe complexes [(C6H5)3P]4Pd and [(C6H5)3P]2Ni(NO)Cl react with SOX2 to trans [(C6H5)3P]2PdX2 (X = Cl, Br) resp. to [(C6H5)3PX][NiX3] (X = Cl). Furthermore (C6H5)3PO and (C6H5)3PS are formed. In contrast SOCl2 is added oxidatively by [(C6H5)3P]2Ir(CO)Cl to the complex [(C6H5)3P]2Ir(CO)(Cl2)SOCl.
    Notes: Die Komplexe [(C6H5)3P]4Pd und [(C6H5)3P]2Ni(NO)Cl reagieren mit SOX2 zu trans-[(C6H5)3P]2PdX2 (X = Cl. Br) bzw. [(C6H5)3PX][NiX3] (X = Cl). Weiterhin bilden sich (C6H5)3PO und (C6H5)3PS. Im Gegensatz dazu wird SOCl2 durch [(C6H5)3P]2 Ir(CO)Cl oxydativ zu dem Komplex [(C6H5)3P]2 Ir(CO)(Cl2)SOCl addiert.
    Additional Material: 1 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 432 (1977), S. 160-166 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Use of Elemental Phosphorus as Ligand in Iron CarbonylsWhite phosphorus and Fe2(CO)9 react in benzene at room temperature to the monomeric diamagnetic complex [(CO)4Fe]3P4. The Mössbauer spectrum proves the presence of penta- and hexacoordinated Fe atoms in the ratio 1:2. The i.r. spectrum also suggests different bonded Fe(CO)4 groups. As the 31P-n.m.r. spectrum shows, the 4 P atoms are equivalent. It is supposed that one Fe(CO)4 group fluctuates between the P atoms. At 70°C P4 and Fe2(CO)9 react to the polymeric diphosphorous complex [(CO)3FeP2]n. Its synthesis succeeds also with Fe(CO)5 and P4 under u.v. irradiation. Additionally [(CO)4Fe]3P4 can be decomposed to [(CO)3FeP2]n by warming or irradiation. The Mössbauer spectrum of this complex shows equivalent Fe atoms with the coordination number 6. Possible structures are discussed.
    Notes: Weißer Phosphor und Fe2(CO)9 reagieren in Benzol bei Raumtemperatur zu dem monomeren, diamagnetischen Komplex [(CO)4Fe]3P4. Das Mössbauerspektrum belegt die Anwesenheit fünffach und sechsfach koordinierter Fe-Atome im Verhältnis 1:2. Auch das IR-Spektrum legt unterschiedlich gebundene Fe(CO)4-Gruppen nahe. Wie das 31P-NMR-Spektrum zeigt, sind alle 4 P-Atome äquivalent. Es wird angenommen, daß eine Fe(CO)4-Gruppe zwischen den P-Atomen fluktuiert. Bei 70°C setzen sich P4 und Fe2(CO)9 zu dem polymeren Diphosphorkomplex [(CO)3FeP2]n um. Dessen Synthese gelingt auch aus Fe(CO)5 und P4 unter UV-Bestrahlung. Ebenso kann [(CO)4Fe]3P4 durch Erwärmen oder Belichten in [(CO)3FeP2]n zersetzt werden. Das Mössbauerspektrum dieses Komplexes zeigt äquivalente Fe-Atome mit der Koordinationszahl 6. Mögliche Strukturen werden diskutiert.
    Additional Material: 5 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 345 (1966), S. 69-78 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: A hypothesis is presented on the formation of stable covalent metal boron bonds in molecular compounds, and the synthesis of X2B—Mn(CO)4P(C6H5)3 and XB[Mn(CO)4P(C6H5)3]2 (X = C6H5, C4H9, Cl, NR2, OCH3) is described. These compounds are more stable than the corresponding Mn(CO)5-derivatives. This is attributed to differences in the electron density at the manganese atom. 11B - NMR studies are interpreted in terms of back-donation of metal d-electrons to the tervalent boron atom.
    Notes: Nach kurzer Erörterung einiger Leitgedanken, die dem Aufbau kovalenter Bor - Metall Bindungen in molekularen Verbindungen zugrunde liegen, wird die Synthese von X2B—Mn(CO)4P(C6H5)3 und XB[Mn(CO)4P(C6H5)3]2 (X = C6H5, C4H9, Cl, NR2, OCH3) beschrieben. Diese Verbindungen sind stabiler als die entsprechenden Mn(CO)5-Derivate, was wahrscheinlich auf Unterschieden in der Elektronendichte an den Manganatomen beruht. 11B-kernresonanzspektroskopische Untersuchungen weisen auf eine Beteiligung der Metall-d-Elektronen an der Mangan--Bor-Bindung hin.
    Additional Material: 3 Tab.
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