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  • Organic Chemistry  (75)
  • Computational Chemistry and Molecular Modeling  (26)
  • Wiley-Blackwell  (101)
  • 1990-1994  (67)
  • 1980-1984
  • 1955-1959  (34)
  • 1990  (67)
  • 1957  (13)
  • 1955  (21)
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  • Wiley-Blackwell  (101)
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  • 1990-1994  (67)
  • 1980-1984
  • 1955-1959  (34)
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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 332 (1990), S. 367-374 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Investigations on Regioselectivity of Wittig-Horner and Reformatsky-Reactions on Selected 3,17-Dioxo SteroidsThe Reformatsky synthesis and the Wittig-Horner olefination of 3,17-dioxo steroids like androsta-1,4-diene-3,17-dione (ADD) 1 and androst-4-ene-3,17-dione (AD) 2 is described. There are differences in the regioselective introduction of identical substructures with these two methods resulting from different nucleophilicity and stereoelectronical relations of these two reagents. In Reformatsky synthesis the oxo group in 3-position predominantly reacts, whereas in the Wittig-Horner olefination (in the case of 1) the reaction occurs mainly in the 17-position.The structures of all new compounds has been confirmed by spectroscopical data.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 153-166 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A pair-excitation-multiconfigurational-self-consistent-field (PEMCSCF) study with 10 configurations has been carried out on 3-methyl-1,2,4-oxadiazolin-5-one (3-methyl pseudosydnone) which has normal covalent bonds but is isoelectronic with 3-methyl sydnone for which no single covalent valence bond structure can be drawn. The PEMCSCF results were found to be very similar for the two isoelectronic compounds and an attempt was made to represent the bonding of the sydnone in only two simple molecular-orbital-valence-bond (MOVB) configurations using a Luken-type correlating orbital. A compact minimum basis of Slater-Transform-Preuss functions fitted by six cartesian gaussian orbitals (STP-6G) is used to express the compact representation for chemical comparison to experiment. The molecular geometry was gradient-optimized at the single determinantal level using a 6-31G extended basis set. “Orthonormal Resonance Analysis” is given for the two dominant configurations by noting that the Boys-Reeves configuration interaction algorithm is identical to the Pauling valence bond algorithm except for use of orthogonal molecular orbitals instead of atomic hybrid orbitals. This equivalence permits use of PEMCSCF atomic charges, bond orders, and dipole moments in a slightly modified valence bond interpretation of the unusual bonding of this compound. Although forcing a larger PEMCSCF problem into a minimum basis and only two configurations raises the energy, chemical interpretation is simplified. This comparison between a mesoionic compound and an isoelectric compound with normal bonding offers new understanding of the mesoionic effect.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Applied Organometallic Chemistry 4 (1990), S. 375-378 
    ISSN: 0268-2605
    Keywords: Antitumor agent ; cisplatin ; bioisostere ; aminoalkylsilane platinum complex ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: [Bis(aminomethyl)dimethylsilane]platinum(II) dichloride (1) was synthesized by a three-step procedure. The antitumor activity of 1 was evaluated in the i.p. implanted mouse L1210 leukemia model. A 10 mg kg-1 dose administered every fourth day for a total of three injections extended the median life span of the dying mice by at least 100% and resulted in 40-50% survivors (day 30) in two experiments corresponding to an approximate 6 log10 reduction in tumor burden at the end of treatment. Compound 1 appeared at least as active as cisplatin under the testing protocols utilized. The closely related bis[aminomethyltrimethylsilane]platinum(II) dichloride complex was inactive in this mouse model.
    Additional Material: 1 Tab.
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 73 (1990), S. 1805-1817 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: High-level ab initio calculations have been made for fluoromethylamine to study structural and energetic effects of the relative orientation of the N lone pair to the C—F bond. The anti-conformer (N lone pair anti-planar to the C—F bond) corresponds to the global energy minimum. It has the longest C—F distance, the shortest C—N distance, and is 7.5 kcal·mol-1 more stable than the related perpendicular conformation (lone pair perpendicular to the C—F bond). The syn-conformation also shows hallmarks of the anomeric effect: long C—F bond, short C—N bond, and energetic stability when allowance is made for the two pairs of eclipsed hydrogens. The transition state for N inversion is close to the syn-structure; rotation about the C—N bond is strongly coupled with this inversion process. Small bond distance changes of ca. 0.02 Å between parallel and perpendicular conformations are associated with dissociation energy differences of ca. 30 kcal·mol-1. Various criteria for assessing the strength of the anomeric effect are discussed.
    Additional Material: 10 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 173-179 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This short review concerns the protonation of Schiff bases by halogenic or carboxylic acids with a bias toward the chromophore of visual and bacterial rhodopsins. It is pointed out that the weak acids available in these pigments could not protonate the retinyl Schiff base 100% and that a supporting mechanism is needed to achieve full protonation. Our Fourier transform infrared studies both at room and low temperatures relating to this problem are summarized, and the propable role of water is emphasized.
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 501-520 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The role, and limitations, of the fundamental physical quantities used in our current system of dosimetry for the protection of individuals against the hazardous effects of ionizing radiation is discussed briefly. A major limitation is the inability to correlate biological data, in a unified way, as a function of linear energy transfer with the consequent necessity for quality factors.From consideration of the various interaction processes undergone by charged particles in the equilibrium slowing down spectra generated by the incident radiation field, it is shown that good correlation of biological effects, for all radiation types, can be achieved in terms of linear primary ionization. The implication is that delta-ray effects play at most a very minor role, at moderate fluences, and that, consequently, the absorbed dose is an unsuitable parameter for describing radiation effects. Structure in the radiosensitive targets is observed to have a critical dimension of about 2 nm. It occurs only when double-stranded DNA is present and the magnitude of the inactivation probability is consistent with double-stranded breaks being the significant lesion. Calculation is made of the yield of lesions as a function of the mean free path for primary ionization.Differential spectra of radiation quality are obtained for monoenergetic electrons (0.2 keV to 30 MeV); for characteristic X-rays from carbon, aluminium, neon, potassium, copper, silver, and tungsten; for 50 kV X-rays, 250 kV X-rays, 241Am, 137Cs, and 60Co gamma rays; and for neutrons with energies between 0.1 and 50 MeV. Damage by electrons is shown to be predominant at the ends of their tracks between 50 and 200 eV, whereas this is not so for the proton recoil spectrum generated by neutrons above 1 MeV.Proposals are made for a unified system of dosimetry that is independent of radiation type and that obviates the need for quality factors. The method is thought to be of general applicability to irradiations by nuclides incorporated into mammalian cells, by ingested emitters, and by external sources.
    Additional Material: 6 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 717-719 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 8
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of racemic analogues of phosphatidylinositol (PI) and phosphatidylinositol 4,5-bisphosphate (PIP2) starting from myo-inositol is described. Inositol derivatives with and without homologalion at C(l) and with and without ionic groups (phosphate or sulfate) at C(4) and C(5) were prepared as well as homologated derivatives with deoxy composition at C(2) and/or C(6). In all these compounds, palmitate ester groups were introduced in place of the diacylglyceryl group of PI or PIP2.
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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 141-151 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Density functional calculations - with a local density approximation for the exchange and correlation energy - provide a numerically efficient method for determining total energy variations in molecules. Coupled with molecular dynamics techniques such as simulated annealing, they provide a scheme for probing large regions of configuration space in molecules. We outline the main features of the method and apply it to different ring isomers of S7O, S8, S7Se, Se8, and O8.
    Additional Material: 2 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 767-780 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In classical mechanics, the equations of motion for conservative systems, i.e., systems in which the sum of the kinetic energy T and potential energy V is constant, can be derived from a Lagrangian function \documentclass{article}\pagestyle{empty}\begin{document}$ L(\dot q,q) = T(\dot q) - V(q) $\end{document} via the Euler-Lagrange equation \documentclass{article}\pagestyle{empty}\begin{document}$ \left( {{d \mathord{\left/ {\vphantom {d {dt}}} \right. \kern-\nulldelimiterspace} {dt}}} \right)\left( {{{\partial L} \mathord{\left/ {\vphantom {{\partial L} {\partial \dot q}}} \right. \kern-\nulldelimiterspace} {\partial \dot q}}} \right) - {{\partial L} \mathord{\left/ {\vphantom {{\partial L} {\partial q}}} \right. \kern-\nulldelimiterspace} {\partial q}} = 0 $\end{document}, or from the Hamiltonian function H(p, q) = T(p) + V(q) via the Hamiltonian equations \documentclass{article}\pagestyle{empty}\begin{document}$ \dot q = {{\partial H} \mathord{\left/ {\vphantom {{\partial H} {\partial p}}} \right. \kern-\nulldelimiterspace} {\partial p}},\dot p = {{ - \partial H} \mathord{\left/ {\vphantom {{ - \partial H} {\partial q}}} \right. \kern-\nulldelimiterspace} {\partial q}} $\end{document}. The Hamiltonian function represents the energy of the system in terms of generalized coordinates q and momenta p, and is used as a basis for the so-called canonical quantization to obtain the corresponding Hamiltonian operator and, thus, the Schrödinger equation for the system. For dissipative systems, i.e., systems where mechanical energy is lost due to frictional forces, difficulties arise in the analogous for formalism even on the classical level. Although formal Lagrangian functions yielding the correct equations of motion can be given, problems exist in the physical interpretation of these Lagrangians and the corresponding Hamiltonians. This becomes even more obvious when these Hamiltonians are quantized in the usual canonical way. A major problem is connected with the violation of the uncertainty principle. A new classical Lagrange-Hamilton formalism will be proposed, which not only yields the correct equations of motion for position and momentum, but also allows a physical interpretation of the Hamilton function in terms of the energy of the system. Following the canonical method, the time derivative of physical quantities can be obtained via a modified Poisson bracket formalism. The question of the quantization of such classical dissipative systems is discussed using the most important examples, the damped harmonic oscillator, and the damped free particle. Special attention is paid to the problem of vanishing uncertainty products.
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