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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Theoretical chemistry accounts 69 (1986), S. 247-258 
    ISSN: 1432-2234
    Keywords: Substituted polymethines ; Energy spectrum of ∼ ; Complex substituents
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract It is shown that upon substitution of polymethines R-(CH)N-R with complex many-atom substitution R-, in the energy gap of polymethine chains (N → ∞) may arise states which are responsible for longest-wavelength transition. For certain substituents the energy of the electron transitions may be considerably lower than 1 eV, i.e. the transitions may be in the near infra-red.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: MO-LCAO Calculations on Sulfur-containing π-Electron Systems. L. Synthesis and UV/VIS Spectral Properties of Derivatives of 1H-Perimidine-2-thioncarbonic AcidEsters of the 1H-perimidine-2-dithiocarbonic acid are easily accessible from 1.8-diamino-naphthalene and chloroacetyl chloride and subsequent thiolation of the reaction product under mild conditions and alkylation. The dithioesters react with aliphatic and aromatic amines to form thioamides. Both the resulting dithioesters and thioamides are clearly distinguished by their colour from the vast majority of known derivatives of thioncarbonic acids. While dithioesters and thioamides are generally red and yellow, respectively, in solution the corresponding derivatives of the 1H-perimidine are blue and red, respectively. The detailed examination of the experimental data has revealed that the colour determining longest wavelength absorption bands are due to the π→π* rather than to the n→π* transitions. Due to the efficient mixing of the lowest energy locally excited (LE) state of the heterocyclic moiety and the lowest energy perimidine-to-substituent charge transfer (CT) state the low-intensity longwavelength π→π* transition of perimidine undergoes a pronounced red shift by acceptor substituents of high electron affinity in 2-position. This interpretation of the deep colour of the 1H-perimidine-2-thiocarbonic acid is in harmony with substituent effects and fully born out by Pariser-Parr-Pople(PPP) type calculations completed by additional analyses of electronic state (Baba-Suzuki-Takemura analysis) and electronic transitions (Ohta-Kuroda-Kunii analysis).
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: MO-LCAO Calculations on Sulfur-containing π-Electron Systems. XLIX. Tetramethine Bridged Derivatives of the Oxalic Acid - Novel Coloured Pigments of Indigoid StructureWhereas thioamides react with the oxalylchloride to Δ2-thiazoline-4,5-diones 1, which are precursors of the versatile thioacylisocyanate 2 synthons, the analogous reaction between thioamides and oxalyl-bis(arylimidchlorides) completely fails. In the case of aliphatic thioamides the intermediate 2-methyl-Δ2-thiazoline-4,5-diimides 3 undergo oxydative dimerization. The poorly soluble products are tetramethine bridged heteroanalogous oxalates 4 or isomers. The u.v./vis spectra of the blue compounds are in favour with structure 4 rather than with structure 6. This conclusion has been drawn from the results of Pariser-Parr-Pople(PPP) type calculations. According to the calculated position of the colour band of the pigments and of different molecular subunits, and the correspondence of their electronic states involved in the excitation, the dye molecules can be thought as consisting of two symmetrically crossed polymethine chains. This structural feature is inherent to the H indigo chromophore.
    Additional Material: 2 Ill.
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  • 4
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Non-Kelulé polymethines are polymethine dyes that cannot be written by single Kekulé-type formulae. As demonstrated with 3,3′-dimethyl-3,3′-pyridocyanines (1) the electron distribution and term level ordering of them differ greatly from those of the related simple open-chain polymethines (streptopolymethines), considering the latter ones as constitutive elements of these dyes according to Dähne's polymethine concept. Non-Kekulé dyes are, however, closely related to isoconjugated classical polymethine dyes. The peculiar features of the non-Kekulé polymethines are well understood in terms of simple MO theory. Orbital tracing assisted by MOA (molecular orbital analysis) reveals crossing between the frontier orbitals of these dyes and those of the related open-chain polymethine substructures. Additional insight into peculiarities of 1 is gained at the semiempirical level by analyzing the π-electronic system in terms of the heterocyclic end groups and the interconnecting odd-alternant hydrocarbon (carbopolymethine) chain. Numerical predictions are made based on MNDO optimum geometries. According to CNDO/S and PPP calculations the non-Kekulé dyes considered absorb at longer wavelengths than the isoconjugate classical dyes. In the case of the first members of series 1 the lowest-energy transition is less determined by the characteristic polymethinin charge redistribution inherent to polymethine dyes than by notable heterocycle-to-chain charge transfer (CT). The interfragmental CT upon excitation reduces the transition probability of this electronic transition. Some calculations performed beyond the monoexcitation approximation indicate a certain birdicaloid character of the non-Kekuléan dye structures. The exceptional position of these dyes is also indicated by the higher heats of formation of 1 relative to the isomeric classical dyes.
    Additional Material: 5 Ill.
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  • 5
    ISSN: 0021-9541
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: The role of monovalent cationic gradients in human polymorphonuclear leukocyte (PMNL) stimulation was investigated by monitoring immune complex-stimulated transmembrane depolarization and superoxide production, events which accompany - and have been used as indicators of - PMNL activation. Abolishing only the Na+ gradient by substitution of choline for extracellular Na+ did not affect the resting membrane potential but reduced the rate of stimulus-induced transmembrane depolarization to 50% of control. In contrast, collapsing both Na+ and K+ gradients by suspension in K+ buffer (high K-PRK) depolarized the cells and reduced the stimulus-induced rate of depolarization to 11% of control. Pretreatment of cells suspended in Na+ buffers with 5-(N,N-dimethyl)amiloride hydrochloride (DMA) or with valinomycin reduced by one-half the rate of immune complex induced membrane depolarization. Conversely, in the absence of either or of both Na+ or K+ gradients, or in the presence of valinomycin, immune complex elicited an enhanced rate of superoxide production. However, PMNL prepared via NH4CI (NH4CI-PMNL) instead of H2O (H2O-PMNL) lysis of residual red blood cells exhibited an absolute requirement for an intact Na+ gradient in cell stimulation. The present results thus demonstrate that: (1) both Na+ and K+ gradients participate equally in the membrane depolarization elicited by immune complex; (2) neither a Na+ or a K+ gradient is required for immune complex activation, or for activity of the respiratory burst; and (3) an artifactual requirement for an intact Na+ gradient occurs in neutrophils prepared by the NH4CI lysis technique.
    Additional Material: 6 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 6 (1985), S. 429-431 
    ISSN: 0192-8651
    Keywords: Computational Chemistry and Molecular Modeling ; Biochemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Computer Science
    Notes: Timings are reported for 6-31G*/UMP2 calculations on planar allene, twisted ethylene, cyclopropenyl anion, allyl, ethyl, isopropyl and CF3 radicals performed by means of the programs GAUSSIAN 80 and HONDO UMP2. The comparison of the two programs is used for pointing out several factors affecting the speed of MP2 calculations.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
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