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  • 1
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 30 (1992), S. 1155-1161 
    ISSN: 0887-624X
    Schlagwort(e): adsorption ; desorption ; association ; polystyrene ; NMR ; polymer transitions ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Composition-studies were carried out in which samples of films composed of poly(styrene-co-divinylbenzene) particles enmeshed by poly(tetrafluoroethylene) fibers were saturated with dichloromethane and then allowed to evaporate at 23°C to virtual dryness as the 1H-NMR signals and residual weight of sorbed liquid were monitored. The correlations, of 1H-NMR line-widths with the corresponding log of the number, αt of residual sorbed molecules per monomer unit show that sharp changes occur as αt passes through αG the composition that exists when all the liquid not sorbed (i.e., not present within the liquid-saturated particles), has been eliminated, and again as αt passes through αg the composition that exists when the particles attain the rigidity characteristic of the glassy state. Correlation of the corresponding T1 relaxation times with log αt show that sharp changes occur when αt becomes equal first to α′s and then to α′g the compositions that exist respectively when, firstly, all the sorbed liquid not immobilized by adsorption to the polymer chains within the particles has been eliminated, and then when the desorption of immobilized liquid from the chains causes the composition to begin to undergo transition from its rubbery state to its glassy state.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 2
    Digitale Medien
    Digitale Medien
    Springer
    Journal of inclusion phenomena and macrocyclic chemistry 36 (2000), S. 287-299 
    ISSN: 1573-1111
    Schlagwort(e): crown ether ; NMR ; complexation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Asymmetrical cis-5,6-dimethyl-6-oxyacetoxy-(2,3)(9,10)-dibenzo-16-crown-5 was synthesized by a multi-step sequence and its stereochemistry determined by NOE experiments. Introduction of the 6-methyl group markedly reduces the stability constant for complexation of Na+ and K+ by the ionized form of the lariat ether carboxylic acid.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 3
    Digitale Medien
    Digitale Medien
    Springer
    Journal of inclusion phenomena and macrocyclic chemistry 16 (1993), S. 91-95 
    ISSN: 1573-1111
    Schlagwort(e): Dibenzo-14-crown-4 ; NMR ; conformation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The preferred conformations in solution for substituents onsym-dibenzo-14-crown-4 ethers are shown by NMR to depend on the atom, carbon or oxygen, linking the substituent to the crown ring.
    Materialart: Digitale Medien
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  • 4
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The ambident reactivity of phenoxide ion towards 1,3,5-trinitrobenzene (TNB) was re-examined by means of a novel reaction system(CD3CN-glyme-d10) which allows the investigation of species formed at low temperatures (-40°C), contrasting with previous studies in dimethyl sulfoxide (DMSO) at ambient temperature. The new method coupled with 400 MHz NMR spectroscopy has allowed the definitive observation of both O- and C-bonded phenoxide σ-complex adducts for the first time, confirming the formation of the former through kinetic control and of the latter through thermodynamic control. The corresponding O-bonded σ-adduct in the TNB-mesitoxide system (whereC-bonded σ-adduct formation is not possible but where there is competing nitro group displacement) has also been characterized by 1H and 13C NBR. Another O-bonded aryloxide adduct characterized is that from the reaction of TNB with3,5-di-tert-butylphenoxide; in this system there is also competing NO2 displacement. Stereoelectronic factors in the O-bonded σ-adducts and aryl ethers are discussed.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 5
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Peptide Science 2 (1996), S. 240-244 
    ISSN: 1075-2617
    Schlagwort(e): solid-phase synthesis ; peptide synthesis ; multiple synthesis ; inclusion volume synthesis ; Chemistry ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Solid-phase synthesis of peptides was carried out using only the volume of the solvent included in the swollen solid-phase resin beads [inclusion volume synthesis]. This approach enables (i) the use of higher concentrations of activated amino acids, resulting in increased coupling rates, (ii) drastically decreased consumption of solvents, and (iii) the construction of multiple peptide synthesizers having virtually no reaction vessels.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 6
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 15 (1994), S. 233-240 
    ISSN: 0192-8651
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Informatik
    Notizen: Rigid inhibitors suffer a smaller loss of conformational entropy when they bind to a macromolecular receptor than their acyclic counterparts. They can also be useful for elucidating pharmacophores due to their reduced conformational space and may be more amenable to synthesis. Computational approaches to rational drug design should therefore take these factors into consideration when suggesting possible compounds. We describe how an acyclic chain which links two parts of a receptor site can be ‘braced’ using ring templates. The acyclic chains may be produced from a number of sources, including lattices or the structures of known inhibitors. The resulting structures contain a rich variety of isolated and fused ring systems, which provide many useful molecular skeletons for subsequent inhibitor design. © 1994 by John Wiley & Sons, Inc.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 7
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 33 (1995), S. 501-505 
    ISSN: 0749-1581
    Schlagwort(e): NMR ; solid-state NMR ; 13C NMR ; magic angle spinning ; steroids ; fluorinated compounds ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: High-resolution carbon-13 NMR spectra were obtained for three solid fluorinated steroids. Assignments were carried out using several approaches, including two-dimensional spectra of the compounds in solution. Solid-state and solution-state chemical shifts are compared. Signals from one of the fluorine-containing carbons in each compound show the effect of interplay between shielding, dipolar and indirect scalar (J) coupling tensors. One sample is found to be a mixture of two polymorphic forms.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 8
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 32 (1994), S. 375-378 
    ISSN: 0749-1581
    Schlagwort(e): NMR ; 1H NMR ; 13C NMR ; Crown ethers ; Dibenzo-14-crown-4 ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Dibenzo-14-crown-4 and eight substituted dibenzo-14-crown-4-ethers were studied by 1D and 2D 1H and 13C NMR and their chemical shifts are reported.
    Zusätzliches Material: 3 Tab.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 9
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 24 (1992), S. 447-454 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The kinetics of solvolysis of the title compound (QAc) in undried DMSO-d6 to give 4-(1-ethoxycarbonyl-1-cyano)methylquinoline (QH) and HOAc at ambient temperature were investigated by 1H nmr spectrometry. With a limited excess of water the solvolysis follows a three-step process of \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm QAc} + {\rm H}_2 {\rm O}\mathop \to \limits^{k_1} {\rm QH} + {\rm HOAc}, $\end{document} , and \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm Ac}_{\rm 2} {\rm O} + {\rm H}_2 {\rm O}\mathop \to \limits^{k_3} {\rm 2\,HOAc}, $\end{document} where k2 〉 k1 and k3 〈 k1. Addition of pyridine-d5 to the reaction mixture markedly catalyzes the overall solvolysis, while addition of CF3CO2D to the reaction mixture simplifies the kinetics to pseudo first-order in [QAc] with k = 4.3 × 10-3 min-1.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 10
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 24 (1992), S. 455-466 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: We have studied the kinetics of a reaction in which starting materials A and B react to form the products C and D directly, as well as by way of two additional intermediate reactions. In the first intermediate reaction, A and C react to form D and E, and in the second intermediate reaction, B and E react to form 2C. There are three conservation laws, which effectively reduce the number of variables to two, resulting in nonlinear coupled first order differential equations for [A](t) and [B](t). These equations are readily solved by standard numerical procedures, for various values of the relative reaction rates and starting concentrations. Our results are used to fit experimental data for the case in which A and B are 1-acetyl-4-(1-ethoxycarbonyl-1-cyano)methylene-1,4-dihydroquinoline and water, for which the first and third reverse reactions can be neglected.
    Zusätzliches Material: 12 Ill.
    Materialart: Digitale Medien
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