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  • Polymer and Materials Science  (62)
  • Organic Chemistry  (12)
  • intestinal permeability  (3)
  • 1
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We present the application of several homo- and heteronuclear 1D- and 2D-NMR techniques to assign the 1H-NMR chemical shifts of the dominant conformation of didemnin B (2; three different conformations in (D6)DMSO solution in the ratio 8:1:1) and its conformational analysis, as well as the solution conformation of didemnin A (1). The conformations were refined by restrained molecular-dynamics calculations using the GROMOS program and by MOMO, a novel personal-computer-based interactive molecular-graphics and molecular-mechanics package, using experimental distances (via a H…H pseudo potential function) as restraints. The solution structures of 1 and 2 obtained by GROMOS and MOMO calculations were compared with each other and related to the recently solved crystal structure of 2. Focusing on the main conformer, the two kinds of the distance-restrained conformational calculations for 2 yielded a ‘solution structure’ close to the crystal structure. Almost all of the 40 restrained H…H distances coincided (within the estimated standard deviations) with those observed in the crystal structure. One more hydrogen bond was detected in solution involving the lactoyl OH group (disordered in the crystal structure) and the dimethyltyrosine (Me2Tyr5) carbonyl O-atom. The macrocyclic ring system in the modeled solution structure of 1 exhibited a topology close to those of the solution and crystal structures of 2. The main difference between 1 and 2 could be traced back to a significant change in the Ψ angle of the N-methyl-D-leucine (MeLeu7) residue. In 1, the N-methyl moiety of MeLeu7 points inward within the macrocyclic ring toward the 1st and Hip region. We also tested the suitability of structures obtained from NMR data as ‘search fragments’ in the ‘Patterson search approach’ of crystal-structure analysis. It proved possible to resolve the crystal structure of 2 a posteriori with the Patterson search program PATSEE, in this way.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The crystal structure of [3,O-didehydro-MeBmt1, Val2]cyclosporin (PSC-833; 1) was investigated by X-ray analysis. Data were collected from two different crystal modifications. Modification I crystallizes in P3121, a = b = 21.419 (2) Å, c = 32.101 (3) Å with one molecule in the asymmetric unit, modification II in P3221, a = b = 21.313 (2) Å, c = 62.053(3) Å with two molecules per asymmetric unit. This non-immunosuppressive analogue of cyclosporin A adopts a similar backbone conformation to that found in the crystal structure of cyclosporin A and other analogues. Three different data sets of modification I were collected using an Enraf-Nonius-CAD4 diffractometer with CuKα radiation at 20°, a Stoe-Siemens four-circle diffractometer with MoKα radiation at - 120°, and an EMBL image-plate scanner with synchrotron radiation at 12°. The quality of the data sets was evaluated by internal consistency, independent structure solution, and refinement. The structural parameters reported here for modification I are based on the synchrotron data.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of fifteen 1H-1,4-benzothiazine ylides were obtained by alkylation of the corresponding 4H-1,4-benzothiazines 1. Ylides of type 2g-r showed slight [1,2] rearrangements upon thermolysis besides main dealkylation to 1 and olefin production. The ylides of this type underwent redox reactions when treated with hydrazine hydrate alone, giving 3,4-dihydro-2H-1,4-benzothiazines mainly, while ylides of type 2a-f failed to react.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The crystal structure of a glycopeptide antibiotic A-40926 aglycone was investigated by X-ray analysis at -120°. A-40926 crystallises in the orthorhombic space group P212121 with two monomers in the asymmetric unit, a = 21.774(4), b = 28.603(7), c = 29.757(4) Å. ‘Conventional’ direct methods approach failed to solve the structure, but a novel iterative real/reciprocal space procedure was successful. Refinement against 11248 F2 data led to R1 = 13.3% for 6770 F 〉 4σ (F). The two monomers of A-40926 have similar conformations and are bound by antiparallel H-bonds to form a ‘chain’ structure of connecting dimers. The antibiotic molecule possesses a ‘binding pocket’ for the C-terminal carboxy group of the cell-wall protein, which is consisten with suggestions based on NMR data and the recently reported crystal structure of ureido-balhimycin. In A-40926 the monomers are polymerically linked by H-bonds, quite unlike the tight dimer formation observed in ureido-balhimycin.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 79 (1996), S. 1635-1642 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The crystal structure of isocyclosporin A (1), a rearrangement product of the immunosuppressant drug cyclosporin A, has been determined at 193 (2) K. Crystals are orthorhombic with cell dimensions a = 26.684 (7), b = 26.936 (3) Å, c = 28.549 (7) Å, space group C2221. The structure was solved by direct methods and refined by full-matrix least-squares methods to a conventional R value of 0.110. In contrast to the structure of cyclosprin A in solution and in the crystal, isocyclosporin A (1) has no regular secondary structural elements. The backbone adopts an open, irregular conformation with cis amide bonds between residue 2 and 3, and 3 and 4, respectively. All the other amide bonds and the ester linkage are trans. Contrary to crystal structures of cyclosporin derivatives, this crystal structure is stabilized by two transannular and four intermolecular H-bonds.
    Additional Material: 6 Ill.
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  • 6
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 7
    ISSN: 0887-624X
    Keywords: photopolymerization ; photoinitiator ; aroyl xanthates ; methyl methacrylate ; laser flash photolysis ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new sulfur-containing photoinitiator, S-benzoyl O-ethyl xanthate (2) has been prepared and used for the photopolymerization of methyl methacrylate (MMA). The photoinitiation property of 2 has been examined by conventional polymerization methods and nanosecond laser flash photolysis studies. Upon 308 nm laser pulse excitation, 2 gave rise to transients with absorption maxima at 350 and 650 nm, assigned to the benzoyl radical (3) and (ethoxythiocarbonyl)thiyl radical (4), respectively, on the basis of their quenching by nitroxy radicals and spectral similarity to analogous species, reported in the literature. © 1993 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 24 (1986), S. 2415-2424 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Aminophenoxycyclotriphosphazenes have been used as curing agents for epoxy resins. The thermal curing was performed in stages at 120-125 and 175-180°C followed by postcuring at 225°C to give tough brown polymers. The thermal curing reaction was monitored using FTIR and differential scanning calorimetry. Thermogravimetric analysis of the cured resins has shown thermal stability up to 350-340°C. The char yield obtained in nitrogen at 800°C was about 55-42% and in air at 700°C was about 40-32%. Graphite cloth laminates were prepared. The mechanical properties evaluated were found superior to those of commonly used epoxy resin systems. These resins are useful for making fire- and heat-resistant composites, laminates, molded parts, and adhesives.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 2543-2561 
    ISSN: 0887-624X
    Keywords: ammeline-melamine-formaldehyde resins ; ammeline-formaldehyde resins ; hydroxymethylation ; formaldehyde ; ammeline ; melamine ; methylolation ; water tolerance ; cloud point ; reaction time ; bis-N-hydroxymethylammeline ; A-stage resin ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ammeline-melamine-formaldehyde resins (AMF Resins) containing 5-100 mol % of ammeline, were synthesized by polymerization of the preformed sodium salt of ammeline, melamine, and formaldehyde in basic medium by three methods. These resins, when cured, constitute a new class of thermosets. The rate of hydroxymethylation of the amino groups of the ammeline salt with formaldehyde was somewhat larger then that of the amino groups on melamine. At higher pH values ammeline insolubility was not a problem. The AMF resin composition was approximately equal to the mol ratio of the components originally charged. Both ammeline and melamine were consumed over the entire reaction period. Thus, it is possible to make approximately uniform random ammeline-melamine-formaldehyde resins (AMF) with any mol ratio of ammeline salt to melamine. By controlling the pH of the solution from which the resins were isolated, the (SINGLE BOND) O- Na+/(SINGLE BOND) OH ratio could be varied. Resin melting points varied widely with the mol fraction of ammeline and the (SINGLE BOND) O- Na+/(SINGLE BOND) OH ratio. AMF resin solubilities, shelf lives, cloud points, and water tolerance depended upon the method of preparation, pH, and other factors. The sodium salt of ammeline was hydroxymethylated in water more readily than ammeline. More highly methylolated ammeline species were readily formed in solution but upon precipitation only bis-N-hydroxymethylammeline was isolated. © 1996 John Wiley & Sons, Inc.
    Additional Material: 12 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    Pharmaceutical research 5 (1988), S. 372-376 
    ISSN: 1573-904X
    Keywords: In vitro apparatus ; diffusion cell ; intestinal permeability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A new diffusion cell, derived from the Ussing chamber, was developed for the measurement of tissue permeability. This cell incorporates the attributes of using a single material and laminar flow across the tissue surface. In addition, the design allows the cell to be manufactured in a wide range of sizes to allow optimization of surface area to volume for a variety of tissues. The apparatus is applicable to the evaluation of transport of compounds through mucosal/epithelial barriers, i.e., gastrointestinal tissue. Active transport, permeability enhancers, enzymatic degradation, and absorption in various tissue sections can be explored. Preliminary data are consistent with the expected effects of molecular size and partition coefficient of a transported molecule on permeability in epithelial tissue. In addition, active transport of D-glucose and inhibition by phloridzin and ouabain can be demonstrated.
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