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  • Electronic Resource  (1,034)
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  • 1990-1994  (1,034)
  • 1991  (1,034)
  • Organic Chemistry  (822)
  • Industrial Chemistry and Chemical Engineering  (212)
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  • Electronic Resource  (1,034)
  • Loose Leaf
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  • 1990-1994  (1,034)
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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 3 (1991), S. 2-13 
    ISSN: 0899-0042
    Keywords: drug stereochemistry ; cyclothiazide ; stereoisomerism ; chiral HPLC ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: There is a great deal of current interest in the role and importance of chirality in the development of new drugs, but little attention is being paid to the stereochemistry of older drugs. Indeed, many older chiral drugs were introduced without adequate information on their stereochemical identity or composition. We have examined one such drug, the antihypertensive diuretic agent cyclothiazide. Standard sources of drug information and the research literature do not provide data on the stereochemical composition of clinically used cyclothiazide, although scattered reports indicate that the drug may consist of “several stereoisomers.” Inspection of the chemical structure of the drug, 6-chloro-3,4-dihydro-3-(5-norbornen-2-yl)-2H-l,2,4-benzothiadiazine-7-sulfonamide 1,1-dioxide, shows that it can exist as eight stereoisomers that may form four racemates. Using synthesis, fast-atom-bombardment mass spectrometry, gas-liquid chromatography, chiral and nonchiral high-performance liquid chromatography, and nuclear magnetic resonance spectroscopy, we determined that pharmaceutical cyclothiazide is in fact a mixture of the eight stereoisomers in the form of the four racemates. The two racemates with endo configuration at the norbornene moiety predominate over the exo racemates, and small but significant differences in isomer distribution between different batches of the drug were observed. We urge that in studies of older drugs the stereochemical details be considered.
    Additional Material: 9 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 3 (1991), S. 30-34 
    ISSN: 0899-0042
    Keywords: propafenone ; enantiomers ; α1-acid glycoprotein ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The interaction of propafenone enantiomers with human α1-acid glycoprotein was studied using high-performance liquid chromatography. Each of the two optical antipodes interacted with one class of high-affinity binding sites characterized by Ka(R) = (6.18 ± 0.93) × 105 M-1, n(R) = 1.34 ± 0.09 for the (R)-isomer and Ka(S) = (8.93 ± 1.82) × 105 M-1, n(S) = 0.99 ± 0.08 for the (S)-isomer. Nonspecific binding to secondary low-affinity high-capacity binding site(s) was only slightly greater in the case of the (S)-enantiomer (n′k′(S) = (1.06 ± 0.09) × 104 M-1) compared to the (R)-enantiomer (n′k′(R) = (6.87 ± 0.72) × 103 M-1). It was concluded that both enantiomers interact with common single class of high-affinity binding sites on AAG (along with nonspecific binding) exhibiting only slight stereoselectivity for propafenone.
    Additional Material: 3 Ill.
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  • 3
    ISSN: 0899-0042
    Keywords: enzymatic resolution ; chiral HPLC ; enantiomeric ratio ; enantiomeric excess ; 2-(phenoxy)propionate ; 2-(4-chlorophenoxy)propionate ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: (R)- and (S)-Methyl 2-(phenoxy)propionate and their acids could be separated simultaneously by a Chiralcel OD or OK column, while (R)- and (S)-methyl 2-(4-chlorophenoxy)propionate and their acids were separated concurrently only by an OK column. This is a novel and facile way to measure the enantiomeric excesses of the remaining substrate and product in the reaction of enzymatic resolution; enantiomeric ratios could then be calculated.
    Additional Material: 2 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 3 (1991), S. 88-89 
    ISSN: 0899-0042
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 3 (1991), S. 157-157 
    ISSN: 0899-0042
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 3 (1991), S. 151-155 
    ISSN: 0899-0042
    Keywords: (-)-(R) and (+)-(S) [8] gingerol ; enantiomers synthesis ; chiral stationary phase ; HPLC ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: (+)-(S)-5-Hydroxy-1-(4-hydroxy-3-methoxyphenyl)-3-dodecanone 1a commonly named (+)-(S)-[8] gingerol is a natural product known to have cardiotonic activity.1-5 A total synthesis of both enantiomers is described with details for the first time using a general synthetic scheme which was recently outlined in the literature.6 This synthesis relies both on the separation of the diastereoisomers 4a and 4b by simple column chromatography on silica gel and on an HPLC analysis on a chiral phase to determine the optical purity of the enantiomers 8a and 8b of protected [8] gingerol. The gingerol isomers were thus obtained in good chemical yields in greater than 96% enantiomeric excess.
    Additional Material: 3 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 3 (1991) 
    ISSN: 0899-0042
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 3 (1991), S. 161-164 
    ISSN: 0899-0042
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 3 (1991), S. 158-158 
    ISSN: 0899-0042
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 10
    ISSN: 0899-0042
    Keywords: chiral ; chiral solvating agent ; stereochemistry ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The N-(n-butylamide) of (S)-2-(phenylcarbamoyloxy)propionic acid, easily prepared starting from the inexpensive L-ethyl lactate, can be used as convenient chiral solvating agent (CSA) to determine the enantiomeric composition of N-(3,5-dinitrobenzoyl)amino acid methyl esters.
    Additional Material: 2 Ill.
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  • 11
    ISSN: 0899-0042
    Keywords: cellulose triacetate ; tribenzoylcellulose ; methylbenzoylcellulose ; chiral phase ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2,2,2-Trifluoro-1-(9-anthryl)ethanol (TFAE) has now been widely used as a powerful chiral solvating agent for NMR spectroscopy. In connection with the development of a new general synthesis of halogenoalkylalkanols, starting from the corresponding ketone or aldehyde, we synthesized some halogenoalkyl-1-(9-anthryl)methanol derivatives liable to work as chiral solvating agents. The racemic anthryl derivatives were preparatively resolved into their corresponding enantiomers by chromatography on triacetyl cellulose (CTA I) or on meta-methylbenzoyl cellulose beads as chiral stationary phases. Their effectiveness as chiral solvating agents was measured as the magnitude of the splitting induced in the 1H-NMR spectra of 1-phenylethylamine and of (1-phenylethyl)methyl ether in comparison with splitting caused by TFAE. While TFAE induced the largest splitting for 1-phenylethylamine, 2,2,3,3,3-pentafluoro-1-(9-anthryl)propanol 2 was more effective in the case of (1-phenylethyl)methyl ether, pointing out that depending on the substrate, other derivatives of the TFAE type can be very useful as chiral solvating agents.
    Additional Material: 1 Ill.
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  • 12
    ISSN: 0899-0042
    Keywords: chiral chromatography ; cellulose-based chiral stationary phase ; aromatase inhibitor ; cyclohexylaminoglutethimide and metabolite ; enantiomeric separation ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Racemic cyclohexylaminoglutethimide (±ChAG) and its acetylated metabolite (±ChAG) were resolved by a direct chromatographic method using a Chiracel OD column without derivatization. Maximum resolutions (R) of 4.89 and 0.74 were obtained for the enantiomers of cyclohexylaminoglutethimide and its acetylated metabolite, respectively.
    Additional Material: 5 Ill.
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  • 13
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 3 (1991) 
    ISSN: 0899-0042
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 14
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 3 (1991), S. 242-253 
    ISSN: 0899-0042
    Keywords: steric effects ; geometric model ; ester hydrolysis ; ester conformation ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: With the early aim of quantifying steric consequences of chirality, efforts to define a nonempirical steric parameter of chemical groups are reported. Steric hindrance of a reacting center by any acyclic saturated R group has been characterized by a geometric “axial steric parameter”: the solid angle of R. When the group is a “symmetric top substituent” (i.e., when all the terminal atoms are equivalent), the solid angle matches the solid angle of a cone envelope of R. The definition of this cone is compared with Tolman's definition of a ligand cone in organometallic complexes. The chemical significance of this parameter is shown by an excellent correlation with the Dubois' experimental steric parameter E′s. Modeling steric repulsion by the cone of R, and correcting solid angles for conformational effects, only 3 empirical coefficients are needed to calculate 33 values of E′s with less than 10% error. The cone model is suggested to be relevant within the limits of random and independent free rotations about all the bonds in the C-R group. A separation between “axial cone steric hindrance” and other steric effects is proposed. The basic model and the corrections proposed allow the conformational features of esters to be discussed.
    Additional Material: 8 Ill.
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  • 15
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 3 (1991), S. 263-267 
    ISSN: 0899-0042
    Keywords: aloe ; feroxidin ; absolute configuration ; tetralins ; helicity ; Cotton effect ; conformation ; half-chair cyclohexene ring ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The configuration of carbon-8 in feroxidin (1) was proven to be (S) by chemical correlation with (S)-methylsuccinic acid. Previous demonstration that 6-hydroxy and 8-methyl groups are equatorial and pseudoaxial, respectively, in a half-chair conformation of the cyclohexene ring (relative configuration) allowed the absolute stereochemistry of the whole molecule to be established (Fig. 3). The CD spectrum of feroxidin represents the first experimental test confirming the applicability of Snatzke's helicity rules to tetralins m-disubstituted on the aromatic ring.
    Additional Material: 5 Ill.
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  • 16
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 3 (1991), S. 285-291 
    ISSN: 0899-0042
    Keywords: macromolecular ; optical activity ; polyisocyanate ; deuterium ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In contrast to random coil polymers, polyisocyanates maintain a highly extended helical conformation in solution. This structural characteristic causes unusually large chiral optical properties to arise from copolymerization of tiny proportions of optically active monomer isocyanates with achiral isocyanates or even from stereospecific placement of deuterium in the side chain of poly(n-hexyl isocyanate). These effects can be understood as phenomenologically related to the optical activity amplification properties of vinyl polymers studied by Pino and his co-workers and ascribed to breaking the energetic degeneracy of the otherwise equally populated left- and right-handed helical states of the backbone. Statistical thermodynamic calculations, based on this model, and analogous to those carried out earlier on the vinyl polymers, allow matching the temperature and molecular weight dependence of the optical activity in poly((R)-1-deuterio-1-hexyl isocyanate) to the approximate responsible energy terms.
    Additional Material: 5 Ill.
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  • 17
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 3 (1991), S. 315-317 
    ISSN: 0899-0042
    Keywords: ↕ β6.3-model ; ↕ β-model ; ↕ β7.2-structures ; closed structures ; open structures ; non-conducting dimers ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It is suggested that the conducting transmembrane channels formed by the linear gramicidins A, B and C may be head-to-head (formyl end-to-formyl end) dimers of double-stranded parallel β-helices. This possibility is not in conflict with any of the various experimental findings bearing on the molecular organization of the channels and represents a plausible alternative to Urry's model of a head-to-head dimer of single-stranded β6.3-helices.
    Additional Material: 1 Ill.
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  • 18
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 3 (1991), S. 1-1 
    ISSN: 0899-0042
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 19
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 3 (1991), S. 19-23 
    ISSN: 0899-0042
    Keywords: aporphine enantiomers ; serotonin 5-HT1A receptors ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The two enantiomers of the title compound have been prepared by different synthetic routes. Both bind strongly to 5-HT1A receptors from rat forebrain membrane tissue. However, in a guinea pig ileum preparation, the (R)-enantiomer exhibits properties consistent with its being an agonist, whereas the (S)-enantiomer shows no agonist effect, but it blocks the actions of the (R)-enantiomer and of 8-hydroxy-2-di-n-propylaminotetralin (8-OH-DPAT), a 5-HT1A agonist. These data are presented as a rare example of enantiomers which demonstrate opposite pharmacological effects at the same receptor.
    Additional Material: 1 Tab.
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  • 20
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 3 (1991), S. 341-344 
    ISSN: 0899-0042
    Keywords: enantioselectivity ; carbonylation ; hydroformylation ; hydroalkoxycarbonylation ; para-substitution ; 2-phenylpropene ; platinum catalyst ; palladium catalyst ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The enantioselective hydroformylation catalyzed by [(R,R)-Diop]Pt(SnCl3)Cl7 and the enantioselective hydroisopropoxycarbonylation catalyzed by [(R,R)-Diop]PdCl28 or by [(R,R)-Diop-dbp]PdCl29 of some para-substituted 2-phenylpropenes (para substituents = NO2, H, CH3O, Cl, CF3) was investigated in order to recognize possible electronic influences on the regioselectivity and on the enantioface selection which take place in such carbonylation reactions. The catalytic systems used gave no carbonylation products when the nitro compound was the substrate. 7 and 8 show similar regioselectivities, the less branched isomer being exclusively formed for all substrates except p-methoxy-2-phenylpropene which gave small amounts of the alternative regioisomer. The enantioselectivity depends on the σp effect of the substituent in both cases; the differences are, however, rather small and the trend is opposite in the two cases. The regioselectivity displayed by 9 is still in favour of the less branched isomer but it is high only in the case of p-trifluoromethyl-2-phenylpropene. Larger differences with respect to the other catalytic systems were also observed for enantioselectivity but the trend for both regioselectivity and enantioselectivity is not linear.
    Additional Material: 1 Ill.
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  • 21
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 3 (1991), S. 355-369 
    ISSN: 0899-0042
    Keywords: enantiomerically pure compounds ; chiral drugs ; enantioselective hydroformylation ; enantioselective catalysts ; biologically active compounds ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The asymmetric hydroformylation reaction represents a potential powerful synthetic tool for the preparation of large number of different chiral products to be used as precursors of several organic compounds endowed with therapeutic activity. Essential and nonessential amino acids, 2-arylpropanoic acids, aryloxypropyl- and β-phenylpropylamines, modified β-phenylethylamines, pheniramines, and other classes of pharmaceuticals are available through enantioselective oxo-reaction of appropriate functionalized olefins; this process is catalyzed by rhodium or platinum complexes with chiral ligands, mainly chelating phosphines, and sometimes affords very high enantiomeric excesses. Furthermore, the application of many simple optically active aldehydes arising from asymmetric hydroformylation as chiral building blocks for the synthesis of complex pharmacologically active molecules such as antibiotics, peptides, antitumor macrocycle compounds, and prostaglandins is conveniently emphasized. The possibility of a future application of this asymmetric process for the production of many synthons to obtain other valuable pharmaceuticals is widely discussed too.
    Additional Material: 2 Ill.
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  • 22
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 3 (1991) 
    ISSN: 0899-0042
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 23
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 3 (1991), S. 389-392 
    ISSN: 0899-0042
    Keywords: chirality ; origin of life ; Bose condensation ; organic superconductivity ; electroweak interaction ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We review a recent paper20 in which a specific enhancement factor (i.e., a phase transition into a condensed Bose mode) is proposed to account for the observed amplification of the ground state energies of the L- and D-amino acid enantiomers; the difference between these energies is assumed to be due to the neutral parity-violating electroweak interaction. This physical effect initially shifts the enantiomer energies by about 3 × 10-19 eV. The proposed phase transition is characterized by a critical temperature Tc, which may be studied theoretically by enlarging the standard electroweak theory to include either the top quark or supersymmetry21. Possible experimental means of finding Tc are discussed.
    Additional Material: 1 Ill.
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  • 24
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 3 (1991), S. 418-421 
    ISSN: 0899-0042
    Keywords: chiral bioinversion ; pharmacokinetics ; (+)-(S)-ibuprofen ; (-)-(R)-ibuprofen ; rac-ibuprofen ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using a pharmacokinetic model recently proposed to explain ibuprofen disposition in man,1 plasma concentrations of pure ibuprofen enantiomers were simulated following oral administration of (-)-(R)-ibuprofen, (+)-(S)-ibuprofen, or rac-ibuprofen. Simulated and literature values for AUC's were used to compare S/R ratios for different cases of the model and for different methods of calculating the fraction of R bioinverted to S. Numerical simulation using STELLA confirmed previous results for different cases of bioinversion. Simulated S/R AUC ratios, for administration of the racemate, ranged from 4.0 (presystemic bioinversion) to 1.66 (systemic bioinversion). Literature values for S/R AUC ratios averaged 1.53±0.2 for administration of the racemate; therefore, systemic bioinversion was concluded to be representative of ibuprofen disposition. Additional simulations of S/R AUC ratios, for administration of (-)-(R)-ibuprofen only, ranged from 1.5 (presystemic bioinversion) to 0.66 (systemic bioinversion). Literature values for S/R AUC ratios averaged 0.50±0.9 for administration of (-)-(R)-ibuprofen only, which again supported conclusions of systemic bioinversion. Using different equations for estimation of fraction of R inverted to S (FR→S), results based on simulated data were identical; however, FR→S values based on literature data were different. Therefore, assumptions made for different FR→S equations do not appear to be rigorous. Calculations of FR→S, based on literature data, averaged 0.52 overall, indicating bioavailability of (+)-(S)-ibuprofen may be similar for a 150 mg dose of (+)-(S)-ibuprofen compared to a 200 mg dose of racemate.
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  • 25
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 3 (1991) 
    ISSN: 0899-0042
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 26
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 3 (1991), S. 451-453 
    ISSN: 0899-0042
    Keywords: enantioselective ; stereoisomers ; β-blockers ; adrenergic β-receptor blockaders ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have studied the stereochemistry of accumulation of the hydrophilic β-adrenoceptor antagonist rac-atenolol by human platelets in vitro. The accumulation was slow, not reaching equilibrium until 90 min at 37°C. The uptake was temperature dependent with the accumulation at 37°C being 3-4 times greater than at 4°C. The accumulation was also stereoselective at 37°C, favoring the active (-)-enantiomer over the (+)-enantiomer by 2.3-fold. Reserpine, but not desipramine, inhibited the platelet accumulation of rac-atenolol enantiospecifically. This uptake profile is different from the platelet uptake of lipophilic β-blockers, which is characterized by nonspecific membrane binding, but similar to the carrier-mediated accumulation of the neurotransmitter norepinephrine by storage granules within the platelet.
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  • 27
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 3 (1991), S. 454-459 
    ISSN: 0899-0042
    Keywords: phenytoin ; product inhibition ; p-HPPH ; rat liver microsomes ; ligand-exchange chromatography ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Different doses of rac-p-HPPH (0.4 and 4 mg/h) were given repeatedly to rats infused with [14C]phenytoin. The serum levels of 14C-labeled and unlabeled p-HPPH, and [14C]phenytoin were measured by an HPLC method and radiometric analysis. The clearance of phenytoin and p-HPPH was determined by rate of dosing divided by the steady-state concentration. The phenytoin clearance was significantly lower in the high dose p-HPPH injection group than in the low dose group (87 versus 262 ml/h), whereas p-HPPH clearance showed no difference. The formation clearance of [14C]p-HPPH was also significantly lower in rats injected with high dose of p-HPPH (35 versus 169 ml/h). The clearance of other elimination pathways was also lower in rats with high dose of p-HPPH (53 versus 89 ml/h). The serum protein binding of phenytoin was lower in rats injected with high dose of p-HPPH. The result indicated that injections of rac-p-HPPH mainly inhibited on the formation of p-HPPH itself. The formation of (R)-p-HPPH and (S)-p-HPPH in microsomal preparation was measured by a ligand-exchange chromatographic method. The formation of (S)-p-HPPH or (R)-p-HPPH was not only inhibited by the enantiomer itself, but also cross-inhibited by the other enantiomer. To the formation of either (S)-p-HPPH or (R)-p-HPPH, (S)-p-HPPH showed a higher inhibitory activity. The use of rac-p-HPPH to inhibit phenytoin metabolism in vivo involved several mechanisms. In addition to binding displacement on the serum proteins, one is the product inhibition by the respective p-HPPH metabolite, the other is the competitive inhibition by the other p-HPPH enantiomer.
    Additional Material: 4 Ill.
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  • 28
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 3 (1991), S. 212-219 
    ISSN: 0899-0042
    Keywords: oxazepam ; demoxepam ; 3-O-acyl-1-(N,N-dimethylcarbamyl)oxazepam ; 1-(N,N-dimethylcarbamyl)oxazepam ; 3-O-(N,N-dimethylcarbamyl)oxazepam ; camazepam ; norcamazepam ; 1,3-O-bis(N,N-dimethylcarbamyl)oxazepam ; kinetics of racemization ; enantioselectivity of esterases ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Three N,N-dimethylcarbamyl derivatives of oxazepam {1-(N,N-dimethylcarbamyl)oxazepam, 3-O-(N,N-dimethylcarbamyl)oxazepam, and 1,3-O-bis(N,N-dimethylcarbamyl)oxazepam} and a 3-O-acyl-1-(N,N-dimethylcarbamyl)-oxazepam were synthesized from either oxazepam or demoxepam. Enantiomeric pairs of these derivatives and of camazepam were resolved by high-performance liquid chromatography on at least two of three commercially available chiral stationary phase columns employed. Absolute configurations of resolved enantiomers were established by comparing their circular dichroism spectra to those of enantiomeric oxazepams with known absolute stereochemistry. Similar to those of oxazepam, enantiomers of 1-(N,N-dimethylcarbamyl)oxazepam undergo rapid racemization (t½ 1.9 min at 23°C and 0.9 min at 37°C) in an aqueous solution at pH 7.5. The (R)-enantiomer of rac-3-O-acyl-1-(N,N-dimethylcarbamyl)oxazepam was hydrolyzed ∼4.6-fold faster than the (S)-enantiomer by esterases in rat liver microsomes, whereas the (S)-enantiomer was hydrolyzed ∼43-fold faster than the (R)-enantiomer by esterases in rat brain S9 fraction.
    Additional Material: 3 Ill.
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  • 29
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    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 3 (1991), S. 233-241 
    ISSN: 0899-0042
    Keywords: circular dichroism ; 1(S),1′(S)-dimethylbisheptylsulphosuccinate sodium salt ; spectroscopy ; optical activity ; surfactant ; chiroptical properties ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Four chiral analogues of the surfactant Aerosol-OT (AOT) have been synthesized and characterized. All of them form reverse micelles in apolar solvents in the w0 range 0-30 (w0 = [water]/[tenside]). Reverse micellar solutions have been investigated by UV absorption and circular dichroism spectroscopies with the aim of clarifying whether the formation of the macromolecular micellar structure induces the appearance of new chromophoric bands or perturbs the existing ones. Methanolic solutions of the surfactants, in which no micellar aggregates are formed, were taken as references. One of the products 1(S),1′(S)-dimethylbisheptylsulphosuccinate sodium salt (MH-AOT) was capable of forming reverse micelles of relatively high water content (w0 up to 40) and this process was accompanied by a specific increase in the intensity of the circular dichroism band associated with the ester absorbance of the molecule. As no concomitant changes were seen in the UV absorbance spectrum, it was concluded that this observation reflected conformational events occurring within the surfactant rather than chromophoric perturbation. These results are qualitatively similar to those found recently for lecithin reverse micelles which, however, form gels at sufficiently high water contents. The chiroptical properties of these supramolecular aggregates are compared with those of covalent macromolecular systems such as polypeptides.
    Additional Material: 10 Ill.
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  • 30
    Electronic Resource
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    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 3 (1991), S. 257-262 
    ISSN: 0899-0042
    Keywords: chiral photochemistry ; excitation transfer ; optical activation ; circular dichroism ; dissymmetry factor ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The physics involved in photochemistry with circularly polarized light, the warnings on its inherent limitations, as well as some examples of application on organic molecules are briefly reviewed.
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  • 31
    ISSN: 0899-0042
    Keywords: asymmetric polymerization ; stereospecific polymerization ; optically active polymer ; helix ; (+)-tartaric acid ; L-proline ; (+)-(S)-2-(1-pyrrolidinylmethyl)pyrrolidine ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polymerization of diphenyl-2-pyridylmethyl methacrylate was carried out with the complexes of organolithium compounds with 22 chiral ligands. Helix-sense-selectivity of the polymerization was largely affected by a slight structural difference of chiral ligands. (+)-(S)-2-(1-Pyrrolidinylmethyl)pyrrolidine was the most effective ligand in producing a one-handed helical polymer with narrow molecular weight distribution.
    Additional Material: 3 Ill.
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  • 32
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    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 3 (1991), S. 307-314 
    ISSN: 0899-0042
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The preparation is reported of two side chain polyacrylate samples 1a,b containing a sulfide group linked to the mesogenic core. By oxidation with a preferentially chiral oxaziridine, samples 1a,b were chemoselectively and enantioselectively converted to the corresponding sulfoxide containing polymers 2a,b with an estimated 20% asymmetric induction. The mesophasic behaviour of the parent and oxidized polymer samples is analyzed by thermal and optical techniques. The modification of the prochiral sulfide groups into chiral sulfoxide groups slightly depresses the propensity of the resulting polymers to give stable and persistent mesophases.
    Additional Material: 5 Ill.
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  • 33
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    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 3 (1991), S. 318-323 
    ISSN: 0899-0042
    Keywords: nuclear magnetic resonance ; circular dichroism ; β-turn conformation ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(X-Gly-Gly), simple structural models for the hydrophobic, proline-devoid, regions of elastin, have been synthesized and studied by circular dichroism and NMR spectroscopies. The results gave evidence of type II β-turns as the only ordered structure present in the polymers. The stability of the turns has been shown to decrease on hydration and to increase in the series Leu 〈 Ala 〈 Val 〈 Ile.
    Additional Material: 7 Ill.
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  • 34
    ISSN: 0899-0042
    Keywords: asymmetric synthesis ; enantioselectivity ; diastereoselectivity ; double stereodifferentiation ; chiral ferrocenyl ligands ; bis(1,3-diketonato)oxovanadium(IV) complexes ; oxazolines ; dihydropyrones ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The notion of internal (or intramolecular) cooperativity of chirality is reviewed on the basis of various examples of diastereoisomeric ferrocenylphosphine ligands used in the gold(I)-catalyzed aldol reaction. It was found that the stereochemical outcome of this reaction strongly depends on the specific combination of the absolute configuration of the different stereogenic centers present in the ligand. Thus, individual chirotopic segments in these ligand molecules can act either in a cooperative or noncooperative manner in determining both diastereo-and enantioselectivity. Furthermore, several examples of application of the strategy of double stereodifferentiation (external, or intermolecular cooperativity of chirality) in the gold(I)-catalyzed aldol reaction and the vanadium(IV)-catalyzed hetero Diels-Alder condensation are presented. Based on our work it is apparent that, whether the diastereoselectivity of these two reactions is controlled by the catalyst or by a chiral substrate, cannot be predicted and very much depends on the nature of every individual reactant. Thus, it was found that in both reactions the chiral aldehyde substrate usually has a strong impact on the diastereoselectivity, leading to interesting patterns of double asymmetric induction. On the other hand, chiral isocyanoacetate and chiral-activated dienes, respectively, showed little or no effect on the stereochemical outcome of the reactions.
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  • 35
    Electronic Resource
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    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 3 (1991), S. 376-385 
    ISSN: 0899-0042
    Keywords: circular dichroism ; detection system ; chromatography ; chiral discrimination ; enantiomeric excess ; elution order ; dissymmetry factor ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A circular dichroism-based detection system presents several advantages in the HPLC analysis of chiral compounds because of the selective monitoring of optically active molecules. Its use allows reliable determination of enantiomeric excesses and elution order. To this end, the application of empirical, semiempirical, and nonempirical methods to get stereochemical information from the CD signal is reported. Furthermore, recording the CD spectra on line and evaluation of the dissymetry factor make the CD detection very powerful in characterizing the stereochemistry of chiral eluates.
    Additional Material: 10 Ill.
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  • 36
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 14 (1991), S. 11-19 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Inclined plates are often installed as mechanical separation aids in gravity settlers for the separation of liquid-liquid systems. The authors investigated the process of coalescence of single drops on trickling films flowing off inclined plates. The method of investigation was developed by Blass and Rautenberg. It ensures that, under certain conditions, only hydrodynamic parameters influence the coalescence process to any significant extent. The coalescence time of the drops characterizes the process of coalescence. Short time between 1 and 3 seconds provide favourable conditions for coalescence whereas long times, often ten times as long or even longer are unfavourable. This contribution introduces a criterion for clear demarcation between these two ranges and also a determination of separation parameters for favourable conditions for coalescence. Furthermore, the function of the plates is described, which is determined by hydrodynamic and wetting processes. The characteristic operating regions of a plate are shown in a working diagram.
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  • 37
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: When declaring and using process engineering data such as, for exmple, mixing times or kLa values, it is assumed that these apply to the entire reactor contents. The condition of uniform mixing, necessary for this, is generally met in the regime of turbulent flow. When highly viscous and, above all, strongly non-Newtonian liquids are stirred in small reactors, there are frequently also regions of laminar flow and completely stagnant zones, which are only partially mixed or not at all. The present paper pursues the question to what extent is the gas-liquid mass transfer in stirred, highly non-Newtonian liquids influenced by the mixing behaviour of the reactor. The results show that, below certain Reynolds numbers, three relatively distinct regions exist, with different mixing intensities. Between an almost ideally mixed region in the vicinity of the stirrer and a completely stagnant and dead one, there is a zone of very slight motion. This finding demonstrates that the usual determination of integral or volume-based data in the literature is neither logical nor adequate for the case under consideration. Thus, the gas-liquid mass transfer takes place mainly in the relatively well mixed region. Therefore, use of a kLa value also requires the volume of this region to be declared. Only the knowledge of this volume enables us to correlate the kLa values in such a way that the sorption characteristics thus obtained appear suitable for scale-up. This procedure, which is illustrated by numerous examples of measured results for different stirrers, is important whenever design data for highly viscous liquids are to be worked out on the basis of laboratory measurements. Only when larger equipment is used, in which turbulent flow can be achieved, this problem does not arise because of the relatively uniform mixing of reactor contents.
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  • 38
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The variation in the behaviour of bulk solids as a result of sudden pressure changes in the surrounding gas phase is of interest in the application of lock hoppers for transfer of bulk solids into pressure vessels. By using such sluice systems, problems occur due to consolidation of the pressurized bulk solids. This paper presents the results of experimental and theoretical research, which allow to describe the influence of several parameters on pressure compensation and the degree of consolidation. With reference to the forces and mechanisms responsible for consolidation, it is possible to describe the different consolidation behaviour of incompressible (limestone) and compressible (hard coal) bulk solids.
    Additional Material: 12 Ill.
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  • 39
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    Chemical Engineering & Technology - CET 14 (1991), S. 65-72 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A study was made of the flow characteristics of large oscillating drops of pure liquid-liquid systems, using a thermostatically-controlled, rising drop column, 50 mm in diameter and 1000 mm in length. Mirrors in the jacket enabled front and side views of drops to be photographed simultaneously. Single drops in the size range 5-10 mm were investigated with both mutually-saturated phases and when the solute was being transferred from the dispersed phase. The systems studied were (1) toluene and acetone (dispersed)-water (continuous), and (2) n-heptane and acetone (dispersed)-water (continuous). Acetone concentrations were varied up to 3.75 kmol/m3. The oscillations of a travelling drop were asymmetrical; therefore, the amplitude cannot be expressed accurately in terms of only two axes. The area change of the drop compared to that of a sphere of equal volume ‘ε’, was shown to represent the amplitude accurately. The periods of droplet oscillation were uniform for the mutually saturated systems of constant physical and flow properties but changed when mass transfer was taking place. The interfacial tension exerted a marked effect on the amplitude, which also depended upon the oscillation frequency. The amplitude changed with droplet size in a similar manner to the terminal velocity, i.e. it increased with increasing size until it reached a maximum, subsequently decreasing less rapidly. The drag coefficient increased with increasing rate of mass transfer from the drop. Correlation of the results and the area eccentricity ‘ε’ by dimensional analysis embracing all possible parameters and physical properties affecting drop oscillation, resulted in the correlation ε = 0.22 Sr0.42 We-0.53 M0.13 with a mean deviation of ± 14%. This will facilitate more accurate prediction of the interfacial area for mass transfer calculations, relating to equipment containing droplets in the oscillating regime.
    Additional Material: 7 Ill.
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  • 40
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 14 (1991), S. 89-95 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The correct choice of packing is of decisive importance for optimum process efficiency in the operation of two-phase countercurrent columns. An important criterion for this choice is the pressure drop in the gas flow. Theoretical relationships are derived for calculating the pressure drop in beds with dry and trickle packings. It has been demonstrated by comprehensive experiments that these relationships allow the pressure drop to be determined more accurately than by previous methods. The experiments were performed at the Department of Thermal Separation Processes of Bochum University on 54 different packed beds, using 24 different systems.
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  • 41
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A multipurpose apparatus was designed, built and operated with the aim of a simultaneous determination of enthalpy of mixing, heat capacity, kinematic viscosity and density of liquid mixtures at 240 〈 T 〈 370 K and 1 〈 p 〈 25 bar. Its operation was monitored by a PC. Details of design and the first experimental results are presented.
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  • 42
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 14 (1991), S. 20-28 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A method is proposed for solving the vapour-liquid equilibrium problem in binary distillation processes, when pressure and temperature are known. Special attention is paid to the applicability of the method for control purposes. Therefore, a comparison between measured and estimated concentrations is included for the case of propane-propylene distillation. The method is based on an improved Soave-Redlich-Kwong equation of state and is easy to implement on a process computer. It yields a close approximation of experimental vapour and liquid volumes. On applying the original SRK-equation at high pressures, an error in excess of 20% is obtained in the liquid volume which is one of the reasons why this equation cannot be used for control where high accuracy is required. In addition, the conventional mixing rule cannot reproduce the mole fractions correctly. Therefore, a new density-dependent mixing rule is put forward for modelling of experimental results.
    Additional Material: 12 Ill.
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  • 43
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    Chemical Engineering & Technology - CET 14 (1991), S. 59-64 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Environmental hazards caused by halogenated hydrocarbons and increasingly stringent regulations for limiting their emission require comprehensive investigations of these substances. The present work deals with the adsorption and desorption of halogenated hydrocarbons on activated carbon. The results could be useful in the utilization of landfill gases because halogenated hydrocarbons must be removed in order to avoid pollution and the loaded activated carbons have to be regenerated. Activated carbons are well suited to removal and recovery of halogenated hydrocarbons from gas flows.
    Additional Material: 5 Ill.
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  • 44
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Influence of intraparticle total pressure change on pore mass transport is investigated in physical gas phase adsorption of a single component from an inert carrier medium. The Dusty Gas Model is applied to quantify pore mass transport, assuming local equilibrium between pore fluid and adsorbed phase. Calculated results for single pellet adsorption kinetics of cyclohexane on activated carbon and CO2 on molecular sieve 5 Å are compared with experimental data. It is found that the total pressure drop in the pore system may be as much as 1% of the ambient total pressure. This results in a maximum viscous flow contribution of 13% for the cases studied. Since this contribution is obtained only under conditions of low overall transport rates of the adsorbed component, the assumption of isobaric conditions within the pore system of a porous adsorbent appears justified for most cases of practical calculations.
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  • 45
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 14 (1991) 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 46
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 14 (1991), S. 307-310 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Fluidized bed drying finds important applications in the chemical industry on account of the following advantages: (a) rapid exchange of heat and mass between drying media and particles yields the desired product quality and reduces the overall drying time and (b) easy handling of feed and product. There is much scope for improving the existing modelling techniques as applied to predicting the performance characteristics of the dryers. This should provide a sound basis for the implementation of appropriate control strategies. This report is a review of prevailing modelling, identification techniques and control strategies. Hopefully, the up to date information in this paper will be found useful for research work on fluidized bed dryIng.
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  • 47
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 14 (1991) 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 48
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 14 (1991), S. 379-385 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A three-parameter model for mass transfer by absorption, based on a combined effect of non-steady-state molecular and eddy diffusion through a resistance zone has been suggested, which encompasses all the existing theories on mass transfer at the gas-liquid interface. King's approach [5] to describing gas-liquid mass transfer phenomena through an eddy-diffusivity model can explain some experimental results, but does not provide a general mathematical solution of the problem. The shortcomings of the King's model are overcome in the present work and a general solution is presented. This solution confirms the experimental findings of Versteeg et al. [10] for liquid phase mass transfer. The steady-state solution of the present theory, valid for the dimensionless number α 〉 0, shows a close agreement with experimental data of Luk [22], the only source of all the information necessary for model verification.
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  • 49
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Dynamic behaviour of a stirred liquid-liquid extraction column was studied experimentally. Various input variables of the column were varied stepwise and the resulting variations in the system and output variables were measured. In addition to experimental work, a computer model was developed on the basis of the dispersion model to simulate the dynamic behaviour of the extractor. This model forms a component program of the dynamic process simulator DIVA, developed at the TU Stuttgart. The experiments showed that the hydrodynamic parameters exhibit no significant dynamic behaviour of their own. Therefore, changes occurring in these parameters closely follow variations in input and system variables. As a result, steady-state relationships for the calculation of flow parameters could be used in the simulation program. The simulator satisfactorily reproduced the experimental results for a number of disturbances. However, this was not always the case. As shown in the following, the model did not take into account the column level controller which, under certain conditions, exerts a very strong influence on the column's dynamic behaviour. As a result, larger differences occurred between experimental and simulated data. This influence on the extractor's dynamic behaviour can, however, be eliminated by a simple modification of the level controller arrangement.
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  • 50
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 14 (1991), S. 333-347 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Power consumption (Part I) and liquid phase mixing time (Part II) were measured in 0.57, 1.0 and 1.5 m i.d. vessels. A pitched blade downflow impeller (PTD) was used. Design details of the PTD impeller such as diameter (0.22T to 0.5T), blade width (0.25D to 0.4D) and blade thickness (2.8, 4.3 and 6.4 mm) were studied. The effect of sparger type and geometry on power consumption has been investigated. For this purpose, pipe, ring, conical and concentric ring sparger were employed. Design details of the ring sparger such as ring diameter, number of holes and hole size were also studied in depth. Sparger location with respect to the impeller was found to be the most important parameter and was therefore varied for nearly all the spargers studied. A correlation for the power consumption has been developed.
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  • 51
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 14 (1991) 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 52
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    Chemical Engineering & Technology - CET 14 (1991), S. 367-375 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Accumulation of the reactant supplied to a cooled semibatch reactor (SBR) will occur if the mass transfer rate across the interface is insufficient to keep pace with the supply rate. Then, due to a low starting temperature or supercooling, the reaction temperature does not rise fast enough to the desired value. This accumulation may eventually lead to a temperature runaway. We investigated the possibility of such an event for reactions of the type “chemically enhanced mass transfer” or “fast” and found that only low distribution coefficients, i.e. 10-4 or lower, can lead to accumulation. At higher distribution coefficients, the mass transfer rate across the interface of a well-mixed dispersion is generally sufficient to prevent accumulation. A thermal runaway in the fast regime exerts a moderate effect, because the effective activation energy is halved. Calculations for the “instantaneous” reaction regime, regarded as a special case of fast reactions, show that there is no runaway possible.
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  • 53
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    Chemical Engineering & Technology - CET 14 (1991), S. 386-393 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Liquid phase mixing time was measured in 0.57, 1.0 and 1.5 m i.d. mechanically agitated gas-liquid reactors. Transient conductivity technique was used for the mixing time measurement. Pitched blade downflow turbine was employed. The design details of PTD impellers such as diameter (0.22 T to 0.5 T) and blade width (0.25 D to 0.35 D) were studied. The influence of sparger types and their design on mixing time has been investigated. For this purpose, pipe, ring, conical, and concentric ring spargers were employed. The design details of the ring sparger, i.e. ring diameter, number of holes and hole size were also studied in depth. Sparger location with respect to the impeller was found to be the most important variable and, therefore, it was varied for practically all the spargers studied in this work. It was found that the liquid phase mixing time depends on the impeller design, sparger design, sparger location, impeller speed and superficial gas velocity. Correlations have been developed for the dimensionless mixing time.
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  • 54
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    Chemical Engineering & Technology - CET 14 (1991), S. 399-405 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A control algorithm which has been acclaimed as the best algorithm for a real system may not be the best algorithm for a different real system. Therefore, various self-tuning algorithms for real distillation columns have been evaluated, in order to compare their performances. A variable forgetting factor algorithm is modified using a filter which permits the employment of one instead of two covariance matrices for distillation control. A cautious self-tuning control of SISO system is extended to MIMO system of distillation control. Multivariable self-tuning regulator, multivariable self-tuning controller and multivariable cautious self-tuning controller are implemented with modified variable forgetting factor for linear transfer function model, Waller et al. column, and rigorous non-linear model, Wood and Berry column. For distillation control, a multivariable cautious self-tuning algorithm with modified variable forgetting factor is much simpler than earlier reported algorithms. This has produced better results and demonstrated its effectiveness, even in the presence of noise when other adaptive controllers give unsatisfactory performance.
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  • 55
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The influence of particle size dispersity on thermal conductivity of packed beds without fluid flow is investigated. For this purpose, new experimental data for bi- and polydispersed packings are presented and data from the literature reviewed. All data are tabulated. The results of numerical calculations carried out for regular arrangements of spheres are also discussed. The impact of particle size dispersity on thermal conductivity is shown to be primarily due to the change in bed porosity. Thus, prediction can be carried out in the same way as for monodispersed packings if based on the actual bed porosity. A model developed by Schlünder and co-workers is revised and recommended for practical application.
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  • 56
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    Chemical Engineering & Technology - CET 14 (1991), S. 357-362 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The effects of particle size (layer thickness), BET surface area and pore size distribution on the reactivity of CaO derived from limestone were studied by using a pH-stat and the BET method. Visual analysis was obtained with SEM, and X-ray diffraction was used to determine the crystalline components present. It was found that the pore size distribution, including pore volume and pore surface distribution, affected the sulphatization behaviour. The larger pores (D 〉 50 Å) with their pore volume and pore surface were to some extent responsible for both initial reactivity and ultimate capacity of CaO.
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  • 57
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    Particle and Particle Systems Characterization 8 (1991), S. 1-7 
    ISSN: 0934-0866
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Describing the disperse state is important for quality assurance, operational safety and the design and modelling of processes, especially in solids technology. Starting materials, intermediates and end products have to be characterized. Apart from representative sampling, preparation greatly influences the results of particle characterization. Very fine particles are normally agglomerated unless a highly dispersed state is stabilized by an additive. For a meaningful measurement, they must be preserved in this state or be definitely dispersed, depending on the type of problem.If the point of interest is the present disperse state with regard to the processing characteristics, e.g. for a filtration, the system should not be changed by the preparation method. If it is necessary to determine the property functions, i. e. the functional relationship between technological and physical properties, it is necessary in general to use a high dispersion energy or a long dispersing time in order to obtain the best achievable dispersion. The finer and more unstable a disperse phase is, the more the correct processing is important for the result. The problems of dispersion in gases and liquids are discussed with some examples.
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  • 58
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    Particle and Particle Systems Characterization 8 (1991), S. 48-54 
    ISSN: 0934-0866
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Crystals and crystal agglomerates exhibit a number of specific shape features which evolve in close relation to the conditions of growth and agglomeration. Hence the quantitative evaluation of these shape features by adequately defined shape parameters can serve to obtain a deeper insight into the mechanisms and kinetics of crystal agglomerate formation and to quantify more precisely the quality of crystallization products.
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  • 59
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    Particle and Particle Systems Characterization 8 (1991), S. 40-47 
    ISSN: 0934-0866
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The response of optical particle counters to nonspherical particles is analyzed theoretically and on the basis of experimental results. Theoretical approximations valid for particle diameters d ≪ λ and d ≫ λ (where λ is the wavelength of light) are used to derive some general predictions about the influence of the particle shape on light scattering. These predictions are compared with experiments on six optical particle counters using nonspherical particles. The instruments differ in the kind of illumination (laser or incandescent light), the mean scattering angle and the receiver aperture. When the particle size is smaller than the wavelength the light-scattering diameter of a nonspherical particle comes very close to its volume-equivalent diameter. For irregularly shaped particles larger than the wavelength better conditions than giving a “projected area” response cannot be achieved with an optical arrangement for single-particle detection.
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  • 60
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    Particle and Particle Systems Characterization 8 (1991), S. 63-71 
    ISSN: 0934-0866
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Many commercially important pigments such as titanium dioxide and carbonblack are produced as fumes from a combustion process. The fuming process generates open structured agglomerates conforming to a morphology predicated by physical considerations. For this reason widely different chemical pigments often manifest common physical structure. This structure can be characterized using the concepts of fractal geometry. In this communication the potential usefulness and physical significance of descriptive parameters of the agglomerate structure of fumed pigments based on the concepts of fractal geometry are explored. Similar structures present in high energy ceramic powders are discussed and the potential importance of fractal dimension parameters for the prediction of the physical behaviour of powders is outlined.
    Additional Material: 14 Ill.
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  • 61
    ISSN: 0934-0866
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Based on physical assumptions, simple equations have been derived for the probability of breakage of particles, for the dependence of fragmentation energy on particle size and for the fragment size distributions as a function of mass-specific energy. The particles were considered as spheres, and Hertz theory of the stress distribution at the contact between a sphere of brittle material and a flat surface was applied in combination with Weibull statistics of failure. The predicted dependence of the probability of breakage on particle size and mass-specific energy agrees well with experimentally obtained data for single-particle experiments, even if the particles were not spherical. The resulting fragment size distribution could be predicted by the application of fracture mechanics. The theory can also be applied to rock drilling, where the breaking material is considered as a flat surface and the drilling tool as being of spherical shape. In both comminution and drilling, the experimental results agree fairly well with the theory.
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  • 62
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    Particle and Particle Systems Characterization 8 (1991), S. 79-85 
    ISSN: 0934-0866
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The evaporation rates of particles of solid KBr or NH4Cl suspended in argon were studied under high-temperature conditions behind incident shock waves. The mass-transfer process during particle evaporation was observed by two optical techniques allowing the measurement of scattered light from a particle ensemble and also from individual particles. The scattered light flux signals were interpreted on the basis of the Mie theory, resulting in values for the time-dependent particle size and for the refractive index of particle materials. The experiments were performed in the gas-phase temperature ranges TG = 1070-1300K (KBr) and 525-650K (NH4Cl). The initial size of the suspended particles ranged between 0.6 and 1.0 μm. From the measured decrease in the particle size during the mass-transfer process the evaporation coefficients of both materials were determined as a function of the gas-phase temperature. They depend on the vapour pressure and the diffusion coefficient for vapour into gas. Typical parameters (àKBr, m) describing the diffusion coefficient of KBr vapour in argon and the vapour pressure of NH4Cl could be determined.
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  • 63
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    Particle and Particle Systems Characterization 8 (1991), S. 72-78 
    ISSN: 0934-0866
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A combined experimental and theoretical study of the droplet deposition and mist supercooling in a turbulent channel flow has been performed. The measurement of droplet deposition on the unheated and heated channel wall was carried out using a particle-sizing two-dimensional reference-mode laser-Doppler anemomentry technique in a 41 mm × 41 mm vertical square channel at Re = 1.0 × 104 - 6.05 × 104. The dimensionless deposition coefficient kd/uZ. H. Yang Prof. S. L. Lee Department of Mechanical Engineering, State University of New York at Stony Brook, Stony Brook, NY 11794 (USA) is analyzed theoretically based on a new unified theoretical approach for the entire transverse flow region from the turbulent core to the quasi-laminar region next to the boundary wall. The proposed analytical model shows satisfactory agreement with the results of present experimental measurement. In the mist supercooling, the heated surface is cooled by the evaporation on the outside surface of an extra thin continuous liquid film which is maintained by the continuous deposition of extremely small droplets of an optimal size determined by a selection process on the droplets transverse migration due to the dynamic interaction between the phases in a parallel turbulent mist flow. The heat transfer enhancement coefficient depends on droplet deposition rate, droplet size, concentration and the Reynolds number.
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  • 64
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    Particle and Particle Systems Characterization 8 (1991), S. 170-172 
    ISSN: 0934-0866
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: British Standards committee GME/29/4 is concerned with “Particle sizing methods other than sieving”. Its work covers not only particle size distribution analysis but also methods of estimation of surface area and pore size distribution, as well as a glossary of terms relevant to those subjects. The current British Standards in the BS 3406 series (particle size analysis) and BS 4359 series (surface area) are reviewed, and a progress report is given on the status of several new and revised Standards which are in preparation.
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  • 65
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    Particle and Particle Systems Characterization 8 (1991), S. 164-169 
    ISSN: 0934-0866
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An increased interest in the development of new techniques for fine grinding has resulted in a growing concern over the accuracy of size distributions for extremely fine particles. Since most particle size analyzers have lower detection limits, care must be taken when comparing size distributions which have not been properly mass balanced.An automated technique has been developed in which a completely mass balanced size distribution can be obtained using an Elzone 80XY particle size analyzer. A computer program is used to blend the data from successively smaller orifice tubes, and to determine the weight percent of material finer than the lower detection limit of the analyzer. This result is then used to correct the distribution for the missing fine material. Experimental results indicate that size distributions obtained using this procedure are reproducible and compare favorably with those obtained using other size analysis techniques.
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  • 66
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    Particle and Particle Systems Characterization 8 (1991), S. 200-208 
    ISSN: 0934-0866
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An automatic measuring system was developed to perform simultaneous measurements of particle size and charge distributions in a clean room and other aerosol sources. The system consists of an electrostatic condenser (EC) and an optical particle counter (OPC), which are controlled by a personal computer (PC). The PC automatically varies the voltage on the EC and converts the corresponding OPC counts to charge distributions. The reliabilities of the data inversion method and the automatic measuring system were confirmed by theoretical and experimental examinations, respectively. In the theoretical examination, inverted charge distributions were tested and compared with various assumed input distributions. In the experiment where monodisperse aerosols neutralized by a 85Kr neutralizer were used, the measurement results agreed well with the theoretical Boltzmann charge distribution. The application of this technique is demonstrated by the measurement of charge and size distributions of aerosols in a clean room.
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  • 67
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    Particle and Particle Systems Characterization 8 (1991), S. 209-214 
    ISSN: 0934-0866
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The motion of real oblate particles of different cross-section can be described with sufficient accuracy by equation valid for spheroids. The proof was effected by means of velocity measurements.The application of theoretical considerations to sedimentation analysis allows it to be used to calculate apparent distributions occurring in the sedimentation of monodisperse particles of uniform shape at any orientation relative to the direction of sedimentation. The transfer to polydisperse systems involves several difficulties, which can be avoided in part by suitable approximations. In the case of a particle system with a polydisperse distribution of a main axis, but a constant particle shape, it is possible to calculate the resulting apparent distributions and their deviations from those distributions obtained when applying the volume equivalent particle diameter.
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  • 68
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    Particle and Particle Systems Characterization 8 (1991), S. 215-221 
    ISSN: 0934-0866
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The behavior of particles at the phase transition between a gas or liquid and another liquid phase may be characterized by the so-called wetting (or contact) angle. In contrast to plane surfaces, which allow such measurements to be conducted relatively easily, the determination of the wetting angle between a liquid and the surfaces of fine particles demands extensive preparative measures. The method adopted by Heertjes and Kossen [12] for example, involves compressing a tablet from the powder in question, from which the wetting angle may then be derived. The compression process naturally modifies the superficial structure of the particles, and hence their wetting characteristics. This paper describes a preparation technique with which the wetting angle between a liquid and fine particles can be derived without modifying the surface texture. This involves coating and adhering a monolayer of the powder on a carrier plate and measuring the composite wetting angle of the particles and the adhesive film. The specification of the adhesive's wetting angle and areal porosity of the carrier medium allows the wetting angle of the given powder subsequently to be evaluated.
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  • 69
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    Particle and Particle Systems Characterization 8 (1991), S. 243-243 
    ISSN: 0934-0866
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
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  • 70
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    Particle and Particle Systems Characterization 8 (1991), S. 243-244 
    ISSN: 0934-0866
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
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  • 71
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    Particle and Particle Systems Characterization 8 (1991), S. 245-258 
    ISSN: 0934-0866
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Mathematical tools are provided for computation of the scattered field produced by a spherical particle moving through the region of interference of two crossing laser beams. This formulation is readily applicable to laser Doppler and phase Doppler anemometers (PDAs). In particular, the geometry of PDAs is treated in the most general terms. The cases of very large and very small particles are considered in detail. In the first part the theory underlying the computer code STREU, which was produced during the present work, is discussed and relevant mathematical formulations are presented. Also, graphical tools are provided for the convenience of the designers.In Part 2 the utility of the computer code is demonstrated with the help of examples in the area of phase Doppler anemometry. It is shown that the phase Doppler technique may be used for sizing of submicron particles in addition to large particles. Measurement of particle refractive index, in addition to the diameter, is also made possible.
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  • 72
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    Particle and Particle Systems Characterization 8 (1991), S. 287-293 
    ISSN: 0934-0866
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The range of the parameters of the Nukiyama-Tanasawa distribution function was analysed, leading to the identification of the physically relevant parameter space. The analysis was also applied to the Rosin-Rammler distribution function.
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  • 73
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    Particle and Particle Systems Characterization 8 (1991), S. 282-286 
    ISSN: 0934-0866
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Dynamic light scattering is a technique used for the optical determination of a colloidal particle size distribution. A simple procedure, based on a trapezoidal model for the linewidth distribution function, is given for obtaining a constrained regularized inversions of correlation data obtained in dynamic light scattering experiments, and estimating the accuracy of such inversions. Based on the eigenfunction decomposition of the Laplace integral equation, error bars, which are directly related to the accuracy of the correlation data, may be placed on both analytical and discrete inversions. By using a regularization procedure, and a nonnegativity constraint, problems with statistical noise in data may be handled effectively.
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  • 74
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    Particle and Particle Systems Characterization 8 (1991), S. 294-296 
    ISSN: 0934-0866
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The calibration of electrical sensing zone instruments is normally achieved by using spherical particles with a certified size. An alternative and more fundamental procedure, known as mass or self-calibration, is to use particles of the material under test.This work concerns the mass calibration technique, in particular the equations used to calculate the mass calibration constant. It is demonstrated that some of the published expressions are inconsistent. An expression particularly suitable for the Coulter Counter Model ZM has been derived and validated. Some experiments were also performed using irregular particles, in order to compare both calibration methods.
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  • 75
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    Particle and Particle Systems Characterization 8 (1991), S. 323-323 
    ISSN: 0934-0866
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
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  • 76
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    Chirality 3 (1991) 
    ISSN: 0899-0042
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 77
    ISSN: 0899-0042
    Keywords: debrisoquine ; nortriptyline ; desipramine ; polymorphism ; phenocopy ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1A single oral dose (50 mg) of quinidine significantly increased the debrisoquine metabolic ratio in six healthy volunteers. For four of the volunteers the metabolic ratio changed to that typical of the poor metaboliser (PM) phenotype.2The effect of quinidine in producing debrisoquine oxidation “poor metaboliser” phenocopies persisted for at least 3 days but had disappeared by 1 week.3The debrisoquine metabolic ratios for the same six subjects were not significantly altered by the oral administration of quinine (200 or 400 mg), the dia-stereoisomer of quinidine.4The plasma pharmacokinetic parameters of both nortriptyline and desipramine in healthy volunteers were all changed to those more typical of the debrisoquine PM phenotype following the concomitant administration of quinidine (50 mg).5It is concluded that quinidine, but not its diastereoisomer quinine, is a potent selective inhibitor of the in vivo oxidation of debrisoquine and can produce an artifactual PM phenocopy in persons who are phenotypically extensive metaboliser (EM) phenotype status. The clinical implications of this observation are discussed.
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  • 78
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    Chirality 3 (1991), S. 43-55 
    ISSN: 0899-0042
    Keywords: beads ; polymer ; enantiomer ; chiral phase ; interaction ; alcohol ; diol ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cellulose-based stationary phases are known to be very efficient and versatile chiral sorbents for the chromatographic resolution of racemates. Except for microcrystalline cellulose triacetate (CTA I), basically all other cellulose-based phases have been prepared by coating of ca. 20% weight polymer on a wide pore silica gel used as a carrier. In this work we describe the preparation of benzoylcellulose (TBC) beads in the pure polymeric form (without inorganic carrier) from an emulsion of the organic polymer. The new material has been fully characterized and used as a chiral stationary phase for the resolution of various classes of racemic compounds such as benzylic alcohols or acetate derivatives of aliphatic alcohols and diols. The structural variety of the separated solutes as well as the irrational influence of the aromatic substituent in different classes of aryl compounds suggest that multiple interaction sites are involved in the complexation, making a prediction of the separation difficult. The benzoyl cellulose beads exhibit a very high loading capacity, which is particularly useful for preparative purposes as demonstrated for selected examples.
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  • 79
    ISSN: 0899-0042
    Keywords: molecular recognition ; chiral recognition ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Molecular dynamics simulations were performed on complexes of (S)-methyl N-(2-naphthyl)alaninate (NAP) with the enantiomers of N-(3,5-dinitrobenzoyl)leucine n-propylamide (DNB), which are used as models for chiral stationary-phase systems developed by Pirkle and co-workers. These studies were undertaken to qualitatively examine (pictorially) the role of entropic effects in these systems. The results of the dynamics calculations were used to refine the search for low-energy conformers. The structures were refined by the use of BioDesign's molecular mechanics method implemented in Biograf. The results of the structural refinements support our previous observation that the SR complex can achieve the same three primary interactions which are observed in the SS structure (i.e., two intermolecular hydrogen bonds and pi stacking) without a significant increase in energy. In addition, these primary interactions are conserved during molecular dynamics simulations with the occurrence of conformations which differ only in the rotational states of the alkyl side chains and ester group (which bears two potential hydrogen bond acceptors utilized in both the homo- and heterochiral complexes). The major difference in the two complexes is the relative position of the sec-butyl group and hydrogen atom on DNB's chiral center, both of which are outside the primary interaction region. All other local minima which have different relative pi orientations (“front-back,” “back-back,” and “back-front” as defined herein) are not sufficiently populated to make more than a negligible contribution to the statistical (time- or energy-averaged) analysis of the (SS)- and (SR)-NAP-DNB complexes. Thus the entropic effects observed in this study (e.g., alkyl side chain or ester group rotations) do not show evidence of qualitative differential effects on the maintenance of the same three primary interactions by both the homo- and heterochiral complexes. The reliability of the present study, which provides pictorial representations of the entropic effects, is not sufficient to determine whether the entropic effects observed herein are sufficient to achieve enantiomeric discrimination alone or in conjunction with other factors (e.g., conformational strain energy). Thus, all of the computational studies we have performed to date (i.e., our previous studies, which include strain energy and through-space field effects, and the present study, which includes entropic effects) show no evidence of any qualitative difference in the homo- and heterochiral complexes in terms of maintaining the same three “contact points”.
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  • 80
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    Chirality 3 (1991), S. 71-75 
    ISSN: 0899-0042
    Keywords: crystal structure ; aldosterone conformation ; correction of assigned configuration ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In the presence of dilute alkali at room temperature aldosterone undergoes rearrangement to form 11β,18:18,21-diepoxy-20,21-dihydroxy-4-pregnen-3-one (V). X-Ray crystallographic analysis demonstrates that isomers of both 18R, 20S, 21S and 18R, 20S, 21R configuration are formed rather than the 18R, 20R, 21R isomer postulated on the basis of examination of 1H-NMR spectra. The spectra appears to be consistent with the major component of the mixture. The 20S configuration observed is in agreement with the chirality assigned to the degradation product obtained when the same alkaline solution of aldosterone is subjected to reflux. The crystals of (V) are monoclinic P21, Z = 4 with a = 20.891(2), b = 6.3848(5), c = 16.067(2)Å, β = 122.09°(1) with two molecules in the asymmetric unit. Molecule A has the 20S,21S configuration and the molecules in the second site are a mixture of the 20S, 21S and 20S, 21R configuration in the ratio of 3:2.
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  • 81
    ISSN: 0899-0042
    Keywords: warfarin ; human liver ; competitive inhibitor ; chiral interactions ; kinetics ; enantiomers ; racemate ; drug metabolism ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Inhibition of the metabolism of (S)-warfarin, the more pharmacologically active enantiomer of the racemic drug, by (R)-warfarin was investigated in microsomes obtained from three human livers. In each case the production of both (S)-6- and (S)-7-hydroxywarfarin was found to be competitively inhibited by (R)-warfarin. The Kis for inhibition of (S)-6- and (S)-7-hydroxylation by (R)-warfarin ranged from 7.0 to 8.4 μM and from 6.0 to 6.9 μM, respectively, while the Kms for the 6- and 7-hydroxylation of (S)-warfarin ranged from 3.6 to 3.8 μM and from 3.3 to 3.9 μM, respectively. In contrast, except for the 4′-hydroxylation pathway (S)-warfarin was found to be a weak inhibitor of the metabolism of (R)-warfarin. Possible implications of these findings include the following: (1) the kinetic parameters defining the interactions of two enantiomers of a racemic drug with the cytochrome P-450s or other macromolecular systems in the living organism can only be properly defined from experiments with the pure enantiomers, (2) an enantiomer of a racemic drug may contribute significantly to biological effect not by its inherent activity but by altering the pharmacokinetics of the eutomer, and (3) enantiomeric interactions are not easily detected unless directly sought and may be relatively common.
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  • 82
    ISSN: 0899-0042
    Keywords: chiral derivatization ; pharmacokinetics ; enantiospecific assay ; fluorescent derivatization ; flunoxaprofen ; acyl glucuronides ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The major biotransformation pathway for the chiral lipid-regulating agent beclobrate is conversion to the corresponding carboxylic acid, which is then metabolized to the acyl glucuronide. An enantiospecific assay for biological material was developed that is based on chiral derivatization with N-ethyl-N′-(3-dimethylaminopropyl)carbodiimide (EDAC) and the primary amine S-FLOPA, a new chiral coupling component for carboxylic acids derived from the 2-arylpropionic acid S-flunoxaprofen. Conversion of beclobric acid to the acyl chloride prior to coupling with the amine is also feasible. From plasma or urine beclobric acid was extracted into n-hexane/ethanol (9:1) at pH 4 after addition of sodium chloride. Clofibric acid was used as internal standard. Derivatization with EDAC/FLOPA was performed under addition of 1-hydroxybenzotriazole in anhydrous dichloromethane containing trace amounts of pyridine (ambient temperature/2 h reaction time). The chromatographic separation was performed on a silica gel stationary phase (Zorbax Sil) using n-hexane-chloroform-ethanol (100:10: 0.75, by vol) as mobile phase [flow rate, 2 ml/min; fluorescence detection, 305/355 nm; elution order of the derivatives, (-) before (+)]. Coefficients of variation were between 1.3 and 9.3% for both plasma and urine. Limit of quantification was 20-25 ng/ml for plasma based on a sample volume of 0.2 ml. Application of the assay in a pilot pharmacokinetic study showed significant differences between the kinetics of the two enantiomers. In plasma and urine, the concentrations of the dextrorotatory enantiomer exceeded those of the levorotatory enantiomer significantly.
    Additional Material: 4 Ill.
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  • 83
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    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 3 (1991), S. 76-83 
    ISSN: 0899-0042
    Keywords: chiral flavour compounds ; chiral cyclic acetals NMR data ; diastereoisomer/enantiomer separation ; crystal structure elucidation ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of several 2-alkoxy-5-alkyl-tetrahydrofurans is of interest in our investigations of structure-function relationships of chiral flavour compounds. For the preparation of the enantiomeric acetals the unambiguous configurational assignment of the cis and trans series of these compounds is indispensable. By means of crystalline acetal derivatives the absolute structure of a model compound in the cis and the trans configuration is revealed by X-ray measurement and correlated with the corresponding cis and trans configurated aroma compounds. The first complete structure elucidation of the class of 2-alkoxy-5-alkyltetrahydrofurans has been carried out.
    Additional Material: 4 Ill.
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  • 84
    Electronic Resource
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    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 3 (1991) 
    ISSN: 0899-0042
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 85
    Electronic Resource
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    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 3 (1991), S. 165-169 
    ISSN: 0899-0042
    Keywords: ibuprofen ; enantiomer ; stereoselectivity ; chiral inversion ; pharmacokinetics ; dog ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Inversion of inactive (R)-ibuprofen to active (S)-ibuprofen has been suggested to occur presystemically only. In order to investigate the site of inversion in dogs we administered both enantiomers either intravenously or intraduodenally (10 mg/kg) to adult, male beagle dogs (n = 3) in a crossover design. Plasma, urine, and bile were collected for up to 6 h and analyzed stereospecifically by HPLC, according to a previously published method. Pharmacokinetic parameters were calculated using a linear computer program. Absorption after intraduodenal administration occurred rapidly, resulting in maximum plasma concentrations 0.2 h after giving the enantiomer. Approximately 70% of the (R)-enantiomer (according to AUC) was inverted to the S-enantiomer independent of route of administration. No R-ibuprofen could be detected in plasma after (S)-ibuprofen administration. Mean residence time was found to be 2 to 3 times longer for (S)-than for (R)-ibuprofen. Total systemic clearance from plasma was twice as high for (R)- than for (S)-ibuprofen. There were no differences between plasma clearances after intravenous and intraduodenal administration. Between 8 and 17% of dose was recovered in bile [especially as free and conjugated (S)-ibuprofen] and 3-12% in urine [as (S)-ibuprofen, hydroxy- and carboxyibuprofen, free and conjugated forms]. Small amounts of (R)-ibuprofen were detected in bile after intraduodenal administration of (R)-ibuprofen only (1.8% of dose). In short, the unidirectional inversion of R-ibuprofen appears to occur systemically rather than presystemically in dogs.
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  • 86
    Electronic Resource
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    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 3 (1991), S. 188-195 
    ISSN: 0899-0042
    Keywords: fast analysis times ; enantiomers ; chiral stationary phase ; Pirkle-concept ; achiral derivatization ; rapid screening ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A Pirkle-concept chiral stationary phase (CSP) derived from N-(1-naphthyl)leucine was evaluated for developing methods to reduce analysis times and investigating techniques in the rapid screening of a variety of chiral compounds over a given chiral selector. The effects of reduced column lengths and elevated temperatures were studied to shorten analysis times.
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  • 87
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    Chirality 3 (1991), S. 208-211 
    ISSN: 0899-0042
    Keywords: neuroleptic ; dopamine ; receptor ; enantioselectivity ; schizophrenia ; stereochemistry ; isomers ; racemate ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The relative configuration of the enantiomers of thioridazine was defined to explore the stereochemistry associated with the selective binding of (-)-thioridazine to dopamine D-1 receptors and (+)-thioridazine to D-2 receptors. Using a seven-step stereoconservative synthesis, (-)-(S)-2-piperidinecarboxylic acid was converted to (-)-(S*)-2-(2-chloroethyl)-1-methylpiperidine, a literature (-)-thioridazine synthetic precursor. Accordingly, (-)- and (+)-thioridazine are the (S)- and (R)-enantiomers, respectively.
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  • 88
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    Chirality 3 (1991), S. 221-222 
    ISSN: 0899-0042
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 89
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    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 3 (1991), S. 484-491 
    ISSN: 0899-0042
    Keywords: propylene sulfide ; cadmium thiolate ; stereospecific polymerization ; living polymerization ; anionic polymerization ; ring-opening polymerization ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerization of racemic methylthiirane in homogeneous phase, initiated by bis(isopropyl-S-cysteinato) cadmium is a living process. The resulting polymers are isotactic and optically active at partial conversion. The optical purity of the residual monomer may reach 27% at half conversion. The propagation occurs mainly on one valency of Cd, however oligomers grow slowly on the second valency. The stereoregularity of the polymer chain appears only when the length of the oligomer becomes high enough, making possible a bicoordination of the Cd counterions. The stereoregularity of the polymer is characterized by the molar fraction σ of isotactic diads which varies from 0.5 for atactic chains - formed at the beginning - to about one for isotactic segments formed for longer chains. The stereospecifictity also depends on temperature of propagation and on initiator concentration. The kinetics observed (zero order in monomer and one-half in Cd) are explained by monomer coordination before insertion and dimeric association of the thiolate end groups. The enantioasymmetric process observed results from an unbalance in the number of the two different types of active sites and possibly from a difference in their reactivities. Enantioasymmetry has been found to decrease significantly when the dielectric constant ε of the medium increases.
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  • 90
    Electronic Resource
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    Chirality 3 (1991), S. 227-232 
    ISSN: 0899-0042
    Keywords: DNA ; liquid crystal ; ethidium ; circular dichroism ; X-ray diffraction ; optical microscopy ; intercalation ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The influence of the intercalation of ethidium bromide (EB) on the characteristics of the DNA cholesteric and hexagonal mesophases is studied by optical microscopy, circular dichroism, and X-ray diffraction. The distance between DNA rods in the hexagonal phase is not modified by the presence of EB whereas the pitch of the cholesteric mesophase is considerably shortened by the dye. This seems to be related to the stereochemical effect of the intercalation rather than to the presence of a random distribution of the positive charge of the dye.
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  • 91
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    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 3 (1991), S. 223-226 
    ISSN: 0899-0042
    Keywords: enantiomers ; diastereomers ; chirality ; circularly polarized radiation ; circular dichroism ; parity violation ; electroweak interaction ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Fischer demonstrated (1890-1919) that functional biomolecules are composed specifically of the D-sugars and the L-amino acids, and that in the laboratory synthetic reactions of such molecules propagate with chiral stereoselectivity. Given a primordial enantiomer, biomolecular homochirality followed without the intervention of the chiral natural force conjectured by Pasteur (1860), except prebiotically. Polarized solar radiation and other classical chiral forces were proposed as agencies generating a prebiotic enantiomeric excess, but the forces then known were found to be evenhanded on a time and space average, exemplifying parity conservation (1927). The weak nuclear force, shown to violate parity (1956), was unified with electromagnetism in the electroweak force (1970). Ab initio estimations including the chiral electroweak force indicate that the L-amino acids and the D-sugars are more stable than the corresponding enantiomers. The small energy difference between these enantiomer pairs, with Darwinian reaction kinetics in a flow reactor, account for the choice of biomolecular handedness made when life began.
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  • 92
    ISSN: 0899-0042
    Keywords: tumor necrosis factor-α ; secondary structure ; circular dichroism ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The circular dichroism (CD) spectrum of tumor necrosis factor-α has been measured into the vacuum UV to 168 nm. Analysis of the CD for secondary structure is in good agreement with X-ray diffraction results, but the analysis is somewhat unstable. Adding the CD of this protein together with its X-ray determined secondary structure to the basis set should improve subsequent analyses of CD spectra for other all-β proteins.
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  • 93
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    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 3 (1991), S. 268-276 
    ISSN: 0899-0042
    Keywords: absolute configuration ; peptidomimetics ; retro-inverso modifications ; 2-aminocyclopentanecarboxylic acid ; nuclear magnetic resonance (NMR) ; nuclear Overhauser effect ; bioactive peptides ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A modern method is reported for the assignment of absolute configuration for peptidomimetics in bioactive peptides by use of 1H-NMR parameters in solution. Four peptide systems incorporating either retro-inverso modifications or 2-aminocyclopentanecarboxylic acid (2-Ac5c) as a peptidomimetic for proline are discussed. (1) Two 14-membered cyclic dermorphin analogs Tyr-c[D-A2bu-Phe-gPhe-(S and R)-mLeu] with a reverse amide bond between gPhe and mLeu residues where gPhe denotes a gem-diamino analog of Phe and mLeu refers to a malonyl analog of Leu. (2) Two cyclic hexapeptides related to somatostatin, c[gSar6-(S and R)-mPhe7-D-Trp8-Lys9-Thr10-Phe11], with a reverse amide bond between the gSar and mPhe residues where the gSar and mPhe denote the gem-diamino and malonyl analogs of the Sar and Phe residues, respectively. The superscript numbers refer to positions in native somatostatin. (3) Cyclic hexapeptide somatostatin analogs containing 2-Ac5c [trans-(1S,2S)-2-Ac5c, trans-(1R,2R)-2-Ac5c, cis-(1R,2S)-2-Ac5c, and cis-(1S,2R)-2-Ac5c] in place of proline c[(2-Ac5c)6-Phe7-D-Trp8-Lys9-Thr10-Phe11]. (4) Morphiceptin related analogs incorporating a cis-2-Ac5c residue as shown in Tyr-cis-2-Ac5c-Phe-Val-NH2. The methodology described in this investigation could be applied to a wide variety of peptide systems.
    Additional Material: 7 Ill.
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  • 94
    ISSN: 0899-0042
    Keywords: photochromic polymers ; chiral polymers ; stereoregular polymers ; 4-methacryloxyethylenoxyazobenzene ; (-)-menthyl methacrylate ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Copolymers of the photochromic monomer 4-methacryloxyethylenoxyazobenzene with the optically active comonomer (-)-menthyl methacrylate, having different stereoregularity, were investigated in order to obtain a better understanding of the relationship between microstructure and photochromism in synthetic macromolecules. No appreciable effect was observed by copolymer composition, sequence distribution, and microtacticity on the photoinduced trans → cis isomerization of the azobenzene side chains. This last, however, is reflected in changes of the chiroptical properties, type and entity of the photoinduced variation being dependent on chain structure. The long spacer separating the azo chromophore from the main chain limits the extent of chiroptical properties dependence on irradiation.
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  • 95
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    Chirality 3 (1991), S. 324-330 
    ISSN: 0899-0042
    Keywords: bis(μ-methyl-1,3-dimethyl-η3-allylnickel) ; menthyl phosphines ; menthoxy phosphines ; carbon monoxide ; parity control ; complementarity control ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bis(μ-methyl-1,3-dimethyl-η3-allylnickel) reacts in the presence of phosphorus(III) ligands (phosphines, phosphites) with CO to give 3-methyl-(E)-4-hexen-2-one. Systematic experiments were performed using chiral ligands containing menthyl or menthoxy groups and different achiral groups on the P atom to determine the influence of ligand structure and concentration on the direction and extent of chiral induction in this ketone synthesis. It could be shown that reversion of enantioselectivity can be obtained not only by the obvious method of reversing the absolute configuration of the ligand (“parity control”) but also by modifying the nonchiral substituents of the phosphorus ligand (“complementarity control”). The synthesis, physical, and spectroscopic properties of several new menthyl phosphines and phosphites are reported.
    Additional Material: 6 Ill.
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  • 96
    ISSN: 0899-0042
    Keywords: iridium ; asymmetric hydrogenation ; dehydroamino acid esters ; enamide complexes ; resolution ; homogeneous catalysis ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of chiral diphosphines with a configurationally pure cationic bis-enamide complex of iridium, bis(menthyl (Z)-α-benzamidocinnamate)-iridium tetrafluoroborate, is described. When the reactant ligand is racemic then kinetic resolution occurs with high specificity under the appropriate conditions. Since the iridium diphosphine complex is catalytically inactive in homogeneous hydrogenation, the residual enantiomer may be reacted with bis(norbornadiene)-rhodium tetrafluoroborate to produce an active catalyst. This effects the hydrogenation of methyl (Z)-α-acetamidocinnamate in optical yields comparable with those obtained separately with the enantiomerically pure ligand rhodium complex. The reaction of pure (+)- or (-)-enantiomer of bis(menthyl (Z)-α-benzamidocinnamate)-iridium tetrafluoroborate with enantiomerically pure diphosphines has been studied. Invariably one hand of the diphosphine reacts rapidly with a given enantiomer of the iridium complex to give a stable diphosphine iridium enamide complex in which the original configuration of the coordinated olefin is maintained. The other combination of enantiomers reacts much more slowly, in keeping with the kinetic resolution work, and produces an enamide complex which is unstable in solution, isomerising to a second diastereomer. Since the absolute configuration of the iridium bis-enamide complex has been established by X-ray crystallography, this experiment affords a method of determining the configuration of rhodium enamide complexes in asymmetric hydrogenation (assuming structural homology between Rh and Ir). In all cases the disfavoured enamide complex was the one involved in the catalytic pathway.
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  • 97
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    Chirality 3 (1991), S. 370-375 
    ISSN: 0899-0042
    Keywords: enantioselective catalysis ; (2S)-ethyl-2-hydroxy-4-phenylbutyrate ; (S)-ethyl lactate ; α-hydroxy esters ; (2S,3S)-NORPHOS ; rhodium diphosphine catalyst ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The enantioselective hydrogenation of several α-keto acid derivatives with rhodium diphosphine catalysts has been investigated using a random screening approach. The neutral rhodium catalyst prepared in situ from bis(2,5-norbornadiene rhodium chloride) and NORPHOS has been found to be an excellent catalyst for preparing aliphatic α-hydroxy esters in high optical purities. The reaction parameters for the hydrogenation of ethyl 2-oxo-4-phenyl-butyrate, an intermediate for the ACE inhibitor Benazepril, were optimized and the best optical yields obtained were 96%.
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  • 98
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    Chirality 3 (1991), S. 387-388 
    ISSN: 0899-0042
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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  • 99
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    Chirality 3 (1991), S. 480-483 
    ISSN: 0899-0042
    Keywords: biscarbamoylpiperidine ; stereoisomer separation ; enantioselectivity ; circular dichroism ; α1-acid glycoprotein ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: α,α′-Bis[3-(N,N-diethylcarbamoyl)piperidino]-p-xylene dihydrobromide, a novel antiplatelet agent, was resolved into three isomers A, B, and C, on a chiral α1-acid glycoprotein analytical column using a mobile phase of 0.025 M phosphate buffer containing 0.025 M tetrabutylammonium hydrogen sulfate, at a pH of 6.5. The effect of molarity, temperature, pH, flow rate, and organic modifiers on the enantioselectivity was examined. Based on circular dichroic spectra at 220 nm, A and C appear to be the (-)- and (+)-enantiomers, respectively, and B the meso diastereomer. Attempts at resolution using Pirkle type columns gave unsatisfactory results. It appears that both hydrophobic and polar interactions between the compound and the stationary phase are important determinants of resolution.
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  • 100
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    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 3 (1991), S. 503-505 
    ISSN: 0899-0042
    Keywords: racemisation of an S-enantiomeric Schiff base ligand ; potassium isocyanato-{N-salicylidene-(RS)-alaninato}cuprate(II) ; EPR spectrum ; basalcrystallographic data ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Copper(II) N-salicylidene-(S)-alaninate trihydrate reacting as the S-enantiomeric parent compound with KOCN in hot diluted methanol yielded by slow crystallisation from the cooled reaction mixture (in the course of 1 day) the racemic product K[Cu{sal-(RS)-ala}(NCO)]. The parameters of the axial type EPR spectrum in X-band region and the LF band position in the electronic spectrum are typical of an axially distorted square pyramidal coordination of the Cu(II) atom in this complex. The spectral properties of the complex cuprate prepared and its basal crystallographic data are consistent with those of the earlier studied15 K2[Cu2{sal-(RS)-ala}2(μ-NCO)2] synthetized by using [Cu{sal-(RS)-ala}(H2O)].H2O as the racemic parent complex in the reaction mixture with KOCN.
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