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  • 1985-1989  (3,664)
  • 1965-1969  (4,648)
  • 1900-1904  (976)
  • Organic Chemistry  (7,597)
  • Industrial Chemistry  (1,691)
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  • 1
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 26-34 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A set of 4-monosubstituted cyclopentenes, , were synthesized and their relative rates (kX/kH) for bromination and chlorination were determined in methanol, ethanol and acetic acid at 25 °C by competitive method. log(kX/kH) for most of the substituents can be correlated by means of Taft's equation, log(kX/kH) = ρI σI + C. In methanol ρI, Br2 = -2·91, ρI, Cl2 = -0·49, in ethanol ρI, Br2 = -3·07, ρI, Cl2 = -0·70 and in acetic acid ρI, Br2 = -1·64, ρI, Cl2 = -0·65. The presence of C(〈0) is due to a constant steric effect. The deviation of X = H is ascribed to the absence of the steric effect and that of X = CO2Me and CO2Et is accounted for in terms of anchimeric assistance. For chlorination no anchimeric assistance was observed.
    Additional Material: 1 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 57-88 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The cation radical vinylcyclobutane (VCB) rearrangement is found to be a reaction of substantial scope, synthetic utility, and exceptional kinetic facility. In conjuction with cation radical cyclobutanation, it constitutes an effective method for net (indirect) Diels-Alder addition to electron rich dienophiles. Reactions can be carried out with either aminium salt or photosensitized electron transfer (PET) initiation and are powerfully facilitated by ionizable substituents such as p-anisyl, phenylthio, and phenoxy at the 2-position of the vinylcyclobutane. The intramolecularity of the reaction is clearly established and in four discrete systems preferred sr (suprafacial/retention) stereochemistry is observed. A theoretical basis for sr stereochemistry in the cation radical VCB rearrangement is advanced. The transition state for the reaction is considered to be similar to that for the direct cation radical Diels-Alder cycloaddition, another cation radical pericyclic reaction which converges on the same product. This model of the VCB rearrangement transition state is used to rationalize the strong rate-retarding effect of a Z-methyl substituent attached to the vinyl group and of a methyl substituent at the 4-position of the vinylcyclobutane ring cis to the vinyl substituent.
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  • 3
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 1-14 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The mechanism of aromatic nucleophilic substitutions by amines in protic solvents is well established; on the contrary the mechanism/s of the reactions in aprotic solvents is/are still subject of controversy. The present paper describes several systems for which fourth-order kinetics (third-order in amine) were observed. A mechanism is proposed to account for this as well as other observation such as: overall negative energies of activation, quadratic dependence of kA with non-nucleophilic tertiary bases, spectacular effects of hydrogen-bond donor (HBD) and hydrogen-bond acceptor (HBA) catalysts, etc. Other alternative mechanisms are also discussed.
    Additional Material: 5 Ill.
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  • 4
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics and mechanisms of the reactions between 1-phenylethyl benzenesulfonates (1-PEB) with N,N-dimethylanilines are investigated in methanol at 35·0°C. Reactivity and selectivity trends were found to be similar to those for the reactions of 1-PEB with anilines, but the magnitudes of cross interaction constants, ρXZ, between substituents X in the nucleophile and Z in the leaving group were substantially smaller indicating no hydrogen-bond bypass bridge formation in the transition state. However, the magnitude of ρXZ suggested a direct electrostatic interaction between the reaction centers in the nucleophile and leaving group in the frontside nucleophilic attack with a loose transition state structure.
    Additional Material: 6 Tab.
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  • 5
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 183-186 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The harmonic vibrational frequencies were calculated analytically at the 6-31** level for azetidine using the GAUSSIAN 82 program. The results strongly indicate the presence of several errors in a recent assignment of the fundamentals of azetidine based on a normal coordinate analysis and a revised assignment is suggested. It is concluded that reliable vibrational data for azetidine in the gas phase are needed in order to resolve the remaining ambiguities in the interpretation of the spectra.
    Additional Material: 1 Tab.
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  • 6
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989) 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 110-116 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The transamination reaction of α-amino acids with glyoxylic acid as catalyzed by copper(II) ions was investigated kinetically in an aqueous medium at pH 5·0 and 30·0°C. L-Phenylalanine transferred its amino group to glyoxylic acid most readily among seven different amino acids used here in the single-walled bilayer vesicle formed with N,N-dihexadecyl-Nα-[6-(trimethylammonio)hexanoyl]-L-histidinamide bromide (N+C5His2C16). Such rate enhancement was found to originate from the cooperative trifunctional catalysis: a coordination effect exercised by copper(II) ions, a general acid-base catalysis by the imidazolyl group of the lipid, and a hydrophobic field effect provided by the bilayer vesicle. Lack of any of the three functions failed to give out significant rate enhancement. As regards correlation between the reactivity and the nature of α-amino acids, the copper(II)-catalyzed transamination was progressively enhanced as hydrophobicity of the α-amino acid was increased in the N+C5His2C16 vesicle.
    Additional Material: 4 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 43-50 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The cyclic vinyl ether dihydro-1,4-dioxin is converted to its cyclic hemiacetal hydration product, 2-hydroxy-1,4-dioxane, in aqueous solution by an acid-catalyzed reaction for which kH+ = 1·80 × 10-5 M-1 S-1 at 25°C. This reactivity and the solvent isotope effect kH+/kD+ = 2·2 show that the reaction occurs by rate-determining proton transfer from catalyst to substrate and not by a pre-equilibrium mechanism as recently proposed.2
    Additional Material: 1 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 161-176 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Cyclobutanediyl (2) has been studied in both its singlet and triplet states by ab initio electronic structure theory. The triplet, which is the ground state of the molecule, exists in both C2h and C2v forms which interconvert via a Cs transition state. For the singlet, only a C2h form is found. It passes, via a Cs transition state, onto the C2v surface on which bicyclobutane (3) is the only minimum. The ring-flipping (inversion) process in 3 includes the singlet biradical as an intermediate, and involves a novel, non-least motion path similar to one previously proposed by Gassman. Semiclassical periodic orbit theory indicates that the various minima on both the singlet and triplet surfaces can interconvert via quantum mechanical tunneling.
    Additional Material: 5 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 89-92 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Spectral characteristics of several simple substituted B,B-bis(mesityl)pyrroloboranes are reported which support a theoretical treatment by Bonacic-Koutecky and Michl (J. Am. Chem. Soc. 107, 1765 (1985)) describing the excited states of simple aminoboranes as an example of twisted internal charge transfer. In the aminoboranes the pyrrolo moiety functions as the electron donor group and the empty p-orbital of the boron atom as the acceptor.
    Additional Material: 1 Ill.
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  • 11
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 103-109 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A preliminary theoretical study of the mechanisms for the reactions of the perchlorofluoroethanes CF2ClCCl3 (1), CF2ClCCl2F (2) and CF3CCl3 (3), with nucleophiles has been carried out by the MNDO method, following the experimentally suggested process shown in Scheme 1. The unlikely chlorophilic attack in the first step of Scheme 1 has been shown to be feasible for 1, 2 and 3 by analysis of the MO interactions. The second step has been found to be affected by the anionic hyperconjugation which stabilizes the anions CF2ClCCl2- (4), CF2ClCClF- (5) and CF3CCl2- (6) and would make reactions (2) (the second step) unfeasible in gas phase, but in solution reaction (2) may still easily occur for 4 and 5.
    Additional Material: 2 Ill.
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  • 12
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 146-160 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The alkaline hydrolysis of several alkylphosphonates and alkylphosphonyl chlorides has been investigated by molecular mechanics calculations (MM2, 1985 version). The difference of the steric energies (ΔE) between tetracoordinate substrate and pentacoordinate transition state of phosphorus compounds represents the activation energy (ΔE≠) in hydrolysis. The change of ΔE for various alkyl groups relative to methyl group (ΔΔER) is suggested as a measure of the steric effect of substituents. Thus the correlation analysis involving log k and ΔΔER of the branched alkyl group gives good results and it is reasonable to anticipate that analogous treatment using ΔΔER for the straight chain alkyl group is not satisfactory owing to the minor contribution of steric effect of the latter. However, the multiple regression analysis of log k with ΔΔER and Taft's σ* provides very good results. As shown by us, for the hydrolytic reactions studied, the proposed ΔΔER is much better than Taft's Es and Charton's ν, the commonly used well-known steric parameters in the chemistry of carbon compounds.
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  • 13
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 205-213 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Mechanism of the Grignard reactions of aromatic ketones in THF was studied by spectroscopic and kinetic methods. The stable radical intermediates generated in the initial electron transfer from Grignard reagent to ketones are in a state of aggregated dimer of corresponding ion-radical pairs; in which two ketone anion radicals are bridged by a dimer di-cation of Grignard reagent. Subsequent alkyl radical transfer from dimeric Grignard reagent cation moiety to ketone anion radical aggregated each other are promoted by a participation of another neutral Grignard reagent. Proposed mechanism by present authors is able to explain well addition products/reduction products ratios in the Grignard reactions.
    Additional Material: 2 Ill.
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  • 14
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 232-242 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Characteristic vector analysis of a set of six physical and empirical parameters of 103 commonly used organic solvents (bp, ∊r, μ, nD, ETN, and δ) gives four vectors describing 95% of the total data variability. Non-hierarchical cluster analysis, applied to our results, leads to ten separate classes of organic solvents.
    Additional Material: 3 Ill.
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  • 15
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989) 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 16
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 15-25 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Solvolysis of 2-X-2-phenylpropane (1-X) in 25 vol% acetonitrile in water at 25°C produces 2-hydroxy-2-phenylpropane (1-OH) and 2-phenylpropene (3). The carbocationic intermediate discriminates between different nucleophiles; azide anion, acetate anion, and methanol are more efficient nucleophiles than water, kN3/kH2O = 42 kOAc/kH2O = 3, and kMeOH/kH2O = 2·9 (ratio of second-order rate constants). The fraction of the elimination product 3 increases with increasing basicity of the leaving group X as well as by addition of general bases. The Brønsted parameter for this catalysis is small, β = 0·13, with substituted acetate anions. The kinetic deuterium isotope effect for the dehydronation of the intermediate has been measured (assuming the reaction from intermediate to alcohol is insensitive to isotopic substitution) employing the hexadeuterated substrate d6-1-X as k3H/k3d6 = 3·5 ± 0·2 for the chloride 1-Cl with acetate anion, and, without added base, 3·1 ± 0·2 for the acetate 1-OAc, and 3·1 ± 0·2 for the p-nitrobnzoate 1-PNB, respectively, and ∼5 for the protonated methyl ether 1-OMeH+. The variation in isotope effect with change in leaving group is discussed in terms of elimination from contact ion pairs and ‘free’ carbocation. The overall kinetic isotope effect for the solvolysis was found to be kobsH/kobsd6 = 1·31 (1-OMeH+), 1·38 (1-OAc), 1·40 (1-PNB), and 5·7 (1-OH2+). These isotope effects consist of the isotope effect k12H/k12d6 for the formation of the substitution product 1-OH and k13H/k13d6 for production of the olefin 3. It is concluded that the latter isotope effect is enlarged owing to a branched mechanism in which the deprotonation of the carbocationic intermediate competes with formation of the substitution product. As large an isotope effect as k13H/k13d6 ∼6·5 has been measured for 1-OMeH+.
    Additional Material: 2 Ill.
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  • 17
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 99-120 
    ISSN: 0899-0042
    Keywords: asymmetry ; enantiomers ; geometric isomers ; (+)- (-)-isomers ; D- and L-isomers ; R- and S-isomers ; Z- and E-isomers ; drug metabolism ; stereoselectivity and stereospecificity in drug action ; stereoselectivity and stereospecificity in drug metabolism ; psychotropic drugs ; stimulants ; antidepressants ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Many drugs contain a chiral centre, or such a centre is introduced during metabolism of the drug in man and in animals. If a single chiral centre is present, the drug will normally exist as a mixture of two enantiomers, of which one may have quite different pharmacologic and/or toxic effects than the other. Chiral drugs that are used in psychiatry, and some other pharmacologically related drugs are identified, and the implications of the presence of one or two chiral centres in these drugs are discussed. Differences in pharmacologic properties of drug and metabolite enantiomers are identified and discussed. Also reviewed are the properties of some drugs used in psychiatry that both are chiral and display geometric isomerism.
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  • 18
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 10-13 
    ISSN: 0899-0042
    Keywords: (S)-, (R,S)-propranolol ; pharmacokinetic ; human study ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pharmacokinetics of (S)-propranolol were compared after the oral administration of a 40 mg dose of the pure enantiomer and an 80 mg dose of a racemic mixture of (R,S)-propranolol. The results of this study indicate that the bioavailability of (S)-propranolol, as expressed by the mean area uner the concentration-time curve (AUC) and maximum serum concentration, is lower after 40mg of the optically pure drug than after the racemic drug.
    Additional Material: 2 Ill.
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  • 19
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989) 
    ISSN: 0899-0042
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 20
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 192-196 
    ISSN: 0899-0042
    Keywords: propranolol enantiomers ; enantiomers ; propranolol ; β-receptor-blocking drugs ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Only limited information is available on the stereochemistry of the in vivo distribution of β-receptor-blocking drugs. In this study we determined the levels of the propranolol enantiomers in plasma, cerebrospinal fluid (CSF) and central nervous system (CNS), and peripheral tissues in the dog following an intravenous dose of a deuterium-labeled pseudoracemate. The appearance of the propranolol enantiomers in the CSF was rapid and nonstereoselective, with maximum concentrations reached at 15 min after dosing. The levels of the enantiomers in both CSF and plasma then declined in a parallel biphasic fashion, with a terminal t1/2 of about 125 min. Except for an early high CSF/plasma concentration ratio of 0.35, the CSF propranolol levels corresponded to the unbound concentration in plasma, CSF/plasma 0.20. All areas of the brain showed a similar uptake of propranolol, with a tissue concentration exceeding that in plasma about 10-fold during the terminal phase of elimination. The uptake of propranolol by peripheral tissues varied widely, ranging from a 50-fold accumulation by the lungs compared to plasma to no accumulation by adipose tissue. However, as for the CSF, there was no evidence of stereoselective uptake of propranolol by any CNS or peripheral tissue except for the liver. A significantly higher level of (+)- vs. (-)-propranolol in liver tissue presumably was a reflection of stereoselective hepatic metabolism of (-)-propranolol by this tissue. The slight stereoselectivity in plasma binding of propranolol known to exist in the dog had no significant influence on tissue or CSF distribution.
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  • 21
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 209-215 
    ISSN: 0899-0042
    Keywords: enantiomeric separation ; bioanalysis ; α1-acid glycoprotein column ; disposition (R)- and (S)-atenolol ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method for the determination of (R)- and (S)-atenolol in human plasma and urine is described. The enantiomers of atenolol are extracted into dichloromethane containing 3% heptafluorobutanol followed by acetylation with acetic anhydride at 60°C for 2 h. The acetylated enantiomers were separated on a chiral α1-AGP column. Quantitation was performed using fluorescence detection. A phosphate buffer pH 7.1 (0.01 M phosphate) containing 0.25% (v/v) acetonitrile was used as mobile phase. The described procedure allows the detection of less than 6 ng of each enantiomer in 1 ml plasma. The relative standard deviation is 4.4% at 30 ng/ml of each enantiomer in plasma. The plasma concentration of (R)- and (S)- atenolol did not differ significantly in two subjects who received a single tablet of racemic atenolol. The R/S ratio of atenolol in urine was ∼ 1.
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  • 22
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 246-248 
    ISSN: 0899-0042
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 23
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 243-245 
    ISSN: 0899-0042
    Keywords: stereochemistry ; enantiomers ; direct separation ; alfuzosin ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Described is a direct enantioselective separation of the enantiomers of alfuzosin hydrochloride on the second generation α1-AGP column which offers improved efficiency, shorter analysis, and improved stability with respect to the first generation columns. The method has been applied to the analysis of drug substance in rat plasma. This highly efficient extraction method and the use of fluorimetric detection result in selective and sensitive determination of the enantiomers. The analytical validation parameters demonstrate the applicability of this method to pharmacokinetic and metabolic studies.
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  • 24
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 251-264 
    ISSN: 0899-0042
    Keywords: optical activity ; optical rotation ; chiroptical detection ; enantiomeric purity ; chiral separation ; enantioselective reactions ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chiroptical detection for HPLC is particularly useful as a selective detection method for chiral molecules, and in enantiomeric purity determination with partial chiral separation or without chiral separation. The recent development of laser-based polarimeters with microdegree sensitivity has increased the applicability of optical rotation detection in HPLC. The detection limit of these instruments is submicrogram on-column for many chiral compounds in analytical HPLC. A variety of applications of the selective detection of optically active molecules are reviewed. The use of polarimetric detection with partial chiral separation is considered, both as an aid to method development and for enantiomeric purity determination. Finally applications to enantiomeric purity determination without chiral separation are reviewed, with the dual use of nonchirally selective and chiroptical detectors to determine the total amount and optical purity of the analyte. Determinations of chiral purity for samples of high enantiomeric excess are described, which with laser-based instrumentation may give accuracies of better than ± 1% with sample loadings of 50 μg on an achiral column. Applications to the study of enantioselective reactions are also considered, with determination of enantiomeric excess in near-racemates to better than ± 0.1%.
    Additional Material: 9 Ill.
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  • 25
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 271-275 
    ISSN: 0899-0042
    Keywords: HSA-affinity chromatography ; interconverting conformers ; conformational selectivity ; conformational diastereomers ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2,3-Benzodiazepines containing a centre of asymmetry at C-5 possess both central and helical chiralities, and the solution of their racemates contains four molecular species. The binding of these compounds to human serum albumin (HSA) was studied by affinity chromatography. The binding strength depended both on the steric orientation of the 5-ethyl substituent and on the conformation of the diazepine ring. Conformation P (defined by the positive sign of C-1-N-2-N-3-C-4 torsion angle) is favoured, while the quasiaxial orientation -of the 5-ethyl substituent is not favoured by the albumin molecule.
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  • 26
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 293-300 
    ISSN: 0899-0042
    Keywords: optical isomers ; chirality and odour ; chiral flavour compound resolution ; enantiomer separation ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The enantioseparation of the sherry aroma components 5-oxo-4-hydroxyhexanoic acid γ-lactone (solerone) and 4,5-dihydroxyhexanoic acid γ-lactone (solerole) is achieved, using Chiraspher (Merck) as the chiral HPLC phase and the optical purity ascertained directly by HRGC with heptakis(3-O-acetyl-2,6-di-O-pentyl)-β-cyclodextrin (Lipodex D) as the chiral stationary phase. The absolute configurations of 4,5-dihydroxyhexanoic acid γ-lactones are assigned by 1H-NMR spectral data of diastereomeric α-methoxy-α-trifluoromethylphenylacetic acid (MTPA) esters, according to Mosher's model. Sensory qualities of the isomers are given.
    Additional Material: 4 Ill.
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  • 27
    ISSN: 0899-0042
    Keywords: ifosfamide enantiomers, GC chiral stationary phase, pharmacokinetic studies, clinical validation ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An enantioselective gas chromatographic method has been developed and validated for the determination of the plasma concentration of the enantiomers of the anticancer drug ifosfamide (IFF). In this approach, the IFF enantiomers are separated from the plasma matrix by solid phase extraction, chromatographically resolved by gas chromatography on a chiral stationary phase, and detected by mass selective detection using selective ion monitoring. The assay has been validated for routine clinical and pharmacokinetic use and has a limit of detection in plasma of 250 ng/ml of each isomer.
    Additional Material: 3 Ill.
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  • 28
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 15-19 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Effective interfacial area a and volumetric liquid-side mass transfer coefficient kLa of an RTL contactor were obtained at different stirring speeds by absorption of oxygen from air into 0.8 kmol/m3 sodium sulphite solution, in the presence of Co++ ions. The values of a and kLa ranged from 80 to 150 m2/m3 and 0.0003 to 0.00053 s-1, respectively, when stirrer speed was increased from 8 to 40 rpm. When kL alone was evaluated, it was found to be practically constant, irrespective of stirring speed.
    Additional Material: 5 Ill.
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  • 29
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The vapour phase hydrogenation of 1,3-cyclo-octadiene (COD) over Pd on alumina has been studied in the gas phase, using a recycle reactor. The dependences of COD hydrogenation rates and those of the consecutive cyclo-octene (COE) hydrogenation on the reaction conditions are well described by a model which takes into account mass transfer in the porous layer of palladium. The kinetics of the COE hydrogenation is of a Langmuir-Hinshelwood type. The hydrogenation of COD is of first order with respect to hydrogen. The reaction order with respect to COD is -0.15. If the catalyst surface is completely covered by COD, the hydrogenation of COE is totally suppressed. This indicates a much stronger adsorption of COD than of COE. Hydrogenation of COE can only occur in the innermost part of the pores when the transport of COD by diffusion is insufficient to supply the entire active surface of the catalyst. This happens if the ratio PH2/PCOD exceeds 2/ϕ2 with ϕ being the Thiele's modulus. This relationship permits a simple evaluation of the effective diffusion coefficient in the porous Pd-layer.
    Additional Material: 14 Ill.
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  • 30
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 71-87 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In the course of polymerization in homogeneous systems, the viscosity of the reaction mass increases by several orders of magnitude. The viscosity increase is affected by reaction conditions, concentration and properties of the formed polymer. Empirical correlations for homogeneous and heterogeneous polymerizations are given. Viscosity significantly affects the polymerization kinetics as well as heat, mass and momentum balances of the polymerization reactor. The influence of viscosity and its increase on conductive heat transfer, stirrer power input and cooling capacity, molecular diffusion and mass transfer coefficients, mixing time and residence time distribution in homogeneous and heterogeneous polymerizations in stirred tank and tubular reactors is reviewed.
    Additional Material: 16 Ill.
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  • 31
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 89-96 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Depressurization of a pressure vessel, containing a liquid or a gas is limited by the maximum possible mass flux. This flux occurs at a certain drop in pressure. The ratio of ambient pressure to that inside the vessel must be less than a certain critical value. The critical pressure ratio depends on the thermodynamic state of the fluid inside the vessel and on the geometry of the outlet cross-section. The outlet can be a pipeline, a safety valve or a rupture disk. The results of known theoretical and experimental work are presented. In previous experiments, saturated liquids, two-phase flows or pure vapours were examined. In order to predict the critical pressure ratio, certain assumptions are necessary. These are derived for three well-defined cross-sections of the vessel outlet.
    Additional Material: 17 Ill.
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  • 32
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 235-244 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Film theory under consideration of one-sided diffusion is a satisfactory basis for the calculation of vapour condensation from a flowing turbulent mixture with non-condensable gases. At atmospheric pressure and low condensate flow rates, coefficient equations for smooth tubes are used as a rule. At higher pressures and thus, at higher temperatures and gas densities, there are additional parameters. For instance, non-ideal behaviour of the gas phase or the surface roughness affects the condensation process. These parameters were examined in a test plant under variation of pressure, steam concentration and temperature in a vapour/air mixture. At pressures of up to 21 bar, the Reynolds number of the gaseous phase reaches a maximum value of 128 000 and of 720 for the condensed phase. After description of the test facility, the experimental results are explained and discussed. It is shown that the experimental results are not in a good agreement with the common calculating methods. Taking into account the non-ideal behaviour of the steam/air mixture and the roughness of condensate surface by using a friction factor ξr, all the results could be calculated with an accuracy of ± 20%. This was achived with a modification of the coefficient equation of Gnielinski [1] and by using the equation of Andreussi [2] for the friction factor of a cocurrent annular flow. With respect to one-sided diffusion, the film theory is still applicable. The described method for the determination of local transfer coefficients includes the common calculating method. It represents an extension of the general validity of the film theory.
    Additional Material: 15 Ill.
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  • 33
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 226-233 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The explosion behaviour of CH4/air mixtures inside a closed 0.065 m3 spherical and a 1 m3 cylindrical vessel was investigated to determine the effect of turbulence on the structure and propagation rate of transient turbulent flames for different initial turbulence levels generated by 4 ventilators installed inside the equipment. Laser-Doppler and hot wire anemometry were used to measure the turbulent motion. It was found that fairly uniform turbulence could be achieved in the central zones of the vessels and that the RMS-values of flow velocity were proportional to the ventilator speed. The evaluation of burning velocity from the pressure/time records showed that, starting from an initial burning velocity which depends on the initial turbulence level, the flame accelerates as a result of pressure, temperature and turbulence effects. Maximum burning velocity coincides with the inflexion point of the pressure/time curve, and is followed by a rapid deceleration of the flame front. A linear relationship between burning velocity and measured RMS-velocity is recognized in the observed range of RMS-values.
    Additional Material: 13 Ill.
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  • 34
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 245-248 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Mass transfer data are presented for absorption of oxygen in a centrifugal film apparatus. The apparatus was designed to exclude the formation of foam by gas dispersion in liquid. Cells and micro-organisms are not subjected to high shear stress. Therefore, this equipment can be applied in fermentation processes. In the present work, experimental data and correlations were obtained on splitting of the liquid film and oxygen absorption into the film through a spiral ridge formed on the conical surface. The performance of the apparatus is found to be equivalent to those of other types of absorbers.
    Additional Material: 6 Ill.
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  • 35
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 255-261 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The Carman-Kozeny equation is applicable in the viscous flow regime but, as the powder becomes finer, this equation fails. The controlling factor is the ratio of the hydraulic diameter to the mean free path of gas molecules (rH/λ) and, as this approaches unity, “slip flow” occurs. This effect increases with (a) increasing fineness, i.e. rH reduced, (b) decreasing porosity, i.e. rH reduced, and (c) decreasing pressure, i.e. λ increased. In order to account for the enhanced flow arising as a result of this failure, a second term is introduced into the equation and this includes an unknown “constant” (δK0/K), the coefficient of slip. It was considered probable that this so-called constant was a function of (rH/λ), and an attempt was made to investigate this relationship.
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  • 36
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 262-269 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Studies of flow characteristics and residence time distribution, (RTD), have been undertaken in a range of geometrically similar, laboratory nozzle-type reactors. High-speed cine-photography was employed to record the complex phenomena of liquid mixing in the reactor and also to record on film the colour of an injected tracer solution leaving in the effluent. A novel atomic absorption spectrophotometric (AAS) technique was applied to transform the results of the latter film into response curves. This technique provide detailed quantitative data on the residence time distributions (RTD) for different feed rates. A multiparameter model, comprising a network of CSTR's and plug flows, was developed to simulate the experimental response data. Good agreement was obtained between model predictions and experimental results. The experimental technique and theoretical approach are recommended for analyzing the flow patterns and mixing mechanisms in such reactors.
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  • 37
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 269-273 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 7 Ill.
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  • 38
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 280-288 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A cubic equation of state is modified in such a way that prediction of PVT data from 40 model compounds, typical of coal oil, becomes possible with an absolute mean deviation of less than 2% for saturated liquid volumes and vapour pressures 〉 1 bar. Additional correlations for binary interaction parameters are obtained by an optimization procedure using vapour-liquid euilibrium (VLE) data from known heavy hydrocarbon liquid/light gas systems. When the modified equation is applied to coal-derived liquids, only specific gravity and boiling analysis data of the coal liquids are required, primarily in order to determine the equation-of-state parameters. The proposed equation is shown to allow a good prediction of VLE data for systems consisting of wide-boiling-range coal oils and light gases. Experimental values were obtained at elevated temperatures and pressures with a circulation flow apparatus.
    Additional Material: 11 Ill.
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  • 39
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Heat transfer and fluid mechanical data were computed for laminar channel flows containing strong longitudinal vortex pairs. The strong vortices are generated by thin delta wings and delta winglet pairs of low aspect ratios and large angles of attack. These wings are attached to the channel walls. The data show that longitudinal vortices cause high local peaks in heat transfer and marked increases in the overall channel heat transfer. These increases occur over a wide region of channel wall, compared to the vortex generating wing area. The results are of special interest for compact heat exchangers. The heat transfer enhancement allows a considerable reduction in the heat transfer area which, in turn, reduces the manufacturing and operating costs.
    Additional Material: 8 Ill.
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  • 40
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A superposition of simple physical equations allows a satisfactory, comprehensive fluid dynamic description of jet-loop reactors in multiphase operation up to a dispersed phase hold-up of 15%. In the case of higher concentrations, there are further interactions which are not yet included in the model description. Apart from the drag coefficient of the single-phase jet loop, information on the particle swarm behaviour, i.e. on the slip velocity of the dispersed phase is required. Explicit formulation of the influence of the relevant geometrical parameters permits a reliable scale-up without additional adaptation parameters.
    Additional Material: 11 Ill.
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  • 41
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: To improve the rate of convergence of random search optimization procedures, the incorporation of a gradient-oriented one-dimensional search is investigated. With this modification to the random search procedure based on uniform sampling and region contraction [1], convergence to within 0.01% of the global optimum was obtained substantially faster for typical chemical engineering problems. It was also found that the reliability of obtaining the global optimum was improved.
    Additional Material: 4 Ill.
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  • 42
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Grade efficiencies must be measured in order to characterize particle collection in cyclones. For real, irregularly shaped partcles, the grade efficiencies depend on the shape and orientation of the particles and the flow around them. Therefore, the collection characteristics of cyclones should be defined in relation to spherical particles. Deviations occurring on the use of real, irregularly shaped dusts can then be attributed to a material influence. A fast and accurate measuring technique to determine the collection characteristic for spherical particles is described, followed by the presentation of results of extensive investigations on small model cyclones. A similarity relationship is presented. The validity of this relationship was confirmed by investigations with similar, larger cyclones.
    Additional Material: 9 Ill.
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  • 43
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An independent preliminary mechanistic prediction method for leakage rates through small slit-shaped through-wall cracks, based on coupled pressure drop and (critical) mass flux calculation is presented. The predictions are verified against initially subcooled liquid refrigerants and water data collected during experiments in real and model cracks in a wide range of parameters. The achieved accuracy of prediction is already comparable to that of the experimental results. Further model modifications are put forward.
    Additional Material: 11 Ill.
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  • 44
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The knowledge of the heat transfer coefficient on the inner side of a heated vessel wall is of the utmost importance for the design of agitated vessels. In the case of large Reynolds numbers, the heat transfer is mainly determined by these numbers whereas, with small Reynolds numbers, the heat transfer is better described by considering the Grashof number. Investigations of heat transfer in agitated narrow vessels have shown that the height/diameter ratio exerts virtually no influence on the heat transfer when multi-impeller stirrers are used. The heat transfer to stirred suspensions can be described by relationships valid for liquids if the characteristic data of the liquid are replaced by those of the suspension and when the solids volume concentration is also taken into account. This relationship allows the heat transfer coefficient to be calculated for given solids volume concentrations of up to 60%.
    Additional Material: 22 Ill.
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  • 45
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In order to achieve optimal energy-saving, load-dependent operation of rectification columns, development and implementation of model-based control concepts are necessary. This paper reports on the design and step-by-step testing of a state observer for the estimation of two state variables which cannot be measured directly, namely the vapour rate and the location of mass transfer zone (temperature front) in the stripping section of a production column. The procedure is described, and the relevant simulation and operation results are presented and discussed. Initial experience, gained when the concept was put into practical operation, is reported.
    Additional Material: 9 Ill.
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  • 46
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 333-339 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The most important investigations on liquid weeping and entrainment in plate columns with downcomers are reveiwed. The formulae for calculating column plate efficiency under conditions of liquid weeping and entrainment have been derived on the basis of mass balance equations. The presented model is a generalization of the models of AIChE and Colburn. Sample results are shown graphically. The effect of liquid entrainment on tray efficiency predicted by the model is in agreement with experimental data of FRI.
    Additional Material: 9 Ill.
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  • 47
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 356-357 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 1 Ill.
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  • 48
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 345-350 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Continuous crystallization of potassium carbonate was investigated in a mixed suspension mixed product removal (MSMPR) crystallizer with 7.0 1 working volume. Highly polydispersed product was obtained, with x50 varying between 320 and 670 μm. Crystal growth rates can be described by the model of Abegg, Stevens and Larson (ASL) (size dependent crystal growth rate). Values of G0 = 8.6 × 10-9 to 3.6 × 10-8 m/s and B0/ϕ = 2.7 × 108 to 4.2 × 109 1/m3s were obtained for mT = 45 to 92 kg/m3 and ε = 0.45 ± 0.05 W/kg. Nucleation kinetics at 27 °C can be described by the equation: B0/ϕ = kBϕsε0.73G02.5. Since G0 ∝ σ, convection and/or diffusion rather than surface integration are the crystal growth controlling mechanisms.
    Additional Material: 11 Ill.
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  • 49
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Combustion rate of flat graphite plates in oxidizing flows with velocities of up to 80 m/s and stagnation temperatures between 1600 and 2500 K were investigated. The flow field and its local properties were recorded in addition to surface temperature of the solid sample and change in surface structure. The experiments, in which the surface temperature of graphite was adjusted and carefully controlled by radiation shields, indicated that, under these experimental conditions, between 15 and 20 wt-% of carbon was lost as particles of up to 100 μm which burnt rapidly in the boundary layer region. Subtraction of erosion rates from the recorded global combustion rates yield the heterogeneous chemical reaction rates, which are approximated by an Arrhenius type function for the mathematical modelling. Since steep temperature and concentration gradients occur in the boundary layer, the local values of the multicomponent transport coefficients were evaluated in order to design a more realistic computational procedure which, in addition, also includes radiative heat transfer. Computational checks revealed that, in the past, the assumption of mean constant values for the transport coefficients has led to errors of up to 100% in the evaluation of the chemical reaction and global combustion rates.
    Additional Material: 9 Ill.
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  • 50
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This study describes the gas and liquid distributions in a column with structured packings. The column is 0.5 m in diameter. It is equipped with a total of 1289 detectors in the top and bottom cross-sections. These detectors provide a detailed picture of the gas and liquid flows through elements of only 25 × 25 mm2. The maldistribution in the gas bulk flow is negligible. Only the observed wall can contribute to malperformance. The gas flows in parallel to sheet orientation, thus introducing a radial transport. Together with the change in the orientation of subsequent packing elements, this results in good gas mixing. It was observed that the liquid wall flow rate decreases when the gas velocity exceeds 1.7 m/s. Up to the loading point, the maldistribution of the liquid is constant. Above this point, the equality of the distribution deteriorates rapidly, due to the occurrence of large-scale liquid segregation.
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  • 51
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The “nozzle scrubber” is a wet scrubber in which the scrubbing water is dispersed in dust laden gas stream by means of one or more pneumatic nozzle. This scrubber is distinguished by an excellent collection efficiency for submicron dust at an unusually low energy and water consumption. So far, the physical effects affecting the separation cannot be explained by a well-defined theory. Therefore, it is sensible to investigate the collection efficiency with regard to the mechanisms of inertial impaction, turbulent diffusion and coalescence induced by turbulence. The experimental equipment is of a very simple design. A light scattering device was used to measure the particle distributions. In addition, electron micrographs were analyzed to obtain information about the submicron particles. The influence of operating parameters on grade efficiency has been demonstrated by their systematic variation. The contribution of turbulent diffusion to the collection efficiency has been confirmed; nevertheless, grade efficiencies were also measured when inertial impaction prevailed.
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  • 52
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    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 137-141 
    ISSN: 0899-0042
    Keywords: resolution by crystallization ; racemic mixture ; dansyl-D-leucine ; dansyl-L-leucine ; dansyl-D-norleucine ; dansyl-L-norleucine ; dansyl-D-phenylalanine ; dansyl-L-phenylalanine ; β-cyclodextrin ; γ-cyclodextrin ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Optical enrichment from racemic dansyl-leucine, dansyl-norleucine, and dansyl-phenylalanine with both β- and γ-cyclodextrins in water is reported. Initial crystallization yielded the dansyl-L-leucine isomer complexed in excess with β-cyclodextrin with an optical purity of 62-78% depending on experimental conditions. The optical purities obtained for L-norleucine and L-phenylalanine were 71 and 64%, respectively. The optical purity can be increased with continued recrystallization. The dansyl-D-leucine isomer was obtained in the mother liquor with an optical purity of 54-93% depending on experimental conditions. The optical purities obtained for D-norleucine and D-phenylalanine were 72 and 58%. The optical purity of the isomer depended on the molar ratio of host:guest and the pH value of the solution. Optimum enrichment of both enantiomers was achieved with host:guest ratios of 2 : 1 and 3 : 1. Although maximum crystalline yield of the dansyl-leucine/CD inclusion complex was obtained at a pH of 3.5, optical purity of both enantiomers was less than that obtained at other pHs. The influence of the molar ratio of host:guest and the pH value of the solution are discussed. This method is suitable for large-scale enantiomeric separations.
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  • 53
    ISSN: 0899-0042
    Keywords: enantiomeric separations ; chiral stationary phase ; Pirkle-type phases ; HPLC ; anthelmintics ; benzimidazole sulfoxides ; albendazole ; fenbendazole ; oxfendazole ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The direct enantiomeric resolution of albendazole sulfoxide (SOABZ), an anthelmintic drug belonging to the benzimidazole class, is reported on a chiral stationary phase (CSP) synthesized by covalent binding of (S)-N-(3,5-dinitrobenzoyl)tyrosine-O-(2-propen-1-yl) methyl ester on a γ-mercaptopropylsilanized silica gel. A comparison with the resolution achieved on commercially available Pirkle-type CSPs obtained from N-(3,5-dinitrobenzoyl) derivatives of (R)-phenyglycine or (S)-phenylalanine is described. Some structurally related chiral sulfoxides including oxfendazole (SOFBZ) are also studied. Optimization of the mobile phase nature and composition is investigated showing that a hexane-dioxane-ethanol ternary mixture affords an almost baseline resolution (Rs = 1.25); however, in this case, albendazole sulfone (SO2ABZ) is eluted between the two sulfoxide enantiomers; accordingly, a hexane-ethanol mobile phase would be preferred for biological samples containing both metabolites. The influence of temperature on the resolution is depicted with a hexane-ethanol mobile phase. Finally, application to the enantiomeric assays of SOABZ in plasmatic extracts of rat, sheep, bovin, and man after oral administration of albendazole (sulfoxidized to SOABZ and SO2ABZ) is reported. Some distortions in the enantiomeric ratios are evidenced depending on the species.
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  • 54
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    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), 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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  • 55
    ISSN: 0899-0042
    Keywords: terutaline ; enantiomers ; determination ; liquid ; chromatography ; coupled columns ; cyclodextrin ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The purpose of this work was to develop and validate a method for the separation and determination of the enantiomers of terbutaline in plasma and intestinal juice. Terbutaline was extracted from plasma and intestinal juice by liquid-solid extraction on small C18 cartridges. The extract was then analyzed by coupled column liquid chromatography with amperometric detecton. For ciral separation a β-cyclodextrin phase was used.The within-day variation (Cv) on spiked plasma samples was in the rane 0.8-6.4% at 3.8-33.8 nmol/liter for the (-)-enantiomer, and 2.6-23.0% at 1.3-11.3 nmol/liter for the (+)-enantiomer. The between-day variation on spiked plasma samples was 5.5% at 10.7 nmol/liter and 13.6% at 4.3 nmol/liter for the (-)- and (+)-enantiomers, respectively. The within-day variation for inestinal juice was i the range 0.7-1.5% at 5.6-30.0 μmol/liter for the (+)-enantiomer.
    Additional Material: 7 Ill.
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  • 56
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    Chirality 1 (1989), S. 69-79 
    ISSN: 0899-0042
    Keywords: chiral recognition ; three-point model ; distance matrix ; molecular graph ; molecular complexes ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A general criterion is formulated for molecular recognition. The criterion for recognition is the ineqality of the distance matrices of complexes of different compounds with a resolving agent under ambient experimental conditions. It is shown how this criterion provides for an objective, cell-defined, and simple explanation for recognition of chiral compounds. This approach may be used to explain models (e.g., three-point of attachment1) and relationships for chiral recognition. It is also shown how one-, two-, or three-point mechanisms are equivalent in this formalism and could result in chiral recognition. Examples are used to illustrate how the so called one- or two-point mechanisms may be operative in many experimental findings. Symmetry rreqirements of resolving agents may also be derived from considerations of distance matrices. Finally, the reciprocal relationship of chiral resolving agents is easily derived from the present method of analysis.
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  • 57
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    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989) 
    ISSN: 0899-0042
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 58
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    Chirality 1 (1989), S. 97-97 
    ISSN: 0899-0042
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 59
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    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 57-62 
    ISSN: 0899-0042
    Keywords: chiral stationary phase ; α-amino phosphonate ; chromatographic separation of enantiomers ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A chiral statonary phase (CSP) derived from an N-(3,5-dinitrobenzoyl)-α-aminobenzylphosphonate has been prepared and evaluated for its utility in the direct separation of enantiomers. This CSP, 2, is structurally related to earlier N-(3,5-dinitrobenzoyl)-α-acids acid-derived phases (e.g., CSP 1), but the mode of attachment to the support is different. In scope; CSP 2 is qualitaively similar to CSP 1. However, it differs quantitatively from CSP 1, showing either greater or lesser selectivity for different pairs of enantiomers.
    Additional Material: 2 Ill.
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  • 60
    ISSN: 0899-0042
    Keywords: enantiomeric separations ; chiral stationary phases ; tyrosine chiral selector ; γ-mercaptopropyl silica gel ; HPLC ; SubFC ; preparative LC ; chiral recognition mechanisms ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chromatographic applications of three novel chiral stationary phases (CSPs) deriving from (S)-(N)-(3,5-dinitrobenzoyl)tyrosine are reported, under liquid chromatographic (LC) and subscritical fluid chromatographic (SubFC) conditions. Two grafting modes of the chiral moiety have been experimented starting either from γ-mercaptopropyl-silanized (type 1) or γ-aminopropyl-silanized (type 2) silica gels. For type 2 CSPs an evaluation of the stability of the amide linkage was achieved by means of SubFC; the relative contriution of ionic and covalent bindings to the ciral recognitio aility was then outlined. The chromatographic properties of these CSPs were compared with those of the corresponding CSPs deriving from phenylglycine, p-hydroxyphenylglycine, and phenylalanine for the resolution of some tertiary phosphine oxide, naphthoyl amide, and α-methylene γ-lactam enantiomers. Some simple requirements regarding the solute and CSP structures for chiral recognition ability can be inferred from these results. In addition, the resolutio of π-acid α-N-(3,5-dinitrobenzoyl)amino esters was investigated on these π-acid CSPs. An example of preparative scale chromatography is also presented.
    Additional Material: 9 Ill.
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  • 61
    ISSN: 0899-0042
    Keywords: crystal structure ; inclusion ; chiral host ; complexation ; glucopyranose ; cellulose triacetate ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: X-ray analysis of the crystalline product obtained by reaction of 2,3,4,6-Tetra-O-acetyl-D-glycopyranose with phenylethylamine revealed the formation of a real one-to-one inclusion complex. This complexaion is highly stereoselective, because only the (+)-R-enantiomeric form of the amine is included. Analogies to the mode of complexation of cellulose triaceate with chiral molecules in „inclusion chromatography“ are discussed.
    Additional Material: 5 Ill.
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  • 62
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    Chirality 1 (1989), S. 89-91 
    ISSN: 0899-0042
    Keywords: asmmetric induction ; bacterial cell wall ; D-Ala-D-Ala ; dipeptide ; peptidoglycan ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Absolute stereochemical control is employed in the synthesis of isosteres for dipeptide subunits 1; see Fig. (1) in which the amide linkage has been replaced by a trans carbon-caron double bond. The synthesis affords access to the four stereoisomers of 1 in which R and R' = CH3, including the isostere of D-alanine-d-alanine (D-ala-D-Ala), 2.
    Additional Material: 1 Ill.
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  • 63
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    Chirality 1 (1989), S. 92-93 
    ISSN: 0899-0042
    Keywords: ciral resolution ; high-performance liquid chromatography ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Epinephrine enantiomers were derived into diastereoisomers with the chiral reagent 2,3,4,6-tetra-O-acetyl-β-D-glucopyranosylisothiocyanate. The resolutions was carried out on a C18 column. The RS between (-)-R- and (+)-S-isomers was 2.3. The retention time could be changed by adding a proper amount of acetonirile into the mobile phase. The results showed that (+)-S-isomer in the epinephrine hydrochloride injections increased during the period of storage.
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  • 64
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    Chirality 1 (1989), S. 183-191 
    ISSN: 0899-0042
    Keywords: enantiomorphism ; dissymmetry ; chirality ; enantioselectivity ; diastereoselectivity ; steric complementarity ; asymmetric induction ; three-point contact ; circularly polarized radiation ; circular dichroism ; parity nonconservation ; electroweak interaction ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pasteur's conjecture (1860) that biomolecular homochirality arose from a chiral natural force as yet inaccessible in the laboratory was supplanted by Fischer's (1894) “key and lock” hypothesis of stereoselection in enantiomer to diastereomer conversions, whether in the laboratory or in living organisms. Elaborations of the “key and lock” hypothesis by Haldane (1930) and Pauling (1948) have been illustrated and supported with modification by X-ray diffraction crystal structures of enzyme-substrate complexes over the past quarter century.Two types of mechanism for the product diastereoselectivity in the reactions of an enantiomer with an achiral reagent, early proposed, have recent support: one proposes a quasidiastereomeric structure for the enantiomer attacked in the ground state, the other for the corresponding transition state of the reaction. Approaches to the differential biological activity of two enantiomers postulate either the complete binding of each isomer to a chiral receptor site, resulting in diastereomeric complexes with inequivalent bioactivities, or the differential binding of the two isomers to a set of three sites, with which only one isomer is sterically congruent.Biochemical homochirality, based on the chiral stereoselectivity of both biosynthetic and metabolic reactions, derives from the evolutionary pressure for a progressive enhancement of the kinetic efficiency and economy of those reactions. Recently Pasteur has been vindicated in part, and the problem of the original prebiotic enantiomeric excess left outstanding by Fischer has been solved. The unification of the electromagnetic with the weak interaction provided a universal chiral natural force, the electroweak interaction, which favours the chiral series selected during the course of biochemical evolution, both the D-sugars and the L-amino acids.
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  • 65
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    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989) 
    ISSN: 0899-0042
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 66
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    Chirality 1 (1989), S. 249-250 
    ISSN: 0899-0042
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 67
    ISSN: 0899-0042
    Keywords: benzo[a]pyrene diol-epoxides ; benzo[a]pyrene tetrols ; high-performance liquid chromatography ; chiral stationary phase ; optical isomers ; resolution of enantiomers ; absolute configuration ; circular dichroism spectra ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Enantiomers of diastereomeric benzo[a]pyrene (BP) diol-epoxides, r-7,t-8-dihydroxy-t-9,10-epoxy-7,8,9,10-tetrahydro-BP (BP 7,8-diol-anti-9,10-epoxide), r----7,t-8-dihydroxy-c-9,10-epoxy-7,8,9,10-tetrahydro-BP (BP 7,8-diol-syn-9,10-epoxide), r-9,t-10-dihydroxy-t-7,8-epoxy-7,8,9,10-tetrahydro-BP (BP 9,10-diol-antiy7,8-epoxide), and several 7,8,9,10-tetrahydroxy-7,8,9,10-tetrahydrobenzo[a]pyrenes (BP tetrols) were resolved by high-performance liquid chromatography (HPLC) using columns packed with either (R)-N-(3,5-dinitrobenzoyl)phenylglycine[(R)-DNBPG] or (S)-N-(3,5-dinitrobenzoyl)leucine [(S)-DNBL], which is either ionically or covalently bonded to γ-aminopropylsilanized silica. Resolution of enantiomers was confirmed by ultraviolet-visible absorption and circular dichroism spectral analyses. Resolved enantiomers of BP diol-epoxides were each hydrolyzed in acidic solution to a pair of diastereomeric tetrols which were separated by reversed-phase HPLC. Absolute stereochemistries of enantiomeric diol-epoxides were deduced by the absolute configuration of their hydrolysis products.
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  • 68
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    Chirality 1 (1989), S. 284-292 
    ISSN: 0899-0042
    Keywords: absolute configuration ; crystal structure ; resolution ; solid-state circular dichroism ; torsional isomerism ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The crystal structure and absolute configuration of the (-)589-dibenzoylmonohydrogentartrate salt of the cation [Co(pyridine)4Cl2]+ have been determined from a three-dimensional X-ray analysis. Single crystals were grown from dimethylsulfoxide: space group P212121, Z = 4, and cell dimensions a = 21.463(4), b = 23.112(3), and c = 7.490(1) Å. Full-matrix least-squares refinement on F converged at R = 0.075, 196 variables and 2029 observations. The cation has pseudotetragonal coordinate geometry, with axial Cl and equatorial N atoms. The dihedral angles between the pyridine ligands and the equatorial plane are 47(1), 39(1), 50(1), and 45(1)° and torsional isomerism is responsible for the solid-state chiroptical properties of the cation. The preferential crystallization of the P atropisomer of the cation is attributed to a general electrostatic attraction between cation and anion.
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  • 69
    ISSN: 0899-0042
    Keywords: enantiomers ; diastereoisomeric ureas ; high-performance liquid chromatography (HPLC) ; fluorophores ; inversion of optical rotation ; antiarrhythmics ; propranolol ; plasma ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis and analytical testing of two new fluorescent chiral derivatizing agents (-)-(S)-flunoxaprofen and (-)-(S)-naproxen isocyanate, is described. In a few simple steps the free carboxylic acids [(S)-flunoxaprofen and (S)-naproxen] are activated with ethyl chloroformate/sodium azide and transformed to the corresponding isocyanates. The crystalline reaction products display high enantiomeric and chemical purity and stability. The direction of the optical rotation of both substances is inverse to that of the corresponding carboxylic acids. At ambient temperature the reagents swiftly react with primary and secondary amines, yielding highly fluorescent ureas. The applicability of the two reagents for the resolution of racemic amines was tested with a number of pharmaceuticals (antiarrhythmics, β-adrenergic antagonists, calcium channel blockers, centrally acting antidepressants). The diastereoisomeric derivatives were efficiently resolved and separated from side-products by means of normal and reversed-phase high-performance liquid chromatography (HPLC). The use and sufficient sensitivity of the two reagents for pharmacokinetic studies were demonstrated with a determination of plasma levels of propranolol enantiomers after oral administration of the racemic drug [80 mg (R,S)-propranolol-HCl] to two volunteers.
    Additional Material: 7 Ill.
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  • 70
    ISSN: 0899-0042
    Keywords: optical resolution ; HPLC ; chromatography ; antiinflammatory drug ; ibuprofen ; ketoprofen ; flurbiprofen ; tiaprofenic acid ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Direct optical resolution of antiinflammatory drugs such as ibuprofen, ketoprofen, flurbiprofen, and tiaprofenic acid were attempted by high-performance liquid chromatography using tris(3,5-dimethylphenylcarbamate)s of cellulose and amylose as chiral stationary phases. Although ibuprofen was not sufficiently resolved, the other three 2-arylpropionic acids were completely resolved by amylose tris(3,5-dimethylphenylcarbamate). Ibuprofen was resolved as anilide derivative.
    Additional Material: 2 Ill.
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  • 71
    ISSN: 0899-0042
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The stereoselectivity of carvedilol, a novel β-adrenoceptor antagonist and vasodilator with one asymmetric carbon atom, was examined at α1- and β1-adrenoceptors in vitro and in vivo. (-)-(S)-Carvedilol is a potent, competitive antagonist of the β1-adrenoceptor-mediated positive chronotropic response to isoproterenol in guinea pig atrium, with a dissociation constant (KB) of 0.4 nM. (+)-(R)-Carvedilol was more than 100-fold less potent than the (-)-S-enantiomer as an antagonist of β;1-andrenoceptors, having a KB of approximately 45 nM. Consistent with these findings (-)-(S)-carvedilol (0.1 mg/kg, i.v.) produced a 25-fold rightward shift in the β1-adrenoceptor-mediated positive chronotropic response to isoproterenol in pithed rats, whereas the (+)-R-enantiomer had no β1-adrenoceptor blocking activity in vivo at this dose. In contrast to the marked degree of stereoselectivity observed at βl1-adrenoceptors, both (-)-(S)- and (+)-(R)-carvedilol produced equal antagonism of the α1----adrenoceptor-mediated vasoconstrictor response to norepinephrine in rabbit aorta, with KB values of 14 and 16 nM, respectively. Furthermore, in the pithed rat, the α1-adrenoceptor-mediated pressor dose-response curve to cirazoline was shifted approximately 6-fold to the right by both the (+)-R- and (-)-S-enantiomers of carvedilol at a dose of 1 mg/kg, i.v. In anesthetized spontaneously hypertensive rats, (-)-(S)-carvedilol was 6-fold more potent as an antihypertensive than (+)-(R)-carvedilol. The vasodilator and acute antihypertensive activity of carvedilol results from α1-andrenoceptor blockade produced by both enantiomers, and the concomitant β1-adrenoceptor blockade produced by the (-)-S-enantiomer, which prevents reflex tachycardia that can offset the antihypertensive response, leading to greater overall antihypertensive potency of (-)-(S)-carvedilol relative to the (+)-R-enantiomer. These data also suggest that distinct regions of the carvedilol molecule are responsible for blocking α1- and β1-adrenoceptors, with β1-adrenoceptor blockade resulting from an area of the molecule containing the asymmetric carbon atom, specifically the carbazolyloxy propanolamine moiety, and α1-adrenoceptor blockade resulting from a part of the molecule that does not contain the asymmetric carbon atom, most likely the phenoxyethylamine moiety.
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  • 72
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    Chirality 1 (1989), S. 309-312 
    ISSN: 0899-0042
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 73
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    Chemical Engineering & Technology - CET 12 (1989) 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 74
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The chlorination of an alumina with BET surface area of 100 m2/g has been studied in situ by transmission IR measurements at about 670 K. The chlorinating gases consisting of Cl2 and CO were employed individually and in equimolar proportion. The IR results do not reveal the presence of a phosgene surface species which could support the only mechanism proposed so far to explain the chlorination. A detailed alternative reaction mechanism is suggested for the high temperature chlorination reaction, taking into account the IR results, together with the known electron donor-acceptor properties of the activated alumina and the reaction gases: Cl2 molecules accept electrons from oxide ions with a lower coordination number on the alumina surface, leading to the formation of Cl-and Oad. While Cl- yields AlCl3, Oad reacts further with CO producing CO2.
    Additional Material: 4 Ill.
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  • 75
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This contribution reports on the theory underlying a uniform representation of heat transfer to submerged surfaces in fixed bed reactors and of gas convective part of heat transfer in fluidized beds with coarse-grained bulk solids and/or at elevated pressure. Based on an analysis of the pressure drop behaviour of fixed bed percolation at different gas pressures and with different bulk solids, a new dimensionless pressure drop parameter was developed. Fixed bed heat transfer data are very well correlated by this new dimensionless number. As soon as fluid throughput is in excess of minimum fluidization velocity, the pressure drop parameter transforms into the well-known Archimedes number. These two dimensionless numbers are connected by the condition of equilibrium for pressure drop and mass of practices in a fluidized bed. This equilibrium is fulfilled as soon as fluidization commences. Up to now, the Archimedes number has been generally accepted as the significant parameter, determining the gas convective part of heat transfer in fluidized beds; however, without any physical interpretation of this parameter. Introduction of the pressure drop number, which is consistent with the Archimedes number, reduces the heat transfer behaviour to pressure drop characteristics. The usefulness of this concept is proven by the comparison of experimental results and prediction.
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  • 76
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    Chemical Engineering & Technology - CET 12 (1989), S. 33-37 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The absorption of nitric oxide (NO) in phosphoric acid esters and polyethylene glycol ethers which contain cupric halides has been investigated. Due to high solubility of cupric halides and high equilibrium constants of formed nitrosyl complexes, the effective solubility of nitric oxide can be enhanced to about 100-fold its solubility in the salt-free organic liquid which itself amounts to only about 5-fold the NO-solubility in water. Calculations taking into account flue gas conditions indicate that the required gas-liquid ratio in industrial absorption processes will lie in the normal range of flue gas scrubbing processes, namely in the region of 400:1 to 1000:1 in volume. Thus, such a reversible absorption process could a viable alternative to SCR-processes in flue gas denitrification.
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  • 77
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    Chemical Engineering & Technology - CET 12 (1989), S. 54-63 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: When a chemical reactor is depressurized or pressure in a vessel, filled with saturated liquid, has to be decreased, generally both vapour and liquid flow out through the relief valve. Since chemical reactors are usually operated with toxic and explosive fluids, the discharged liquid which vaporizes on the ground around the vessel may reach dangerous concentrations, causing explosions or accidents with the poisonous gas. During a research project, some fundamentals were developed for the design of separation systems which separate liquid from vapour and store it in a receiver. The requirement for a separation efficiency of a least 80% is related to the condition that the separated liquid should flow back into the reactor still during the pressure relief phase. For safety reasons, both separation and re-storage are to be carried out without the supply of external energy. Theoretical and experimental investigations of pressure distribution within the piping to the relief valve and in an integrated separator show that re-storage of the separated liquid in the vessel can be achieved under certain flow conditions. Therefore, the separator must be integrated in the pipe at a certain height above the vessel, so that the hydrostatic pressure of the separated liquid, corresponding to the difference in height, is sufficient to lead it back through another pipe against the internal pressure of the vessel. First, several separators were tested with air-water mixtures. A swirl separator and a reversing separator have been developed to such an extent that they appear suitable for the set task. Experimental results with air-water mixtures and refrigerant R12 upon pressure relief show separation efficiencies of between 90 and 100% at low pressure drops within the whole operating range. As an alternative to separation outside the vessel, a rotary separator was also developed which is fixed to the outlet opening in the vessel. A centrifugal field is produced by the separator rotor and the heavier liquid is largely separated from the vapour so that only drops in the range 〈 100 μm flow together with the vapour towards the central standpipe. The outflowing vapour leaves the separator via 4 tangentially arranged nozzles, under critical conditions. The vapour flow momentum drives the separator rotor. The arrangement was developed and tested during various series of experiments, under conditions or pressure relief with refrigerant R12. So far, separation efficiencies between 60 and 95% have been achieved at stirring speeds of up to 2500 min-1.
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  • 78
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    Chemical Engineering & Technology - CET 12 (1989), S. 63-70 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: It is shown in this report that, under certain conditions, cleaning of exhaust air by absorption presents an interesting alternative to the existing methods. In particular, this process can be used with advantage for small quantities of exhaust air, high and strongly fluctuating solvent concentrations and solvent mixtures such as those occurring in batch operation. A washing agent was employed which had not been previously used for this purpose. Its properties, which were investigated in the laboratory, were confirmed during a 15-months' trial period in a semi-industrial plant. The process and plant were optimized for practical use. Through its option of solvent recovery from exhaust air, this physical absorption process contributes to environmental control.
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  • 79
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The prediction of leak areas in pressure vessels is an important objective in the safety analysis of chemical plants. Using suitable design rules, a leak-before-break behaviour can be achieved. This contribution outlines a procedure for the leak-before-break design of nozzle attachments and the determination of the size of the corresponding opening area. In addition, K1-factors and leak areas for a number of nozzle geometries have been calculated and plotted.
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  • 80
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    Chemical Engineering & Technology - CET 12 (1989), S. 358-364 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The energy consumption of ammonia plants based on steam reforming of naphtha or natural gas can be reduced by shifting the reforming load from the primary to the secondary reformer. It is shown that lowering of the primary reformer operating temperature 20 °C results in 2% increase of unconverted methane content in the outlet stream. The increased methane content can be processed in the secondary reformer if the process air inlet temperature is increased to 400 °C. The lower operating temperature reduces the energy consumption of the primary reformer by about 6% (and the overall consumption by about 2%) and also prolongs the service life of reformer tubes.
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  • 81
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Fermentation under modified gravity could be of interest in application to (a) increasing productivity of growth and growth linked production with microorganisms at high cell densities and (b) increasing the productivity of highly viscous pseudoplastic polysaccharide fermentation. In both cases, higher oxygen transfer rates in centrifugal fields result in higher productivities since these fermentations are usually oxygen limited. A further aspect of fermentation under increased gravity is the reduction of foam since foam coalescence time decreases with acceleration number. On the other hand, under microgravity, shear reduction would allow growth and production even for very shear sensitive organisms. In order to carry out fermentations under modified gravity, a special type of fermenter-the centrifugal field bioreactor CFBR-has been developed at the Institute of Chemical Engineering (Head: Prof. Mersmann) of the Technical University of Munich. For the first time, exoprotein biosynthesis of lipase with S. carnosus has been carried out under sterile and controlled conditions in this novel bioreactor, in presence of increased mass forces.
    Additional Material: 17 Ill.
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  • 82
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An experimental technique and evaluation method is described for the determination of local heat transfer coefficients in tubes or other ducts. By means of a rotary mixing valve, cold and warm fluid flows are mixed in order to generate an arbitrarily shaped but periodically oscillating inlet temperature profile at the test tube. The propagation of the fundamental harmonic oscillation from the fluid to the outer surface of the tube wall is calculated analytically. Comparison of fluid and wall oscillations yields the heat transfer coefficient to be measured. The inaccurate measurement of fluid bulk temperature in the centre of the cross-section is compensated by an additional correction. Experiments were carried out with turbulent water flow through a copper tube. Measured heat transfer coefficients were compared to values calculated using Hausen's equation and good agreement was obtained.
    Additional Material: 4 Ill.
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  • 83
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 374-378 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Wall shear rate vectors in a bubble column and an airlift-loop reactor were measured using the limiting-current electrodiffusion technique. In connection with a new circular three-segment probe, the magnitudes and directions of shear rates were determined. The results for the bubble column are in good agreement with hot film-anemometry measurements in the same column. Moreover, the spiral flow structure, postulated in the shear-zone model of Franz, has been confirmed. In addition, the measuring technique was used to determine the flow structure in an airlift-loop reactor employed for the cultivation of animal cells. The region above the gas distributor of this fermenter has been identified as critical for mechanical damage to the cells.
    Additional Material: 11 Ill.
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  • 84
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 395-399 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Mean droplet diameter of the dispersed phase in pulsed plate extraction columns was measured for binary and ternary systems. A change in the droplet size in the presence of solute, dependent on such factors as the direction of mass transfer, droplet size in the binary system, radio of diffusion coefficients, viscosity of the continuous phase, interfacial tension and driving force for extraction was observed. Two new empirical correlations of mean droplet sizes in mass transfer conditions are proposed. These correlations have been successfully applied to other extraction columns.
    Additional Material: 5 Ill.
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  • 85
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Flow phenomena, local heat and mass transfer and pressure drop of corrugated passages in process equipment are examined. Based on a method for measuring local heat and mass transfer, developed in previous investigations, a procedure has been formulated for the determination of local heat and mass transfer in corrugated passages. Using the analogy between heat and mass transfer, this technique allows the determination of heat transfer distributions in any structures with high local resolution. The corresponding pressure drop is presented together with the local and integral heat and mass transfer of different structures. It is shown that differences in heat and mass transfer as well as in pressure drop are due to different flow phenomena which also characterize mixing behaviour.
    Additional Material: 16 Ill.
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  • 86
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 406-413 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: During molecular distillation in a falling film apparatus, temperature and concentration of the more volatile components undergo a marked decrease in axial and radial directions, due to the distillation in vacuo. The gradients produce changes in the rate of surface evaporation and separation efficiency along the flow path. A theoretical study of this problem is presented for binary mixtures. The respective differential equations for heat and mass transfer in the liquid film are solved numerically. As the results demonstrate, the aspect ratio of an apparatus should be large when a high separation is required and small when a high distillation rate is more important.
    Additional Material: 11 Ill.
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  • 87
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 12 (1989), S. 419-426 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This paper considers the dynamic performance of instruments in control systems. Errors connected with transient measurements are discussed. It is shown that it is not always proper to assign common statistical properties to these dynamic errors. Emphasis is placed on temperature sensors. Common industrial thermometers are described and factors affecting their response discussed. An a-priori dynamic performance prediction procedure is presented. This permits preinstallation estimation of response characteristics of sensors used in industrial processes. Sensors in service also require performance assessment since they can deteriorate with use. In-situ testing is useful for this purpose and a recently develolped procedure is described.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 88
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Crystallizer design has to take into account the physical and chemical properties of the solution and solids as well as the geometry, type and operating conditions of the crystallizer. The most important property of a crystallizing system is its solubility. High solubility leads to low relative supersaturation and large mean crystal size, and vice versa. High solubility systems can be sensitive to abrasion and attrition. For low solubility systems, mixing is crucial.
    Additional Material: 6 Ill.
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  • 89
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The principle of ultrasonic spectrometry is based on the measurement of the ultrasonic extinction caused by the presence of particles. From measurements at different frequencies and with the knowledge of the ultrasonic extinction cross section of the particles, a system of linear equations can be established and solved to obtain the particle size distribution and particle concentration. With an experimental apparatus covering the frequency range from 1.7 MHz to 81 MHz, particles ranging from 20 to 1000 μm in diameter may be analyzed. The measurements can be carried out with particle concentrations as high as 10% by volume.
    Additional Material: 9 Ill.
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  • 90
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 7-9 
    ISSN: 0899-0042
    Keywords: substrate enantioselectivity ; product enantioselectivity ; Michaelis-Menten analysis ; intrinsic activity ; potency ; receptor affinity ; efficacy ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 91
    ISSN: 0899-0042
    Keywords: affinity ; efficacy ; dissociation ; constants ; steroselectivity ; entropy ; enthalpy ; receptor ; interaction ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: After alkylation of a fraction of the total α-adrenoreceptors by phenoxybenzamine in rat vas deferens, the dissociation constants of (-)- and (+)-epinephrine in functional studies were 7 × 10-7 M and 2 × 10-5 M, respectively. In the adrenoreceptor-containing tissue fraction, when 3H-labeled WB4101 was used as the interacting ligand, for each enantiomer who affinity sites were found. Only the low-affinity dissociation consant for each isomer correlates with the constant obtained from the functional studies. If the change in Gibb's free energy. ΔG°, is calculated from the low-affinity binding constants, the values -8.1 and -6.2 kcal/mol for (-)- and (+)-isomer, respectively, are obained. The small difference in the value between isomers forms a hydrogen bond with the receptor. The interaction of epinephrine with this receptor appears to be driven largely by the entropy of the drug-receptor interaction with only a small nonsteroselective contribution from the enthalpy of ineraction.
    Additional Material: 3 Ill.
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  • 92
    ISSN: 0899-0042
    Keywords: column liquid chromatography ; chiral separations ; chymotrypsin on silica ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The stereochemical separation of free and derivatized amino acids on active α-chymotrypsin bonded to silica is governed by two mechanisms based on the structure of the solutes or on the enzymatic activity of the enzyme. Te deactivation of the hydrolytically active site of the enzyme demonstrated that a significant portion of the retention on this support is due to hydrophobic interactions at other sites. These sites appear to be stereoselective for the ester derivatives of amino acids but not for the other studied solutes.
    Additional Material: 3 Ill.
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  • 93
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 63-68 
    ISSN: 0899-0042
    Keywords: optical resolution ; chromatography ; amino acid derivatives ; molecular recognition ; preparative ciral separation ; macroporous polymers ; mass transfer limitaions ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A moleclar imprinting technique based on electrostatic and hydrogen bonding interactions was used to prepare polymers of high selectvity for the original print molecule (D or L form of an amino acid derivative). In the chromatographic mode ig enantioselectivity was observed, in particular for amino acid amides and basic amino acid esters. As indicated y he broad peaks obtained, the mass transfer, including the kinetics of the binding and dissociation process, was slow and appeared to be slower in systems where a higher number of interactions between the solute and the stationary phase could be expected. In such systems enhanced selectivity was observed. For polymers prepared at a lower temperature the mass transfer was more rapid and a higher selectivity was observed, wich allowed the separations to be performed at room temperature. A more rapid mass transfer and a higher selectivity could also be achieved by increasing the column temperature. Furthermore the polymers showed a high sample load capacity and a high stability, and the can easily be prepared.
    Additional Material: 2 Ill.
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  • 94
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 86-88 
    ISSN: 0899-0042
    Keywords: stereochemistry ; stereoselective snthesis ; (S)-2-hydroxypropanoic acid ; chiral synthon ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The (+)- and (-)-enantiomers of benproperinium dihydrogen phosphate, an antitussive drug, have been assigned the R- and S-configurations, respectively, by syntheses of both enantiomers using (S)-2-hydroxypropanoic acid (L-lactic acid) as chiral synthon. The key intermediate, (S)-2-metyl-2-[-2-(phenylmethyl)phenoxy]ethyl p-toluenesulfonate, was subjected to an SN2-type reaction with piperidine furnishing (+)-(R)-benproperinium dihydrogen phosphate. (-)-(S)-Benproperinium dihydrogen phosphate was obtained by submitting the same tosylate to two consecutive SN2-type reactions with Br- and piperidine, respectively, acting as nucleophiles.
    Additional Material: 1 Ill.
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  • 95
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 94-95 
    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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  • 96
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 170-173 
    ISSN: 0899-0042
    Keywords: phenglutarimide enantiomers ; enantioselectivity ; antiparkinsonian drugs ; M1-selective antagonists ; rabbit vas deferens ; pirenzepine ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The affinity of the enantiomers of phenglutarimide at three muscarinic receptor subtypes was examined in vitro using field-stimulated rabbit vas deferens (M1 receptors) and guinea pig atria (M2α receptors) and ileum (M2β receptors). Extremely high stereoselectivity was observed and higher affinities (up to 6000-fold) were found for the (+)-S-enantiomer. The stereoselectivity ratios were different at the three subtypes, and the stereochemical demands made by the muscarinic receptors were most stringent at M1 receptors. (+)-(S)-Phenglutarimide was found to be a potent M1-selective antagonist (pA2 at M1 = 8.53). Its receptor selectivity profile is qualitatively similar to that of pirenzepine. (-)-(R)-Phenglutarimide showed no comparable discriminatory properties.
    Additional Material: 1 Ill.
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  • 97
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989) 
    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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  • 98
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 2-6 
    ISSN: 0899-0042
    Keywords: optical isomers ; stereochemistry ; enantiomers ; Food and Drug Administration ; drug development ; drug regulation ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The current regulatory position of the Food and Drug Administration is discussed with regard to the approval of racemates and pure stereoisomers. Circumstances in which stereochemically sensitive analytical methods are necessay to ensure the safety and efficacy of a drug are described. Regulatory guidelines are interpreted for applications for the approval of a pure enantiomer in which the racemate is marketed, for the approval of eitehr a racemate or a pure enantiomer in which neither is marketed, and for clinical investigations to compare the safety and efficacy of a racemate and its enantiomers. Examples of te basis for such regulation are drawn from historical situations (thalidomide, benoxaprofen) as well as currently marketed drugs (arylproionic acids, disopyramide, indacrinone).
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  • 99
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 27-37 
    ISSN: 0899-0042
    Keywords: mutarotation ; sugars ; carbohydrates ; isomeric ; separation ; temperature effects ; selectvity ; optimization ; hemiacetal ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A brief review of sugar stereochemistry is given. The separation of 84 different pairs of anomers was accomplished on both α- and β-cyclodextrin columns. Five different mobile phases were evaluated. The separation of anomers temperature, flow rate, and so on. The separation of anomers that mutarotate is somewhat more difficult than those that do not. Prior knowledge as to the rate of mutaroation is useful so that the chromatographic conditions can be arranged to minimize any deleterious effects on the separation.
    Additional Material: 7 Ill.
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  • 100
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 121-126 
    ISSN: 0899-0042
    Keywords: stereoselective metabolism ; sulfate conjugation ; in vitro sulfation ; sympathomimetic amines ; chiral separation ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Little is known about the stereochemistry of sulfation of chiral phenolic drugs. In this study we examined several in vitro approaches to this question, using (+)-, (-)-, or (±)-terbutaline as the substrate and the rat liver cytosol as the phenolsulfotransferase enzyme source. The cosubstrate PAPS was either generated by the cytosol from inorganic sulfate and ATP or added to the cytosol. The intact sulfate conjugates formed were determined by HPLC. Using the PAPS generating system, which is best suited for the production of relatively large quantities of sulfate conjugates, with the individual enantiomers as substrates, (+)-terbutaline was conjugated to a much greater extent than (-)-terbutaline; the (+)/(-)-enantiomer ratio was 7.3 ± 0.3 (mean ± SE). When (±)-terbutaline was the substrate and chiral derivatization was employed to separate the sulfate enantiomers formed, a similar (+)/(-)-enantiomer ratio of 7.9 ± 0.2 was obtained. With PAP35S added to the cytosol, an approach best suited for kinetic studies, the substrate concentration dependence of sulfation could be determined. The Km app for this reaction was identical for (+)- and (-)-terbutaline. However, the Vmax app was 8.1 ± 0.4 times greater for (+)-terbutaline. This study for the first time shows enantioselectivity in sulfation of a chiral phenolic drug. The experimental approaches used should be valuable for human studies of stereoselectiven sulfation of terbutaline and other chiral drugs.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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