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  • Analytical Chemistry and Spectroscopy  (1,522)
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  • 1995-1999
  • 1990-1994  (2,210)
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  • 101
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Biomedical Chromatography 6 (1992) 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Type of Medium: Electronic Resource
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  • 102
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    New York, NY : Wiley-Blackwell
    Biomedical Chromatography 6 (1992), S. 227-230 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A new method for the detection of gangliosides based on the lipophilic fluorescence agent 4-(N,N-dihexadecyl)amino-7-nitrobenz-2-oxa-1,3-diazole (NBD dihexadecylamine) and its application for preparative high performance thin layer chromatography is described. Brain gangliosides were chromatographed on silica gel coated thin layer plates and located with non-destructive fluorochrome under longwave ultraviolet light. The fluorescent zones were scraped off and the gangliosides were extracted with a mixture of chloroform/methanol/water (30/60/8; v/v/v). The gangliosides were separated from uncharged NBD dihexadecylamine by anion exchange chromatography and impurities were removed by Iatrobeads chromatography. The method described offers a simple and succesful preparative thin layer chromatographic strategy to obtain pure gangliosides in microgram and milligram quantities.
    Additional Material: 4 Ill.
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  • 103
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Biomedical Chromatography 6 (1992) 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Type of Medium: Electronic Resource
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  • 104
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A gas chromatographic/mass spectrometric procedure has been developed for the quantiation in human plasma of the enatiomers of rimanatadine and its three hydroxylated metabolites. The assay utilized derivatization of all analytes with the optically active reagent S-α-methyl-α-methoxy(pentafluorpheyl)acetic acid, selective ion monitoring, methane negative ion chemical ionization mass spectrometry and stable isotope dilution techniques. This method has been used to meausure plasma concentrations of the enantiomers of rimantadine, m-hydroxyrimantadine and p-hydroxyrimantadine (equatorial and axial epimers) in the ranges 2.5-250, 2.5-50, 1.25-62.5 and 1.25-62.5 ng/mL, respectively, in six subjects given a single 200 mg dose of racemic rimantadine. Although there are no significant differences in the concentration-time profiles of R- and S-rimantadine, large stereospecific differences in the disposition of their metabolites are observed.
    Additional Material: 3 Ill.
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  • 105
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    New York, NY : Wiley-Blackwell
    Biomedical Chromatography 6 (1992), S. 53-53 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Type of Medium: Electronic Resource
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  • 106
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    New York, NY : Wiley-Blackwell
    Biomedical Chromatography 6 (1992), S. 84-87 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A universal peroxyoxalate-chemiluminescence detection system for high performance liquid chromatography, available for a variety of mobile phases, has been developed. The system consisted of a dual-head short-stroke pump and a chemiluminescence detector. The standard conditions using bis(2,4,6-trichlorophenyl) oxalate (TCPO) as aryl oxalate were as follows. The first postcolumn solution was the mixture of 0.5 M imidazole-nitric acid (pH 7.5) and acetonitrile (1:4, v/v). The second was acetonitrile containing TCPO-hydrogen peroxide. These two solutions were delivered by the two pump-heads. After the pH of the column eluate was adjusted to the optimum range (6.5-7.5) by the first postcolumn solution, the solution was mixed with the second postcolumn solution. After flowing through a reaction coil, the chemiluminescence of the mixture was monitored. Using this system, a high sensitivity (fmol level) was obtained for perylene as an analyte with mobile phases having different pH values (2.0-8.0). Polycyclic aromatic hydrocarbons became detectable to a high sensitivity even after the column separation using an acidic mobile phase. The detection sensitivity of nitrated pyrenes after on-line electrochemical reduction using an acidic mobile phase was also increased. This system might be available for other aryl oxalates by some modifications of the postcolumn solutions.
    Additional Material: 2 Ill.
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  • 107
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    Biomedical Chromatography 6 (1992), S. 99-105 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: The plasma concentrations of metoprolol enantiomers have been determined by means of a direct phenyl carbamate-cellulose-based chiral high performance liquid chromatography assay using fluorimetric detection. This assay has been used to investigate the pharmacokinetics and pharmacodynamics of metoprolol enantiomers in the conscious goat. There is evidence that the pharmacokinetics of metoprolol in the goat occurs stereoselectively and that enantiomer-enantiomer pharmacokinetic interactions occur. R-Metoprolol is less effective in reducing the mean arterial blood pressure than S- and R/S-metoprolol.
    Additional Material: 5 Ill.
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  • 108
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    New York, NY : Wiley-Blackwell
    Biomedical Chromatography 6 (1992), S. 59-62 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: The method for the simultaneous determination of angiotensin-converting enzyme (ACE) inhibitor enalapril and its active metabolite enalaprilat in plasma and urine was developed by gas chromatography/mass spectrometry. Enalapril and enalaprilat in plasma and urine were extracted and cleaned up by using Sep-Pak C18 and silica cartridges. Derivatization was carried out using diazomethane and trifluoroacetic anhydride. Detection by selected ion monitoring was selected to m/z 288 (enalaprilat) and 302 (enalapril). The detection limit of enalapril and enalaprilat was 200 pg/mL in plasma and 2 ng/mL in urine. This method was applied to the pharmacokinetic analysis of enalapril and enalaprilat in body fluids.
    Additional Material: 4 Ill.
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  • 109
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A highly sensitive and selective method for the determination of spermidine and spermine has been developed. A polyamine oxidase (Aspergillus terreus) immobilized column was used as a postcolumn reactor. The detection limit was 0.2 pmol/injection for both spermidine and spermine with a linear range of three orders of magnitude.
    Additional Material: 1 Ill.
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  • 110
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A sensitive and specific high performance liquid chromatographic method is described for measuring imidazole dipeptides and 3-methylhistidine in human muscle biopsies, serum and urine. Muscle extract, serum or urine was reacted with o-phthaldialdehyde and the derivatives were separated by reversed phase chromatography with column swithing and fluorescence detection.
    Additional Material: 5 Ill.
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  • 111
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    Biomedical Chromatography 6 (1992), S. 35-38 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A simple and rapid method for analysis of the core of 2′,5′-oligoadenylates, mainly based on the use of high performance liquid chromatography (HPLC), is described. Perchloric acid extracts of tissues or cells were first treated with nuclease P1. Portions of the extracts were then digested with alkaline phosphatase. HPLC analysis of the extracts was performed on a column system composed of an Ultrasphere ODS precolumn (4.6 × 45 mm) and an Ultrasphere Octyl column (4.6 × 250 mm) by stepwise elution using a 50 mM ammonium phosphate buffer, pH7, containing 3.5 and 7% methanol. Three species of the core of 2′,5′-oligoadenylates (dimer, trimer and tetramer) from a number of samples were eluted separately with 7% methanol, and the concentration of each core was directly estimated using constant values calculated with the standard core. The level of the core of 2′,5′-oligoadenylates in tissues and cells determined by our method is similar to that reported by other authors who used biological, radiobinding or radioimmunological assays.
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  • 112
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    New York, NY : Wiley-Blackwell
    Biomedical Chromatography 6 (1992), S. 50-52 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Orosomucoid, a member of the lipocalin family, may function in the in vivo transport of lipophilic compounds such as basic and neutral drugs. We describe the identification of 7-chloro-1-methyl-1,5-benzodiazepine-2,4-dione (clobazam) bound to the serum orosomucoid from individuals actively taking this tranquillizer. This suggests not only that other endogenous factors limit access to the benzodiazepine binding site on human serum albumin, but also that the differential binding of benzodiazepines and their metabolites by orosomucoid should be considered in determining therapeutic doses, particularly in the acute phase response.
    Additional Material: 2 Ill.
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  • 113
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    Biomedical Chromatography 6 (1992), S. 278-282 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: An automated analytical method utilizing laboratory robotics has been developed and validated for quantifying concentrations of a new antiepileptic drug candidate (CGP 33101) in human plasma. The robotic system aliquots the biological sample, adds the internal standard (CGP 23901) and pH 12 buffer, extracts the compounds from the basified matrix into an organic phase (methyl-t-butyl ether:dichloromethane, 2:1) and concentrates the extracts for reversed-phase, high performance liquid chromatographic (HPLC) analysis. The robotic system is directly interfaced with the HPLC system. Separation is achieved on a Hypersil 3 μm C18 column (4.6 × 50 mm) with ultraviolet detection of the analytes at 230 nm. Specificity was demonstrated by the lack of interfering peaks at the retention times for both the drug and internal standard. Recovery and reproducibility assessments indicated good accuracy (overall mean relative recovery of 102.7%) and precision (coefficient of variation of 4.4 to 7.7%) for CGP 33101 over the concentration range of 50-4000 ng/mL. The limit of quantification (LOQ) is 50 ng/mL. The method has been successfully applied to a clinical study in which normal volunteers received single oral doses of 400--1200 mg of this new drug candidate.
    Additional Material: 4 Ill.
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  • 114
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    Biomedical Chromatography 6 (1992), S. 287-290 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: The technique of high performance immunoaffinity chromatography was used to measure the levels of recombinant interferon in chronic lymphocytic leukaemia patients enrolled in a phase II recombinant interferon clinical trial. The technique employed a short high pressure chromatography column packed with minute glass beads which had monoclonal antibody, directed against recombinant alpha interferon, immobilized to their surface. This system was used to measure interferon levels in a variety of different human body fluids. A good correlation was found when interferon levels, detected by chromatographic separation, were compared to levels obtained by a conventional radioimmunoassay.
    Additional Material: 3 Ill.
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  • 115
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    Biomedical Chromatography 6 (1992), S. 258-258 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
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  • 116
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    Biomedical Chromatography 6 (1992), S. 259-262 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Type of Medium: Electronic Resource
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  • 117
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    Biomedical Chromatography 6 (1992), S. 265-268 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Six estrogens - estrone, equilin, estradiol, sodium estrone sulphate, sodium equilin sulphate and sodium 17-α-dihydroequilin sulphate in dog serum were successfully separated and quantified by a high performance liquid chromatographic method developed in our laboratories. The mobile phase was optimized by studying the effects of an organic modifier (acetonitrile) and an ion pairing reagent (tetrabutylammonium hydroxide). The serum sample work-up procedure was designed to recover both conjugated and unconjugated estrogens. The optimum method involved acetonitrile to precipitate serum proteins/peptides and extract estrogens. Residues were reconstituted in 50% acetonitrile in water for injection. The detection limits for these six estrogens via UV detection ranged from 0.5 to 5 ng on-column with a signal-to-noise ratio (S/N) of 10 for a 20 μL injection and via fluorescence 0.1 ng on-column for 17-β-estradiol. Validation data are included for all six estrogens.
    Additional Material: 3 Ill.
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  • 118
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A sensitive and selective liquid chromatographic method to quantitate MDL 201,012 in human plasma was developed and validated. MDL 201,012 (I), diethyl-MDL 201,012 (internal standard, II) and desmethyldiol-MDL 201,012 (masking agent, III) were isolated from basified plasma (2 mL) by solid phase extraction using Bond-Elut® C-18 cartridges. Endogenous components were selectively removed prior to eluting the analytes from the sorbent. Components were separated using on-line LC column switching with a cyanopropyl precolumn and a phenyl analytical column. The analytical column effluent was monitored electrochemically at a glassy carbon electrode at a potential of + 1025 mV vs. Ag/AgCI. Peak-height ratios were proportional to the amount of MDL 201,012 added to plasma over the range 125-7500 pg/mL MDL 201,012. Absolute recovery of MDL 201,012 from human plasma was 〉94% across the calibration range. The minimum quantitation limit was 125 pg/mL. Assay precision (%RSD) ranged from 5.2 to 13% based on the analysis of quality control standards containing 125, 250, 500, 1000, 2500, 5000 and 7500 pg/mL MDL 201,012. Corresponding assay accuracy (% relative error) was ±8.5%. The method has been successfully used to quantitate MDL 201,012 in samples from acute dose tolerance studies in human volunteers.
    Additional Material: 3 Ill.
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  • 119
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A high performance liquid chromatographic method for the analysis of chlortetracycline (CTC) using postcolumn fluorescence detection has been developed. After chromatographic separation of CTC on a polystyrenedivinylbenzene copolymer column, a highly fluorescent derivative isochlortetracycline (iso-CTC) was formed postcolumn in an on-line reaction coil with the addition of 25% NaOH (w/v). Chromatographic separation was achieved on a PRP-1 column, 15 cm × 4.6 mm, with 27:73 acetonitrile:0.2% perchloric acid (v/v), at 1.0 mL/min. Fluorescence derivatization was achieved by the on-line addition of 25% NaOH (w/v), at a flow rate of 0.2 mL/min, into the column eluant in a post-column reaction coil. The reaction coil was 9 m of teflon (1/16 in o.d., 0.3 mm i.d.) knitted into a six-sided coil. The fluorescent derivative was detected at λex 355 nm and λem 〉389 nm. Using this method after a simple sample cleanup, CTC can be detected in milk at 0.04 μg/mL, which is comparable to that obtained by microbiological assays. The detection method was linear between 0.02 μg/mL and 4 μg/mL. Because of the chromatographic separation, the method is more selective than microbiological assays and more sensitive than ultraviolet detection. With the chromatographic system described, the keto tautomeric forms of CTC and 4-epi-CTC are separated in a system which minimizes their formation on-column. In acidic aqueous organic solutions, the keto tautomer of CTC is the only product formed to any significant amount.
    Additional Material: 7 Ill.
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  • 120
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    Journal of Chemometrics 6 (1992) 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 121
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    Journal of Chemometrics 6 (1992), S. i 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 122
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    Journal of Chemometrics 6 (1992), S. 63-64 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 123
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    Journal of Chemometrics 6 (1992), S. 65-83 
    ISSN: 0886-9383
    Keywords: Trilinear decomposition ; Receptor modeling ; Source identification ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In many cases, monitoring data for ambient airborne particles can be organized in the form of a three-way data table with one way for chemical species, one for sampling periods and one for sites. A direct trilinear decomposition followed by a matrix reconstruction (DTDMR) is developed to analyze such a data table as a whole. The three-way data set is composed into three two-way matrices by a direct trilinear decomposition (DTD). The column vectors of each of the matrices are called ‘source profiles’, ‘emission patterns’ and ‘site coefficients’ respectively. Particulate sources are identified by examining both their source profiles and emission patterns. After the sources have been identified, emission patterns and site coefficients are used to produce a three-way matrix that gives estimates of mass contributions of sources to the samples collected at every site in every period. By simulation study, not only has the method been verified, but a good indicator has been found that shows the number of factors (i.e. sources) in the system. Unlike other receptor models, DTDMR does not require source profile data and does not involve trial-and-error procedures. Since DTDMR identifies sources based on variations in two dimensions, it has a higher potential to distinguish two sources that have similar chemical compositions. The DTDMR model has provided excellent results with simulated data and has been applied in a real world three-way data set.
    Additional Material: 7 Ill.
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  • 124
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    Journal of Chemometrics 6 (1992), S. 113-116 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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  • 125
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    Journal of Chemometrics 6 (1992), S. 117-118 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 126
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    Journal of Chemometrics 6 (1992), S. 151-161 
    ISSN: 0886-9383
    Keywords: NIR spectroscopy ; Wavelength selection ; Interaction effects ; Multicomponent mixtures ; Partial least squares ; Generalized least squares ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Modern scanning (near-)infrared reflectance/absorption (NIR) spectroscopes measure the absorptions or reflectances at a sequence of around 1000 wavelengths. Training data may consist of 10-100 carefully designed sample mixtures for which the true composition of the mixture is either known by formulation or accurately determined by wet chemistry. In future one wishes to predict the true composition from the spectrum. In this paper we compare a simple wavelength selection approach with methods which retain all the wavelengths. It offers a powerful yet simple technique for choosing those wavelengths that are specific to each pure component as against the other components (including the medium) for the varying compositions. In the presence of a defined range of ingredients in thus chooses wavelengths which are highly selective for each particular component. It has the added advantage of selecting wavelengths which are little effected by interaction effects and consequent non-linearities.The calibration data used consist of 125 observations of three sugars, each varying at five levels in a full 53 design. The validation set consists of 21 further samples specially selected to have compositions outside the range of the training sample. The selection methods perform much better on this prediction set than methods which retain all the wavelengths, 700 in this case. The leave-one-out cross-validation internal to the calibration data would point to the opposite finding and suggests that such crossvalidations may be overly flattering to techniques such as partial least squares and may encourage overfitting. After selection, simple straightforward least squares methods may be used, eschewing the need for ‘shrinkage’ methods such as partial least squares or ridge regression.
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  • 127
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    Journal of Chemometrics 6 (1992), S. 247-255 
    ISSN: 0886-9383
    Keywords: Analysis of variance ; Assumptions ; Graphics ; Models ; Validation of model ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The computer has made it possible to scrutinize data rapidly by means of graphics. This should be done prior to the application of any model to the data, since the model must be validated before using it as a means of analyzing the data. The procedure is illustrated in terms of two examples of real experimental data.
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  • 128
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    Journal of Chemometrics 6 (1992), S. 284-285 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 129
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    Journal of Chemometrics 6 (1992), S. 307-334 
    ISSN: 0886-9383
    Keywords: Non-linear PLS ; Quadratic regression ; Non-linear models ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We treat here an extension of linear PLS regression to include regression on quadratic PLS components. The quadratic regression can be viewed as a natural extention of linear PLS regression to quadratic PLS according to the H-principle of mathematical modelling. The numerical implementation is treated in detail. It is shown that this approach can be used for models with large numbers of variables. Some modelling strategies are discussed depending on the purpose of the modelling. Applications of this approach are treated.
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  • 130
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    Journal of Chemometrics 6 (1992), S. 357-357 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 131
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    Journal of Chemometrics 6 (1992) 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 132
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    Journal of Chemometrics 6 (1992), S. 29-40 
    ISSN: 0886-9383
    Keywords: Factor analysis ; Window factor analysis ; Multicomponent analysis ; Flow injection analysis ; Self-modeling curve resolution ; Bismuth chloride complexes ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Window factor analysis (WFA) is a self-modeling method for extracting the concentration profiles of individual components from evolutionary processes such as flow injection, chromatography, titrations and reaction kinetics. The method takes advantage of the fact that each component lies in a specific region along the evolutionary axis, called the window. Theoretical equations are derived. The method is used to extract the concentration profiles and spectra of seven bismuth species from data obtained by Gemperline and Hamilton, who injected bismuth perchlorate into a flowing stream of hydrochloric acid.
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  • 133
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    Journal of Chemometrics 6 (1992), S. 57-62 
    ISSN: 0886-9383
    Keywords: Closure ; Baseline ; Mean centering ; Rank ; Exploratory data analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This paper describes an investigation into the relationship of closure, a baseline offset and mean centering to the interpretation of matrix rank. The equivalence of a certain type of closure to a constant baseline (i.e. a simple numerical offset which may vary between response channels but is constant over all samples) is demonstrated. A systematic approach to the interpretation of the rank of a matrix is given.
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  • 134
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    Journal of Chemometrics 6 (1992), S. 97-102 
    ISSN: 0886-9383
    Keywords: Between-group variances ; Canonical variate criterion ; Eigenvalues ; Eigenvectors ; Orthogonal projection ; Within-group variance ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Canonical variate analysis is the appropriate descriptive technique for multivariate data which have an a priori group structure, but problems arise with this technique when there are more variables than within-group degrees of freedom because of singularity of matrices. In such cases it is shown through illustrative examples that principal component analysis is a viable substitute provided that the principal components are ranked according to the canonical variate criterion (ratio- of between- to within-group variances) rather than the usual criterion of total variance. This ranking can also be used to select components for subsequent discriminant analysis.
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  • 135
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    Journal of Chemometrics 6 (1992) 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 136
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    Journal of Chemometrics 6 (1992), S. 119-133 
    ISSN: 0886-9383
    Keywords: Mass spectra ; Classification ; Structure description ; Fragmentation ; Ion series ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to investigate correlations between the functionality of compounds and the classification of their mass spectra, low-resolution spectra of monofunctional compounds have been classified by four supervised classification methods. The new classes are characterized by structural features and the correlation between functionality and classification is explained by fragmentation rules. Systematic misclassifications show that low-resolution mass spectra alone are not suitable for reliable identification of functionality.
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  • 137
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    Journal of Chemometrics 6 (1992), S. 163-175 
    ISSN: 0886-9383
    Keywords: Multiple-correspondence analysis ; Starch granule description ; Image analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Raw starch is composed botanically of characteristic granules of various sizes and shapes, so that each kind of starch may be characterized by the population of its granules. In the present study ten commercial starch species were studied: wheat, rice, manioc, potato, arrowroot, amylomaize, normal maize, waxy maize and two different banana species. Six variables measuring the size and shape of granules were obtained by image analysis. The objective was to find a method to describe and compare the granule populations of the ten species. For such a study, multiple-correspondence analysis (MCA) was applied. MCA makes it possible to draw similarity maps of categories and objects. For each starch species the frequency distributions (histograms) of the six variables were assessed and each granule was characterized by its species and the classes of histograms to which it belonged. MCA was applied to the granule table and a description of the histogram classes and the granules was obtained. From the variables description a general typology of the granules was deduced. The similarity maps showed considerable scatter of the granules for all species except rice. A particular species could therefore not be identified by a single granule, but the granule distribution seemed to be characteristic. MCA was an appropriate method to analyse these data because it points out non-linear relationships between quantitative and qualitative variables.
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  • 138
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    Journal of Chemometrics 6 (1992), S. 177-188 
    ISSN: 0886-9383
    Keywords: PLS ; Prediction error ; Background constituents ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A modification of a technique proposed by Lorber and Kowalski for the estimation of prediction errors is presented. The method is applied to five data sets. The results show that for some data sets the estimated prediction errors are close to the actual prediction errors for samples within the calibration range, while samples outside the calibration range must be background corrected before quantification of the prediction error.
    Additional Material: 10 Ill.
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  • 139
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    Journal of Chemometrics 6 (1992), S. 189-198 
    ISSN: 0886-9383
    Keywords: Robust regression ; Partial least squares ; QSAR ; Perturbation study ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A robust partial least squares (PLS) regression algorithm is developed. This is achieved by substitution of the univariate regression steps in the iterative PLS2 algorithm by a robust alternative. The angle between loading vectors from both perturbed and unperturbed solutions is used as a measure of robustness. By means of a perturbation study on a structure-activity data set, it is demonstrated that the stability of the robust method is superior to standard PLS.
    Additional Material: 4 Ill.
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  • 140
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 141
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    Journal of Chemometrics 6 (1992) 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 142
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    Journal of Chemometrics 6 (1992), S. 267-281 
    ISSN: 0886-9383
    Keywords: Genetic algorithms ; Feature selection ; Multivariate analysis ; Optimization methods ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Genetic algorithms have been created as an optimization strategy to be used especially when complex response surfaces do not allow the use of better-known methods (simplex, experimental design techniques, etc.). This paper shows that these algorithms, conveniently modified, can also be a valuable tool in solving the feature selection problem. The subsets of variables selected by genetic algorithms are generally more efficient than those obtained by classical methods of feature selection, since they can produce a better result by using a lower number of features.
    Additional Material: 2 Ill.
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  • 143
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    Keywords: Derivatization reaction ; Factorial design ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A number of nucleophiles have been successfully identified and quantified using the Kröhnke reaction with 2,3-diphenyl derivatives of quinolizinium salts. Optimization of the reaction conditions by means of a mathematical model involving analysis of the response surface has led to a better understanding of the factors exerting an influence on the above reaction.The parameters chosen were temperature, reaction time, base concentration, water concentration and nucleophile concentration. The reaction was developed in polar aprotic solvents (acetone, acetonitrile). To facilitate the nucleophilic attack, the presence of an organic base (triethylamine) was necessary, although concentrations in excess of 0·15M did not alter the development of the reaction. Since pharmaceutical solutions are often aqueous, the influence of water on the reaction was studied. Low water volumes have no significant influence on the opening of the quinolizinium ring by the nucleophilic reagent. However, when the water proportion exceeded that of the organic solvent, the fluorescence intensity was lower than expected. Development of the fluorescent reaction product was first detected 5 min after the reaction started. The fluorescence intensity reached its optimum value after 138 min.
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  • 144
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    Journal of Chemometrics 6 (1992), S. i 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 145
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    Journal of Chemometrics 6 (1992), S. 85-96 
    ISSN: 0886-9383
    Keywords: Optimization ; Calibration ; Simulated annealing ; Experimental design ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This paper utilizes variable step size generalized simulated annealing (VSGSA) to design multicomponent calibration samples for spectroscopic data. VSGSA is an optimization procedure which is capable of converging to exact positions of global optima located on multidimensional continuous functions. On the basis of analysis sample response vectors, optimally designed calibration concentration matrices are obtained assuming knowledge of components present. The complexity of response surfaces established by the optimization criteria is described.
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  • 146
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    Journal of Chemometrics 6 (1992), S. 103-111 
    ISSN: 0886-9383
    Keywords: Mean centering ; Preprocessing ; Multivariate calibration ; Error propagation ; Principal component regression (PCR) ; Partial least squares (PLS) ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Traditionally, one form of preprocessing in multivariate calibration methods such as principal component regression and partial least squares is mean centering the independent variables (responses) and the dependent variables (concentrations). However, upon examination of the statistical issue of error propagation in multivariate calibration, it was found that mean centering is not advised for some data structures. In this paper it is shown that for response data which (i) vary linearly with concentration, (ii) have no baseline (when there is a component with a non-zero response that does not change in concentration) and (iii) have no closure in the concentrations (for each sample the concentrations of all components add to a constant, e.g. 100%) it is better not to mean center the calibration data. That is, the prediction errors as evaluated by a root mean square error statistic will be smaller for a model made with the raw data than a model made with mean-centered data. With simulated data relative improvements ranging from 1% to 13% were observed depending on the amount of error in the calibration concentrations and responses.
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  • 147
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    Journal of Chemometrics 6 (1992), S. i 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 148
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    Journal of Chemometrics 6 (1992), S. 135-150 
    ISSN: 0886-9383
    Keywords: 2D surface ; Multivariate analysis ; Non-congruent ; Unfolding ; Folding ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The use of latent variable projection for analysis of non-congruent 2D surfaces is presented. We give a formal description of the folding/unfolding process. A simulated 2D oscillator evolving in time is studied in detail to illustrate interpretation aspects of the method.
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  • 149
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    Journal of Chemometrics 6 (1992), S. i 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 150
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    Journal of Chemometrics 6 (1992), S. 199-216 
    ISSN: 0886-9383
    Keywords: MARS ; Splines ; Multivariate calibration ; Non-linear ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This tutorial paper presents a simplified view of one of the more recently published multivariate calibration methods particularly suited to dealing with non-linear data sets. The method is referred to as MARS and stands for multivariate adaptive regression splines. Simple examples are provided to explain the workings of the method.
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  • 151
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    Journal of Chemometrics 6 (1992), S. 228-228 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 152
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    Journal of Chemometrics 6 (1992), S. 229-229 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 153
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    Journal of Chemometrics 6 (1992), S. 231-246 
    ISSN: 0886-9383
    Keywords: Integration methods ; Taylor series method ; Optimization methods ; Kinetic mechanisms ; Kinetic determinations ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A general equation to derive kinetic models up to any order is given. This equation greatly facilitates the application of the Taylor series method to the integration of kinetic models up to very high orders. When dealing with non-stiff models, computing time is always reduced by increasing the integration order, at least up to the 20th order. When the model is stiff, the integration order should be optimized; however, a twelfth order is recommended to integrate weakly stiff models. The use of an algorithm which permits the immediate calculation of the integration step size required to maintain a given accuracy leads to further reductions in computing time. When implemented as recommended here, a high-order Taylor series method is more rapid and accurate than Runge-Kutta and predictor-corrector methods and can be advantageously used in combination with optimization methods to perform mechanism studies and in multicomponent kinetic determinations.
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  • 154
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 155
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    Journal of Chemometrics 6 (1992), S. 289-305 
    ISSN: 0886-9383
    Keywords: Chemical structure database ; Conformational searching ; Similarity searching ; Substructure searching ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This paper presents a review of the rapid developments that have taken place over the last few years for the searching of databases of three-dimensional (3D) molecules. The geometric arrangement of the atoms in a 3D molecule is described by an interatomic distance matrix. This is a form of labelled graph that can thus be searched using the subgraph-isomorphism algorithms that are widely used for searching databases of two-dimensional (2D) molecules. Several in-house and commercial systems have been developed for 3D database searching that are based on such techniques. These systems are reviewed and their effectiveness demonstrated by examples of their use in the discovery of novel, biologically active molecules. Current systems represent a molecule by one or a small number of low-energy conformations and there is hence much interest in the development of representational techniques and searching algorithms that account for the full set of geometric arrangements that can be adopted by a flexible molecule.
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  • 156
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 157
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    Keywords: GOLPE ; PLS ; Regression ; SDEP ; Variable selection ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A procedure called GOLPE is suggested in order to detect those variables which increase the predictivity of PLS models. The procedure is based on evaluating the predictive power of a number of PLS models built by different combinations of variables selected according to a factorial design strategy. Examples are given of the efficiency of this variable selection procedure, which shows how these predictive PLS models are better than those obtained by all variables and better than the corresponding ordinary regression models.
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  • 158
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    Journal of Chemometrics 6 (1992), S. 11-28 
    ISSN: 0886-9383
    Keywords: Three-way PLS ; PARAFAC ; Unfolding ; Validatory tools ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The methods PARAFAC and three-way PLS are compared with respect to their ability to predict reversed-phase retention values. Special attention is paid to simple validatory tools, the meaning and use of which are explained.
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  • 159
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    Journal of Chemometrics 6 (1992), S. 41-56 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The principal properties, here called the ρ-scales, of peat have been calculated on the basis of chemical analysis. The scales were derived from quantitative contents of carbohydrates, Klason lignin, amino acids, amino sugars and conventional chemical peat measurements. The variation in the chemical parameters was compressed using principal component analysis (PCA). Partial least squares (PLS) regression was used for prediction of botanical, microbial, physical and dewatering data. A rapid estimation of the scales has been made from near-infrared (NIR) spectroscopy and offers, indirectly, rapidly obtainable, chemically interpretable, biological information. A reduced scale based on carbohydrate data was also tested. The ρ-scales offer an interface between different areas of peat research. Strategies are outlined for the selection of a subset of chemical measurements among the variables used for characterization. A multivariate strategy based on these ideas is discussed.
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  • 160
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    Journal of Chemometrics 6 (1992) 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 161
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    Journal of Chemometrics 6 (1992), S. 217-225 
    ISSN: 0886-9383
    Keywords: Principal component regression ; Calibration ; Optimality ; Principal component selection ; Quantitative structure-activity relationship ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Principal components (PCs) for principal component regression (PCR) have historically been selected from the top down for a reliable predictive model. That is, the PCs are arranged in a list starting with the most informative (PC associated with the largest singular value) and proceeding to the least informative (PC associated with the smallest singular value). PCs are then chosen starting at the top of this list. This paper discusses an alternative procedure of treating PC selection as an optimization problem. Specifically, without any regard to the ordering, the optimal subset of PCs for an acceptable predictive model is desired. Five data sets are analyzed using the conventional and alternative approaches. Two data sets are spectroscopic in nature, two data sets deal with quantitative structure-activity relationships (QSARs) and one data set is concerned with modeling. All five data sets confirm that selection of a subset without consideration to order secures the best results with PCR. One data set is also compared using partial least squares 1.
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  • 162
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    Journal of Chemometrics 6 (1992), S. i 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 163
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    Journal of Chemometrics 6 (1992), S. 257-266 
    ISSN: 0886-9383
    Keywords: Principal factor analysis ; Factor analysis ; Eigenvalue analysis ; Multivariate analysis ; Weighted factor analysis ; Procrustean analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two approximate methods for weighted principal components analysis (WPCA) were devised and tested in numerical experiments using either empirical variances (obtained from replicated data) or assumed variances (derived from unreplicated data). In the first (‘spherical’) approximation each data vector was assigned a weight proportional to the geometrical mean of its variances in all dimensions. The arithmetical mean of variances was used instead in the other approximation. Both the numerical experiments with artificial data containing random errors of various kinds (constant, proportional, constant plus proportional, Poisson) and the analysis of two sets of Raman spectra clearly indicated the necessity of introducing statistical weights. The spherical approximation was found to be slightly better than the arithmetical one. The application of statistical weighting was found to improve the performance of PCA in estimation problems.
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  • 164
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 165
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    Keywords: Predictive ability ; Regression ; PLS ; SDEP ; Cross-validation ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The standard deviation of prediction errors (SDEP) is used to evaluate and compare the predictive ability of some regression models, namely MLR, ACE and linear and non-linear PLS, the last being the best one. The parameter is determined by a cross-validation approach as an average of several runs obtained on forming groups in a random way. The variation in SDEP with the number of latent variables in PLS is also discussed.
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  • 166
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    AIChE Journal 38 (1992), S. 15-25 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Quantitative results are presented on mean coordination number and coordination number distribution, contact normal distribution and fabric tensor of simulated anisotropic granular deposits with resulting solid fractions between ca. 15% for ballistic deposits and 58%, corresponding to a random loose packing. The deposits, generated by the capture of uniform size spherical particles arriving normal to a target, were simulated using a simple algorithmic model.We focus on microstructural quantities which explicitly take into account the discrete nature of the granules comprising the deposit. Such measures are important in determining the heat transport properties of the deposits for Fourier conduction through the solid phase, as well as their mechanical and sintering properties. The variation of mean coordination number with deposit solid fraction was successfully correlated using a unit-cell model (Eq. 13). This correlation, in conjunction with entropy maximization arguments (after Nayak and Tien, 1978) has been further used to predict the coordination number distribution. The usefulness of the results reported here is illustrated by computing an upper bound to the deposit effective thermal conductivity (Jagota and Hui, 1990) and comparing it to both ‘exact’ simulation results (Tassopoulos and Rosner, 1991b) and experimental data (Koh, 1971).
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  • 167
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    AIChE Journal 38 (1992), S. 56-66 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The tortuosities of fibrous media in the heretofore unexplored transition and ordinary regimes are computed using a Monte Carlo scheme based on the Einstein equation for random walkers. The model structure is that of fully penetrable cylinders (FPC) in a unit simulation volume. The mean square displacement technique is combined with the first passage time distribution to accelerate the progress of the walkers at low Knudsen number. The results include the computation of transition regime transport coefficients for the first time. The calculated ordinary tortuosities are approximately equal to the reciprocal of the porosity over a wide range, while the transition tortuosities are shown to deviate from the reciprocal porosity with a simple dependence on Knudsen number. The limits of the transition regime are shown to correspond roughly to Knudsen numbers of 0.50 and 100, respectively. The calculated Knudsen tortuosities are shown to improve on earlier results obtained by the authors using a flux-based technique.
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  • 168
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    AIChE Journal 38 (1992), S. 101-115 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Singularity theory, large activation energy asymptotics, and numerical methods are used to present a comprehensive study of the steady-state multiplicity features of three classical adiabatic autothermal reactor models: tubular reactor with internal heat exchange, tubular reactor with external heat exchange, and the CSTR with external heat exchange. Specifically, we derive the exact uniqueness-multiplicity boundary, determine typical cross-sections of the bifurcation set, and classify the different types of bifurcation diagrams of conversion vs. residence time. Asymptotic (limiting) models are used to determine analytical expressions for the uniqueness boundary and the ignition and extinction points. The analytical results are used to present simple, explicit and accurate expressions defining the boundary of the region of autothermal operation in the physical parameter space.
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  • 169
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    AIChE Journal 38 (1992), S. 153-157 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 5 Ill.
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  • 170
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    AIChE Journal 38 (1992), S. 318-319 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 10 Ill.
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  • 171
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    AIChE Journal 38 (1992), S. 321-327 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Aqueous solutions of phenol were oxidized in a flow reactor at temperatures between 300 and 420°C (0.89 ≤ Tr ≤ 1.07) and pressures from 188 to 278 atm (0.86 ≤ Pr ≤ 1.27). These conditions included oxidations in both near-critical and supercritical water. Reactor residence times ranged from 1.2 to 111 s. The initial phenol concentrations were between 50 and 330 ppm by mass, and the initial oxygen concentrations ranged from 0 to 1,100% excess. The oxidation experiments covered essentially the entire range of phenol conversions. Analysis of the kinetics data for phenol disappearance using a combination of the integral method and the method of excess revealed that the reaction was first order in phenol and 1/2 order in oxygen, and influenced by pressure. The global reaction order for water was taken to be nonzero, and the global rate constant was assumed to be independent of pressure so that the only effect of pressure was to alter the water concentration and hence the reaction rate. This approach led to a global reaction rate law that was 0.7 order in water and had a rate constant with an activation energy of 12.4 kcal/mol. The implications of these rate laws to the design of a commercial supercritical water oxidation reactor are also explored.
    Additional Material: 7 Ill.
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  • 172
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    AIChE Journal 38 (1992), S. 1027-1037 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A mathematical model is presented to describe coking and activity characteristics of porous catalysts in supercritical reaction mixtures. These characteristics are determined by the way in which temperature and pressure affect the simultaneous physicochemical rate processes involving the effective diffusion of reactants in the pore, coke formation, and coke extraction. For a parallel coking reaction, the model predicts that when the reaction mixture density is isothermally increased from subcritical to low-to-moderate values, the ensuing higher reaction rates and restricted diffusion lead to pore-mouth plugging and decreased catalyst effectiveness factors. At dense supercritical conditions, however, the enhanced coke solubilities in the reaction mixture alleviate pore-mouth restrictions, resulting in a recovery of catalyst activity and increased effectiveness factors. The model predicts an optimum supercritical density at which catalyst activity is maintained at a maximum value. At smaller than optimum density values, the reaction rate is limited by coke extraction and at larger than optimum values, the rate is subject to pore diffusion limitations. These predictions are qualitatively consistent with reported experimental observations.
    Additional Material: 11 Ill.
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  • 173
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    AIChE Journal 38 (1992), S. 1079-1091 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A computer model for a hot gas-fluidized bed has been developed. The theoretical description is based on a two-fluid model (TFM) approach in which both phases are considered to be continuous and fully interpenetrating. Local wall-to-bed heat-transfer coefficients have been calculated by the simultaneous solution of the TFM conservation of mass, momentum and thermal energy equations. Preliminary calculations suggest that the experimentally observed large wall-to-bed heat-transfer coefficients, frequently reported in literature, can be computed from the present hydrodynamic model with no turbulence. This implies that there is no need to explain these high transfer rates by additional heat transport mechanisms (by turbulence).The calculations clearly show the enhancement of the wall-to-bed heat-transfer process due to the bubble-induced bed-material refreshment along the heated wall. By providing detailed information on the local behavior of the wall-to-bed heat-transfer coefficients, the model distinguishes itself advantageously from previous theoretical models. Due to the vigorous solids circulation in the bubble wake, the local wall-to-bed heat-transfer coefficient is relatively large in the wake of the bubbles rising along a heated wall.
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  • 174
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    AIChE Journal 38 (1992), S. 1129-1134 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 4 Ill.
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  • 175
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    AIChE Journal 38 (1992) 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 176
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    AIChE Journal 38 (1992), S. 1-14 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Adaptive control techniques, with their capability for providing satisfactory control even when the process changes with time, are promising candidates for dealing with common problems encountered in photolithography processing such as batch-to-batch variations in resist properties and inconsistencies in resist curing. In this article, an adaptive control strategy for the photolithography process is proposed and evaluated. The design utilizes a reduced-order lithography model, an on-line parameter estimator, and a nonlinear model-inversion controller.The width of the printed resist lines, a crucial output of photolithography, is controlled by automatically adjusting the exposure energy. In the calculation of the appropriate exposure adjustment, the controller uses both measured critical-dimensions as well as estimated values produced by the process model. The control system is capable of tracking changes in the photolithography process by automatic updating of key model parameters as the process evolves in time. Simulation studies of the closed-loop adaptive control strategy, using the PROLITH simulation package to represent the lithography process, demonstrate the feasibility of this approach.
    Additional Material: 16 Ill.
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  • 177
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    AIChE Journal 38 (1992), S. 76-82 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The liquid circulation model of Rice and Geary (1990) is extended to include turbulence originating at the wall. Thus, two possible length scales are considered: one originating from rising bubbles and the other emanating from the wall. The appropriate scale for small columns should be based on bubble size, while for larger systems the proper mixing length is proportional to column diameter. It is proposed that the film Reynolds number may be the key in distinguishing the two cases.
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  • 178
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    AIChE Journal 38 (1992), S. 116-127 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Singularity theory is combined with asymptotic analysis to determine the exact uniqueness-multiplicity boundary and ignition and extinction locus for the non-adiabatic, autothermal tubular reactor model. It is found that the steady-state behavior of the nonadiabatic reactor is described by the two limiting cases of adiabatic and strongly cooled models. The adiabatic case has been examined in a previous study. Here, we develop limiting models to describe the strongly cooled asymptotes. We also classify the different types of bifurcation diagrams of conversion vs. residence time using the results of singularity theory with a distinguished parameter. Analytical criteria are developed for predicting the conditions under which autothermal operation is feasible when heat losses are significant.
    Additional Material: 14 Ill.
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  • 179
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    AIChE Journal 38 (1992), S. 149-152 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 4 Ill.
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  • 180
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    AIChE Journal 38 (1992) 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 181
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    AIChE Journal 38 (1992), S. 201-210 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Two-and one-dimensional steady-state isothermal mathematical models of monolith reactors for selective catalytic reduction (SCR) of NOx by NH3 are compared for circular, square and triangular geometry, as well as for linear and Rideal kinetics. Solutions for the two-dimensional model demonstrate that, as the reaction rate decreases from infinity to zero, the Sherwood number varies from the values of the Nusselt number characteristic of the Graetz-Nusselt problem with constant wall temperature to those with constant wall heat flux but with peripherally varying temperature. A lumped-parameter treatment, based on similarity with the constant wall temperature heat transfer problem, agrees satisfactorily with the solutions for a far more expensive two-dimensional model. The agreement is excellent for square channels, but the NH3 slip tends to be underestimated in the triangular geometry. The one-dimensional model reproduces successfully experimental effects of the NH3/NO feed ratio, and of the area velocity and the size of monolith channels.
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  • 182
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    AIChE Journal 38 (1992), S. 219-226 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Current AC (alternating current) techniques are used often to characterize the energetics at a semiconducting solid phase/electrolyte interface. For thin layers having a strongly disordered or amorphous structure (such as oxide-passive layers anodically grown on valve metals), interpretative models currently used for crystalline semiconductors may produce misleading data.A new interpretation of the admittance data, based on recent models for amorphous semiconductors (a-Sc) Schottky barriers, is presented for passive films of Nb, W and Ti. The physical bases of the model are presented as well as its advantages and disadvantages. The new theory views the solid/electrolyte interface more satisfactorily and provides information on the solid-state properties and the electronic structure of the electrode useful for interpreting the electron exchange between the solid phase and redox couples in solution.
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  • 183
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    AIChE Journal 38 (1992), S. 26-40 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The design of controllers for nonlinear, nonminimum-phase processes is one of the most difficult control problems currently faced. Current available control algorithms for nonlinear processes rely implicitly or explicitly on an inverse of the process. Linear control methods for nonminimum-phase processes are based on a decomposition of the process into a minimum-phase and a nonminimum-phase part. Such a decomposition is an open problem for nonlinear systems.In this work, a control structure called the minimum-phase output predictor for nonlinear, nonminimum-phase processes is developed. The structure is based on the notion of statically equivalent outputs; a minimum-phase, statically equivalent output is estimated on-line and then an available nonlinear control algorithm is used to control it to set point. The advantage of the proposed formulation is that it is based on the calculation of an output function, not on a decomposition of the process dynamics. The proposed control methodology is applied and its performance is evaluated for a chemical engineering example.
    Additional Material: 8 Ill.
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  • 184
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    AIChE Journal 38 (1992), S. 67-75 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Clarke et al. (1986) have developed a model-based verification method and have applied it to validation of VLSI circuits. We have used the method to test automatically the safety and operability of discrete chemical process control systems. The technique involves: (1) a “system model” describing the process and its software; (2) “assertions” in temporal logic expressing user-supplied questions about the system behavior with respect to safety and operability; and (3) a “model checker” that determines if the system model satisfies each of the assertions and provides a counterexample to locate the error if one exists. Temporal logic is used for reasoning about occurrence of events over time. To reveal discrete event errors, we have applied the verification method to a simple combustion system and an alarm acknowledge system.
    Additional Material: 18 Ill.
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  • 185
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    AIChE Journal 38 (1992), S. 93-100 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: One of the major obstacles to overcome for the realization of economical hydrogen-oxygen, polymer-electrolyte fuel cells is the high capital cost of the inert perfluorosulfonic acid (PSA) membranes, which provide a pathway for ionic transport between the cell electrodes. It has recently been shown that composite polymer membranes can be synthesized by depositing PSA polymers onto porous poly(tetrafluoroethyene) (PTFE) substrates. The resulting membranes are mechanically durable and quite thin relative to traditional PSA membranes; we expect the composite membranes to be of low resistance and cost. In this experimental study, we examine the composite membrane properties as a function of the membrane composition. Our results allow us to form a conceptual model to explain both the equilibrium and transport characteristics of these materials. For high PSA contents, the membrane behavior is similar to that of the PSA polymer; the water permeability, however, is reduced significantly. For intermediate PSA contents, the membranes have a high porosity and match the thickness of the PTFE substrate (≈50 μm); membranes of this composition range are potentially useful candidates for fuel cells because of their high resistance to water transport and reduced ionic resistance. Composite membranes of very low PSA content demonstrate characteristics similar to the hydrophobic PTFE substrate and are not of interest for fuel cells.
    Additional Material: 8 Ill.
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  • 186
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    AIChE Journal 38 (1992), S. 479-479 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 187
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    AIChE Journal 38 (1992), S. 489-501 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The coupled, unsteady Navier-Stokes, convective diffusion, and thermal energy equations that describe spin coating of colloidal suspensions are solved numerically. The theoretical model, absent of any adjustable parameters, is used to explore the effects of angular velocity, initial solvent weight fraction, solvent properties and spin coating protocol on the evolution of temperature and concentration profiles in the liquid film during spin coating. The predicted coated film thickness is found to be in excellent quantitative agreement with spin coating experiments performed with both hard-sphere and nonhard-sphere suspensions of monodisperse latex particles in water. The coated film thickness, determined by ellipsometry, is shown to depend on the inverse square root of the angular velocity except at high ionic strength when the dependence on angular velocity is weaker. Timescales that characterize spin coating of colloidal suspensions are shown to be quite different from those that characterize spin coating of polymer solutions, and consequently simple models for predicting the coated film thickness of polymer solutions (Bornside et al., 1991; Lawrence, 1989) are shown to be inadequate for colloidal suspensions. Rapid substrate acceleration, high rotation rates, partial saturation of the overlying gas phase, and high initial solids concentration are identified as spin coating protocols that suppress a convective instability that produces radial striations in the coated film.
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  • 188
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    AIChE Journal 38 (1992), S. 535-543 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A hybrid model is developed and implemented for predicting the limiting bound of the reactant conversion rate in an isotropic turbulent flow under the influence of a reaction of the type A + B Products. This model is based on the amplitude mapping closure of Kraichnan for the molecular mixing of a stochastically distributed scalar, and the eddy-damped quasi-normal Markovian (EDQNM) spectral closure for the two-point scalar covariance. The results predicted by this model compare well with available experimental data in both gaseous and aqueous plug-flow reactors, but point to the need for more detailed measurements in future experimental studies. With the implementation of the mapping closure, a simple analytical expression is obtained for the decay rate of the unmixedness. This expression is very convenient and is recommended for direct practical applications in the modeling and design of plug-flow reactors.
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  • 189
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    AIChE Journal 38 (1992), S. 237-243 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An experimental study has been carried out of the in situ thermal degradation of a commercial dehydrogenation catalyst in a fixed-bed reactor. The activity of catalyst particles sampled at different reactor positions after several reaction-regeneration cycles has been related to their time-temperature history, according to the following kinetics: \documentclass{article}\pagestyle{empty}\begin{document}$$ - da_0 /dt = 0.147{\rm exp}(- 73,600/RT)a_0^{2.2} $$\end{document}The above equation represents the loss of activity under coke-free conditions, that is, activity loss due to sintering. The results of the study show that important differences in catalytic activity can be obtained for different positions of a fixed-bed catalytic reactor after several operation-regeneration cycles.
    Additional Material: 8 Ill.
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  • 190
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    AIChE Journal 38 (1992), S. 259-272 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The diffusion of proteins in polymer matrices is an important step in the adsorptive and chromatographic processes used for protein purification, as it is often rate-limiting. Methods for the estimation of the intraparticle diffusivity in polymer gels have been developed and were applied to the diffusion of seven model proteins in agarose particles. The intraparticle diffusivity was not affected by particle diameter. A correlation based on the restricted diffusion model of Ogston et al. (1973) and Cukier (1984) has been proposed. This correlation allows the estimation of protein diffusivity in these matrices based on the molecular weight of the protein and the polymer concentration.
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  • 191
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    AIChE Journal 38 (1992), S. 291-296 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The concept of optimal catalyst activity distribution is studied experimentally for the ethylene epoxidation reaction network on a Ag/α-Al2O3 catalyst in a single-pellet reactor. The Dirac delta-type distribution of the catalyst is approximated by a step distribution of narrow width. For a fixed amount of silver, the influence of location and width of the catalytically active layer on the conversion of ethylene and on the selectivity and yield to ethylene oxide is investigated under oxygen-rich conditions in the temperature range 210-270°C. The results clearly demonstrate that for optimum selectivity and yield to ethylene oxide, the silver catalyst should be placed in a thin layer at the external surface of the pellet.
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  • 192
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    AIChE Journal 38 (1992), S. 315-315 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 193
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    AIChE Journal 38 (1992), S. 1871-1880 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The dynamic behaviour of an adiabatic tubular plant reactor during the startup is demonstrated, together with the impact of a feed-pump failure of one of the reactants. A dynamic model of the reactor system is presented, and the system response is calculated as a function of experimentally-determined, time-dependent, manipulated variables. The values of model parameters are estimated by using the SimuSolv (1991) computer program. The data set collected during the reactor start-up is used for the parameter estimation procedure. An excellent agreement is obtained between the experimental and the calculated system response. Many continuously-operated commercial reactors require a complete conversion of one of the main reactants at the reactor exit. It is shown that for an industrial tubular reactor a much higher initial reactor temperature is required during the startup, compared to the reactor inlet temperature during normal steady-state operation, to ensure a complete reactant conversion. Much more research is necessary to determine whether this is a generally valid rule.
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  • 194
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    AIChE Journal 38 (1992), S. 1913-1915 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A semi-empirical model of the radial segregation of solids in upward flow of dilute gas-particle suspensions in riser systems is presented on the basis of a reduced form of the fundamental two-phase flow governing equations and experimental evidence concerning the solids concentration at the wall. The following simple expression for the radial solids concentration profile is obtained: \documentclass{article}\pagestyle{empty}\begin{document}$$ \frac{{1 - {\rm \varepsilon }}}{{{\rm 1} - {\rm \varepsilon }}} = 2\left( {\frac{r}{R}} \right)^2 $$\end{document} and is in agreement with experimental data over a wide range of operating conditions: superficial gas velocity from 1.4 to 15.3 m/s, riser diameter from 0.032 to 0.40 m, imposed solids flux from 6.60 to 207 kg/m2·s, mean particle size from 32 to 120 μm and particle density from 1,000 to 3,500 kg/m3.The model confirms the existence of the core-annulus flow structure in gas-particle suspensions reported in riser reactors, circulating fluidized beds, and the freeboard of bubbling fluidized beds.
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  • 195
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    AIChE Journal 38 (1992), S. 835-846 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Batch, fed-batch, and single-stage CSTR bioreactors operate without external sources of biomass after they have been inoculated. However, other kinds of bioreactors, such as the second and subsequent reactors in a cascade of CSTRs, operate with continuous introduction of biomass from one or more external sources. The biomass in a bioreactor with an external source is not homogeneous with respect to past history of environmental conditions, and growth of this biomass is not balanced (steady-state) growth even when the bioreactor operates in steady state. So-called unstructured models of growth, which assume biomass to lack any internal structure or to have an invariant internal state, can give only a first approximation to the growth rate behavior of the biomass in a bioreactor with an external source of biomass. Structured models, which endow biomass with a changeable internal structure, are required to obtain more accurate predictions of growth rate behavior in such reactors. Introduction of structure is not sufficient for improved accuracy, however, and the fact that biomasses from different sources are remain segregated from one another must also be accounted for by any structured growth model used. This article presents, among others, the systems of different equations that result from application of the notions to the reactors of a cascade of CSTRs.
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  • 196
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    AIChE Journal 38 (1992), S. 1309-1328 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: We examine the simplest homogeneous azeotropic distillation sequence of industrial relevance, where an entrainer is added to a binary azeotrope to recover both azeotropic constituents as pure products. Despite its apparent simplicity, such distillation columns can exhibit an unusual behavior not observed in zeotropic distillation: For some mixtures, separation as a function of reflux goes through a maximum. At infinite reflux, no separation is achieved.In some cases, achieving the same specifications with a larger number of trays requires a larger reflux.Sometimes the only feasible separation yields the intermediate component as a pure distillate, while the bottom product contains the light and heavy components.Sometimes the only feasible separation yields the intermediate component as a pure bottom product while the distillate contains the light and heavy components.While these unusual features can be regarded as curiosities, they are essential for proper entrainer selection and design. For a minimum boiling azeotrope, the existing and conflicting entrainer selection rules state that one should use a component that introduces no distillation boundary between the azeotropic constituents (Doherty and Caldarola, 1985), and either a low or high boiling component that introduces no additional azeotrope or a component which introduces new minimum boiling azeotropes (Stichlmair et al., 1989). By taking advantage of the curious aforementioned features, as well as our experience involving more than 400 mixtures, we have been able to analyze the assumptions behind these criteria, show when those assumptions break down, and therefore understand the limitations of the criteria.
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    AIChE Journal 38 (1992), S. 1161-1169 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The overlapping grain model was used to describe the sulfidation of zinc oxide and zinc-titanium oxide powders at temperatures between 400-700°C in H2S-H2-N2 gas mixtures. Experimental data were collected under conditions free of mass-transfer and pore diffusion limitations. Thus, the only resistances to reaction were due to intrinsic sulfidation kinetics (surface reaction) and diffusion through the product layer. The product layer diffusion coefficient was used as a fitting parameter in the model. As the relative amount of titanium in the sorbent was increased, the product layer diffusion coefficient decreased. Similar activation energies (26.6 kcal/mol) were obtained for the product layer diffusion coefficient of ZnO and Zn-Ti-O sulfidation. From the similarity in activation energies, it is proposed that for both types of sorbents diffusion occurs primarily through ZnS.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
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  • 198
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 38 (1992), S. 1243-1253 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The degree of hydrogen bonding and macroscopic thermodynamic properties for pure and mixed fluids are predicted with the hydrogen bonding lattice fluid (LFHB) equation of state over a wide range in density encompassing the gas, liquid and supercritical states. The model is successful for molecules forming complex self-associated networks, in this case pure methanol, ethanol, and water, and the mixture 1-hexanol-SF6. In supercritical water, significant hydrogen bonding is still present despite all the thermal energy and is highly pressure- and temperature-dependent. A fundamental description of pressure and temperature effects on hydrogen bonding is presented for a well-defined case, the formation of a complex between a donor and acceptor in an inert solvent, where no self-association is present. The partial molar enthalpy and volume change on complexation both become pronounced near the critical point, where the density is highly variable with temperature and pressure.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
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  • 199
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 38 (1992), S. 1477-1480 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 200
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 38 (1992), S. 1488-1488 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
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