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  • Articles: DFG German National Licenses  (2,948)
  • 2000-2004
  • 1985-1989  (2,948)
  • 1945-1949
  • 1987  (1,625)
  • 1985  (1,323)
  • Analytical Chemistry and Spectroscopy  (2,078)
  • Engineering  (870)
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  • Articles: DFG German National Licenses  (2,948)
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  • 2000-2004
  • 1985-1989  (2,948)
  • 1945-1949
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  • 201
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Biomedical Chromatography 2 (1987), S. ii 
    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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  • 202
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: The fluorogenic Edman reagent 4-N,N-dimethylamino-1-naphthyl isothiocyanate (DNTC) was reacted with amino acids and peptides, cyclized by acid and the liberated 4-N,N-dimethylamino-1-naphthyl thiohydantoin (DNTH) amino acids were then separated and detected by HPLC. The fluorescence intensities of DNTH-amino acids except DNTH-proline and -serine were dramatically increased in the alkaline solution and organic solvent. Thus, the postcolumn reaction with alkaline acetonitrile solution was adopted in HPLC. The polar and aromatic amino acids afforded two DNTH-amino acids on derivatization with DNTC and cyclization with acids. These were suggested to be stereoisomers of DNTH-amino acids. The sequence analysis of 0.5 nmol Leu-enkephalin was achieved by the double coupling method with DNTC and phenyl isothiocyanate followed by the proposed HPLC system.
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  • 203
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    Biomedical Chromatography 2 (1987), S. 148-151 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Cytidine deaminase is an enzyme of nucleic acid metabolism, the measurement of which has been proposed as a useful test for the early detection of pre-eclamptic toxaemia in pregnancy. The enzyme converts the nucleoside cytidine to uridine, with the release of ammonia, and it is the measurement of this latter compound that forms the basis of the conventional methods for the assay of cytidine deaminase. The low activity of the enzyme requires long incubation times, which in turn increase the possibility of contamination by exogenous ammonia. We have developed a new method for determining cytidine deaminase activity, utilising high performance liquid chromatography to measure the production of uridine. This method uses much shorter incubation times and is unaffected by ammonia contamination. This paper describes the development of the method and its comparison with the established assay. The relative merits of each are discussed. Finally, the adaptation of incubation and chromatographic conditions, in order to measure other enzymes of nucleic acid metabolism which are of clinical interest, is briefly mentioned.
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  • 204
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    Biomedical Chromatography 2 (1987), S. 173-176 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A new method for the chromatographic determination of polyamines is presented. The procedure consists of the reaction of 9-fluorenylmethyl chloroformate (FMOC-Cl) with polyamines at 50 ± 1°C for 10 min, followed by stepwise elution chromatography. The reaction is simple and the derivatives are stable. All the polyamine-FMOC derivatives can be separated within 13 min. The linearity of this method is satisfactory in the range of 0.5-100 pmol. The detection limits for putrescine, cadaverine, spermidine and spermine are 83.3 fmol, 109 fmol, 25.5 fmol and 22.7 fmol respectively.
    Additional Material: 8 Ill.
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  • 205
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    Biomedical Chromatography 2 (1987) 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
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  • 206
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    Biomedical Chromatography 2 (1987), S. 1-3 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A reversed-phase HPLC method for the determination of epinephrine, norepinephrine, dopamine, and vanillylmandelic acid (VMA) has been developed. The concentration of VMA in the urine of hypertensive patients was measured by direct injection after centrifugation. The method is useful for the diagnosis of pheochromocytoma.
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  • 207
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: An ion pair HPLC method which can simultaneously detect the major metabolites of an exocrine pancreatic function testing agent (NBT-PABA) in plasma and urine has been developed. This assay has been applied to a pharmacokinetic study of PABA and its metabolites in 3 healthy adult volunteers following the oral administration of 1 g NBT-PABA. The 6 h testing period currently used to collect urine following the NBT-PABA ingestion is adequate for the recovery of PABA and its metabolites. Plasma determination of these compounds may provide an improved evaluation of the pancreatic performance in patients with abnormal liver or kidney function.
    Additional Material: 6 Ill.
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  • 208
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    Biomedical Chromatography 2 (1987), S. 20-23 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A new hydrophobic interaction HPLC column is used for the rapid purification of proteinase inhibitors isolated from arrowhead. The inhibitors, partially purified by DEAE-cellulose column chromatography, are resolved into three components with a mobile phase gradient of decreasing salt concentration from 1.1 M ammonium sulfate in 0.01 M phosphate buffer to phosphate buffer alone. This new HPLC column is found to be very useful for rapid, semipreparative purification of hydrophobic protein and sample loading of up to 1.6 mg of inhibitors can be fully resolved on an analytical column.
    Additional Material: 5 Ill.
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  • 209
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A simple and effective chemical method has been developed for quantitatively reducing quinones, which is based on their reaction with zinc metal and zinc ions. Comparison of this method with conventional electrochemical reduction revealed the chemical method to be considerably superior. The reduction of quinones to their corresponding hydroquinones was verified by ultraviolet spectrophotometry. The reduction methodology has been applied to derivatize phylloquinone and its metabolite, namely phylloquinone 2,3-epoxide, ‘on-line’, with subsequent fluorometric detection of the generated hydroquinones.
    Additional Material: 6 Ill.
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  • 210
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    Biomedical Chromatography 2 (1987), S. 17-19 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A rapid and specific HPLC method for the simultaneous determination of gastrodin and its metabolite gastrodigenin (p-hydroxybenzyl alcohol) in rat plasma, bile, liver, urine and faeces is described. The separation was achieved by using a reversed phase column (YWG-C18) eluted with methanol-water (2.5:97.5 v/v). Phloroglucinolum was used as internal standard and the peaks were detected at UV 221 nm. The protein precipitation with ethanol was a very simple and rapid method for sample preparation. The gastrodin and gastrodigenin were quantitated by measuring the peak-height ratios. There was a linear concentration range of 10-320 μg/mL in the assay for both compounds. The coefficients of variation (within-day) for samples spiked with gastrodin and gastrodigenin were 2.94% and 3.08%, respectively. The method demonstrated a high specificity and was suitable for use in pharmacokinetic studies.
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  • 211
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    Biomedical Chromatography 2 (1987), S. 34-37 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A simple HPLC method has been developed to measure the antiarrhythmic agent penticainide and its N-desalkyl metabolite in biological fluids. Solvent extraction of a small (200 μL) sample volume with direct analysis of the extract is used to measure the plasma and urinary concentrations of these compounds attained during chronic therapy, although a larger sample volume (1.0 mL) and prior concentration of the extract are required for single oral dose work. In each case chromatographic analysis is performed using a microparticulate (5 μm) silica column and methanolic ammonium perchlorate (10 mM, pH 6.7) as eluent with UV detection (260 nm). No endogenous sources of interference have been encountered and potential interference from other drugs is minimal.
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  • 212
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    Biomedical Chromatography 2 (1987), S. ii 
    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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  • 213
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    Biomedical Chromatography 2 (1987), S. ii 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
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  • 214
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    Biomedical Chromatography 2 (1987), S. 53-56 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: An HPLC method with polarographic detection for the trace determination of artemether in plasma and whole blood was developed and applied to pharmacokinetic and clinical pharmacological studies. The method showed high sensitivity and selectivity because of the easy reduction of the peroxide linkage of artemether at the mercury drop electrode. The detection limit was 10 ng and the detector response was linear over the range of 10 ng to 1 μg artemether injected onto the column. The largest relative standard deviation of 10 replicate measurements of standard solutions (concentrations of 10 ng/mL-1 μg/mL) was 8%. The recovery from whole blood and plasma of added drug (concentrations of 15-48 ng/mL) was 71-100%.
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  • 215
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    Biomedical Chromatography 2 (1987), S. 71-75 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A method utilizing HPLC to estimate ferrochelatase activity in human liver cells is presented. A partially purified homogenate of liver cells is incubated with mesoporphyrin IX and cobalt(II) ion. The ferrochelatase in the homogenate incorporates the cobalt(II) ion into the mesoporphyrin. After a fixed time (90 min) the porphyrins are extracted into an ethyl acetate-acetic acid mixture. The porphyrins are then separated using reversed phase HPLC with a mobile phase of methanol-acetonitrile-phosphate buffer pH 3.0 (200:60:30 v/v). The enzyme activity is estimated by measuring the rate of utilization of mesoporphyrin. The optimum pH and substrate concentration for the reaction have been determined.
    Additional Material: 8 Ill.
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  • 216
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Expired air samples have been analyzed from three groups of human subjects (normal, liver dysfunction, lung cancer) and the baboon (Papio anubus). Of the several hundred compounds present, three compounds were of particular interest due to their structural relationship to the isoprenoid-type intermediates in the sterol pathway. These compounds were 1-methyl-4-(1-methyl-ethenyl)-cyclohexene, 6-methyl-5-hepten-2-one, and 6,10-dimethyl-5,9-undecadien-2-one. Hydroxyacetone was also found in all samples screened. The relationship of these compounds to the non-sterol pathway of mevalonate metabolism is discussed.
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  • 217
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    Biomedical Chromatography 2 (1987), S. 152-155 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Hydrophobic interaction chromatography was employed for the fractionation of the glycopeptide mixture obtained after autoproteolysis and delipidization treatment of normal human seminal plasma samples. This sequence of procedures led to the elimination of highly hydrophobic components and to the concentration of the carbohydrate-rich fractions. A partial separation between the O- and N-glycosidic-linked oligopeptides was also achieved after the chromatographic step.
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  • 218
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    Biomedical Chromatography 2 (1987), S. 156-158 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: An isocratic HPLC system has been developed which allows for the rapid (single run of 20 min) measurement of creatine phosphate (PCr) and adenine nucleotides (ATP, ADP and AMP) in extracts from freeze-clamped and freeze-dried myocardial tissues. The separation was achieved at room temperature by using a RP18 column and a dual variable wavelength spectrophotometer, set at 210 and 254 nm. The solvent was 30 mM potassium dihydrogen phosphate, 15 mM tetrabutylammonium hydrogen sulfate, pH 6.7, 19% (v/v) acetonitrile. A distinct separation (confirmed with the retention time of standard sample) of these high energy compounds was achieved. Standard curves were linear. In isolated rat hearts the following values were obtained (μmol/g dry wt, mean ± SEM): ATP 21.5 ± 1.3, ADP 4.6 ± 0.2, AMP 1.5 ± 1.1 and PCr 32.5 ± 1.3; which are consistent with previously published values for high energy compounds in this tissue.
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  • 219
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    Biomedical Chromatography 2 (1987), S. i 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
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  • 220
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    Biomedical Chromatography 2 (1987), S. 169-172 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Chondroitin sulfate isomers (ChS isomers) were digested with chondroitinase ABC, and the unsaturated disaccharides produced were converted into fluorescent dansylhydrazine derivatives and analyzed by HPLC. The proposed method was applied to the determination of relative amounts of ChS isomers in normal human urine and analytical results showed that chondroitin-6-sulfate and chondroitin-4-sulfate were excreted in large amounts. Moreover, this method was used for the identification of urinary ChS isomers which were extracted from a cellulose acetate strip after carrying out electrophoresis.
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  • 221
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    Biomedical Chromatography 2 (1987), S. 164-168 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A rapid, reliable, sensitive and reproducible HPLC method was developed for the assay of ferrochelatase activity in rat liver. The assay was carried out aerobically with Zn2+ and mesoporphyrin or protoporphyrin IX as substrates. Zn-porphyrins formed were extracted with dimethyl sulphoxide/methanol (30:70, v/v) containing Zn-deuteroporphyrin as the internal standard for separation and quantification by reversed-phase chromatography. The Km for mesoporphyrin was 5.9 μM, for protoporphyrin IX 8.8 μM and for zinc 6.0 μM. The specific activities were 33.1 ± 5.0 nmol Zn-mesoporphyrin or 13.4 ± 2.0 nmol Zn-protoporphyrin formed per hour per mg of protein for mitochondria and 12.3 ± 2.2 nmol Zn-mesoporphyrin or 4.6 ± 0.9 nmol Zn-protoporphyrin per hour per mg of protein for liver homogenate.
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  • 222
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    Biomedical Chromatography 2 (1987), S. 180-182 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Additional Material: 1 Ill.
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  • 223
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A simple procedure for the determination of benzylpenicillin in serum is described. The assay involves the extraction of the drug and the internal standard (phenoxymethylpenicillinic acid) from the sample into dichloromethane, using tetrabutylammonium hydrogen sulfate neutralized with NaOH and buffered with citrate as an ion-pairing reagent. RP-HPLC was performed on a Spherisorb 5 ODS column, eluting the drugs isocratically with 14% acetonitrile in 10 mM ammonium acetate buffer. Monitoring was by UV detection at 208 nm. Our results show that the method is accurate and reproducible, permitting quantification of serum levels of benzylpenicillin without interference from other drugs commonly used in therapy. Analytical recovery was greater than 79.2%.
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  • 224
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    Biomedical Chromatography 2 (1987), S. i 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
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  • 225
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    Biomedical Chromatography 2 (1987) 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
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  • 226
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    Biomedical Chromatography 2 (1987), S. 242-244 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: An HPLC method was used to monitor the chemical stability of doxorubicin-HCI (DXR) to light in plasma, urine and cell culture medium at room temperature. The results indicated that DXR was very unstable in cell culture medium and urine when exposed to light. It was more stable in plasma under the same conditions. In all the cases, the decrease in the amount of DXR is greatly dependent on light intensity (no noticeable degradation was observed after 8 h in the dark). These observations may be important for the correct interpretation of the effects and the toxicity of doxorubicin on cells incubated in cell medium, and for determination of urinary or plasma pharmacokinetic parameters.
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  • 227
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Analytical methods are described for the quantitative determination of putrescine, cadaverine, spermidine, spermine and the acetylated derivatives of spermidine and spermine in biological fluids using pre-column derivatization with either benzoyl chloride or 3,5-dinitrobenzoyl chloride, which were added to each sample as solutions in diethyl ether. Putrescine, spermidine and spermine can be analysed in seminal plasma at nanogram levels when benzoyl chloride is used as derivatizing agent. In the analysis of putrescine, cadaverine, spermidine and acetyl derivatives of spermidine and spermine, higher sensitivity is obtained with 3,5-dinitrobenzoyl-chloride. This method can readily be used in the determination of acetylated polyamines in urine samples.
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  • 228
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    Biomedical Chromatography 2 (1987), S. 271-273 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: The application of micro HPLC to the determination of amygdalin in Semen pruni armeniacae and Semen pruni persicae is described. Amygdalin is separated at ambient temperature on a reversed phase column of U-Finepak SIL C18(150×0.5 mm) with methanol + water (25: 75 v/v) as the mobile phase at a flow rate of 10 μL/min. The results are calculated by the internal standard method. The linear range is 1-7 μg. The CV and recovery of pure amygdalin are 1.47% (n = 10) and 98.13%, respectively. The results of analysis are lower than those obtained by TLC, but microHPLC is much simpler, faster, and more sensitive and reproducible than TLC.
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  • 229
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    Biomedical Chromatography 2 (1987), S. 226-227 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A rapid method for the determination of 4-methylpyrazole in plasma is described. Internal standard (3-methylpyrazole) is added to the plasma which is subsequently applied to a BondElut SCX column. After washing the column the 3- and 4-methylpyrazoles are eluted with a phosphate buffer and analyzed by isocratic reversed-phase high performance liquid chromatography with UV detection. The concentration of 4-methylpyrazole is calculated from the 4-methylpyrazole/3-methylpyrazole peak high ratio. The method is linear between 2.5 and 100 μmol/L with a within-day precision (CV) of 2.2% (n = 10) and a day-to-day precision of 2.8% (n = 30). The sensitivity is sufficient for analysis of plasma levels in the low micromolar range.
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  • 230
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A one-step HPLC method was developed for the purification of protein G, a cell wall molecule from group C and G streptococci with immunoglobulin G- and albumin-binding properties. Lysed Escherichia coli bacteria infected with lambda-phages containing the protein G gene from group G streptococci were used as a starting material for the preparations. The lysate was applied to a column with immobilized human immunoglobulin G or human serum albumin. Protein G was selectively bound and eluted at pH 2.0. A 750-fold purification was achieved. Sodium dodecylsulfate + polyacrylamide gel electrophoresis showed that the highly purified protein G consisted of three sets of doublets with the apparent molecular weight of 64 and 67, 56 and 58, and 45 and 47 kilodaltons, respectively. A specific method for quantitation of small amounts of protein G was developed and used for specific tracing of the protein after the affinity chromatography. Goat polyclonal antibodies were bound to an antigen coated to the plastic walls of microtiter plates, causing the Fc-region of the immunoglobulins to be directed outwards. Unknown samples of protein G were then allowed to compete with radio-iodinated protein G (solid phase radioassay) or protein G coupled to alkaline phosphatase (enzyme linked sorbent assay) for the Fc-regions.
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  • 231
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    Biomedical Chromatography 2 (1987), S. iii 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
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  • 232
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    Biomedical Chromatography 2 (1987), S. 89-90 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
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  • 233
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 234
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    Biomedical Chromatography 2 (1987), S. i 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
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  • 235
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    Biomedical Chromatography 2 (1987) 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
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  • 236
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    Biomedical Chromatography 2 (1987), S. 195-196 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Tissue concentrations of the amino acids tryptophan, methionine, valine, phenylalanine, isoleucine and leucine were determined in rat liver, skeletal muscle and brain tissue and human plasma. The effect of storage at -20°C for up to 21 days was examined. Significantly elevated levels after 7 and 21 days of storage were observed in liver and brain tissue but no changes were found in muscle and plasma. Minimal changes occurred in liver tissue stored up to 6 hours at -4°C. This study emphasizes the need for rapid deporteinization of tissues to avoid changes in the free pool of amino acids.
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  • 237
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Methods for the determination of CS-570, a chemically stable prostacyclin analogue, in plasma were developed by using an immobilized antibody column followed by fluorescence HPLC and GC/MS. The CS-570 antibody, obtained from rabbit plasma by giving CS-570-BSA for a few months, was coupled to Sepharose 4B and used as extraction phase for sample clean-up and extraction of the drug. A plasma sample was applied to this column, washed with water and the drug was eluted with 90% acetonitrile. 0.02% (w/v) 9-anthryldiazomethane (ADAM) was added to the extract to form a fluorescent derivative. The CS-570-ADAM adduct exhibited high sensitivity when applied to HPLC with fluorescence detection and column switching. The detection limit was 1 ng/mL when 1 mL of plasma was available. Additionally, a pentafluorobenzyltrimethylsilyl derivative of CS-570 showed excellent sensitivity when determined by capillary GC interfaced to negative ion chemical ionization MS using a stable isotope labelled analogue as an internal standard.
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  • 238
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    Biomedical Chromatography 2 (1987), S. 183-188 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: In order to improve the urinary neopterin measurement, the reversed-phase HPLC method has been reevaluated. The parameters which influence the chromatographic behavior of 12 pteridines were studied: nature of buffer, pH,ionic strength, addition of organic modifier to the mobile phase. Accordingly, an isocratic HPLC method is described which offers a good compromise between specificity and analysis time. This method is well-suited to automation in routine clinical laboratory use. Using this HPLC method, urinary neopterin related to creatinine was determined in lung diseases (neoplasm, sarcoïdosis and bronchial asthma) and in kidney allografts. This method was shown to be useful in the diagnosis and in the monitoring of treatment of rejection episodes.
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  • 239
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    Biomedical Chromatography 2 (1987), S. 189-192 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: We have developed a high performance thin layer chromatography (HPTLC) system for quantitative determination of androgens, corticosteroids, mineralocorticoids and gestagens on silicagel KG-60 HPTLC-plates with different solvent systems. A complete separation of androgens, gestagens and metabolites was achieved with dichlormethane/cyclohexane/acetone (70:25:5). Corticosteroids, mineralocorticoids and their derivatives were completely separated with diethylether/isooctane/isopropanol (70:25:5). The quantitative in situ fluorescence determination was carried out after post-chromatographic derivatization with cinnamic aldehyde, 4-dimethylaminobenzaldehyde and sulfuric acid. The sensitivity of detection was found between 500 pg and 1 ng per spot.The steroid metabolism as catalysed by rat liver microsomal oxidoreductases was measured by these procedures, and was compared with determination of steroids by gas chromatography (GC). According to HPTLC, steroids were reduced by NADPH-5α-reductase (EC 1.3.1.4) in the order progesterone 〉 testosterone 〉 aldosterone 〉 cortisol 〉 corticosterone. The enzyme activities as measured by HPTLC agree well with those obtained by GC (r = 0.94). When turnover of enzyme assays, speed of determination, detection limit, application to labile steroids and costs of steroid determination are considered, all points speak in favour of HPTLC.
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  • 240
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    Biomedical Chromatography 2 (1987), S. 216-220 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Cysteamine, an amino thiol, was separated by rapid isocratic cation exchange chromatography and detected by electrochemical oxidation at a platinum electrode maintained at +0.45 V relative to an Ag/AgCl reference electrode. Eluent pH and electrode working potentials were optimized and the effects of alternative buffers and organic modifiers have been examined. On column sensitivity for cysteamine was 1.5 pmol at a signal-to-noise ratio of 5. Although the specificity was good, plasma samples required maximal sensitivity whereas urine samples required greater selectivity, which was achieved by use of lower working potentials. Cysteamine concentrations were determined in serial samples of plasma and urine from volunteers who had received a single oral dose of 200 mg of the drug. Cysteamine was rapidly oxidized in vivo, and detection required prior reduction with dithiothreitol before analysis.
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  • 241
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    Biomedical Chromatography 2 (1987), S. iii 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
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  • 242
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    Biological Mass Spectrometry 14 (1987), S. 39-42 
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The application of gas chromatography/mass spectrometry to three thermally labile phenylurea pesticides is reported. Using alcohols as solvents the decomposition of the pesticides is followed by a reaction in which esters of N-(3,4-dichlorophenyl)carbamic acid are formed. As these reactions occur during the gas chromatographic analysis, it is the esters which are identified in the mass spectrometer. The methyl ester is itself a pesticide so an erroneous conclusion about the original pesticide could be reached when methanol is the solvent.
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  • 243
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    Biological Mass Spectrometry 14 (1987), S. 43-45 
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ions produced by 252Cf plasma desorption are detected by Fourier transform ion cyclotron resonance techniques. Results for CsI and N,N,N-trimethyl-p-aminophenolate iodide show the feasibility of the technique with high resolution (up to 11 000 at m/z 23) and good signal-to-noise ratio (up to 726).
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  • 244
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    Biological Mass Spectrometry 14 (1987), S. 47-48 
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 245
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    Biological Mass Spectrometry 14 (1987), S. 49-50 
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 246
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    Biological Mass Spectrometry 14 (1987), S. 51-51 
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 247
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    Biological Mass Spectrometry 14 (1987), S. 53-61 
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The fast atom bombardment positive ion mass spectra and the [M + H]+ collisional activation spectra of t-butyloxycarbonyl protected peptides and the unprotected analogues have been compared. It is concluded that sequence information, especially from the collisional activation spectra, can better be derived from the underivatized peptides than from the BOC-peptides.
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  • 248
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    Biological Mass Spectrometry 14 (1987), S. 229-233 
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The constant B2E linked scan is shown to be an excellent tool for the profiling of biogenic amines in wine samples. The fragment ion at m/z 169 of the dansylated amines is used for the precursor ion search in combination with direct sample evaporation. Besides the profile a semi-quantification may be achieved when using suitable amines as internal standards with standard deviations of 12-17%. More accurate results with standard deviations of 3-5% are obtained when using deuterated analogues as internal standards. Both methods are applied to the analysis of biogenic amines in synthetic mixtures and actual wine samples.
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  • 249
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    Biological Mass Spectrometry 14 (1987), S. 241-246 
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 252-Californium plasma desorption mass spectrometry was applied to the study of five different classes of phospholipids namely phosphatidylcholine, phosphatidylethanolamine, phosphatidylglycerol, phosphatidylserine and phosphatidylinositol. Positive and negative ion spectra were compared to spectra obtained using other ionization techniques. Plasma desorption mass spectra provide useful information on the molecular weight of compounds from all classes, particularly in the case of phosphatidylserine - a class that has failed to show satisfactory quasimolecular ions with either Fast atom bombardment, FAB or Field desorption, FD. The observed fragmentation is also indicative of the structure of the studied compounds.
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  • 250
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new quantitative assay for the determination of S3341, an alpha-2 agonist antihypertensive drug, has been developed using combined gas chromatography-negative ion chemical ionization mass spectrometry. The [M]-. ions from TFA derivatives of S3341 (m/z 276) and the internal standard (2H4)S3341 (m/z 280) are monitored simultaneously by selected ion monitoring. For S3341 concentrations ranging from the limit of detection (0.2 ng ml-1 using 1 ml of plasma) to 5 ng ml-1, the average assay precision (CV) is approximately 7% while the average assay accuracy (percentage of error) is 4%. Validation of the day-to-day precision and accuracy was realized after analysing control plasma samples (n = 295) concurrently with the biological samples collected during the pharmacokinetic studies conducted over 15 months. The average day-to-day precision (CV) and accuracy (percentage of error) are 10% and 6% respectively, thus indicating that this assay procedure routinely provides reliable analytical data.
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  • 251
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Positive ion fast atom bombardment mass spectrometric sensitivities of seven amino acids and the corresponding di-isopropylphosphorylated derivatives were carefully compared. Results showed that an improvement in sensitivity by factors of 4-29, mostly above 10, were achieved after the derivatization. The chemical noise derived from glycerol matrix was also greatly reduced by this derivatization.
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  • 252
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method has been developed for the quantitative determination of cholesterol and three of its major oxidative metabolites (the 5α,6α-epoxide, the 3β,5α,6β-triol, and the 5β,6β-epoxide) in a single sample of human breast fluid (2-50 μl), using gas chromatography/mass spectrometry with selected ion monitoring. High specificity and reliable quantification is achieved by the use of the inverse stable isotope dilution method, employing deuterium-labeled variants of the compounds as internal standards.
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  • 253
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This paper describes a method for simultaneous determination of the kinetics of the three major bile acids in man using (2,2,4,4-2H4) deoxycholic acid, (24-13C) cholic acid and (24-13C) chenodeoxycholic acid. The gas chromatographic/mass spectrometric-selected ion monitoring technique used provided complete separation of deoxycholic acid, cholic acid and chenodeoxycholic acid, which permitted simultaneous measurement of isotope ratios for all three bile acids. Since measurement of all three pool sizes and fractional turnover rates in a single experiment requires different isotopic labels for deoxycholic acid and cholic acid, we investigated the in vivo stability and applicability of (2,2,4,4-2H4) deoxycholic acid as a stable isotope marker for isotope dilution studies in man. No consistent differences were observed between deoxycholic acid pool sizes and fractional turnover rates determined in serum samples after administration of (2,2,4,4-2H4) deoxycholic acid and (24-13C) deoxycholic acid. Simultaneous administration of (2,2,4,4-2H4) deoxycholic acid (24-13C) cholic acid and (24-13C) chenodeoxycholic acid and isotope ratio measurements in serum permitted determination of pool sizes and fractional turnover rates of the three major bile acid and the 7α-dehydroxylation fraction. Pool sizes, fractional turnover rates and synthesis rates (input rates) agreed well with data obtained previously with (24-13C) labels in independent studies.
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  • 254
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Urines of two children with 17α-hydroxylase deficiency contained a number of 5-pregnane- and pregnenediols, -triols and -tetrols with a hydroxy or oxo group in position 11 of the steroid ring. They are formed mainly from progesterone via 11-hydroxyprogesterone, pregnanolone and corticosterone, respectively, or from pregnenolone. Three metabolites not previously described, 16-hydroxypregnenolone, 6,21-dihydroxypregnanediol and 6-hydroxytetrahydrocorticosterone, were identified.
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  • 255
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    Biological Mass Spectrometry 14 (1987), S. 649-651 
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The identified urinary metabolites of male rats exposed to indan are: 1- and 2-indanone; 1-, 2- and 5-indanol; 2-and 3-hydroxyl-1-indanone; and cis- and trans-indan-1,2-diol. Indan causes kidney damage in male rats in a manner similar to the cyclic hydrocarbons cis- and trans-decalin and JP-10. Lesions produced by indan occur only in male rats and not in female or control rats.
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  • 256
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    Biological Mass Spectrometry 14 (1987), S. 663-668 
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Organic acidaemias are an important part of inborn errors of metabolism. The biochemical diagnosis is based on gas chromatographic/mass spectrometric identification of urinary organic acids. Since 1973 we have used gas chromatographic analysis of the methyl esters of urinary organic acids. Mass spectral identification was performed only when an abnormal gas chromatographic profile was suspected. In 1983 we introduced routine gas chromatographic/mass spectrometric analysis organic acids. More than 1500 urine samples from 1000 children have been analysed and we encountered more than 40 abnormal profiles: 18 classical organic acidaemias (propionic, methyl-malonic, isovaleric, glutaric type I and 3-hydroxy-3-methyl glutaric acidaemias); 6 aminoacidopathies with excretion of branched chain keto acids (leucinosis) or succinylacetone (tyrosinosis type I); 14 massive dicarboxylic acidurias with excretion of suberyl and hexanoyl glycine and deficiency of the medium chain acyl CoA dehydrogenase in four patients. The use of gas chromatography/mass spectrometry routinely allows the identification of abnormal metabolites excreted in small amounts: β-methyl-crotonyl glycine indicative of biotin deficiency: γ-hydroxybutyric acid; and 3-methyl-glutaconic + 3-methy-glutaric acid is in a 3-methyl-glutaconic aciduria type II. Abnormal profiles due to metabolites of drugs as valproate, salicylate and barbiturate can be recognized immediately. This simple gas chromatographic/mass spectrometric system can lead to diagnosis, in one day, of rare but severe diseases needing a specific and early treatment.
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  • 257
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The determination of serum cortisol by thermospray liquid chromatography/mass spectrometry (LC/MS) has been assessed. The method incorporates stable isotope dilution and innumoadsorption extraction. [M + H]+ ions are monitored during LC/MS. The within-assay reproducibility is satisfactory (coefficient of variation 7% at a concentration of 190 ng ml-1), though inferior to that achieved with the (more lengthy) procedure of gas chromatography/mass spectrometry (GC/MS). Satisfactory agreement between LC/MS (y) and GC/MS (x) data was observed (y = 0.934x + 12.4 ng ml-1; r = 0.968; n = 14). It is concluded that the generation of precise reference data for the assessment of routine cortisol assays is at present better achieved by GC/MS. LC/MS, however, provides satisfactory quantitative data via a more simple and rapid method.
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  • 258
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    Biological Mass Spectrometry 14 (1987), S. 737-738 
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 259
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The negative Plasma Desorption Mass Spectra of ten unprotected tri-deoxyribonucleoside diphosphatesHereafter termed tri-deoxyribonucleotides. have been observed and analysed in detail. They all exhibit molecular ions as well as a characteristic fragmentation pattern. The ten trinucleotides selected were chosen in order to understand, in terms of sequence, the main features of the experimental spectra. It is shown that the structure and the sequence of the oligomers can be rapidly and easily derived from their PD Mass Spectrum.
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  • 260
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Positive and negative secondary ion mass spectra of the title compounds were produced by bombardment of solid deposits by 13 and 23 KeV cesium ions, respectively, and analyzed with a time-of-flight mass spectrometer. In addition to familiar protonation and alkali (mainly sodium) ion addition processes observed in the positive ion spectra and proton abstractions in the negative ion spectra (which enable determination of molecular weight) there is evidence from both spectral modes for oxidation-reduction processes in which species such as [M - H]+, [M - H + Na]+. and [M + 1]- are formed. It is argued that these may be formed rapidly from pre-associated molecules during bombardment/ionization rather than as a result of radiation damage. Sodium ion addition is apparently facilitated by the presence of electron pair donor groups, especially if chelation is possible.
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  • 261
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    Biological Mass Spectrometry 14 (1987), S. 257-261 
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This study identified the reason for the poor quantification of Iormetazepam-TMS (1) using negative ion chemical ionization with lormetazepam-1,1,1-2H3-TMS (2) as an internal standard. Mass spectra of lormetazepam and its deuterium labelled compounds determined at various ion source temperatures (100-250°C) gave almost the same behaviour for 1 and lormetazepam-3′,4′,5′,6′-2H4-TMS (3) but a different one for 2, suggesting that the poor quantification was due to an isotope effect. This was confirmed by the findings that the ratios of ion currents of the base peaks of 1 and 3 were independent of the ion source temperature but those of 1 and 2 varied markedly with it. This phenomenon was also observed in the mass fragmentography of the molecular ion, although to a lesser degree than that of the above fragment. In both positive ion chemical ionization and electron impact ionization modes, no isotope effect arose because there was no corresponding fragment to cause the isotope effect.
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  • 262
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    Biological Mass Spectrometry 14 (1987), S. 127-129 
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method is described to assign the positional series of methylene interrupted polyenoic acids, in complex mixtures, isolated from hydrolysed lipid extracts. It entails a simple comparison of the intensities of three ions of m/z 108, 150 and 192.
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  • 263
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The behaviour of 1,1·,1″-phosphinothioylidinetrisaziridine (thiotepa) in water and aqueous salt solution of various acidity was studied by field ionization mass spectrometry (FI-MS), TLC and potentiometric titration. The rate of thiotepa hydrolysis increased with increasing thiotepa, or sodium chloride concentration, and with decreasing pH. As hydrolysis products of thiotepa, mono- and dichloro derivatives formed in neutral, salt-containing and acidic solution, tepa, and products formed by P—N bond cleavage and release of aziridine have been identified.
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  • 264
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Methodology for the qualitative and quantitative analysis of the anthelmintic fenbendazole and its metabolites in goat feces using electron impact (EI)/direct exposure probe (DEP)/mass spectrometric (MS) and tandem mass spectrometric (MS/MS) techniques is presented. Analyses were conducted on extracts from spiked feces and feces from animals treated per os with 5 mg fenbendazole/kg, with samples being collected at zero time and at twelve hour intervals for 144 h. The results of the EI/DEP/MS quantitation of these samples are compared to those for the same samples analysed by high pressure liquid chromatography (HPLC). Mass spectral data for fenbendazole and its metabolites are presented and the advantages of the use of EI/DEP/MS and/or DEP/MS/MS over HPLC are discussed. This methodology may be used as a confirmatory method for the HPLC analysis of fenbendazole and its metabolites or may be used as a method in its own right for the rapid qualitative and quantitative analysis of these compounds.
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  • 265
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Known and possible phenolic and primary and secondary amine metabolites of lidocaine were added to urine from drug-naive rats. These metabolites were derivatized in this aqueous medium by acetylation with acetic anhydride or by pentafluorobenzoylation with pentafluorobenzoyl chloride. The derivatives were simultaneously extracted into an organic solvent. The products were separated by gas chromatography (flame ionization detection for acetates and electron-capture detection for pentafluorobenzoates) and identified by combined gas chromatography/mass spectrometry. Mass spectral fragmentation pathways were readily deduced; diagnostic fragment ions were identified and were valuable for characterization purposes. Structural isomers could be distinguished on the basis of their GC retention times.Extractive derivatization using pentafluorobenzoyl chloride is an attractive analytical procedure for the identification of phenolic and dealkylated metabolites of lidocaine.
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  • 266
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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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  • 267
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    Biological Mass Spectrometry 14 (1987), S. 213-220 
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thermospray HPLC/MS analysis of the metabolites of arachidonic acid proved to be sensitive and specific. The compounds included were hydroxy-fatty acids (5-HETE, 12-HETE, and 15-HETE) and prostaglandins PGD2, PGE2, PGF2α, PGA2, PGA1, TXB2, and 6-Keto-PGF1α. Thermospray HPLC/MS analysis allows for simultaneous monitoring of each compound without the need for additional sample preparation or derivatization. The thermospray spectra for the metabolites exhibited [M + NH4]+ ions and fragment ions because of sequential loss of equivalents of H2O. HPLC/MS showed detection limits in the 0.5 to 5 ng range when using multiple ion detection for most of the metabolites. Post-column derivatization of these metabolites using trimethylanilinium hydroxide (TMAH) to form the methyl esters is also presented. This derivatization resulted in a gain in ion current by a factor of 3-6 for most compounds while adding potential specificity to the analysis. The thermospray spectra of the derivatives were nearly identical to the spectra of the free acid except the peaks were incremented by 14 daltons due to the methyl ester formation. The derivatization of the carboxylic acid group proved to be complete under thermospray conditions producing the maximum ion current and causing no compromise in operation of the interface.
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  • 268
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    Biological Mass Spectrometry 14 (1987) 
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 269
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    Biological Mass Spectrometry 14 (1987), S. 247-248 
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The formation of polyhydrogen adducts of peptide molecules during fast atom bombardment (FAB) mass spectrometry (MS) is shown to be matrix dependent. FAB/MS analyses completed in glycerol solvent produced higher than expected peak intensities at m/z corresponding to (M + 2)+, (M + 3)+, and (M + 4)+ when the contributions of all stable isotopes present in the sample are included. Analysis of the same peptides in thioglycerol by positive or negative ion FAB yielded peak intensity distributions for the protonated molecule which matched those predicted from the natural abundance of stable isotopes. These findings suggest that thioglycerol should be the FAB matrix in analyses of peptides when determination of elemental or isotopic composition is desired.
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  • 270
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    Biological Mass Spectrometry 14 (1987), S. 249-256 
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method for calculating the empirical formulae of peptides from mass spectrometric data is described. Exact mass measurement data and isotopic peak ratios are used to generate a list of potential empirical formulae that fit a given compound within experimental error. The formulae are then analysed by a mathematical algorithm and only those corresponding to chain peptides formed from the basic amino acids are retained. Calculations conducted for typical peptides indicate that the approach may be useful for peptide identification if the experimental values are determined within an acceptable range of errors. Experimental measurements of the exact mass and isotopic peak ratios made using typical peptides demonstrate the feasibility of the approach.
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  • 271
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    Biological Mass Spectrometry 14 (1987), S. 303-303 
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 272
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The structure elucidation of drug metabolites directly from urine by tandem mass spectrometry (MS/MS) for a new bronchodilator is described. When urine samples from human subjects dosed with 400 mg of MDL 257 were examined by MS/MS, three major urinary metabolites previously characterized in animal studies were confirmed and two previously unsuspected metabolites were identified.Using the operational modes of a triple stage quadrupole mass spectrometer, it is possible both to detect and to identify possible metabolites. Since the pure drug and its metabolites often contain common structural daughter ions, the parent spectra of these common daughter ions should contain some or all of the molecular ions of possible metabolites. Daughter spectra of these suspected molecular ions were obtained and the resulting daughter spectra were interpreted for structural information of suspected metabolites.This study confirms the utility of MS/MS to do rapid metabolic profiling and identification directly from complex samples such as urine, with minimal time for sample preparation and analysis. This technique can provide unique and complimentary data when combined with the more classical approaches such as HPLC profiling, isolation, and off-line spectroscopy.
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  • 273
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    Biological Mass Spectrometry 14 (1987), S. 339-342 
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Water is produced by vacuum sublimation of biological fluids directly into reaction vessels in preparation for reduction using zinc. Following heating to 450°C the hydrogen produced is admitted directly to the mass spectrometer. The standard derivation, σ10 of analysis of water samples was 1.08-1.23% while for blood plasma σ6 = 2.02-2.62%. The method allows the determination of very low levels of deuterium in biological fluids, thus allowing very small doses of deuterium oxide to be used in studies of body water in animals and possibly humans.
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  • 274
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    Biological Mass Spectrometry 14 (1987) 
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 275
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    Biological Mass Spectrometry 14 (1987), S. 369-374 
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A previously-unidentified peak occurring in chromatograms of the polycyclic aromatic hydrocarbon fraction from wood smoke particulate extracts analysed by capillary gas chromatography on a DB-5 column was found to correspond in retention index and molecular mass either to benzo(a)fluoranthene or to benzo(1)aceanthrylene, one of a series of four novel and highly mutagenic cyclopentafused isomers of benz(a)anthracene. Detailed sub-fractionation, and re-analysis on a liquid crystal capillary column, indicated that the identity of this peak was most likely to be benzo(a)fluoranthene, a compound not previously reported in woodsmoke.
    Additional Material: 5 Ill.
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  • 276
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    Biological Mass Spectrometry 14 (1987), S. 513-516 
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method was developed to measure bioavailability of lidocaine by simultaneous peroral and intravenous dosing. Lidocaine hydrochloride corresponding to 125 mg base was given perorally. Simultaneously, 30 mg of deuterated lidocaine-d3 were injected intravenously. Blood samples were taken at intervals for 270 min. Plasma samples were spiked with mepivacaine hydrochloride as internal standard, alkalinized to pH 11.7 and extracted with diethyl ether. The extracts were analysed by capillary GC ammonia CI MS using a 15 m × 0.32 mm i.d. glass capillary column coated with SE-54. The ion source pressure was 0.4 Torr of ammonia as reagent gas. Quasimolecular ions were monitored at m/z 235, 238 and 247 for lidocaine, lidocaine-d3 and mepivacaine, respectively.Calibration curves were linear from 0.2 to 5.0 nmol lidocaine ml-1 plasma. Interday reproducibility of this method was 6.9% for lidocaine-d3 (n = 16; 1.90 ± 0.13 nmol ml-1). Bioavailability of lidocaine in 5 normal volunteers ranged from 26 to 36% (mean 31 ± SD 5%) and in a cirrhotic with an end-to-side portacaval shunt it approached 100%, as anticipated. The method is well suited for determination of bioavailability of lidocaine after simultaneous administration of rather small and safe doses both intravenously and perorally.
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  • 277
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    Journal of Chemometrics 1 (1987) 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 278
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    Journal of Chemometrics 1 (1987), S. 1-2 
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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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  • 279
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    Journal of Chemometrics 1 (1987), S. 3-6 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 280
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    Journal of Chemometrics 1 (1987), S. 7-18 
    ISSN: 0886-9383
    Keywords: Kalman filter ; Calibration ; Curve resolution ; Parameter estimation ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The application of the Kalman filter to the solution of a variety of problems in analytical chemistry is reviewed. Five examples are selected from the literature to illustrate the use of Kalman filtering techniques for obtaining least-squares estimates fo several parameters of analytical importance. These examples include multicomponent curve resolution and concentration estimation, correction for variable background responses, calibration with drift compensation, and estimation of kinetic parameters for first-order reactions and for heterogeneous charge-transfer reactions. An adaptive Kalman filtering technique is required for the solution of the background correction problem, and the extended Kalman filter algorithm is required for the solution of the nonlinear kinetic problems. For each case, the results that were obtained are summarized, and some advantages of Kalman filtering over traditional least-squares approaches are discussed.
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  • 281
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    Journal of Chemometrics 1 (1987), S. 19-31 
    ISSN: 0886-9383
    Keywords: Calibration ; Indirect calibration ; Multivariate ; Matrix decomposition ; PLS ; PCR ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Partial least squares (PLS) modeling is an algorithm for relating one or more dependent variables to two or more independent variables. As a regression procedure it apparently evolved from the method of principal components regression (PCR) using the NIPALS algorithm, which is similar to the power method for determining the eigenvectors and eigenvalues of a matrix. This paper presents a theoretical explanation of the PLS algorithm using singular value decomposition and the power method. The relation of PLS to PCR is demonstrated, and PLS is shown to be one of a continuum of possible solutions of a similar type. These other solutions may give better prediction than either PLS or PCR under appropriate conditions.
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  • 282
    ISSN: 0886-9383
    Keywords: Principal component analysis ; Singular value decomposition ; Factor analysis ; Rank determination ; Eigenvector analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The distribution of error eigenvalues resulting from principal component analysis is deduced by considering the decomposition of an error matrix in which the errors are uniformly distributed. The derived probability function is \documentclass{article}\pagestyle{empty}\begin{document}$$ P(\lambda ^0 _j) = N(r - j + 1)(c - j + 1) $$\end{document} Where λ0j is the jth error eigenvalue, r and c are the numbers of rows and columns in the data matrix, and N is the normalization constant. This expression is tested and validated by investigations involving model data. The distribution function is used to determine the number of factors responsible for various sets of spectroscopic data taken from the chemical literature (including nuclear magnetic resonance, infrared and mass spectra).
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  • 283
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    Keywords: Curve resolution ; Liquid chromatography ; Accuracy ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The performance of curve resolution and iterative target transformation curve resolution in quantitative liquid chromatography with a diode array detector is evaluated. Quantitative accuracy of the elution profiles obtained for two- and three-component mixtures has been evaluated as a function of spectral similarity, chromatographic resolution and ratio of the peak areas, using a number of simulations analysed by an analysis of variance. The results obtained by simulation are compared and validated with the results obtained for the separation of phenylene diamines in reversed phase liquid chromatography and proteins in gel permeation liquid chromatography. The results that were obtained are summarized and the chromatographic implications are discussed.
    Additional Material: 3 Ill.
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  • 284
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    Keywords: Multi-way array ; Multiorder array ; Principal components ; PLS ; Multivariate calibration ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Lohmöller-Wold decomposition of multi-way (three-way, four-way, etc.) data arrays is combined with the non-linear partial least squares (NIPALS) algorithms to provide multi-way solutions of principal components analysis (PCA) and partial least squares modelling in latent variables (PLS).The decomposition of a multi-way array is developed as the product of a score vector and a loading array, where the score vectors have the same properties as those of ordinary two-way PCA and PLS. In image analysis, the array would instead be decomposed as the product of a loading vector and an image score matrix.The resulting methods are equivalent to the method of unfolding a multi-way array to a two-way matrix followed by ordinary PCA or PLS analysis. This automatically proves the eigenvector and least squares properties of the multi-way PCA and PLS methods.The methodology is presented; the algorithms are outlined and illustrated with a small chemical example.
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  • 285
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    Journal of Chemometrics 1 (1987), S. 73-73 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 286
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    Journal of Chemometrics 1 (1987), S. 75-75 
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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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  • 287
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    Journal of Chemometrics 1 (1987), S. 74-74 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 288
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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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  • 289
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    Journal of Chemometrics 1 (1987), S. 77-77 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 290
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    Journal of Chemometrics 1 (1987), S. 79-90 
    ISSN: 0886-9383
    Keywords: Numerical deconvolution ; Peak resolution ; Peak separation ; Iterative deconvolution ; Jansson's method ; Super-resolution ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Severely overlapped gas chromatographic peaks can be resolved using Jansson's method. Jansson's method is an iterative nonlinear deconvolution technique and consists of Van Cittert's algorithm with the relaxation factor a function of the kth estimate of the peak shape. The maximum peak amplitude of the instrument and peak non-negativity serve as constraints to improve the peak estimate. Super-resolution is achieved without significantly degrading the chromatogram signal-to-noise ratio. The method only requires a knowledge of the instrument impulse response function and maximum peak height.
    Additional Material: 7 Ill.
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  • 291
    ISSN: 0886-9383
    Keywords: NIR ; Fast Fourier transform ; Principal component analysis ; Discrimination ; Baking quality ; Wheat ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Digitalized continuous near infra-red reflectance (NIR) spectra are composed of a great number of data which must be reduced for microcomputer mathematical treatment. The sequence ‘fast Fourier transform preceding principal component analysis’ was tested to perform data size reduction without a large loss of information. The method was applied on a collection of wheat spectra composed of 351 data. Ten resulting data, which described 99.5% of the total variance, were kept. The relevance of the method was estimated by the ability of the resulting data (i) to regenerate the original signal, and (ii) to discriminate the baking quality of the wheat by stepwise multiple discriminant analysis. The average difference between initial and regenerated spectra was -2.4 × 10-3 log (1/R) units and the standard deviation was 1.16 × 10-3 log (1/R) units. The discrimination treatments gave 89.9% of well classified samples for the calibration test and 90.5% for the prediction test. The application of these mathematical treatments to other continuous signals is discussed.
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  • 292
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    Journal of Chemometrics 1 (1987), S. 91-101 
    ISSN: 0886-9383
    Keywords: Factor analysis ; Retention indices ; Model ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Retention indices for 18 monomeric stationary-phase solvents and 33 organic solutes are factor analyzed. Six factors reproduce the data matrix near experimental error. The solvents diglycerol and zonyl E-7 are shown to be highly unique, whereas none of the solutes behaves uniquely. Combination sets of solvent vectors and of solute vectors from the data matrix lead to models having errors within experimental error. Basic factors which might influence the solute - solvent interactions are identified by the least-squares method of target testing. For the solvents, a number of properties, including McReynolds' constants and molecular weight, test successfully. For the solutes, carbon number and group dipole moment are representative properties which test successfully. The best combination of solvent basic factors gives errors about twice the experimental error. Combination sets composed only of McReynolds' constants do not model the data well.
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  • 293
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    Journal of Chemometrics 1 (1987), S. 111-120 
    ISSN: 0886-9383
    Keywords: Principal component analysis ; Submatrix analysis ; Spectroscopy ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In the treatment of spectroscopic data by principal component analysis, correct determination of the dimensionality of the data is essential. Submatrix analysis, which involves preliminary analysis of subsets of the data matrix, is described, and shown to be valuable in determining both the size of the factor space and estimates of equilibrium constants in the system, even for data containing abnormally large experimental error.
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    Journal of Chemometrics 1 (1987), S. 135-135 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 295
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    Journal of Chemometrics 1 (1987), S. 136-136 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 296
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    Journal of Chemometrics 1 (1987), S. 121-134 
    ISSN: 0886-9383
    Keywords: Multivariate calibration ; NIR ; Cluster analysis ; Experimental design ; Sample selection ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A procedure for selecting samples to use in multivariate calibration, inspired by a paper by Zemroch, is proposed. The method developed is designed for multicollinear data and is based on cluster analysis. It selects among availabe spectra the samples to submit to chemical analysis and calibration. The method is tested on an example from NIR spectroscopy of biscuit dough pieces.
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    Journal of Chemometrics 1 (1987), S. 136-136 
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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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  • 298
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 299
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    Journal of Chemometrics 1 (1987), S. 137-137 
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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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  • 300
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    Journal of Chemometrics 1 (1987), S. 157-173 
    ISSN: 0886-9383
    Keywords: Gas chromatography ; Simplex ; Barycentric co-ordinates ; Discriminant analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This paper proposes an elegant, yet straightforward, model for classifying linear mixtures. A linear mixture is defined as a random vector y in which the variable are a (non-negative) weighted average of corresponding variables, assumed to characterize g component groups. These weights are referred to as ‘mixing proportions’. The model seeks to identify the mixture constituents and estimate the mixing proportions. It is demonstrated within the context of high resolution gas chromatography and the problem of identifying the constituents in polychlorinated biphenyl mixtures.
    Additional Material: 9 Ill.
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