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  • 1995-1999  (226)
  • 1970-1974
  • 1965-1969
  • 1996  (226)
  • Analytical Chemistry and Spectroscopy  (226)
  • Nuclear reactions
  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 19 (1996), S. 111-116 
    ISSN: 0935-6304
    Keywords: Polynuclear aromatic hydrocarbons ; Liquid chromatography ; Alcohols ; Micelles ; Enviromental samples ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method for the separation of polycyclic aromatic hydrocarbons (PAHs) by high-performance liquid chromatography using a hybrid micellar mobile phase is described. The detection of PAHs was carried out using the fluorescence method with programmable excitation and emission wavelength. The method is applied to the analysis of several environmental samples (sea water, sediments, limpets, sea worms) and several of these compounds are quantitated at concentration below 70 ng L-1(kg-1) in the original samples.
    Additional Material: 4 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 19 (1996), S. 99-104 
    ISSN: 0935-6304
    Keywords: Capillary electrophoresis ; Micellear electrokinetic chromatography ; Organic modifiers ; Naphthalene sulfonates ; Surface water ; Thermostatting ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The production and use of naphthalene sulfonates can easily cause pollution of surface and other types of waters. In the present study, capillary electrophoresis in combination with UV absorption detection was used to separate 21 amino- and hydroxy-substituted naphthalene sulfonates which included multiple isomeric compounds. The influence of various parameters such as pH (which turned out to be extremely important), temperature of the surrounding air flow, and the use of buffer additives (micelles, cyclodextrins, organic modifiers) was studied. Complete separation of all analytes including the isomers, was achieved in two runs with a 50 mM boric acid/borate buffer, containing either 100 mM sodium dodecylsulfonate or 15% acetonitrile. The limits of detection obtained for the individual compounds typically were 20μgI-1. River water samples spiked at this concentration level could be analysed using a simple three-step sample clean-up procedure.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 19 (1996), S. 403-408 
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Cryogenic trapping ; Capillary ; Focusing ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cryogenic trapping of solutes leads to narrowing of the chromatographic band. By placing the trap at the end of a capillary column, it is possible to study the effectiveness of the trap in terms of producing a sharpened elution profile. The trap may be heated by supplementary heating, but here convective heating from the GC oven is employed simply by turning off the cryogenic coolant. It is estimated that it takes about 50 s for the trap to heat up sufficiently to allow trapped solute to be remobilized, although this depends upon the oven temperature and thermal mass of the trap. It can also be shown that the more volatile solutes mobilize faster from the trap in this particular mode of operation. The recovery of trapped components shows that there is essentially quantitative trapping, and the solutes are trapped just at the leading edge of the trap.
    Additional Material: 4 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 19 (1996), S. 409-412 
    ISSN: 0935-6304
    Keywords: Micellar electrokinetic chromatography ; Rhei Rhizoma ; Scutellariae Radix ; Coptidis Rhizoma ; Bioactive constituents determination ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A capillary electrophoretic method for simultaneous determination of six bioactive ingredients (berberine, palmatine, baicalin, sennoside B, emodin, and sennoside A) in the Chinse herbal formula San-huang-hsieh-hsin-tang was established. A carrier composed of aqueous buffer solution (50 mM sodium cholate, 15 mM sodium dihydrogen phosphate, and 4.25 mM sodium borate)-acetonitrile (3:2) was found to be the most suitable electrolyte for this separation. Contents of these constituents in a non-pretreated methanol-water extract of San-huang-hsieh-hsin-tang sample could be easily determined within 20 min. The effects of borate, cholate, and organic modifier (acetonitrile) concentration of the carrier on the migration behavior of the solutes were also studied.
    Additional Material: 6 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 19 (1996), S. 418-418 
    ISSN: 0935-6304
    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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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 19 (1996), S. 485-491 
    ISSN: 0935-6304
    Keywords: Capillary GC ; Qualitative analysis ; Quantitative analysis ; Retention indices ; Retention times ; Solvent effect ; Sulfur Chemiluminescence Detection (SCD) ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Gas chromatrography (GC) with sulfur chemiluminescence detection (SCD) is an outstanding combination for selectively determining trace concentrations of sulfur compounds in hydrocarbon samples. GC peaks can be identified by retention times when reproducible, automated injection techniques are used. However, as described in this work, analysts should be on the look out for retention shifting due to solvent effects from sample components. Three examples of retention shifting are presented: (1) thiophene by benzene; (2) methylthiophenes by toluene; and (3) dibenzothiophene by gas oil. Depending on samples and analysis conditions, retention shifts from a few hundredths to 1.5 min have been observed. Such retention shifts are likely to cause errors in peak identifications. Therefore, when using SCD, simultaneous FID monitoring is recommended as an aid in evaluating chromatograms for possible retention shifting due to solvent effects.
    Additional Material: 4 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 19 (1996), S. 497-502 
    ISSN: 0935-6304
    Keywords: α-Monoacetotriacylglycerides ; Celastraceae ; Fatty acids ; GLC ; GLC-(NCI)MS ; Maytenus seed oils ; OV-225-OH, OH-terminated ; SOP-50, methoxy-terminated ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The seed oils of three Maytenus species have been examined by high temperature GLC using SOP-50 (methoxy-terminated) and OV-225-OH (OH-terminated) glasscapillary columns. The main compounds (71-76%) could be identified as α-mono-acetotriacylglycerols by a combination of high temperature GLC-MS in negative chemical ionization mode with a CH4/N2O mixture as reactant gas and other spectroscopical methods (infrared, 1H- and 13C-nuclear magnetic resonance spectroscopy). The OV-225-OH phase demonstrated better separation properties that the SOP-50 phase for this substance class and up to eight species of α-monoacetotriacylglycerols could be separated. The content of usual triacyclglycerols was below 1%. The results of the analysis of the individual fatty acids as their methyl esters by GC and GC-MS are also presented.
    Additional Material: 2 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 19 (1996), S. 521-526 
    ISSN: 0935-6304
    Keywords: LSS model ; Whey proteins ; HIC of proteins ; Circular dichroism ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 19 (1996), S. 527-529 
    ISSN: 0935-6304
    Keywords: High pressure gas chromatography ; Stationary phases ; Hydrocarbons ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 19 (1996) 
    ISSN: 0935-6304
    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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  • 11
    ISSN: 0935-6304
    Keywords: Capillary electrophoresis ; Enantiomeric separations ; Acidic compounds ; Neutral β-cyclodextrins ; Sulfobutyl ether β-cyclodextrin ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: High resolution could be achieved for the enantiomers of acidic drugs, namely, sulindac, fenoprofen, ketoprofen, warfarin, and hexobarbital, in a buffer of pH 3 by the simultaneous addition of uncharged and charged β-cyclodextrin derivatives. The interaction of the analytes with the anionic sulfobutyl ether β-cyclodextrin provides the analytes with an adequate electrophoretic mobility whereas the interaction with various neutral β-cyclodextrins generates high enantioselectivity. Five neutral cyclodextrins, the native β-cyclodextrin, as well as methyl-, dimethyl-, trimethyl- and hydroxypropyl-β-cyclodextrin, were tested to enhance the enantioselectivity of the electrophoretic system. High resolution values and the shortest analysis times for the five drugs tested were achieved in a buffer made of 100 mM phosphoric acid adjusted to pH 3 with triethanolamine and containing dimethyl- or trimethyl-β-cyclodextrin in addition to sulfobutyl ether β-cyclodextrin.
    Additional Material: 5 Ill.
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  • 12
    ISSN: 0935-6304
    Keywords: Chlorobiphenyl congeners ; Aroclors ; DB-XLB phase ; HP-5/HT-5 serial coupled phases ; GC-ECD ; GC-MS-SIM ; GC-Ion Trap MS ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Three HRGC systems (1: 30m DB-XLB capillary with MS-SIM detection; 2: 60m DB-XLB capillary with full-scan, ion-trap MS detection; and 3: Parallel dual-column DB-17 and series-coupled HP5/HT5 with ECD detection) were used to completely characterize multiple lots of 8 different-numbered Aroclor mixtures by quantitative calibration against 9 solutions containing primary standards of all 209 PCB congeners. Despite lower absolute sensitivity and more Aroclor congener coelutions than the dual-column ECD system, the MS systems enabled measurement of more congeners per Aroclor since their greater linear response range did not require dilution of samples and standards. Pairs of different lots of Aroclors 1248 and 1254 displayed markedly different proportions of congeners, and the 1254 pair displayed strong differences in the extent of ortho-chlorine substitution. The tables of congener weight percent distributions among Aroclors are more comprehensive and quantitatively precise than those of prior publications. However, the limitations of single-level calibration precluded measurement of all congeners to the ±10% accuracy desirable for establishing these Aroclors as secondary standards for comprehensive, quantitative congener-specific PCB analysis.
    Additional Material: 3 Ill.
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  • 13
    ISSN: 0935-6304
    Keywords: Capillary electrophoresis ; Mass spectrometry ; Electrospray ionization ; Fourier transform ion cyclotron ; Resonance ; Biomolecule analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We describe the current state of the on-line combination of capillary electrophoresis (CE) electrospray ionization (ESI) Fourier transform ion cyclotron resonance (FTICR) mass spectrometry (MS), and discuss aspects of the FTICR technique relevant to its use as a detection scheme for on-line separations. Aspects including sensitivity, mass resolution, duty cycle, and tandem mass spectrometric capabilities are discussed in the context of online separations with examples from the authors' laboratory.
    Additional Material: 6 Ill.
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  • 14
    ISSN: 0935-6304
    Keywords: HPLC of phenols ; Dianthus caryophyllus ; Carnation vascular wilt ; Fusarium oxysporum f. sp. dianthi ; Root phenolic compounds ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 15
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 19 (1996), S. 43-48 
    ISSN: 0935-6304
    Keywords: Capillary gas chromatography ; Mass spectrometry ; Wax esters ; Festuca arundinacea ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ester portion of epicuticular waxes of tall fescue (Festuca arundinacea Schreb.) is composed of mixtures of homologous series of fatty acids esterfied with fatty alcohols. GC analyses of natural esters gave rise to the separation of several compounds of different chain length. To identify and quantify individual components in the mixture, GC/MS analyses were carried out, and the mass spectra of each peak were recorded and analyzed for characteristic ions. This approach permitted a comparison with data obtained from classical methods using GC analysis of acid and alcohol moieties obtained by hydrolysis.
    Additional Material: 5 Ill.
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  • 16
    ISSN: 0935-6304
    Keywords: Optimization of GC conditions ; Sugar analysis ; Acid analysis ; Chlorogenic acid ; Raffinose ; Pectin decomposition products ; Galacturonic acid ; Arabinose ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Our GC-MS method for the simultaneous quantitation of sugars and acids as their silyl(oxime) derivatives, from one solution by one injection, has been extended to the reproducible determination of high molecular weight compounds sensitive to decomposition yet requiring a high evaporation temperature (e.g. chlorogenic acid and rffinose) and for the quantitation of the decomposition products of pectin (i.e., for the determination of galacturonic acid at low ng levels in the presence of a 10-100 fold excess of glucose eluting just before the acid). The optimized GC procedure has been used for quantitation of the sugar and acid (including chlorogenic acid) composition of potato samples, and for the determination of the increasing amount of the decomposition products of pectin substances in apple pulp after different storage times.
    Additional Material: 1 Ill.
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  • 17
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 19 (1996), S. 66-66 
    ISSN: 0935-6304
    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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  • 18
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 19 (1996) 
    ISSN: 0935-6304
    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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  • 19
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 19 (1996), S. 180-182 
    ISSN: 0935-6304
    Keywords: trans-Fatty acids ; Semi-industrial frying ; Capillary GC ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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  • 20
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 19 (1996), S. 183-188 
    ISSN: 0935-6304
    Keywords: Chelating agents ; Complexation ; Capillary zone electrophoresis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A capillary electrophoretic method has been developed which achieves rapid quantitative separation and determination of ethylenediaminetetraacetic acid, N-(2-hydroxyethyl)ethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminediacetic acid, and nitrilotriacetic acid in Hanford tank waste simulant (TWS). Direct UV detection of Cu2+/chelator complexes is used to achieve enhanced sensitivity. The qualitative and quantitative reliability of the method and the quality of separations, as given by efficiency and resolution, is presented. In addition, the limits of detection and linearity of detector response with concentration are given for each chelator. The selection of Cu as the UV-absorbing species over other transition metals present in the waste is discussed.
    Additional Material: 5 Ill.
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  • 21
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 19 (1996), S. 49-53 
    ISSN: 0935-6304
    Keywords: Polycyclic aromatic sulfur heterocycles ; Crude oil ; Oil maturity ; Fingerprinting ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method is presented for the identification and quantification of C2-substituted benzothiophenes in crude oil. The method will enable analysis of the pattern of these compounds, for example as a basis for differentiating crude oils from one another (fingerprinting) and for investigation of their suitability as indicators of oil maturity. Here results are reported for five crudes from Iraq, Venezuela, Saudi Arabia, the former Soviet Union, and the North Sea. The aromatic fraction of the crudes was oxidized and the dioxides of the heterocycles separated according to the number of carbon atoms in the side chains. The final separation was by capillary GC with atomic emission or flame ionization detection. A fluorinated analog was synthesized and used as internal standard. The concentrations of 2,3-, 2,4-, 2,7-, and 3,7-dimethylbenzothiophene ranged between 11 and 272 ppm. Three other dimethylated benzothiophenes present in lower amounts were also identified.
    Additional Material: 4 Ill.
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  • 22
    ISSN: 0935-6304
    Keywords: Capillary Supercritical Fluid Chromatography ; Mass Spectrometry ; SFC-MS ; On-line combination ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An interface for coupling supercritical fluid chromatography to a magnetic sector mass spectrometer was developed and evaluated. The interface is based on direct introduction of the mobile phase, carbon dioxide, into the ion-source of the mass spectrometer. The SFC-MS system was optimized with respect to the signal-to-noise ratio. Under optimized conditions, the estimated detection limit for n-pentadecane is approximately 30 ppm. Spectra obtained in the electron-impact ionization mode show a very good similarity with library spectra. The performance of the SFC-MS system was evaluated by the analysis of a number of test mixtures. A sample containing several low molecular mass, thermally unstable compounds, which could neither be analyzed by GC-MS nor by LC-MS, was analyzed. Also for the analysis of high molecular mass compounds, the coupled system showed a good performance.
    Additional Material: 9 Ill.
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  • 23
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 19 (1996), S. 37-42 
    ISSN: 0935-6304
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The headspace gas in static headspace gas chromatography contains mostly saturated water vapor. In the case of the cryofocusing enrichment technique this may cause baseline distortion in the early part of the chromatogram or may even lead to ice-plugging of the capillary column. A water-trap is described in which the water vapor is removed from the headspace gas before entering the cryo-trap. The water trap is packed with lithium chloride on a porous support and is regenerated after each analysis by heating under backflush conditions. It therefore can be used for automatic operation. Data are given for the precision and accuracy, and some practical examples, for environmental and flavor analysis are shown.
    Additional Material: 6 Ill.
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  • 24
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 19 (1996), S. 59-61 
    ISSN: 0935-6304
    Keywords: Steam chromatography ; Salt-water stationary phases ; Retention of alcohols ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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  • 25
    ISSN: 0935-6304
    Keywords: Gas Chromatography ; Ion-Trap Mass Spectrometry ; Pesticide residue analysis ; Eggs ; Ardea cinera ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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  • 26
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 19 (1996), S. 65-65 
    ISSN: 0935-6304
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 27
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 19 (1996), S. iii 
    ISSN: 0935-6304
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 28
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 19 (1996), S. 80-84 
    ISSN: 0935-6304
    Keywords: Capillary GC ; Specific detectors ; ECD/FPD response ratios ; Retention indices ; Identification on real samples ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A previous paper reported the possibility of using the ratio between the responses of two different specific detectors to a single compound (detector response ratio, DRR) as an identification criterion for that compound, in combination with its retention index.This article gives some applications of DRR in the identification of some pesticides in four different fruits (apples, apricots, strawberries, and peaches) in a range varying from 0.02 to 1.3 ppm, by means of their ECD/FPD DRRs. After clean-up GC analyses were performed on a single column with dual parallel detection; a personal computer system was used for data analysis.
    Additional Material: 4 Ill.
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  • 29
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 19 (1996), S. 91-94 
    ISSN: 0935-6304
    Keywords: Chiral selector anchored to polysiloxane ; Chiral phase capillary GC ; Immobilization ; Thermal treatment ; High enantioselectivity ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The chiral selector L-t-leucine-t-butylamide has been anchored to a polysiloxane by nucleophilic displacement of 2,2,2-trifluoroethyl ester-functionalized block polysiloxanes with L-t-leucine-t-butylamide. Attempts were made to immobilize the chiral polysiloxanes inside the capillaries by thermal treatment at 300°C for 30-90 min. The polysiloxanes were found to be more resistant than Chirasil-Val to the racemization caused by such high temperature treatment. Capillary columns coated with this type of immobilized polysiloxane have shown very high enantioselectivity and thermal stability.
    Additional Material: 3 Ill.
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  • 30
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 19 (1996), S. 284-284 
    ISSN: 0935-6304
    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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  • 31
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 19 (1996), S. 277-283 
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Coupled columns ; Four factor optimization ; Simplex method ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Optimization of a gas chromatographic system with two capillary columns coupled in series in a single oven for the linear temperature programmed separation of a mixture of C1—C10 hydrocarbons has been carried out using the simplex optimization method. The following four selectivity parameters were optimized: the initial temperature of the oven; the initial hold time; the temperature programmed rate; and the pressure at the mid-point of the system. The optimization procedure was monitored by the Cp criterion.
    Additional Material: 3 Ill.
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  • 32
    ISSN: 0935-6304
    Keywords: Capillary electrophoresis-mass spectrometry ; Membrane preconcentration ; Capillary electrophoresis ; Sulfonated membrane ; Polar drug metabolites ; Toxic oil syndrome ; Eosinophilia-myalgia syndrome ; 3-Phenylamino-1,2-propanediol ; 3-Phenylamino-L-alanine ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
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  • 33
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 19 (1996), S. VII 
    ISSN: 0935-6304
    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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  • 34
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 19 (1996), S. 298-300 
    ISSN: 0935-6304
    Keywords: Dynamic head space ; Coffee berry ; Identification ; Hypothenemus hampei ; Plant-insect relationship ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
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  • 35
    ISSN: 0935-6304
    Keywords: Capillary GC ; Drug screening ; Retention index ; Reporting ; Mean list length ; Blood analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A dual-column gas chromatographic retention index method was evaluated for the toxicological screening for basic drugs in autopsy blood samples. The dual-column approach with DB-5 and DB-1701 capillary columns doubles the Identification Power of the corresponding single column methods. The long-term intralaboratory variation of the dialkylfluoroaniline series based retention indices of drugs in blood ranged from 0.03% to 0.2% which was generally better than that obtained using the relative retention time. Novel software is described for the processing and reporting of the dual-column chromatographic data in analytically useful form. Besides retention data, the response factors served as an additional identification factor.
    Additional Material: 4 Ill.
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  • 36
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    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 19 (1996), S. 327-332 
    ISSN: 0935-6304
    Keywords: Capillary GC ; Separation performance ; Fourier analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A simple procedure is presented for determining separation performance of HRGC analysis of multicomponent mixtures. The procedure is based on the computation of Autocovariance Function (EACVF) from the digitized experimental chromatogram. Graphic inspection of the EACVF plot permits easy computation of the width value of the single component peak, σ; from the EACVF value at t=O the number of component in the mixture, m, can be simply derived. From these two basic quantities all the other chromatographic performance attributes can be calculated. The consistency of the procedure is tested for different chromatograms and compared with the more complex EACVF fitting method. Several features of the multicomponent chromatogram, overloading effects included, are directly detected.
    Additional Material: 4 Ill.
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  • 37
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    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 19 (1996), S. 339-344 
    ISSN: 0935-6304
    Keywords: Capillary gas chromatography ; Trace gas analysis ; Multichannel thick film silicone rubber traps ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Established standard methods for analyzing semi-volatile pollutants by capillary gas chromatography are cumbersome, time-consuming, and expensive. With the longer term aim of replacing the sample preparation procedures with convenient concertrating and thermal desorption steps, thick film silicone rubber traps were constructed in a novel multi-channel configuration. Tests were performed to determine breakthrough volumes and thermal desorption characteristics for total transfer of the trap contents to a capillary column. Initial results are very promising.
    Additional Material: 6 Ill.
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  • 38
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    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 19 (1996), S. 333-338 
    ISSN: 0935-6304
    Keywords: Adsorptive enrichment/thermal desorption ; Microtrap ; VOC and PVOC analysis ; Humid air sample analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An instrument has been developed and tested for the continuous measurement of volatile organic compounds (VOC) in air. The system consists of a gas chromatograph equipped with a dedicated sampling device that allows the sample to be transferred to a cooled microtrap via sampling loops (10, 100, 250 ml) or via a direct pump transfer to the trap. The microtrap is placed in the chromatographic oven just below a modified split-splitless injector, allowing direct liquid injection for calibration of the system; the injector is in communication with the sampling valve equipped with the loop and the sampling pump. The system allows 24-hour sampling and analysis of a large number of VOC (up to 25 individual hydrocarbons ranging from C2—C9) and also polar volatile organic compounds PVOC. Thanks to the particular trap geometry, a minimum consumption of liquid nitrogen (between 150—300 ml) is needed for each analytical run and no water managing system is normally required for humid air samples.
    Additional Material: 5 Ill.
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  • 39
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 19 (1996), S. 353-358 
    ISSN: 0935-6304
    Keywords: Capillary gas chromatography ; Gas chromatography-mass spectrometry ; Essential oil analysis ; Ylang-ylang oil ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Steam distillation (SD), simultaneous distillation-solvent extraction (SDE), and supercritical (CO2) extraction (SFE) were used to isolate volatile secondary metabolites from fresh, totally mature flowers of Colombian ylang-ylang (Cananga odorata). The various extracts were analyzed by capillary chromatography (DB-1, DBWAX, 60 m columns) using FID, NPD or MSD (EI, 70 eV). Kováts indexes, mass spectra, or standard substances were employed for compound identification. 51, 70, and 73 compounds at concentrations above 100 ppb were detected in the SD, SDE, and SFE extracts, respectively. The main constituents of these extracts were linalool (20.7, 28.0, and 16.5%), germacrene-D (10.1, 3.1, and 20.3%) benzyl benzoate (14.1, 2.9, and 3.9%), benzyl acetate (9.6, 17.0, and 6.2%), caryophyllene (3.1, 2.9, and 3.9%), and p-methylanisole (6.8, 6.1, and 2.7%). 85% of the composition of SDE extracts was represented by oxygenated compounds. Heavy hydrocarbons (Cn 〉20) and fatty acids were found only in the SFE extracts, which also had a higher content of nitrogenated compounds (phenylacetonitrile, 4-methylbenzaldoxime, indole, 2-phenyl-nitroethane, and methyl anthranilate) and sesquiterpenes (43% vs 19.5% in SD and 8.1% in SDE) and 1.5 - 2 times lower concentration of monoterpenes and light oxygenated compounds than the SD (49.7%) and SDE (64.5%) extracts.
    Additional Material: 4 Ill.
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  • 40
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    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 19 (1996), S. 359-361 
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Atomic emission detection ; Triclosan ; Dental plaque ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A validated gas chromatographic method for the determination of triclosan in human dental plaque is described. Based on plaque sample weights of 10 mg, the limit of detection (2 × S/N) is 0.5 μg/g. The method is linear (r = 0.9986) from the limit of detection to 50 μg/g. Recoveries from placebos spiked with 2.0, 25, and 50 μg/g of triclosan were 105.6%±7.5%, 107.2%±3.1%, and 99.1%±1.1%, respectively (n = 3 at each level). Twenty replicate preparations and analyses of a homogenized sample, conducted by two operators over the course of 4 days, showed agreement to within 9% RSD. Analyses of dental plaque collected from patients after brushing with dental cream containing triclosan, shows triclosan to be retained in dental plaque at concentrations above the minimum inhibitory concentration (1 μg/g) after 12 h.
    Additional Material: 1 Ill.
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  • 41
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    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 19 (1996) 
    ISSN: 0935-6304
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 42
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    Journal of High Resolution Chromatography 19 (1996), S. 371-371 
    ISSN: 0935-6304
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 43
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    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 19 (1996), S. 377-382 
    ISSN: 0935-6304
    Keywords: Capillary chromatography ; Boiling points prediction ; Identification ; Chlorobenzenes ; Phenols ; Programmed temperature ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Quantitative correlations between physicochemical parameters and structure of various solutes and their gas chromatographic behavior were investigated in order to predict the retention values. The identification of unknown samples in gas chromatographic routine analysis of environmental samples is enhanced by the use of these correlations in conjuction with other chromatographic methods and with mass spectrometry. The boiling points of many compounds are easily found in literature and therefore their correlation with retention values obtained in isothermal or programmed temperature analysis permit restriction of the choice of names of unknown compound to within a narrow range. The correlation between the boiling points and the retention times of chloro- and bromo-benzenes and of some chloro- and nitro- substituted phenols was investigated on non-polar capillary columns and permitted the tentative identification of many compounds belonging to these homologous series.
    Additional Material: 3 Ill.
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  • 44
    ISSN: 0935-6304
    Keywords: Capillary gas chromatography ; FID, O-FID, and MS detection ; Glycol ethers and glycol ether acetates ; Heptafluorobutyryl derivatives ; Mass spectra ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Twelve compounds, commonly used as industrial solvents and belonging to the chemical class of glycol ethers and glycol ether acetates, were investigated. Several analytical conditions, applied to single or connected capillary columns of different length and polarity coating and connected to FID, O-FID and MS detection systems, were assayed. Tests on heptafluorobutyryl derivatives were also attempted to improve the analytical sensitivity. The aims were to establish gas chromatographic methods suitable for analysis of reference standard compounds and to verify their applicability to biological matrix analysis for pharmacokinetic and toxicological studies, since these chemicals have been shown to be hazardous in laboratory animals and are presumed to be dangerous in man.
    Additional Material: 6 Ill.
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  • 45
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    Journal of High Resolution Chromatography 19 (1996), S. 444-448 
    ISSN: 0935-6304
    Keywords: LC-GC coupling ; Loop-type interface ; Alcohols ; Sterols ; Olive oil ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A modified loop-type interface is decribed which uses two 6-way valves and concurrent eluent evaporation to perform an on-line transfer and simultaneous gas chromatographic analysis of two different fractions pre-separated by liquid chromatography. The interface is used to simultaneously analyze aliphatic alcohols and sterols present in olive oil. LC pre-separation is carried out using a normal phase column (20 cm × 0.21 cm i.d.) and hexane-isopropanol (99:1) as a mobile phase at a flow of 0.2 ml/min; for the GC analysis a 5 % phenyl, 95 % dimethyl siloxane (25 m × 0.32 mm i.d., 0.4 μm film thickness) column is used.
    Additional Material: 4 Ill.
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  • 46
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    Journal of High Resolution Chromatography 19 (1996), S. 462-462 
    ISSN: 0935-6304
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 47
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    Journal of High Resolution Chromatography 19 (1996), S. 463-463 
    ISSN: 0935-6304
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 48
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    Journal of High Resolution Chromatography 19 (1996), S. 449-456 
    ISSN: 0935-6304
    Keywords: Supercritical fluid chromatography (SFC) ; Packed columns ; Pressure drop ; Selectivity ; Resolution ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The influence of pressure drop on retention, selectivity, plate height and resolution was investigated systematically in packed supercritical fluid chromatography (SFC) using pure carbon dioxide as the mobile phase. Numerical methods developed previously which enabled the prediction of pressure gradients, diffusivities, capacity factors, plate heights and resolutions along the length of the column were used for the model calculations. The effects of inlet pressure and supercritical fluid flow rate on selectivity and resolution are studied. In packed column SFC with pure carbon dioxide as the mobile phase, the pressure drop can have a significant effect on resolution. The flow rate is shown to have a larger effect than generally realized. The calculated data are shown to be in good agreement with the experimental results. Finally, the variation of the chromatographic parameters along a 5.5 meter long model SFC column is illustrated. The possibilities and limitations of using long packed columns in SFC are discussed. It is demonstrated that long columns with large plate numbers do not necessarily yield better separations.
    Additional Material: 7 Ill.
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  • 49
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    Journal of High Resolution Chromatography 19 (1996), S. 464-464 
    ISSN: 0935-6304
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 50
    ISSN: 0935-6304
    Keywords: Capillary gas chromatography ; Purge and trap extraction ; 1,2,4-TCB ; Environmental analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: High resolution gas chromatography (HRGC) coupled to a “purge and trap” extraction-injection technique is described as a method of determining 1,2,4-trichlorobenzene in water at levels as low as parts-per-trillion (ppt). In order to investigate the interference from other volatile organic compounds (VOCs) several detection systems were compared: flame ionization, electron capture, and mass spectrometry-multiple ion detection. Concentrations ranging from 15 to 600 ng/L were analyzed in 20 ml standard aqueous solutions. The mean accuracy of the method varied from 89 to 103%, and its mean precision varied from ± 0.85 to ± 7.5 % for all detectors. The detection limits were 20 ng/L for FID, 2 ng/L for ECD and 0.5 ng/L for MID-MS detectors. The procedure was successfully applied to the analysis of industrial waste waters. The necessity of an appropriate internal standard to improve the quantitative determination and to determine possible losses or degradation of 1,2,4-trichlorobenzene during handling or storage is discussed.
    Additional Material: 5 Ill.
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  • 51
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    Journal of High Resolution Chromatography 19 (1996), S. 469-471 
    ISSN: 0935-6304
    Keywords: Microextration ; GC/MS ; Chlorobenzenes ; Water samples ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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  • 52
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    Journal of High Resolution Chromatography 19 (1996), S. 465-469 
    ISSN: 0935-6304
    Keywords: Supercritical fluid extraction (SFE) ; Beef ; Anabolic steroids, synthetic ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 5 Ill.
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  • 53
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    Journal of High Resolution Chromatography 19 (1996), S. vii 
    ISSN: 0935-6304
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 54
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    Journal of High Resolution Chromatography 19 (1996), S. 478-480 
    ISSN: 0935-6304
    Keywords: Capillary zone electrophoresis ; Chiral separation ; Cyclodextrins ; Methoxamine ; Lobeline ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 5 Ill.
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  • 55
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    Journal of High Resolution Chromatography 19 (1996), S. 492-496 
    ISSN: 0935-6304
    Keywords: High - speed capillary GC ; Carbon dioxide cryotrap ; Deactivated metal tubing ; Thermal decomposition ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ten different metal tubings were investigated for thermal decomposition of analytes when used as the trap tube in a cryotrap/thermodesorption inlet system. No noticeable sample decomposition of hydrocarbons, chlorinated hydrocarbons and a brominated hydrocarbon was observed for six of the tubings with hydrogen as the carrier gas. This observation may be partly attributed to the developed deactivation techniques that produce inert metal tubings that are being widely adopted by many column manufacturers, the different trap materials used in comparison to previous studies and the decreased sample residence time in the hot trap tube. A cryotrap using carbon dioxide was constructed and tested as a alternative to the previously used liquid nitrogen based systems. This cryotrap was able to trap compounds with a boiling point of 80°C.
    Additional Material: 5 Ill.
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  • 56
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    Journal of High Resolution Chromatography 19 (1996), S. 511-514 
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Enantiomer separation ; Amino acids ; N-Alkyloxycarbonyl alkylamide derivatives ; Nucleophilic substitution ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The enantiomers of amino acids were first converted into N-alkyloxycarbonyl 2,2,2-trifluoroethyl esters, and then into N-alkyloxycarbonyl alkylamides by nucleophilic substitution of the ester group with amines. The first reaction proceeds instantaneously, while the second substitution occurs smoothly with n-propylamine and isobutylamine. The final derivatives were produced for separation on a capillary column coated with Chirasil-Val by GC. Pro, which is difficult to separate completely as its N-perfluoroacyl alkyl ester derivative, showed complete separation of the enantiomeric pair. All amino acids examined in this study showed an increased separation factor.
    Additional Material: 3 Ill.
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  • 57
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    Journal of High Resolution Chromatography 19 (1996), S. 530-533 
    ISSN: 0935-6304
    Keywords: High-performance liquid chromatography ; Paeoniae Radix ; Peony constituent separation ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 58
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    Journal of High Resolution Chromatography 19 (1996), S. 543-548 
    ISSN: 0935-6304
    Keywords: Gas chromatography ; High temperature ; Dead time ; Constants of the n-alkane retention time curve ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In gas liquid chromatography, the column dead time and the constants of the n-alkane retention time curve are calculated by the multiparametric least-squares regression iterative method at high temperature between 180 and 270°C. The method was applied to two types of columns. The first group includes eight packed columns (seven OV polymethylphenylsiloxane and Apolane-87), while the second includes five glass capillary columns (four methylsilicone with different film thicknesses and Apolane-87). The calculated tM and b values were compared with those obtained by Guardino's, Grobler's, and Kaiser's methods. The influences of coating thickness and temperature thereon were investigated.
    Additional Material: 4 Tab.
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  • 59
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    Journal of High Resolution Chromatography 19 (1996), S. 569-570 
    ISSN: 0935-6304
    Keywords: Microbore SFC ; Chiral separation ; 3,5-Dimethylphenyl carbamate derivative of cellulose ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 60
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    Journal of High Resolution Chromatography 19 (1996), S. 559-563 
    ISSN: 0935-6304
    Keywords: Pesticide residue analysis ; Solid phase extraction ; Ground water ; Surface water ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A critical study of a solid phase extraction method using C18 SPE columns for the determination of 23 halogenated pesticides is presented. Type of sorbent, sorbent mass, flow rate in the extraction process, sample concentration of the different compounds, sample volume, pH, ionic strength and type of water were evaluated. Recoveries of pesticides under study yield a linear relationship, except for conazole fungicides and captan. Losses can be expected for heptachlor, aldrin, and captan. Sample volume and flow rate of extraction affect recoveries. Matrix effects from surface and groundwaters were observed. Recoveries for vinelozolin and dieldrin from groundwater were lower than those obtained from nanopure water. In river water losses of these compounds are higher. Captan and penconazole were not present and high losses were obtained for trifluralin, α-BHC, γ-BHC, tri-allate and chlorpyriphos. Impurities arising from the sorbent materials of cartridges have been detected.
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  • 61
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    Journal of High Resolution Chromatography 19 (1996), S. 549-558 
    ISSN: 0935-6304
    Keywords: Size exclusion chromatography ; Petroleum waxes ; Flame ionization detector ; Refractive index detector ; Molecular weight distribution ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Molecular weight distribution of solid petroleum waxes is a key parameter for the general characterization of these materials. Particular interest concerns extremely large components, typically present in oil distillation residua, and solid deposits found in oil production facilities. Molecular weight distributions of oil waxes were determined in this work by high temperature size exclusion chromatography. Separations were carried out with two different eluents, namely toluene and ortho-dichlorobenzene and two detection systems, these being a differential refractive index and a flame ionization detector. Toluene proved to be the best choice when combined with flame ionization detection. Better uniformity of response was the greatest advantage achieved by this approach. The experimental set up permitted analysis of samples containing molecules with up to 138 carbon atoms. Burning properties of very large molecules, isomerism affecting calibration, and signal asymmetry when flame ionization detection was adopted were three issues still requiring additional efforts to understand and to improve analysis accuracy.
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  • 62
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    Journal of High Resolution Chromatography 19 (1996), S. 577-580 
    ISSN: 0935-6304
    Keywords: Phenolic compounds ; Solid phase extraction ; Coal gasification ; GC/MS ; XAD-4 ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
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  • 63
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    Journal of High Resolution Chromatography 19 (1996), S. 588-590 
    ISSN: 0935-6304
    Keywords: Supercritical fluid extraction ; Water samples ; Polycyclic aromatic hydrocarbons ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 5 Ill.
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  • 64
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    Journal of High Resolution Chromatography 19 (1996), S. 585-587 
    ISSN: 0935-6304
    Keywords: Enantioselective gas chromatography ; Volatiles ; 2-Heptanol ; Ethyl benzoate ; (E)-Hex-2-enal ; 1-Terpinen-4-oI ; Rubus glaucus ; Rosaceae ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
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  • 65
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    Journal of High Resolution Chromatography 19 (1996), S. 596-596 
    ISSN: 0935-6304
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 66
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    Journal of High Resolution Chromatography 19 (1996) 
    ISSN: 0935-6304
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 67
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    Journal of High Resolution Chromatography 19 (1996), S. 597-607 
    ISSN: 0935-6304
    Keywords: Capillary gas chromatography ; Atomic emission detection ; Environmental applications ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Environmental applications of capillary gas chromatography coupled with atomic emission derection (GC-AED) have been reviewed with emphasis on both the commercial and laboratory-built systems. Attention was focused on (1) element-selective detection of non-metallic as well as metallic pollutants, (2) identification of contaminants, and (3) sample preparation considerations.
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  • 68
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    Journal of High Resolution Chromatography 19 (1996), S. 613-616 
    ISSN: 0935-6304
    Keywords: Capillary electrophoresis ; Electrochemical detection ; End column detection ; Nickel electrode ; Carbohydrates ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Carbohydrates were separated by capillary electrophoresis (CE) and detected electrochemically using a nickel microelectrode which was operated at a constant applied potential (∼0.6 V vs. Ag/AgCI). A simple capillary electrode holder design facilitated alignment between the separation capillary and the working microelectrode without the use of micro-positioning equipment. The separations were performed under alkaline conditions (pH 〉 11), matching the high pH requirements for amperometric detection at the nickel electrode. The analytical procedure developed showed detection limits for the carbohydrates studied in the micromolar range, showing a linear response in the range tested (micromolar to millimolar). The procedure was used to identify sugars in two real samples (i.e., urine and in a common beverage). The potential use of the system for the determination of amino acids was also demonstrated.
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  • 69
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    Journal of High Resolution Chromatography 19 (1996), S. 691-695 
    ISSN: 0935-6304
    Keywords: HPLC ; Molecular sieve ; Cis-trans isomers ; Phenols ; Selectivity ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A molecular sieve known as Silicalite was used as the column packing for HPLC. Silicalite contains channels (or cavities) approximately 6 Å in diameter but, unlike most other molecular sieves, Silicalite is hydrophobic. The retention times of methyl ketones and substituted phenols containing n-alkyl groups increase with increasing chain length of the substituent. However, phenols with very bulky substituents appear to be excluded from the Silicalite channels and elute very quickly. Excellent separations were obtained for a number of compounds with only slight differences in chemical structure. These include phenol isomers with a primary- or secondary alkyl group, position isomers of substituted phenols, and aliphatic cis-trans isomers.
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  • 70
    ISSN: 0935-6304
    Keywords: Capillary zone electrophoresis ; Chiral separation ; Cyclodextrin ; Anisodamine ; Glycopyrronium ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 4 Ill.
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  • 71
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    Journal of High Resolution Chromatography 19 (1996), S. 622-626 
    ISSN: 0935-6304
    Keywords: Multidimensional capillary chromatography ; Polychlorinated biphenyls ; PCBs ; Congener ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Multidimensional chromatography was used to resolve the specific chlorobiphenyl (CB) congeners 28, 52, 101, 118, 138, 153, and 180 in technical aroclor standards. Single column analysis of polychlorinated biphenyls (PCBs) results in co-elution of key congeners with other components in the mixture; therefore using two columns of different selectivity was necessary to enhance the resolution achievable on just one column. The HT8 column (8% phenylpolycarborane-siloxane phase) has been reported to have specific selectivity characteristics for improved PCB separation. When coupled with a BPX5 column (5% phenylpolysiloxane-silphenylene phase), it has been shown here to provide unambiguous identification of 7 marker compounds which are used to monitor PCB occurrence and distribution. All seven marker CBs are present in aroclor 1254, and by adjusting the size of the heartcut window, it was possible to obtain resolution of the marker congeners from other congeners. Single column analysis is unable to achieve this result. This offers an alternative to GC-MS analysis.
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  • 72
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    Journal of High Resolution Chromatography 19 (1996), S. 647-650 
    ISSN: 0935-6304
    Keywords: Capillary zone electrophoresis (CZE) ; Separation of herbicides ; Chlorophenoxy acid ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 5 Ill.
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  • 73
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    Journal of High Resolution Chromatography 19 (1996) 
    ISSN: 0935-6304
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 74
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    Journal of High Resolution Chromatography 19 (1996), S. 69-79 
    ISSN: 0935-6304
    Keywords: Large volume injection ; PTV injector ; Water analysis ; River sediment ; Pesticides ; Polycyclic aromatic hydrocarbons (PAHs) ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Temperature programmable (PTV) injectors with packed widebore (ca. 3.5 mm i.d.) liners are used for large volume injection in capillary gas chromatography with the aim to simplify and/or improve off-line sample pretreatment proecdures. A simple procedure for optimization of large volume PTV injection is described. The system performance, i.e. linearity and repeatability, is evaluated for polar nitrogen/phosphorus containing pesticides (PTV-GC-NPD) and organochlorine pesticides (PTV-GC-ECD) in river water extracts as well as for polycyclic aromatic hydrocarbons (PAHs) in river sediment (PTV-GC-MS).
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  • 75
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    Journal of High Resolution Chromatography 19 (1996), S. 124-126 
    ISSN: 0935-6304
    Keywords: Reversed-phase HPLC ; Propionic antiinflammatory drugs ; Barbituric sedatives and hypnotics ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
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  • 76
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    Journal of High Resolution Chromatography 19 (1996), S. 128-128 
    ISSN: 0935-6304
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 77
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    Journal of High Resolution Chromatography 19 (1996), S. 129-129 
    ISSN: 0935-6304
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 78
    ISSN: 0935-6304
    Keywords: Capillary electrophoresis ; Chiral separation ; Selenium amino acids ; Vancomycin ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Baseline separation of the enantiomers of the negatively charged 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate (AQC) derivatives of cystine, methionine, ethionine, and their seleno analogs can be achieved in 3-5 min with capillary electrophoresis in polyacrylamide coated capillaries and submillimolar concentrations of vancomycin as the chiral selector.In addition to the vancomycin concentration, the separation is affected by the type, concentration and pH of the buffer. Good buffers are more suitable than phosphate buffer. At pH values above the isoelectric point of vancomycin the mobility difference between the enantiomers becomes smaller. This effect is larger than would be expected from the reversal of the vancomycin migration alone.
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  • 79
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    Journal of High Resolution Chromatography 19 (1996), S. 151-154 
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Atomic emission spectroscopy ; Enantiomeric separation ; Cyclodextrins ; Chemical warfare agents ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of the organophosphorus nerve agents sarin, tabun, and cyclohexyl methylphosphonofluoridate (GF) produces a mixture of two stereoisomers except for soman where four stereoisomers are produced. Significant differences exist in the reported toxicity and AChE inhibition rates of the various stereoisomers. This makes the ability to distinguish between the different stereoisomers desirable. Five different derivatized cyclodextrin stationary phases developed for gas chromatography were tested for their ability to resolve the nerve agent stereoisomers using a gas chromatograph interfaced to an atomic emission detector. Of the five columns that we examined, only the 2,6-di-O-pentyl-3-O-trifluoroacetyl or 2,6-di-O-pentyl-3-O-butyryl γ-cyclodextrins were able to successfully resolve all four soman stereoisomers. The elution order for each column was determined using solutions of isolated soman stereoisomers. Enantiomers of sarin, tabun, and GF were resolved with varying degrees of success on the different cyclodextrin stationary phases. Only the butyryl γ-cyclodextrin was able to separate the enantiomers of all four of the nerve agents examined in this study. The capacity (k) and selectivity (α) factors were determined for each of the chemical warfare agents successfully separated. The TNO Prins Maurits Laboratory in the Netherlands has previously developed several different chromatographic methods to resolve the stereoisomers of soman, sarin, and tabun. The advantage of the method described here is that commercially available cyclodextrin gas chromatography columns were used to resolve the stereoisomers, thereby facilitating rapid and routine analysis of organophosphorus nerve agents.
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  • 80
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    Biospectroscopy 2 (1996), S. 1-8 
    ISSN: 1075-4261
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: Surface-enhanced resonance Raman scattering (SERRS) in silver colloids has been used to study the polyene antibiotic amphotericin B (AmB), its methylester (AmE), and its N-fructosyl derivative (N-Fru-AmB). The intensity of SERR spectra strongly varied with the amphotericin concentration, the nature of added salts, the Ag colloid preparation and the excitation wavelength. The systematic study of all these parameters allowed determination of optimal conditions for the specific detection of AmB and AmE. Under these conditions AmB was detected at 10-10 M in silver colloids prepared according to Creighton et al., with 60m M NaNO3, whereas in the case of AmE the detection threshold was 10-9 M in silver colloids prepared according to Lee and Meisel with 30m M NaCl. Circular dichroism (CD) was used as a complementary technique to study the self-association of the polyenes, characterized by a dichroic doublet at 340 nm. We observed that the addition of silver colloid leads to a modification in the structure of the self-associated species. © 1996 John Wiley & Sons, Inc.
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  • 81
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    Biospectroscopy 2 (1996), S. 9-15 
    ISSN: 1075-4261
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: We found that N-acetyl-L-tryptophanamide (NATA) could be excited at 840 nm using a mode-locked Ti : sapphire laser. The emission spectra of NATA were the same for one-photon (1 hv) excitation at 280 nm as for excitation at 840 nm. The emission intensity of NATA was found to depend on the cube of the laser power at 840 nm, consistent with simultaneous absorption of three 840-nm photons. The intensity-decay times were the same for 280- and 840-nm excitation, suggesting the same excited state is reached for each mode of excitation. However, the anisotropies were different for 280- and 840-nm excitation. At 280 nm the time-zero anisotropy was 0.130, whereas at 840 nm the time-zero anisotropy was negative (-0.06), indicating different orientations of the transition moments for one- and three-photon excitation. These results suggest that the intrinsic fluorescence of proteins may be excited using the fundamental output of a Ti: sapphire laser. © 1996 John Wiley & Sons, Inc.
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  • 82
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    Biospectroscopy 2 (1996), S. 39-45 
    ISSN: 1075-4261
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: Infrared spectroscopy was applied to the investigation of normal and oxidatively modified hepatic nuclei. The hepatic nuclei were oxidized by two different free-radical-generating systems. Infrared spectra of oxidized nuclei were remarkably different from those of normal nuclei; the major alteration found in the spectra of oxidized nuclei was the emergence of a new population of nucleic acids with a hydrogen-bonding pattern different from that of the normal phosphodiester groups, and a redistribution of the hydrogen bonding of the protein amide groups of the histones, indicative of protein-structural rearrangements. The spectral changes in the phosphate bands of the nucleic acid resemble those previously observed in different types of malignant tissue, and suggest that there could be a link between nuclei oxidation and carcinogenesis which may involve a free-radical-mediated process. © 1996 John Wiley & Sons, Inc.
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  • 83
    ISSN: 1075-4261
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: Simultaneous measurements of resonance Raman and absorption spectra were performed for intermediates generated upon addition of hydrogen peroxide to ferric Arthromyces ramosus peroxidase (ARP) using the microcirculating system constructed in this laboratory, which enables generation of desirable intermediates under steady-state conditions. Compound I of ARP generated at neutral pH was stable over tens of minutes in the absence of laser illumination with this circulation system, but was gradually degraded under laser illumination, giving rise to a new irreversible species with an iron-oxo heme. Such photosensitivity was not observed for compound II in the steady state at alkaline pH. Surprisingly, the Raman spectrum of compound I of ARP in the high-frequency region, where characteristic frequency shifts are expected upon oxidation of the macrocycle, was quite close to that of compound II, despite the fact that the reduced Soret absorption indicated the formation of a π-cation radical. The Fe=O stretching (νFe=O) frequency of compound I was observed at 781 cm-1 for the 16O derivative but appeared as a doublet at 744 and 731 cm-1 for the 18O derivative. The isotope sensitivity of the νFe=O mode of compound I was seen upon H216O/H218O solvent substitution but not upon H216O2/H218O2 peroxide substitution in H216O at neutral pH. This directly indicates the occurrence of an oxygen atom exchange between the oxo-heme and bulk water, providing the first example of such exchange in compound I of peroxidases. The oxygen exchange was abolished for compound II at alkaline pH, for which the νFe=o mode was seen at 787/749 cm-1 only upon H216O2/H218O2 peroxide substitution. The oxygen exchangeability seems to depend on protonation of a nearby residue with pKα ∼ 9 and to correlate with stability of compound I. © 1996 John Wiley & Sons, Inc.
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  • 84
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    Biospectroscopy 2 (1996) 
    ISSN: 1075-4261
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
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  • 85
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    Biospectroscopy 2 (1996), S. 261-261 
    ISSN: 1075-4261
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
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  • 86
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    Biospectroscopy 2 (1996), S. 339-340 
    ISSN: 1075-4261
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 87
    ISSN: 1075-4261
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: Time-resolved resonance Raman spectroscopy has been used to probe the structural dynamics at the heme o3 proximal and distal sites subsequent to carbon monoxide photolysis from fully reduced and CO mixed-valence cytochrome bo3 ubiquinol oxidase. The spectra of the transient species exhibit structural differences relative to the equilibrium geometry of heme o3. The most significant of these is a shift of 4 cm-1 to higher frequency of the 208-cm-1 mode in the transient species. Our results indicate that the 208-cm-1 mode observed in the equilibrium-reduced heme o3, which was recently assigned to the Fe2+ His of heme o3, is located at 212 cm-1 in the 10-ns spectrum. The behavior of the Fe2+ His mode in the photolytic transients of cytochrome bo3 indicates that at times ∼ 10 μs subsequent to CO photolysis the proximal heme o3 geometry is fully relaxed. The rate of relaxation of heme o3 is similar to that observed in the heme a3 transients of cytochrome aa3 oxidase. At later times (td 〉 100 μs) the appearance of the 212-cm-1 peak signals the onset of CO rebinding to the previously photolyzed heme o3. Neither the fully reduced nor the mixed-valence species exhibits geminate ligand recombination on a 10-ns time scale. Both species, however, display relaxation of ν(Fe-His) to its equilibrium position, at 208 cm-1, on a 10-μs time scale, and ligand rebinding on a 200-μs time scale. Our results indicate that the rate of relaxation of heme o3 and the CO rebinding to heme o3 are independent of the redox state of the low-spin heme b. Collectively, the transient intermediates of heme o3 suggest significant alterations in the nature of the heme-protein dynamics between cytochrome c aa3 oxidase and quinol cytochrome bo3 oxidase resulting from specific structural differences within their respective proximal and distal hemepockets. © 1996 John Wiley & Sons, Inc.
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  • 88
    ISSN: 1075-4261
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: Two-dimensional infrared (2D IR) spectroscopy has been shown to be a powerful tool for the analysis of spectra with highly overlapped bands, as often found in IR spectra of biological samples. To date, most 2D IR analyses have focused primarily on intensity changes of the bands under investigation. However, information concerning 2D IR characteristics of bands that change in position or width is sparse. We have thus simulated the effects of frequency and bandwidth changes on 2D IR spectra. In the synchronous plot of a band undergoing a frequency shift, two autopeaks and two crosspeaks are found at the initial and final positions, while the asynchronous plot exhibits two weaker crosspeaks for these positions and a stronger, somewhat elongated feature close to the diagonal. The latter feature is characteristic of a shifting band. Thus, to distinguish a frequency shift in a single band from intensity changes of two overlapped bands it is important to examine the asynchronous plot, since the synchronous plots exhibit comparable characteristics in both cases. A bandwidth change results in a series of crosspeaks. However, when bandwidth changes are coupled with either frequency shifts and/or intensity changes, the effect of the bandwidth change is reduced. Finally, it is shown that the resolution enhancement generally found for the asynchronous plot is accompanied by an error in the positions of the original spectral features as determined from 2D IR peaks. The magnitude of the error increases as the original spectral features approach each other in frequency. © 1996 John Wiley & Sons, Inc.
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  • 89
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    Biospectroscopy 2 (1996), S. 353-364 
    ISSN: 1075-4261
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: Two-dimensional (2D) infrared (IR) correlation spectroscopy was used to monitor the ν1, ν3 phosphate contour (900-1200 cm-1) of maturing poorly crystalline hydroxyapatite in synthetic (synthesized at constant and variable pH) and biological (calcified turkey leg tendon) systems. The 2D IR plots of the mineral prepared at variable pH exhibit peaks at 961, 999, 1018, 1036, 1095, 1126, and 1150 cm-1. The peaks at 961, 999, and 1095 cm-1 represent vibrations of PO3-4 in an apatitic/stoichiometric environment of poorly crystalline HA, while those at 1018, 1036, and 1126 cm-1 arise from PO3-4 in a nonstoichiometric/acid phosphate environment of poorly crystalline HA. The 2D IR analysis suggests that the intensities of peaks associated with PO3-4 in a nonstoichiometric/acid phosphate environment decrease as the reaction progresses. The 2D IR plots of the mineral formed at constant pH showed only bands characteristic of PO3-4 in a stoichiometric/acid phosphate environment. Analysis of the 2D IR plots of the mineral from calcified turkey leg tendon reveals peaks at 1019, 1039, 1075, 1126, and 1147 cm-1. The peaks at 1019, 1039, and 1126 cm-1 are characteristic of PO3-4 in a nonstoichiometric/acid phosphate environment of poorly crystalline HA, while the band at 1075 cm-1 is characteristic of PO3-4 in an apatitic/stoichiometric environment of poorly crystalline HA. Thus, the in vitro experiment in which the mineral is formed at variable pH is a better model of the mineral phase in calcified turkey leg tendon. In addition, the asynchronous plots from both the synthetic and biological minerals revealed those peaks which were noncorrelated. Also, this method of data analysis provided enhanced resolution of the highly overlapped ν1, ν3 phosphate contour commonly seen in Fourier transform-IR spectra of calcified tissue. © 1996 John Wiley & Sons, Inc.
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  • 90
    ISSN: 1075-4261
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: The bioxidative transformation of the antitumor drug N(2)-methyl-9-hydroxy ellipticinium (NMHE) by the peroxidase-H2O2 system leads to a highly electrophilic quinoneimine species. This species may react with biological macromolecules such as proteins or nucleic acids, that contain suitable nucleophilic groups, to give covalent adducts through a Michael addition at C(10). When this reaction takes place in the presence of aliphatic primary amines, recyclisation process occurs during coupling leading to adducts of which the oxazolopyridocarbazole (OPC) structure has been established. Surface-enhanced Raman scattering (SERS) spectra of these OPC were recorded and analyzed to serve as references. On the basis of these spectral data, the SERS investigation of adducts obtained with aliphatic amino acids indicated that these species present the same chromophoric OPC-type structure as those obtained with aliphatic amines. On the other hand, we have studied the covalent binding of the drug to calf thymus DNA obtained under the same oxidative enzymatic procedure. Since previous studies have shown that adenosine was the preferential binding target within DNA, to determine the precise structure of DNA adducts we have synthesized a model adduct from this nucleoside to be used as a reference. Characterization by Fourier Transform infrared spectroscopy (FTIR), Near-IR FT Raman, and SERS of this adenosine-NMHE adduct suggests that the covalent binding occurs between the C(10) of the ellipticinium chromophore and the N(6) primary amine of the adenine. Finally, from hydrolysis of DNA adducts, their isolation by high-performance liquid chromatography, and the analysis of the SERS spectrum of the main adduct formed, it appears that the structure is probably the same as that proposed for the adenosine-NMHE adduct. © 1996 John Wiley & Sons, Inc.
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  • 91
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    Biospectroscopy 2 (1996) 
    ISSN: 1075-4261
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
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  • 92
    ISSN: 1075-4261
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: Isotope labeling has been used to assign the resonance Raman spectra of cytochrome c peroxidase, expressed in Escherichia coli [CCP (MKT)], and of the D235N site mutant. 54Fe labeling establishes the coexistence of two separate bands (233 and 246 cm-1), arising from the stretching of the bond between the Fe atom and the proximal histidine ligand, His175. These are assigned to tautomers of the H-bond between the His175 imidazole NΓH proton and the Asp235 carboxylate side chain: In one tautomer the proton resides on the imidazole while in the other the proton is transferred to the carboxylate. When Asp235 is replaced by Asn, the H-bond is lost, and the Fe-His stretching frequency is markedly lowered. Two new RR bands are produced, at 205 and 185 cm-1, as a result of coupling between the shifted Fe-His vibration and a nearby porphyrin mode; the two bands share the 54Fe sensitivity expected for Fe-His stretching. C=C stretching and CβC=C bending vibrations have been separately assigned to the 2- and 4-vinyl groups of the protoheme prosthetic group via selective vinyl deuteration. In the acid form of the enzyme, the frequencies coincide for the two vinyl groups, at 1618 cm-1 for the C=C stretch, and at 406 cm-1 for the CβC=C bend. However, the 2-vinyl frequencies are elevated in the alkaline form of the enzyme, to 1628 cm-1 for C=C stretching, and to 418 cm-1 for CβC=C bending, while the 4-vinyl frequencies remain unshifted. Thus, the acid-alkaline transition involves a protein conformation change that specifically perturbs the 2-vinyl substituent. This perturbation might be a reorientation of the vinyl group, or an alteration of the porphyrin geometry that affects the porphyrin-vinyl coupling. The perturbation is attenuated when CO is bound to the enzyme; the C=C frequency is then unaffected in the alkaline form, while the CβC=C bending frequency is shifted to a smaller extent (412 cm-1). This attenuation is probably linked to inhibition of distal histidine binding to the heme Fe in the alkaline form when the CO is bound. © 1996 John Wiley & Sons, Inc.
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  • 93
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    Biospectroscopy 2 (1996), S. 413-414 
    ISSN: 1075-4261
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 94
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    Biospectroscopy 2 (1996) 
    ISSN: 1075-4261
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 95
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    Biospectroscopy 2 (1996), S. 125-129 
    ISSN: 1075-4261
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: Hole-burning and fluorescence-line-narrowing (FLN) spectroscopies are used to generate high-resolution vibronic spectra of TO-PRO-3 iodide in a glycerol/water glass. The excited-state vibrational frequencies are tabulated along with the associated Franck-Condon factors (FCFs). It is also shown that hole-burning efficiencies are comparable for the free dye and the dye bound to DNA. © 1996 John Wiley & Sons, Inc.
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  • 96
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    Biospectroscopy 2 (1996), S. 131-141 
    ISSN: 1075-4261
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: This paper reports on studies of the IR and UV/Vis spectra of propranolol and three of its fluorinated derivatives (namely, trifluoroethyl-propranolol, pentafluoropropyl-propranolol, and heptafluorobutyl-propranolol). The semi-empirical method, AM1 was used to optimize the structures. In the case of IR spectra the calculated and experimental frequency bands for particular assignments of modes overlap significantly. For the UV spectra main peaks of the theoretical spectra are underestimated by about 60 nm on the average from the experimental spectra, perhaps because the estimations were done in different phases, gaseous for the theoretical and ethanol for the experimental. The UV spectra of the four compounds are very similar. © 1996 John Wiley & Sons, Inc.
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  • 97
    ISSN: 1075-4261
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: Modified nucleoside contributions to tRNA's binding of mRNA codons are not differentiated from that of tRNA's interactions with the ribosome in ribosome-mediated binding assays. Circular dichroism spectrapolarimetry (CD) proved to be a sensitive method for detection of anticodon-codon interaction in the absence of ribosomes. The binding of the yeast tRNAPhe anticodon stem and loop (tRNAPheAC) to coding triplets was studied. Unmodified tRNAPheAC interacted specifically with r(UUC). Mg2+ was not critical to codon binding. Codon binding was accompanied by a change in anticodon domain conformation that was stable below 17°C. In contrast, tRNAPheAC with m5C40 has an anticodon loop closed by two intra-loop base pairs and did not bind codon. The importance of the ribose 2′OH relative to that of modified nucleosides and Mg2+ was investigated using DNA analogs of tRNAPheAC, tDNAPheAC. An open anticodon loop conformation and Mg2+ binding were necessary for tDNAPheAC interaction with d(TTC). The binding of d(TTC) was accompanied by a change in tDNAPheAC conformation, stable below 17°C. With d(m1G)37 maintaining an open loop conformation, tDNAPheAC base paired with d(TTC), but not with d(TCTTC), providing the first physical evidence of how position-37 modifications may maintain the translational reading frame. Position-37 modifications occur in 72% of tRNAs; only one third promote an open loop by negating intra-loop base pairing. Thus, position-37 modifications may have evolved to impart an open and dynamic anticodon loop conformation that is important for effective and correct codon binding. © 1996 John Wiley & Sons, Inc.
    Additional Material: 9 Ill.
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  • 98
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biospectroscopy 2 (1996), S. 225-232 
    ISSN: 1075-4261
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: FT Raman spectra of avidin, streptavidin, and of the two anhydrous biotin complexes were obtained by excitation in near infrared (NIR). As far as avidin and the avidin-biotin complex are concerned, the excitation in NIR did not change the main features of the spectra compared with those previously obtained by visible excitation. However, the intensity of Trp bands did not change due to the formation of the complex when excited by NIR excitation, whereas an intensity increase was observed by 514 nm excitation. The percentages of secondary structure of the two proteins and the biotin complexes were obtained from the Raman spectra. The vibrational results indicate that as a consequence of the interaction with biotin, the percentages of β-sheet conformation of the proteins decrease whereas the percentages of α-helix conformation increase. The observed changes of the conformation of streptavidin induced by biotin interaction are comparable with those obtained with avidin; this fact confirms that the type of the binding should be similar for the two molecules. Moreover, as a result of the biotin binding, the hydrophobicity of the environment of the Trp residues of streptavidin slightly increases according to the increase in intensity of the 1360 cm-1 component. This result could suggest that the streptavidin-biotin complex is stabilized mainly by hydrophobic interactions. © 1996 John Wiley & Sons, Inc.
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  • 99
    ISSN: 1075-4261
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: Age related changes in the lipid composition of human lens membranes have been documented and could be responsible for alterations in the function of lens membranes. To establish age related lipid composition-membrane structure relationships, we have examined spectroscopically the hydrocarbon chain structure of lipid membranes from human lens cortex and nucleus 0-95 years of age. Lipid membranes were extracted from human lenses using a monophasic methanolic extraction. The lipid composition of these membranes was determined by 31P-NMR and has already been reported. Fourier transform near-infrared Raman and Fourier transform infrared spectroscopies were used to determine human lens lipid structure. Lipid compositional differences were related to membrane structure. The frequency corresponding to the CH2 symmetric stretching band was found to increase with age in lipid samples from all regions of the lens. The frequency was used to estimate lipid hydrocarbon order. Lipid order was found to increase with age and was not significantly different for lipids extracted from the cortex compared to those from the nucleus. These results were confirmed qualitatively by comparing the height of the 2880 cm-1 band with the height of the 2850 cm-1 Raman band. Increased lipid order with age was also confirmed by the analysis of the C(SINGLE BOND)C stretching bands. Lipid hydrocarbon chain order increased linearly with increasing sphingomyelin content and decreased linearly with increasing phosphatidylcholine content. This trend, similar to that observed in other types of membranes, suggests that these two lipids may play a role in modulating lipid order. © 1996 John Wiley & Sons, Inc.
    Additional Material: 6 Ill.
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  • 100
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biospectroscopy 2 (1996), S. 143-153 
    ISSN: 1075-4261
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: Fourier-transform infrared (FTIR) microspectroscopy, combined with Principal Component Analysis (PCA), was applied in the study of exfoliated cervical cells from 272 patients. Six spectra were recorded for each patient, and these were visually sorted into two types (type 1 and type 2), based on their profiles. Spectra designated type 1 exhibited a profile characteristic of normal epithelial cells, with intense glycogen bands at 1022 cm-1 and 1150 cm-1, and a pronounced symmetric phosphate stretch at 1078 cm-1. Spectra designated type 2 exhibited features suggestive of dysplastic or malignant transformation, with pronounced symmetric and asymmetric phosphate modes and a reduction in glycogen-band intensity.Of the 272 patients, 68.6% of samples exhibited only type 1 profiles for all six recorded spectra, 29.4% of samples yielded at least one type 2 spectrum in any of the six recorded spectra and 2% of samples were inconclusive. Of the 68.6%, 86% were diagnosed normal by Pap smear with no follow up biopsy ordered, 7% were diagnosed abnormal by biopsy, 5% normal by biopsy and 2% were still inconclusive. For the remaining 29.4% of classified samples, 71% had shown an abnormal Pap result. These 71% were subsequently biopsied, and 87% were confirmed abnormal. The association of type 2 spectra and abnormality was further corroborated by spectra of cultured malignant cells from the HeLa cell line that displayed a profile similar to type 2 spectra in the 1300-950 cm-1 region. PCA decomposition using a reduced data matrix resulted in a score plot that showed general separation of the visually categorised spectra. This study demonstrates the potential of automated FTIR cervical screening technology in the clinical environment. © 1996 John Wiley & Sons, Inc.
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