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  • Electronic Resource  (482)
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  • Analytical Chemistry and Spectroscopy  (212)
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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 20 (1997), S. 10-16 
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Purge and Trap ; Flavors ; Wine ; Polar analytes ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: (not readable) fully autimated purge and trap system has been developed for (not readable) detemination of volatile wine components. The proposed system consists of sampler, a purge and trap instrument, and a GC, (not readable) steps, from the uptake of the infiltrated wine from the sampler (not readable) to the printout of the intergrated chromatograms, proceed(not readable), Typical problems occurring when analyzing polar analytes by the classical purse and trap approach have been specifically addressed. The system has been desiggned to handle such difficult (not readable) analytes. Efforts have been made to improve the reproducibility and the carry-over of these analytes. The measures adopted include: thorough rinsing and subsequent conditioning of the P + T parger; elimination of matrix effects by dilution and high salt (not readable); tight specification of purge relevant parameters; split-inter-(not readable) to improve GC retention time reproducibility.
    Additional Material: 7 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 20 (1997), S. 24-28 
    ISSN: 0935-6304
    Keywords: GC-MS ; Headspace sampling ; On-column injection ; No column replacing ; Reversed carrier gas flow ; Honey aroma compounds ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The paper describes a capillary GC/MS hardware arrangement allowong either:(a)on-line injection of sample of gases and vapors coming from dynamic headspace or purg & trap samplers and their subsequent cryofocusing/thermal desorption prior to the analytical capillary column (first column):(b)direct injection of liquid samples through a cold on-column injector into a second analytical column (counted in series with the first).Chromatographic profiles of acacia honey aromas provide condirmation of the suitability of this system.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 20 (1997), S. 34-38 
    ISSN: 0935-6304
    Keywords: Micellar electrokinetic capillary chromatography, MECC ; Algal toxins ; Microcystin LR, YR, RR ; Nodularin ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Recent methods employed for the analysis of algal toxins have focused on high performance liquid chromatography. However these methods suffer from poor resolution, poor efficiency, and long analysis times. This study involves the investigation of a number of toxins including nodularin, microcystin LR, YR, and RR which are cyclic peptides produced by strains of blue-green algae. The electroseparation mode was micellar electrokinetic capillary chromatography (MECC) using a borate buffer containing sodium dodecyl sulfate (SDS) as the surgactant of choice. The method was optimized with standard toxin compounds and employed for the screening opf toxins in supercritical fluid extracts (SFE) of freeze-thawed algal scum samples.
    Additional Material: 4 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 20 (1997), S. 47-49 
    ISSN: 0935-6304
    Keywords: Capillary gas chromatography ; Atomic emission detection ; On-column injection ; Splitless injection ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 20 (1997), S. 39-45 
    ISSN: 0935-6304
    Keywords: Solud-state NMR spectroscopy ; 1H MAS-only technique ; New stationary phases ; π-π interactions ; Separation of PAH's ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Four new stationary phases for HPLC were prepared by modifying silica gel with a trifrnctional aminoalkyl silane. A conjugated π-electron system was linked to the amino group either directly or with a carboxylic anhydride as a spacer in between. Characterization and dynamic measurements of the new stationary phases were performed by solid state NMR spectroscopy. The results of the 29si and 13C CP/MAS techniques were compared with the recently developed 1H MAS-only technique. Despite strong homonuclear dipole-dipole interactions it was possible to obtain well resolved 1H MAS spectra of those stationaru phases with a high degree of crosslinking. Limited mobility of the aromatic ligand fragments is common for all examined stationaryu phases.The chromatographic properties of the new phases were tested by their ability tio sepatate a mixture of eight PAHS. It could be shown that the π-π interaction mechanism is responsible for the separation of the eight PAHs, because the elution order of the PAHs did not changem despite the use of both a nonpolar mobile phase (n-heptane) and a polar mobile phase (methanol/ water mixture).
    Additional Material: 8 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 20 (1997) 
    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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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 20 (1997), S. 62-66 
    ISSN: 0935-6304
    Keywords: Artemisinin ; Artemisinic acid ; Capillary supercritical fluid chromatography ; Packed supercritical fluid chromatography ; Evaporative light scattering detector ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Artemisinin (an antimalarial compound) and its bioprecursor artemisinic acid, present in the plant Atemisia annua L., were analyzed by supercritical fluid chromatography (SFS) using capillary and packed columns, coupled respectively with a flame ionization detector (FID) and an evaporative light scattering detector (ELSD). Both methods were optimized and validated with columns of different polarity in order to separate artemisinin and artemisinic acid. Analytical results were comparable, but the paced SFC-ELSD method was faster. Indeed, artemisinin and artemisinic acid were separated with an aminopropyl silica column in less than 8 minutes instead of about 25 minutes by capillary SFS. Contrary to conventional gas and liquid chromatography coupled to an UV-visible detector, SFS methods determined both compounds directly, without degradation and/or derivatization in the concentration range expected in the plant material. Results obtained on plant extracts by capillary SFS-FID and packed SFS-ELSD were confirmed by GC-MS.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 20 (1997), S. 72-76 
    ISSN: 0935-6304
    Keywords: Capillary zone electrophoresis ; Alkaline borate buffer ; UV detection ; Unsaturated acidic xylooligosaccharides ; Alditol derivatives ; 4-Deoxy-L-threo-hex-4-enopyranosyluronic acid ; Hexenuronic acid ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several acidic xylooligosaccharides containing unsaturated “hexenuronic acid” units, i.e. 4-deoxy-L-threo-hex-4-enopyranosy-lurinic acid (4-ΔU) units, were separated as their alditol derivatives by capillary zone electrophoriesis in 438 mM borate buffer (pH 10.3) and were detected selectively at the μM level on-column UV detection at 232 nm. These acidic oligosaccharides were obtained from birch and pine kraft pulps on enzymatic hydrolysis with endoxylanases and subsequent treatment with other Trichoderma reesei enzymes. Under the conditions empolyed, acidic 4-ΔU-containing xylooligosaccharides with a molecular size renging from trisaccharides up to nonasaccharides could be separated. Oligosaccharides with higher molecular mass were detected first. Two 4-ΔU-xylotetraose isomers, with the 4-ΔU-group linked to different xylose units in the iligosaccharide backbone, could be resolved from each other with a resolution of about 1. By using a disaccharide (4-ΔU α-(1 → 4) linked to N-acetyl glucosamine) as a model compound the minimum detectable concentration was determined as 10 μM.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 20 (1997), S. 81-84 
    ISSN: 0935-6304
    Keywords: Gas chromatography-atomic emission detection (GC-AED) ; Gas Chromatography-mass spectrometry(GC-MS) ; Amitraz residues ; Hoeny ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Capillary gas chromatography in combination with atomic emission and electron impact-chemical ionizaion mass spectrometry detectors have been used to detect amitraz degradation products in honey storage, characterize their structure, and evaluate their occurrence over a 100 day peroid. To this end, honey samples were extracted with an 8:2 v/v n-hexane/acetone mixture. Amitraz was found to be rapidly decomposed into five related compounds, of which N-(2,4-dimethylphenyl)formamide was the most abundant and persistent.
    Additional Material: 4 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 20 (1997), S. 29-33 
    ISSN: 0935-6304
    Keywords: LSS model ; Whey proteins ; RP-HPLC of proteins ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The behavior of bovine whey proteins in Reversed-Phase High Performance Liquid Chromatography (RP-HPLC) systems has been investigated. The Linear Solvent Strength (LSS) model has been applied to the separation of these proteins studying how their retention time and band broadening change when different gradient parameters are modified. From our results it is deduced that the LSS model describes the behaviour of the whey proteins in RP-HPLC. Also, it seems that ts (the retention time for non-retained solutes) depends on the size of these proteins. The good fit observed between experimental data and the equations deduced from the LSS model allows the prediction of a gradient shape that permits a rapid analysis of the above mentioned proteins.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 11
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 20 (1997), S. 85-93 
    ISSN: 0935-6304
    Keywords: Capillary gas chromatography ; Modified cyclodextrin phases ; Chiral organochlorines ; Biological samples ; Enantiomeric ratios ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Four chiral stationary phases containing modified cyclodextrines diluted in or chemically bonded to a non-chiral phase were used to resolve chiral organochlorine compounds such as α-hexachlorocyclohexane (α-HCH), perdeuterated α-HCH (α-PDHCH), β-and γ-pentachlorocyclohexene (PCCH), oxychlordane, cis-and trans-chlor- dane, cis- and trans-heptachlorepoxide, PCB 95, PCB 132, PCB 149, and Chiral tozaphenes.The elution order was determined by analyzing standards with known enantiomeric excesses.Furthermore, an internal standard was used to even out slight variations in the ratio of peak hights of enantiomers which were determined from injection to injection.None of the chiral stationary phases resolved all chiral organochlorine compounds. However, the β-TBDM(35% heptakis (6-O-t-butyldimethylsilyl-2,3-di-O-methyl)-β-cyclodextrin in OV 1701) column allowed the separation of all compounds under investigation except for PCB 95 and chiral toxaphenes.Emphasis was placed on the separation of as many as possible enantiomers on a chiral phase by application of one temperature program and with respect to unambiguous quantitation of biological samples such as bludder and liver of marine and terrestrial mammals.
    Additional Material: 7 Ill.
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  • 12
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 20 (1997), S. 122-122 
    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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  • 13
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 20 (1997), S. 123-124 
    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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  • 14
    ISSN: 0935-6304
    Keywords: Size-exclusion Chromatography ; Normal-phase liquid chromatography ; Gas Chromatography Coupled LC-LC ; Coupled LC-GC ; Cleanup and analysis ; Group-type separations ; Automation ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An on-line coupling of size-exclusion Chromatography (SEC), normal-phase liquid Chromatography (NPLC), and gas Chromatography (GC) for the characterization of complex hydrocarbon mixtures is described. The hyphenated system separates according to size, polarity, and boiling point. The use of size exclusion as the first separation step allows for the direct injection of complex (“dirty”) samples withont prior clean-up. SEC-NPLC coupling was realized using an on-line solvent evaporator based on fully concurrent solvent evaporation (FCSE) using a modified loop-type interface, vapor exit and co-solvent trapping. Complete reconcentration of the analytes was realized by the introduction of a cryogenic cold trap. For the subsequent hydrocarbon group-type separation an ammo-silica column with n-heptane as eluent was used. The NPLC-GC coupling was based on an on-column interface using partially concurrent solvent evaporation (PCSE) and an early vapor exit. Initial results obtained on the analysis of a residue from the atmospheric crude-oil distillation (a so-called long residue) are presented as an example of the enormous separation power of the SEC-NPLC-GC system. The application of the system for quantitative analysis has not yet been studied.
    Additional Material: 6 Ill.
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  • 15
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 20 (1997), S. 131-137 
    ISSN: 0935-6304
    Keywords: LC-GC hyphenation ; Sulfur chemlluminescence detector ; Organo-sulfur compounds ; Hydrodesulfurizalion ; Middle distillates ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A modified sulfur chemiluniinescence detector (SCO) has been interfaced to a HPLC-HRGC hyphenated system. This combination enables the full characterization and quantitation of the sulfur containing compounds in (heavy) middle distillate oil fractions (boiling range 150-450°C). The system is suited to identify and determine the various groups of orgaiio-sulfur structures such as: thiols + sulfides + thiophencs, benzothiophenes, dibenzothiophenes and benzo-naphthothiophenes. Within these groups a separation according to boiling point is accomplished. Therefore it allows the separation, identification and quantitation of a number of individual species, especially those which are refractory to hydrodesulfu-rization (HDS), such as 3-methyl-benzothiophene, 4-methyl-dibenzothiophene and -J,6-dimethyl-dibenzothiophene. The analysis of these groups and specific compounds is the key in understanding the kinetics of the chemistry involved in HDS. The complete instrumental set-up is fully automated by computer control. To suppress possible interferences and quenching of the sulfur response of the SCL from (large amounts of) hydrocarbons, it is aligned above the adapted flame ionization detector (FID) of the GC. This renders a sensitivity of the SCO for sulfur of 2 pg. s-1, which corresponds to a minimum detectable level for individual sulfur species in oil fractions for the complete system of 1 ppm (mg. kg-1) sulfur. Its linear dynamic range exceeds 105, which means that also untreated, high sulfur containing feedstocks can be analyzed directly. The selectivity of sulfur to carbon of the modified SCO exceeds 106. A number of HDS feedstocks and desulfurized products of different desulfurization levels have been analyzed with the system. From the analysis results the behavior of the refractory compounds in HDS can now be followed closely.
    Additional Material: 8 Ill.
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  • 16
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 20 (1997), S. 143-158 
    ISSN: 0935-6304
    Keywords: High resolution gas chromatography ; Column reproducibility ; Equivalent chain length values ; Fatty acid methyl ester analysis ; Capillary columns ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The equivalent chain length (ECL) values of the methyl esters of 83 defined fatty acids (FAs) have been determined by gas chromatog-raphy (GC) on three fused silica DB-WAX and three DB-1 columns. ECL values of further 46 FAs were calculated by different methods. Conditions of chromatography, methods of ECL values calculation and differences between ECL values on individual columns and between trans- and cis-isomers of corresponding FAs are also discussed.
    Additional Material: 3 Ill.
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  • 17
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 20 (1997), S. 1-9 
    ISSN: 0935-6304
    Keywords: GC-MS ; HPLC ; Non-ortho ; mono-ortho ; di-ortho substituted polychlorinated biphenyls (PCBs) ; 2-(1-Pyrenyl)ethyldimethylsilylated silica column ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A Method has been developed for the separation and enrichemen of there non-ortho, eight mono-ortho, and di-ortho substituted polychlorinated biphenyls (PCBs) from Aroclor formulations and environmental samples. The fractionation is accomplished using high performance liquid chromatography (HPLC) with a 2-(1-pyrenyl)ethyldimethylsilysily silca column. GC-MSD with an optimized temperature program was used for quantitation, Hexane, pentane, cyclohexane, iso-octane, and 2-propanol were tested as a mobile phase for the isolation of the thirteen target PCBs in a Aroclor 1242, 1254, and 1260 (1:1:1) misture, Pentane at room temperature with a slow rate of 0.7 ml/min is the condition of choice. The average recovery of thirteen target PCBs spiked in the Aroclor mixture is 99.5% with an average relative standard deviation of 4.5%. The average method detection limit is 8pg/μl. Targer PCBs in the reference solis, incinarator ash, and sediment samples were measured.
    Additional Material: 6 Ill.
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  • 18
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 20 (1997), S. 179-180 
    ISSN: 0935-6304
    Keywords: Enantiomers ; Chiral stationary phase ; Whelk-O ; Coelution ; Peak overlap ; 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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  • 19
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 20 (1997), S. 181-182 
    ISSN: 0935-6304
    Keywords: HRGC-MS analysis ; Volatile organic compounds ; Thermal desorption ; Air pollution ; 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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  • 20
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 20 (1997), S. 183-185 
    ISSN: 0935-6304
    Keywords: Capillary gas chromatography ; Ethylene glycol ; Migration ; Foods or food simulants ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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  • 21
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 20 (1997), S. 187-188 
    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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  • 22
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 20 (1997), S. 193-200 
    ISSN: 0935-6304
    Keywords: Splitless injection ; Vaporizing conditions ; Experimental design ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Splitless injection conditions were optimized by the use of experimental designs (2-level factorial and central composite designs). Modified parameters were: Type of liner, injection volume, solvent, temperature, splitless time. A prolonged splitless time, considered to be an important parameter, proved to be statistically insignificant. This leads to the conclusion that analytes can penetrate the dead volume between column entrance and split valve. To prevent any penetration of solvents, a small reversed split flow was introduced. It could be shown that this auxiliary flow allows an almost complete transfer of solvents. To further speed up the transfer process, a liner modification was proposed.
    Additional Material: 12 Ill.
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  • 23
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 20 (1997), S. 217-221 
    ISSN: 0935-6304
    Keywords: Capillary gas chromatography ; Headspace solid phase microextraction ; Retention index ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The applicability of the retention index system to hcadspacc solid phase microextraxtion (HS-SPME) was investigated. In headspace SPME, the two equilibria gas phase/matrix and fiber coating/gas phase have to he considered. In this paper the equilibrium fiber coating/gas phase is discussed separately to characterize it more detailed and to investigate several methodical aspects. Therefore, the different distribution constants Kfiber/gas of n-alkanes, which were used for reference compounds, were related to their Kováts retention indices. The validity of the derived linear relationship log Kfiber/gas versus retention index I is demonstrated for various examples. This relation is helpful for the assessment of distribution constants of substances not available and for the choice of a suitable fiber coating. Furthermore, quantification of analytes in the gas phase can be done without authentic substances.
    Additional Material: 2 Ill.
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  • 24
    ISSN: 0935-6304
    Keywords: LC-GC ; Partially concurrent solvent evaporation ; Organochlorines ; PCBs ; Fatty matrices ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Off-line normal-phase LC has been used for the clean-up of compounds in our laboratory for several years. On-line coupling of this LC system, which typically yields 12 ml fractions, is not possible due to its large fraction volume. The maximum transfer volume in on-line LC-GC/ECD is approx. 300 μl. Therefore down-scaling of the LC system was attempted in order to reach these low fraction volumes. Miniaturization resulted in a 240 μ1 LC fraction containing the analytes of interest, which is transferred to GC/ECD via an on-column interface. Sensitivity requires that a minimum amount equivalent to 1-2 mg of sample should reach the GC detector; the selectivity is determined by the separation between the matrix and the last eluting target analyte.For the analysis of fatty samples, limitations were observed in the separation of dieldrin from triglycerides. Other organochlorine compounds, e.g. polychlorobiphenyls (PCBs), the DDT group, HCB and the HCHs can be analyzed with RSDs of 2-4 % (n = 10) at concentration levels of sub-μ/kg in milk fat using a 3 μm Hypersil silica 50 × 1.0 mm i.d. LC column.
    Additional Material: 5 Ill.
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  • 25
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 20 (1997), S. 231-236 
    ISSN: 0935-6304
    Keywords: Gas chromatography/mass spectrometry (GC/MS) of oxindole alkaloids ; HPLC/MS of oxindole alkaloids ; Supercritical fluid extraction ; Oxindole alkaloids ; Uncaria Tormentosa ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Supercritical fluid extraction of oxindole alkaloids from Uncaria Tormentosa is described. The extraction was performed with supercritical carbon dioxide alone and with supercritical carbon dioxide modified with 10% metanol, and the extracts were analyzed by GC/MS and HPLC/MS.
    Additional Material: 8 Ill.
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  • 26
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 20 (1997), S. 227-230 
    ISSN: 0935-6304
    Keywords: Ion chromatography ; Bulk Acoustic Wave (BAW) detection ; Salicylate ; Human serum ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Salicylate is a hydrolysis product of salicylate-containing drugs (such as aspirin) in patients' blood. Monitoring of this ion in blood is helpful for diagnosing of overdosage of these drugs. The present paper describes an ion chromatography (IC) method developed for determination of total salicylate in human serum, in which a hulk acoustic wave (BAW) sensor was used as detector; 0.5 mmoI/L sodium carbonate (Na2CO3, pH 8.5) served as mobile phase. Interference in the determination was negligible. The method is simple, rapid, accurate, and precise. Serum salicylate was analyzed using both the proposed IC-BAW method and the classical Trinder spec-trophotometric method, and the results showed that the two method agreed well.
    Additional Material: 3 Ill.
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  • 27
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 20 (1997), S. 237-241 
    ISSN: 0935-6304
    Keywords: Cimicifuga seed oil ; Δ5-cis fatty acids ; Capillary gas chromatography ; Phylogenetic evolution ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A range of unusual fatty acids with cis-5-unsaturation had been reported in the seed oil of Caltha palustris. Seed oils of Cimicifuga spp. have now been found to contain the same unusual fatty acids as are present in Caltha, plus several other minor fatty acids to give a more complex and more unsaturated seed oil fatty acid pattern.The gas chromatographic fatty acid patterns found seem to be consistent and chemotaxonomically significant, because essentially the same pattern was found in several species of the genus Cimicifuga. These findings may shed a new light on the relation of Cimicifuga to Caltha, and to other genera in the plant family Ranunculaceae.The situation is illustrated by capillary GLC seed oil fatty acid methyl ester “fingerprints” obtained from Cimicifuga and Caltha, and is discussed in relation to other genera. The occurrence in nature of several of these unusual fatty acids, and their chemotax-onomic significance is discussed. The close relation of GLC fatty acid patterns of Caltha and Cimicifuga could indicate monophyly and/or their belonging to the same tribe or subtribe. These observations are not in accordance with the phylogenetic systematic schemes of the genera in this plant family as published by various authors.
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  • 28
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    Journal of High Resolution Chromatography 20 (1997), S. 245-248 
    ISSN: 0935-6304
    Keywords: HPLC ; Enriched foods ; Simultaneous determination ; Vitamin analyses ; B-group vitamins ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The control of the enrichment levels in foods is difficult, due mainly to the lack of appropriate analytical methodologies. The amounts of the five B-group vitamins (nicotinamide, nicotinic acid, ribofla-vin, thiamin, and pyridoxine) have been determined in enriched Brazilian foods by a high-performance liquid chromatography (HPLC) method. Fifty products, such as biscuits, liquid and dry milks, flavored milk drinks, flour, macaroni, and cereals were analyzed. Some products showed the amounts declared on the package. Although some slight quantitative variations were shown in the biscuits, one showed levels of riboflavin 35% lower than the value declared. Of five different corn cereal brands, only one showed the declared vitamin content, the others showing levels 30 % lower than that declared. No B-group vitamins were detected in one brand of enriched macaroni, except for the nicotinic acid naturally present in the flour. On the other hand, one flavored milk drink exhibited vitamins levels 200% higher than the amounts declared and one milk drink mix presented thiamin, riboflavin, and nicotinamide levels 3 to 5 times greater than stated. These results suggest an absence of control of the amount of vitamins in enriched foods.
    Additional Material: 2 Ill.
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  • 29
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    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 20 (1997), S. 257-260 
    ISSN: 0935-6304
    Keywords: Enantioselective GC ; Diterpene Hydrocarbons ; Cyclodextrin derivatives ; Essential oils ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Enantiomeric diterpene hydrocarbons were isolated from different plants and identified by mass spectrometric and NMR investigations. All enantiomeric pairs could be resolved by capillary gas chromatography using either heptakis(2,6-di-O-methyl-3-O-pen-tyl)-β-cyclodextrin or heptakis(6-O-tert-butyldimethylsilyl-2,3-di-O-methyl)-β-cyclodextrin as chiral stationary phases.
    Additional Material: 3 Ill.
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  • 30
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    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 20 (1997), S. 242-244 
    ISSN: 0935-6304
    Keywords: Capillary zone electrophoresis ; Feed flavor enhancer ; Quantitation ; Inosine 5′-monophosphate ; Guanosine 5′-monophosphate ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A capillary zone clectrophoresis method was developed for the determination of IMP and GIMP, commonly used as flavor enhancers in poultry feed, in a real sample of complex composition. A baseline separation of inosine 5′-monophosphate and guanosine 5′-monophosphate was achieved within 10 min and the other components in the sample did not interfere with the separation. Quantitative results obtained from pig feed samples are presented. The separation conditions and experimental reproducibility are also discussed.
    Additional Material: 3 Ill.
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  • 31
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    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 20 (1997), S. 275-283 
    ISSN: 0935-6304
    Keywords: Purge-and-Trap ; GC-FTIR GC-MS ; Aroma Strawberries ; Fragaria anannassa ; Principal components ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The aroma composition of three different Fragaria anannassa cul-tivars Selva, Chandler, and Osso Grande) is studied by purge-and-trap HRGC and the components identified by MRGC-MS and HRGC-FTIR. The chromatographic aroma profiles from four different maturation stages in each variety are compared and the similarities accessed by principal component analysis (PCA). The contents in n-hexanal and hex-2(Z)-enal are characteristic features of the green stage in the three varieties where the content differences in methyl, ethyl, and butyl acetates act as typifying variables among varieties. Ethyl acetate acts as an important differentiation variable for the Selva variety. In the mature stage, the three cultivars may be distinguished from each other through their relative contents of methyl and ethyl 2-methylbutyrate (Selva), methyl 2-methyl-butyrate, methyl butyrate (Chandler), methyl and ethyl butyrates, and methyl caproate (Osso Grande).
    Additional Material: 6 Ill.
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  • 32
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    Journal of High Resolution Chromatography 20 (1997), S. 270-274 
    ISSN: 0935-6304
    Keywords: Capillary electrophoresis ; Migration ; Substituted phenolic additives ; Antioxidants ; Food contact materials ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method has been developed to determine 11 phenolic antioxidants in the food simulants distilled water, 3% acetie acid, and 15% ethanol, using; micellar capillary electrophoresis (MCE). All the phenols could he analyzed within 35 min. The analytical recovery from spiked simulants was 80 to 119% except for 2,6-di-tert-butyl-4hydroxytoluenc (BHT) and octyl gallate, which could not be recovered from 3% acetic acid simulant. Calibration graph correlation coefficients for the 11 phenols were 0.982 to 0.999. Limits of detection (LoDs) were from 2.8 to 8.6 mg/L. These LoDs are well below European Union migration limits for these substances. It is concluded therefore that MCE offers a rapid and reliable analysis for the control of migration from plastics intended for food contact which employ these phenols as antioxidants.
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  • 33
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    Journal of High Resolution Chromatography 20 (1997), S. 284-288 
    ISSN: 0935-6304
    Keywords: HRGC/ECD ; HPLC separation ; 1H-NMR quantitation ; Calibration standards ; Individual components of pyrethrins ; Indoor matrices ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An HRGC/ECD method is presented which permits the identification and quantitation of individual components of pyrethrins (cinerin I, jasmolin I, pyrethrin I, cinerin II, jasmolin II, pyrethrin II) in indoor matrices (airborne particles, house dust) after application of an agent containing pyrethrum. In order to prepare calibration standards for the individual components of the pyrethrum extract, the pyrethrins were isolated hy semi-preparative HPLC and their content and purity were determined by 1H-NMR spectroscopy.
    Additional Material: 7 Ill.
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  • 34
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    Journal of High Resolution Chromatography 20 (1997), S. 265-269 
    ISSN: 0935-6304
    Keywords: Capillary elcctrophoresis ; Micellar Electrokinetic Chromalography (MEKC) ; Dithiocarbamale(s) ; Thiocarbamate(s) ; Carhamate(s) ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Capillary elcctrophoresis (CE) was used for the qualitative and quantitative analysis of eleven compounds of the carbamate, thio-carhamate, and dithiocarbamate classes of pesticides. Micellar elec-trokinetic chromatography (MEKC) was employed for the separation of these substances. The analysis was performed using an uncoated fused silica column, in borate buffer containing SDS and 10% methanol at basic pH, and UV detection at 230 nm. The addition of methanol to the buffer increased the separation and affected intrinsic migration of analytes. The working standard solutions were prepared in acetonitrile/water 50:50. Although these compounds are structurally different, with a large spectrum of chemical properties, such as polarity and solubility, good separation and sensitivity were obtained. Moreover, good recovery of car-bamates was obtained from tap-water using a styrene-divinylben-zene polymer column with the solid phase extraction (SPE) technique.
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  • 35
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    Journal of High Resolution Chromatography 20 (1997), S. 298-299 
    ISSN: 0935-6304
    Keywords: Capillary zone electrophoresis ; Enantiomer separation ; Cyclodextrins ; Amphetamine ; Phenylephrine ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 36
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    Journal of High Resolution Chromatography 20 (1997), S. 300-301 
    ISSN: 0935-6304
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 37
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    Journal of High Resolution Chromatography 20 (1997), S. 301-301 
    ISSN: 0935-6304
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 38
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    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 20 (1997) 
    ISSN: 0935-6304
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 39
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    Journal of High Resolution Chromatography 20 (1997), S. 315-320 
    ISSN: 0935-6304
    Keywords: Capillary gas chromatography ; Gas chromatography-mass spectrometry ; γ-Linolenic acid ; Saussurea seed oil ; Silver ion TLC ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The plant family Compositae is known to produce a set of unusual fattly acids in their seed oil. Saussurea, a genus of the Compositae is less studied in respect to the fatty acid compsition of their seed oil. Only Saussurea candicans was reported to contain crepenynic acid (33%) as seed oil component.In continuation of our exploration of the portential of wild oil seeds, fatty acids in seed oils of seven Saussurea species (S. amara, S. salicifolia, S. lipschitzii, S. pseudoalpina, S. pricei, S. parviflora, and S. dorogostaiskii) growing in Mongolia a were investigated by means of capillary GLC on capiallary columns of different selectivity (Silar 5 CP and BPX 70).γ-Linolenic acid was found at levels up to 11% of the consitituent fatty acids of Saussurea spp. seed oils. This is the first time that γ-Linolenic acid has been found in members of the plant family Compositae. Moreover, the number, position and configuration of the double bonds in γ-linolenic acid and that of other fatty acids was additionally confirmed by silver ion thin layer chromatography and infrared spectroscopy. The occurence and distribution of γ-linolenic acid, which has found considerable interest for pharmaceutical and dietary use, may be of chemotaxonomical significance in the plant family Compositae.
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  • 40
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    Journal of High Resolution Chromatography 20 (1997), S. 305-309 
    ISSN: 0935-6304
    Keywords: HRGC ; GCMS ; XAD-2 ; Sesquiterpenes ; Sesquiterpenoids ; Volatile lipids ; Biomarkers ; Amazon ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to evaluate vloatile compounds, especiallly sesquiter-penoids, in environmental and geological samples a method was penoids, in environmental and geological samples a method was required to characterize these components when they occur at low concentrations. After fractionation of the total sample extracts by TLC the aliphatic fractions were analyzed by HRGC AND THE kovats indices of all resolved peaks were calculated and comkpared with indices of all resolved peaks were calculated and compared with those obtained for commercial standards. As final step, the fractions were analyzed by HRGC-MS and structures confirmed by comparison of their mass spectra with those of certified sesuiterpene standards. Additionally sesquiterpenoids present in the dissolved phase in water samples were concentrated by solid phase extraction using XAD-2 resin. In this initial study, recovery tests with the resin were carried out in order to evaluate its performance rather than validating the methodology.
    Additional Material: 4 Ill.
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  • 41
    ISSN: 0935-6304
    Keywords: Capillary GC ; Continuous liquid-liquid extraction ; Environmental applications ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The applicability of a liquid-liquid extraction system which is coupled on-line with a capillary gas chromatograph was studied for environmental and ecotoxicological analyses. The optimized and automated system was used for the determination of apolar and rather non-volatile organic compounds in aqueous samples. Relevant aspects of sample introduction, phase separation and selection of extraction solvent are discussed. Three routine-tipe applications are described, viz. an improved method for the determination of hexachlorocyclohexanes in ground water and the determination of the so-called NCC-ether and ACC-ether in ecotoxicological studies. Depending on the application studied, the concentration levels varied from 0.1 to 6000 μg/I, using ECD and/or FID detection. Typical coefficients of variation obtained with the total extraction-GC procedure were 2-25%.The system was found to be rugged, it saves time compared with set-ups involving off-line liquid-liquid extraction and considerably reduces the manual work load.
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  • 42
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    Journal of High Resolution Chromatography 20 (1997), S. 333-336 
    ISSN: 0935-6304
    Keywords: Relative retention values ; Pressure effects on relative retention ; Stationary liquid phase ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Equations have been obtained for the dependence of relative retention and retention indexes on average column pressure. The equations suggested conform well with experimental data. It was shown that limiting value of relative retention (at the pressure approaches zero) is an invariant retention value. The nature of the stationary liquid phase used and its film thickness have a substantial influence on the dependence of relative retention and capacity factor on the pressure.
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  • 43
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    Journal of High Resolution Chromatography 20 (1997), S. 343-346 
    ISSN: 0935-6304
    Keywords: Gas chromatographic analysis ; Mass spectrometry ; Purge-and-trap ; Gherkin ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 44
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    Journal of High Resolution Chromatography 20 (1997), S. 349-349 
    ISSN: 0935-6304
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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  • 45
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    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 20 (1997) 
    ISSN: 0935-6304
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 46
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    Journal of High Resolution Chromatography 20 (1997), S. 351-354 
    ISSN: 0935-6304
    Keywords: MDGC ; MCSS ; α-Ketol ; Sherry ; Solerone ; Biogenesis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The enantiomeric distrubution of solerone (5-oxo-4-hexanolide) 1, ethyl 4-hydroxy- 5-oxohexanoate 2, ethyl 5-hydroxy-4-oxohexanoate 3, 4-oxo-5-hexanolide 4, and solerol (5-hydroxy-4-hexanolide) 5 in sherry wines was determined by several HRGC techniques. While gas chromatography-mass spectrometry on chiral cyclodextrin phases (chiral GC-MS) prevented any racemization of α-ketols 2 and 3 caused by keto-enol tautomerization during analysis, multidimensional gas chromatography MDGC (coupled either by “live-T” switching or by “moving column stream switching” MCSS) led to rearranged constitutional-and stereoisomers. The stereochemical results are discussed regarding the biogenesis of sherry constituents 1-5.
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  • 47
    ISSN: 0935-6304
    Keywords: Enantioselective Multidimensional gas Chromatpgraphy-mass spectrometry (enantio-MDGC-MS) ; Methyl chloroformate (MCF) derivatization ; Inherited metabolic disease ; Maple syrup urine disease (MSUD) ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Maple Syrup Urine disease (USUD) is an autosomal recessive inherited metabolic disorder of branched-chain amino acid (L-valin, L-leucine, and L-isoleucine metabolism named after the characteristic smell of affected patients urine. MSUD is caused by a deficiency of the branched-chain α-keto acid dehydrogenase compex resulting in an accumulation of branched-chain aamino acids and the corresponding α-keto-and α-hydroxy acids in blood, urine and cerebrospinal fluid causing neurological damage and mental retardation. The enantioselective analysis of chiral MSUD metabolites and analysis of achiral compounds as corresponding N,O-methoxycarbonyl methyl esters by derivatization with methyl chloroformate (MCF) has been achieved simultaneusly by enantioselective multidimensional gas chromatography-mass spectrometry using heptakis (2,3-di-O-methyl-6-O-tert-butyl-dimethyl-silyl)-β-cyclodextrin as chiral stationary phase. Derivatization with MCF allows the analysis of the structurally different metabolitetes such as branched-chain-carboxylic-, α-oxo-, α-hydroxy- and α-amino acids in a single chromaatographic run. Mass selective detection immensely improves the unequivocaaal identification of metabolites even when they occur as trace compound. The described method allows a reliable screening of MSUD metabolites in patients' urine without time consuming sample preparation and is also suitable for label enrichment analysis without any methodical changes. During this investigation urine sample from three MSUD paatients were analyzed.
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  • 48
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    Journal of High Resolution Chromatography 20 (1997), S. 400-402 
    ISSN: 0935-6304
    Keywords: Electrokinetic chromatography ; Capillary electrophoresis ; Pseudostationary phase ; Colloidal silica ; Sol ; Uncharged compounds ; Nanoparticles ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 49
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    Journal of High Resolution Chromatography 20 (1997), S. 417-420 
    ISSN: 0935-6304
    Keywords: HPLC-MS ; Particle beam ; HRGC-MS ; Arbutus unedo L. ; Triterpenoids ; Allelopathy ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An extract fraction fruits of Arbutus unedo, L., was cleaned-up by column chromatography and shown by NMR to be a mixture of isomers that resists further attempts at separation by conventional chromatographic methods. High resolution gas chromatography-mass spectrometry (HRGC-MS) confirms the presence of triter-penoid isomers but does not allow separation of all the components. This can be improved by trimethylsilylation but the absence of molecular ions and the complex spectra are difficult to interpret. Complete separation can be achieved by high pressure liquid chro-matography (HPLC) coupled to a mass spectrometer by means of a particle beam interface (HPLC-PBMS). Four triterpene com-pounds are identified through analysis of the corresponding mass spectra: α-amyrin, β-amyrin, and Lupeol, have for the first time been identified in Arbutus unedo, L. Fruits. A new natural triterpene tentatively identified as olean-12-en-3β, 23-diol is described for the first time.
    Additional Material: 3 Ill.
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  • 50
    ISSN: 0935-6304
    Keywords: Reversed phase LC-GC ; Vaporizer/percolumn solvent split/gas discharge system ; Phthalates in water ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reversed phase liquid chromatography (RPLC) was coupled on-line to gas chromatography (GC) via the vaporizer chamber/preco-lumn solvent split/gas discharge interface outlined recently. Water-containing eluents were driven into a vaporizer chamber at 300°C by the LC pump. The Vapors were removed through an early vapor exist by the carrier gas. Solvent/solute separation occurred in hte retaining precolumn. Special attention was paid to the parame-ters determining the losses of the most volatile compounds. The oven temperature during transfer was lowered close to the dew point of the eluent (the temperature at which recondensation occurs) in order to maximise the retention power of the retaining precolumn. The dew point depends on the transfer rate, the gas flow rate, and the gas inlet pressure. Sometimes even better retention of the vola-tiles was observed at temperatures below the dew point, i.e. despite partial reconsideration. The method was applied to the analysis of phthalates in drinking and surface waters. The detection limits, using MS, were 5-10 ng/l.
    Additional Material: 10 Ill.
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  • 51
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    Journal of High Resolution Chromatography 20 (1997), S. 427-430 
    ISSN: 0935-6304
    Keywords: Gas Chromatography ; High density polyethylene ; Recycled plastics ; Contaminants ; Food packaging ; Migration ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: High Density polyethylene regranules reprocessed from separated household waste collection were investigated for migratable con-taminants which were not present in virgin material. Although the material originated from different European reprocessors, the de-tected recycling-specific compounds were similar in most of the investigated samples. At a chosen threshold concentration of 0.5 μg/g more than 70 compounds were tentatively identified. Aroma compounds and preservatives were found in the range of 0.5 to 10 μg/g. Limonene, di(ethylhexyl) phthalate, and the isopropyl esters of myristic and palmitic acids were detected in concentrations up to 200 μg/g. These compounds were found in almost all the regranules. Most of the substances identified are constituents of personal hygiene products and cleaning agents and are therefore absorbed by the package during the storage. Owing to European food legislation and German cosmetics regulations, the use of such recycling packaging material appears suitable only for filling with technical products.
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  • 52
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    Journal of High Resolution Chromatography 20 (1997), S. 431-436 
    ISSN: 0935-6304
    Keywords: Supercritical Fluid Extraction ; High resolution gas chromatography-mass spectrometry ; Volatile compounds ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effects of temperature and solvent density on the characteristics of the extracts obtained from supercritical fluid extraction (SFE) of the volatile compounds from Brazilian rosemary (Rosamarinus officianalis L., Labiatae) using carbon dioxide (CO2) as solvent were investigated. The experiments were performed in a semi-batch laboratory scale home-made unit at two temperatures, viz. 310.15 and 320.15 K, over the pressure range of 100-160 bar. This study allowed to determine the crossover point and the maximum solubility of the oil. The products were analyzed by HRGC-MS, and compounds grouped in three different classes according to their molecular mass distribution in order to evaluate the influence of the variables studied on the characteristics of the extracts. The model proposed by Sovová was adopted in an attempt to interpret the mass transfer phenomena in the extraction process.
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  • 53
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    Journal of High Resolution Chromatography 20 (1997), S. 447-450 
    ISSN: 0935-6304
    Keywords: Large Volume cold on-column injection ; Full scan quadrupole mass spectrometry ; Organochlorine and organophosphorus pesticides ; Environmental analyses ; Water ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 5 Ill.
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  • 54
    ISSN: 0935-6304
    Keywords: Capillary gas chromatography ; Temperature programmed gas chromatography ; Modelling of separation ; Carrier gas flow ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A second-order non-linear partial different equation was derived to describe the dependence of carrier gas pressure in the column on the column distance and the time under temperature programmed conditions. This equation was solved numerically by the modified finite difference method for various column parameters. Constant inlet and outlet pressures were used as boundary conditions. The retention times calculated on assumption of a constant pressure profile along the column. Significant differences between retention times of corresponding solutes calculated by the two methods were found, especially when relatively long columns(L〉50m) with small internal diameter(d〈0.3mm)and high temperature program rates (r〉5°/min)are used.
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  • 55
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    Journal of High Resolution Chromatography 20 (1997), S. 456-458 
    ISSN: 0935-6304
    Keywords: HPTLC ; Simultaneous determination ; Column extraction ; Purine alkaloids ; Daily foods ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
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  • 56
    ISSN: 0935-6304
    Keywords: Capillary GC ; Enantiomer resolution ; Chiral stationary phase ; Derivated cyclodextrins ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Three new β-cyclodextrin derivatives, heptakis(6-O-isopropyldi-methylsilyl-2,3-di-O-ethyl)-β-cyclodextrin, heptakis(6-O-thexyldi-methylsilyl-2,3-di-O-ethyl)-β-cyclodextrin, and heptakis(6-O-cy-clohexyldimethyl-2,3-di-O-ethyl)-β-cyclodextrin (IPDE-β-CD, TXDE-β-CD, and CHDE-β-CD), were synthesized and the enan-tioselectivities of these three CD derivatives and heptakis(6-O-tert-butyldimethylsilyl-2,3-di-O-ethyl)-β-cyclodextrin (TBDE-β-CD) were compared for GC separation of a range of chiral test com-pounds. In particular TXDE-β-CD showed much higher enentio-selectivity than TBDE-β-CD. Enentioselectivities of IPDE-β-CD and CHDE-β-CD are somewhat lower than that of TXDE-β-CD and CHDE-β-Cd are somewhat lower than that of TXDE-β-CD. These observations are indicative of significant effects of subtle changes in the structure of the 6-O-substituent on the enantioselec-tivity of the β-CD derivatives. The difference in enantioselectivities of the 6-O-substituted CD derivatives were explained in terms of relative contributions of the effects of hydrophobicity and steric hindrance of the substituent to the inclusion process. CHDE-β-CD showed the lowest enantioselectivity among the threederivatives. It is likely that the unfavorable steric hindrance of the bulky cyclo-hexyl group plays a greater role than the favorable hydrophobicity effect of the cyclohexyl group in the inclusion process in CHDE-β-CD. IPDE-β-CD showed lower selectivity than TXDE-β-CD and TBDE-β-CD. In the case of these CD derivatives having acyclic substituents the relative hydrophobicity of the substituent seems to be a dominant factor affecting the inclusion process. Isopropyl groups factor affecting the inclusion process. Isopropyl groups are less hydrophobic than thexyl and tert-butyl groups.
    Additional Material: 4 Ill.
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  • 57
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    Journal of High Resolution Chromatography 20 (1997), S. 471-481 
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Carrier gas ; Gas viscosities ; Kinetic theory of gases ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: After describing simplified equations exspressing the temparature dependency of the viscosity of carrier gases (helium, nitrogen and hydrogen ) relative to a base value, absolute relationships based on the kinetic theory of gases are discussed. Comparative data obtained using various calculation methods are given and are compared to measured values. Based on the kinetic relationshipsm, of viscosity. Finally, the influence of pressure on the viscosity is also briefly discussed. As a supplement, Viscosity data are tabulated for the three gases in the range of 0°C to 400°C in increments of 2 K, calculated using the kinetic relationships.
    Additional Material: 3 Ill.
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  • 58
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    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 20 (1997), S. 487-492 
    ISSN: 0935-6304
    Keywords: Gas chromatography with thermionic-selective detection ; Solid-phase microextraction ; Organophosphorus pesticides ; Water analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This paper describes the extraction of 49 organophosphorus pesti-cides (OPPs) from water samples using solid-phase microextraction (SPME). Three fibers, including a 15-μm XAD-coated fiber, a 85-μm polyacrylate-coated fiber, and a 30-μm polydimethylsilox-ane-coated fiber (PDMS), were evaluated here. The effects of stirring and the addition of NaCl to the sample were examined for the polyacrylate-coated fiber. The precision of the technique was examined for all three fibers and the extraction kinetics were investigated using the XAD- and polyacrylate-coated fibers. With some exceptions, the XAD- and polyacrylate-coated fibers performed better than the PDMS-coated fiber. The superiority of the XAD-nd polyacrylate-coated fiber. The superiority of the XAD- and polyacrylate-coated fibers over the PDMS-coated fibers can be attribuibuted to the aromatic functionalities of the XAD and the polar functionalities in the polyacrylate. The relatively high percent RSDs indicate that the SPME technique needs to be further refined before it can be used for anything other than screening. A more effective form of agitation than mechanical stirring may be neccessary to reduce variability and achieve a faster equilibrium between the sample and the SPME fiber.
    Additional Material: 8 Ill.
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  • 59
    ISSN: 0935-6304
    Keywords: Cyclodextrin derivatives ; Enantiomer micropreparative GC ; Thick-film wide-bore columns ; Column loading capacity ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Preliminary results on thick-film wide-bore (0.53mm i.d.) columns for GC preparation of pure enantiomers are described. In particular the loading capacity for several racemates of a 3μm, 30% 2,6-di-O-methyl-3-O-Pentyl-β-CD/OV1701 column and of a 2 μm, 30% 2,3-di-O-acetyl-6-O-dimethyl-t-butylyl-β-CD/PS-086 collumn were determined. Consideration is also given to the relation-ship between resolution values of two enantiomers on anayltical columns and their loading capacity and scaling-up to the corresponding micropreparative columns.
    Additional Material: 4 Ill.
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  • 60
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    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 20 (1997), S. 507-510 
    ISSN: 0935-6304
    Keywords: Dynamic head space ; Quantitation ; Virgin olive oil ; Lipoxygenase pathway ; Green sensory attributes ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
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  • 61
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    Journal of High Resolution Chromatography 20 (1997), S. 511-515 
    ISSN: 0935-6304
    Keywords: Supercritical fluid extraction (SFE) ; Preparative SFE ; High resolution gas chromatography (HRGC) ; Gas chromatography coupled with mass spectromestry (GC/MS) ; Peumus boldus Molina ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 5 Ill.
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  • 62
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    Journal of High Resolution Chromatography 20 (1997), S. 519-519 
    ISSN: 0935-6304
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 63
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    Journal of High Resolution Chromatography 20 (1997), S. 520-520 
    ISSN: 0935-6304
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 64
    ISSN: 0935-6304
    Keywords: Chiral discrimination ; 2,3,6-Tri-O-methyl)-β-cyclodextrin ; Capillary Gas Chromatography ; ?-Alkyl-5-methylhydantoin ; Thermodynamic parameters ; Molecular modeing ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Permethylated β-cyclodextrin (hereafter designated perMe-β-CD), dililuted or not in polysiloxane, is an efficient chiral discriminant for native, 3-methylated, and 1,3-dimethylated series of 5-methyl-5-(CnH2n + 1)hydantoins. From thermodynamic data obtained with pure perMe-β-CD and with the aid of molecular modeling, it is concluded that: (i) For native hydantoin derivatives having a carbon chain at the 5-position varying from ethyl to nonyl (2≤n≤9), the retention time is related to their H-bonding capability. The resolution is poor for derivatives with n≤4. For n≤5, the resolution is considerably improved and this increase in resolution is attributed to the long alkyl chain being capable of being buried inside the cyclodextrin cavity. (ii) For 1,3-dimethylhydantion derivatives having a carbon chain at the 5-position varying from ethyl to hexyl(2≤n≤6), the retention time is mainly determined by a steric fit between the solute and the inner volume of the macrocyclic cavity. For n = 2, a particular behavior is observed, consistent with a total inclusion of the solutes inside the cavity. By contrast with the native hydantoins, the selectively is high for light derivatives. Thus, the selectivity does not correlate with a strong docking energy (such as the presence of H-bonds postulated with native derivatives). (iii) For 3-methylhydantoin derivatives having a carbon chain at the 5-position varying from ethyl to octyl (2≤n≤8), as expected, retension time and selectivity are intermediate between that of native hydantoins and 1,3-dimethylhydantoins. For all three series, where n≤5, the increase in chain length (n) does not bring about substantial changes in the chromatographic results. Therefore, for these long alkyl chain derivatives, similar dominant interactions with perMe-β-CD are postulated.
    Additional Material: 5 Ill.
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  • 65
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    Journal of High Resolution Chromatography 20 (1997), S. 565-568 
    ISSN: 0935-6304
    Keywords: Capillary GC ; GC-MS ; Corn stalk and poplar wood lignins ; Ozone ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Corn (Zea mays) stalk and poplar (Populus deltoides) wood lignin was converted into monomeric aromatic compounds and short chain aliphatic carboxylic acids. The main reaction products were separated and identified using capillary gas chromatography-mass spectrometry on an HP-5 column. The compounds were considered as positively identified when their mass spectra and GC retention times agreed with those of authentic standard samples. The quantitative estimation of the identified reaction products was accomplished on an OV-101 capillary column by gas chromatography-FID using the internal standard method. Among the aromatic compounds, aldehydes (p-hydroxybenzaldehyde, vanillin, and syringaldehyde), acids (p-hydroxybenzoic, vanillic, 3,4-dihydroxybenzoic, and syringic), and one phenol (hydroquinone) were determined. In addition, the aliphatic carboxylic acids: glycolic, oxalic, malonic, glyoxylic, butanedioic, glyceric, and malic acid were identified. All the calibration curves of the quantified compounds approximated to a straight line. For both corn stalk and poplar wood lignins, the major components were the aromatic aldehydes (71 and 64% of the characterized fraction, respectively), followed by the aliphatic carboxylic acids (20 and 21% of the characterized fraction, respectively).
    Additional Material: 1 Ill.
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  • 66
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    Journal of High Resolution Chromatography 20 (1997), S. 572-574 
    ISSN: 0935-6304
    Keywords: high temperature-capillary gas chromatography ; Lipid analysis in cheese ; Milk fat analysis ; Triglycerides in cheese samples ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 4 Ill.
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  • 67
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    Journal of High Resolution Chromatography 20 (1997) 
    ISSN: 0935-6304
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 68
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    Journal of High Resolution Chromatography 20 (1997), S. 581-585 
    ISSN: 0935-6304
    Keywords: On-line LC-GC ; Loop type interface ; Mono-, di-, triacylglycerols ; Vegetable oil methyl esters ; Biodiesel ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An on-line LC-GC method for the analysis of mono-, di-, and triacylglycerols in vegetable oil methyl esters has been developed. The concentrations of these components have turned out to be key parameters for the quality of diesel fuel substitutes. Separation of all classes of acylglycerols from the fatty acid methyl ester matrix is achieved by LC after acetylation of the hydroxyl groups. The acylglycerol fraction is transferred on-line to GC, using the loop-type interface and concurrent eluent evaporation. Quantification of mono-, di-, and triacylglycerols is performed by combining external calibration with internal standardization. Both recovery of the procedure and reproducibility of the quantitative results are evaluated.
    Additional Material: 3 Ill.
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  • 69
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    Journal of High Resolution Chromatography 20 (1997), S. 591-596 
    ISSN: 0935-6304
    Keywords: Pesticide residue analysis ; Solid phase extraction ; Water analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A critical study using C18 SPE columns for the determination of organophosphorus, triazine, and triazole-derived pesticides, nap-ropamide, and amitraz is presented. The type of sorbent, sorbent mass, flow rate in the extraction process, sample concentration of the different compounds, sample volume, pH, and ionic strength were evaluated. Special emphasis was placed on the evaporation step of eluates prior to GC determinations and on prefiltration of sample waters. Pesticide recovery is linear over a wide range of concentrations for most of compounds under study. Under general extraction conditions losses can be expected for amitraz, pro-metryn, prometon, dimethoate, penconazole, and propiconazole. At 100 ng L-1, enhanced responses are produced for mevinphos, simazine, malathion, triadimefon, methidathion, and phosmet, which can be attributed to matrix effects. At basic pH, recovery of prometon, prometryn, and penconazole are improved. Low flow rates and high ionic strength enhance the recovery of prometon and prometryn. For phosmet, the influence of sample volume was established. Likewise, the influence of sorbent quantity was established for phosmet and dimethoate. Losses during the evaporation step were observed for mevinphos, dimethoate (〉 50%), penconazole, propiconazole, and prometon (30%). Prefiltration of sample waters did not cause significant variations in the whole process of extraction. Impurities arising from the sorbent materials were not detected.
    Additional Material: 6 Tab.
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  • 70
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    Journal of High Resolution Chromatography 20 (1997), S. 605-610 
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Retention index ; Homologous series ; Local cubic interpolation model ; Multiparametric least-squares adjustsment ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The retention indices of three homologous series (2-alkanones, 1-alkanols, cycloalksanones) have been determined at high temperature by the application of two new adaptation methods: A multiparametric least-squares regressions iterative method based on the dertermination of the adjusted retention times and a cubic interpolation directly using the uncorrected retention times without dead time correction. The two methods were applied to two types of columns. The first group includes eight packed columns (seven OV polymethylphenylsiloxane and Apolane-87 stationary phases), while the second includes five glass capillary columns (four methyl-silicons with different film thicknesses and Apolane-87 stationary phases). The retention indices obtained with a multiparametric and a cubic interpolation methods were compared with each other and with those calculated by Grobler's, Guardino's, Kaiser's and Kovàts' methods. The influence of coating, film thickness, and temperature on them was investigated.
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  • 71
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    Journal of High Resolution Chromatography 20 (1997), S. 619-620 
    ISSN: 0935-6304
    Keywords: Solid Phase micro-extracton (SPME) ; Packed Column supercritical fluid chromatography(PCSFC) ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
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  • 72
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    Journal of High Resolution Chromatography 20 (1997), 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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  • 73
    ISSN: 0935-6304
    Keywords: HPLC ; C60-fullerene stationary phase ; Dehydroiso-α-lapachome ; Quinones ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 5 Ill.
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  • 74
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    Journal of High Resolution Chromatography 20 (1997), S. 631-637 
    ISSN: 0935-6304
    Keywords: High Perfromance liquid chromatography ; supercritical fluid chromatography ; Selectivity ; Hydrogen bonding ; Linear solvation energy relationships ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Linear solvation energy realationships (LSERS) were used to qunatitatively compare the relative contributions of dipolarity/polarizability, hydrogen bonding, and other types of intermolecular interactions to retention and selectivity using various bulk moblie phase component. Using experimental condition which differ only by the compostion of the bulk moble phase component, the factors which cause selctivity to differ between HPLC, subcritical fluid chromatography and supercritical fluid charomatography were decovoluted. Heptance-based HPLC mobile phases showed superior selectivities towards analytes which differ in hydrogen bond donating ability, gas-to-hexadecane partion coefficint and dipolarity/ploarizability. subcritical fluid chromatography with HFC-134a (1, 1, 1, 2-tetrafluoroethane) as the bulk fluid produced superior seclectivities for which differ in hydrogen bond accepting ability and execess molar refraction properties. Many of these factors showed temperature dependences which act to attenuate or accenture the particular intermolcular interaction.
    Additional Material: 3 Ill.
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  • 75
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    Journal of High Resolution Chromatography 20 (1997), S. 643-646 
    ISSN: 0935-6304
    Keywords: Capillary electrophoresis ; Electogenerated chemiluminescence ; Ru(bpy)32+ ; Tripropylamine ; Proline ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A post- column chemiluminescent technique for thedetection of compounds that are poor chromoshores using electorogenerated chemiluminescence following separation by capillartgy electrophoresis is described. The luminrescent signal is generated followintg the reaction of anlyres (e.g. amines) with Ru(bpy)33+, which isx electrochemically generated post-columan from Ru(bpy)32+. Tripropylamine and proline are used as two model compounds to demostrate the feasibility of the method. Detection limits for the prototype system were in the micromolar rage, suggesting that this technnique offers an alternative to indirect detection of compounds that are poor chromophores with an added selectivity advangage. The system includes the use of a conductive joint to isolate the separation field from the potential necessary to drive the elctrogenerated chemiluminescent reactiion. Addition of the chemiluminescent reagent Ru(bpy)32+ post-column did not decrease the efficiency of the separation. The design and favrication of the novel cell is discussed.
    Additional Material: 2 Ill.
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  • 76
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    Journal of High Resolution Chromatography 20 (1997), S. 653-656 
    ISSN: 0935-6304
    Keywords: Capillary electrophoresis ; Metal cations ; Acid solution ; UV detection, direct and indirect ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Methods for the detectionn of metal cations under acidic conditions, near PH 2, in capillary electrophoresis (CE) were investigatged. Conditions for direct UV detection of UV absorbing metal cations such as Cr3+, Cu2+, Fe3+, UO22+, VO2+, and VO2+ were established With aqueous HCl or HClO4 as the electroyte carrier. The speciation of vanadium(IV) and vanadium(V) at PH 2.3 by CE was achieved with direct detection at 185 nm. With the strong absorbance at 185 nm, no complexation was needed to detect the metal cations. An indirect UV detrection scheme for acidic conditions was also investigated. Several background carrier electolytes (BCES) were studied including 4-methylbenzylamince, nicontinamide, pyridazine, guanidine, 3-picoline, and chromium (III) to determine their effectivencess under very acidic conditions. The efect of ioni c surfactants and the nonionic surfactant, Trition X-100, on the peak heights and N Values was also studied.
    Additional Material: 4 Ill.
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  • 77
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    Journal of High Resolution Chromatography 20 (1997), S. 657-664 
    ISSN: 0935-6304
    Keywords: Temperature measurement on column wall ; Solvent recondensation in the precolumn ; Closure of Vapor exit ; Vaporizer/precolumn solvent split ; Loop-type interface ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Temperature measurements on the column outer well were used for detecting recondensation or evaporation of solvent inside the precolumn during injection or on-line transfer of large solvent volumes. This facilitates the choice of the most critical parameter of these techniques, i.e. oven temperature. When using the vaporizer/precolumn solvent split/gas discharge system, the dew point of the solvent is determined, either to just prevent solvent recondensation or to limit it to the capacity of the precolumn to retain liquid. In concurrent eluent evaporation through the loop type LC-GC interface, temperature measurement enables the determination of whether or not the flooded zone exceeds a given limit. Fanally, when solvent trapping is used (on-column injector/partially concurrent solvent evaporation evaporation or vaporizer/partial recondensation), temperature measurement near the front end of the flooded zone is used as a signal for accurate closure of the vapor exit shortly before the end of solvent evaporation.
    Additional Material: 13 Ill.
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  • 78
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    Journal of High Resolution Chromatography 20 (1997), S. 679-687 
    ISSN: 0935-6304
    Keywords: Efficiency-optimized column ; Efficiency-optimized gas velocity ; Fast GC ; High pressure drop ; Speed of analysis ; Speed-optimized column ; Speed-optimized gas velocity ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using hold-up time as a measure of the speed of analysis with a given column efficiency, a theory of pneumatic optimization of a column in the fast high pressure drop isothermal and temperature programmed GC is developed. Expression for the hold-up time as a function of column efficiency, carrier gas velocity and film thickness is derived. Also found are the expressions for the minimum hold-up time and optimum gas velocity in a speed-optimized column. These quantities are compared with their counterparts in the efficiency-optimized column.
    Additional Material: 6 Ill.
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  • 79
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    Journal of High Resolution Chromatography 20 (1997), S. 674-678 
    ISSN: 0935-6304
    Keywords: HPLC ; LC-MS/MS ; Validation ; Cephalexin ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A reversed-phase HPLC method for the analysis of cephalexin (7-[(aminophenylacetyl)amino]-3-methyl-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid) by isocratic separation is described. A comparison is made between the ultrafiltration land the extraction procedure developed in our laboratory. The extraction procedure, based on the deproteinization of plasma with perchloric acid followed by the extraction with dichloroethane and separation of cephalexin on a reversed phase column, gave better recovery. Quantitative validation of our method has been performed by an external standard technique. The relative standard deviations were between 1.1 and 1.9% in the within-day assay and between 1.2 and 2.2% in the inter-day assay. The limit of detection was 0.14ug/ml and the limit of quantification was 0.28ug/ml. This method is rapid, sensitive, simple, and reproducible. The LC MS/MS technique was successfully used for identification and quantification of cephalexin in human plasma samples.
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  • 80
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    Journal of High Resolution Chromatography 20 (1997), S. 703-703 
    ISSN: 0935-6304
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 81
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    Journal of High Resolution Chromatography 20 (1997), S. 697-700 
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Mass spectrometry ; L-Phenylalanine mustard ; Melphalan ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 4 Ill.
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  • 82
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    Journal of High Resolution Chromatography 20 (1997), S. 704-704 
    ISSN: 0935-6304
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 83
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    Biospectroscopy 3 (1997), S. 299-306 
    ISSN: 1075-4261
    Keywords: DNA ; silica ; binding ; Raman spectroscopy ; infrared ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: We studied by infrared and Raman spectroscopy the interaction of calf thymus DNA with various types of silica particles, ranging in size from 7 nm to 60 μm. Preliminary experiments with different samples showed that substantial variations can take place in the 1000-1100 cm-1 region of the attenuated total reflection (ATR) spectrum of silica, where a strong band due to a stretching vibration of the Si-O groups occurs. The position and intensity of this band were found to be dependent on several parameters, such as the size distribution of the solid particles, their proximity to the surface of the ATR crystal, and their degree of packing after sedimentation from the aqueous suspension. Changes observed in the spectra of aqueous solutions of DNA interacting with silica particles are explained by a shift of the main silica band in the mixtures. This interpretation differs from that of a previous study, where important intensity variations of the DNA bands at 1086 and 1053 cm-1 were explained by the formation of hydrogen bonds between the silanol groups of silica and the phosphate groups of DNA. Raman spectra of aqueous solutions of DNA mixed with fumed quartz particles of an average size of 0.007 μm showed but a minor change in intensity (ca. 5%) of the DNA symmetric phosphate band, which supports the conclusion reached in our infrared study. © 1997 John Wiley & Sons, Inc. Biospectroscopy 3: 299-306, 1997
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  • 84
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    Biospectroscopy 3 (1997), S. 329-329 
    ISSN: 1075-4261
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: No abstract.
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  • 85
    ISSN: 1075-4261
    Keywords: doxorubicin ; intercalation ; resonance Raman ; SERRS ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: The interactions of doxorubicin and its derivatives, hydroxyrubicin and adriamycinone, with DNA were studied by resonance Raman (RR) and surface-enhanced resonance Raman scattering (SERRS) spectroscopy. The π-π interaction between the chromophore of the drug and DNA base pairs has been shown to downshift the skeletal stretching mode ∼ 1440 cm-1 by 8, 5, and 4 cm-1 for doxorubicin, hydroxyrubicin, and adriamycinone, respectively. The additional effects of intercalation with DNA on the RR and SERRS spectra for hydroxyrubicin are similar to those for doxorubicin. However, different effects are observed for adriamycinone. These results indicate that the sugar moiety is necessary to maintain the maximum van der Waals contact between the chromophore and the DNA base pairs and that the amine group in the amino sugar is more favored than the hydroxyl group. © 1997 John Wiley & Sons, Inc. Biospectroscopy 3: 307-316, 1997
    Additional Material: 9 Ill.
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  • 86
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    Biospectroscopy 3 (1997), S. 331-346 
    ISSN: 1075-4261
    Keywords: urinary calculi ; FTIR spectroscopy ; Raman spectroscopy ; infrared ; calculi analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: The application of infrared and Raman spectroscopic techniques to the analysis of urinary calculi is reviewed and their relative efficiency and adaptability to routine analysis are discussed. Using the classification of urinary calculi based on their main constituents, infrared and Raman spectra of calcium oxalates, phosphates, uric acid, urates, and cystine are reported. Some characteristic bands are suggested as useful for analytical purposes. References to other constituents such as drugs are included. Although this review is aimed principally at human stones, it also extends to literature references dealing with urinary calculi from canine, feline, and equine animal species. © 1997 John Wiley & Sons, Inc. Biospectroscopy 3: 331-346, 1997
    Additional Material: 16 Ill.
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  • 87
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    New York, NY [u.a.] : Wiley-Blackwell
    Biospectroscopy 3 (1997), S. 317-323 
    ISSN: 1075-4261
    Keywords: growth hormone releasing peptide ; tryptophan ; 2-methyl tryptophan ; GHRP-6 ; hexarelin ; EP7458 ; ultraviolet photolytic degradation ; rate constants ; differential photolysis ; photolysis products ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: Aqueous solutions of three tryptophan-rich growth hormone releasing hexapeptides, GHRP-6 (His-D-Trp-Ala-Trp-D-Phe-Lys-NH2), hexarelin (His-D-2-Me-Trp-Ala-Trp-D-Phe-Lys-NH2), and EP7458 (His-D-Trp-Ala-2-Me-Trp-D-Phe-Lys-NH2), were exposed to varying durations of ultraviolet (UV) light. Using NMR spectroscopy, first-order rate constants for the UV photolytic degradation of the tryptophan(s)/2-methyl tryptophan residues within each peptide were obtained by plotting the decrease in the area of the indole N-H resonances with respect to UV photolysis time. A significant differential photolytic effect was observed between the two tryptophan residues of GHRP-6 and the tryptophan/2-methyl tryptophan residues of EP7458. A somewhat smaller differential photolytic effect was observed between the tryptophan/2-methyl tryptophan residues of hexarelin. In addition, the three peptides were degraded at different rates, suggesting that the effect of UV light on each peptide is dependent on whether a tryptophan or 2-methyl tryptophan is the second or fourth residue in the primary sequence. © 1997 John Wiley & Sons, Inc. Biospectroscopy 3: 317-323, 1997
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  • 88
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    New York, NY [u.a.] : Wiley-Blackwell
    Biospectroscopy 3 (1997), S. 347-369 
    ISSN: 1075-4261
    Keywords: urinary calculi ; infrared spectroscopy ; kidney biopsy ; etiology ; papillary calculi ; drug-induced calculi ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: Crystal-induced kidney disease is a frequent occurrence in human pathology. It is becoming more and more apparent that knowledge of kidney stone composition and structure appears to be the key for establishing the etiology of stone disease. A number of analytical methods may be applied to stone analysis, but only a few of them are able to quickly and easily provide extensive information on both stone structure and composition relevant for clinical diagnosis. More than 12,000 calculi were analyzed using a combination of microscopic examination, sequential infrared (IR) analysis by Fourier transform infrared spectroscopy (FTIR) of each part of stone, and quantification of all components present. We also investigated 50 biopsies using FTIR microscopy. Our results confirm that IR spectroscopy is a reliable and accurate technique for both molecular and crystalline identification. Some limitations of standard procedures, because of very small samples or due to absorption band overlap, can be solved using FTIR micromethod or a particular method like IR microscopy. In such cases, the spectrum identification must be conducted in different manners. Until now, spectral identification procedures based on computerized spectra libraries must be used with caution because of false results, mainly for mixtures of mineral compounds. Trained eyes always provide the best results for reading spectra from common stones. In routine practice, accurate identification of all components present in calculi is necessary for understanding urolithiasis mechanisms, but only semiquantitative assessment is sufficient to guide physicians toward establishing correct etiology. © 1997 John Wiley & Sons, Inc. Biospectroscopy 3: 347-369, 1997
    Additional Material: 13 Ill.
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  • 89
    ISSN: 1075-4261
    Keywords: brown pigment stone ; PAGE ; mid-IR spectroscopy ; far IR spectroscopy ; FT-Raman ; bezoar ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: Spectroscopic studies of various types of gallstones carried out in China are reviewed. Three basic classes of gallstones are surveyed: cholesterol stones, brown pigment stones, and black pigment stones. The emphasis of this review is on brown gallstones. The primary spectroscopic methods used in the studies surveyed are Fourier transform infrared absorption and Fourier transform Raman scattering. Chemical components studied in gallstones include cholesterol, bile pigments, glycoproteins, proteins, bilirubin metal complexes, and salts of calcium and other metals. Further studies are needed characterize the relationship of these components to more complex features of gallstones. © 1997 John Wiley & Sons, Inc. Biospectroscopy 3: 371-380, 1997
    Additional Material: 13 Ill.
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  • 90
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1737-1746 
    ISSN: 0887-6266
    Keywords: free volume ; dual mode ; diffusion ; glassy polymer ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The development of a new model for the diffusion of gas molecules in glassy polymers is presented which utilizes concepts from free volume theory and relies on a dual-mode interpretation of sorptive dilation in glassy polymers. Three assumptions are made in the development of the model. First, the free volume available for molecular transport processes is taken as constant below the glass transition temperature. Second, two populations of gas molecules are assumed to exist - one which contributes to the maintenance of an iso-free volume state upon sorptive dilation and one which does not contribute owing to sorption into regions of unrelaxed volume. Third, the former population is assumed to be mobile while the latter is not. The resulting model predicts, at constant temperature, a diffusion coefficient that is independent of solute volume fraction. This is in contrast to the widely used dual-mode sorption model with partial immobilization for gas transport in glassy polymers which leads to a diffusion coefficient that is dependent on solute mole fraction through the molar gas concentration. The new model is used to interpret gas transport data from permeation experiments for carbon dioxide, methane, and ethylene in three polycarbonates. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1737-1746, 1997
    Additional Material: 9 Ill.
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  • 91
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1793-1805 
    ISSN: 0887-6266
    Keywords: rutile ; surface modification ; diblock copolymer ; inverse gas chromatography ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Various functional diblock copolymers have been used as surface modifiers for rutile pigment in an effort to condition the solid for eventual use in multicomponent polymer systems. Coated surfaces were analyzed by inverse gas chromatography at infinite and finite dilution of the vapor phase, and by XPS. At high coverages (about 10% by weight of the pigment), the diblocks were randomly oriented at the air interface, effectively masking the surface of the rutile. At low diblock concentrations acid/base interactions dominated the orientation of the adsorbed molecule at the rutile interface, thereby also affecting the orientational states at the air interface. In this condition, the performance of the pigment in specified host polymer systems may be expected to vary with the selection of the diblock copolymer modifier. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1793-1805, 1997
    Additional Material: 5 Ill.
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  • 92
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1843-1854 
    ISSN: 0887-6266
    Keywords: crystallization ; DNA ; fractionation ; gel-electrophoresis ; morphology ; phase transition ; SALLS ; sonication ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polydisperse DNA of reasonable molecular weights was prepared from a mammalian source via sonication and fractionation. A method for characterizing the molecular weight using gel electrophoresis is described. Quiescent crystallization was studied in thin films of one of the fractions induced by rapidly changing the hydration state isothermally. We report the occurrence of the semicrystalline nature of DNA. The crystal growth occurring via aggregates is best described as sheaves and spherulites from DNA gels in the relative humidity range (RH) corresponding to A-DNA. These habits exhibit primary nucleation and secondary growth, which closely resemble those of melt-crystallized, synthetic macromolecules and, in a follow-up report, will be shown to be lamellar in nature. Small, needle-like crystals are observed for B-DNA hydration levels, and are unstable at lower hydration levels. A transformation from needle to lamellar crystals can occur, even when the primary nucleation of lamellar forms is otherwise absent at that hydration level, through a cylindrical phase exhibiting selective reflection of colored bands. The hydration level plays, in part, the role of the supercooling in this system and the long-known hysteresis in the formation and dissolution of the A-DNA (crystals) can now be viewed in light of those factors known to operate in semicrystalline systems. A morphological phase diagram is developed and is in accord with the known physical evidence. Because this preparation and these morphological observations are without precedence, substantial detail into methodology is included for this first article in the series. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1843-1854, 1997
    Additional Material: 10 Ill.
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  • 93
    ISSN: 0887-6266
    Keywords: kraft lignin ; thermoplastics ; polymer association ; poly(vinyl acetate) ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Interest in the development of lignin-containing polymeric materials has been upheld more or less continuously for the past 20 years. Tendencies toward high moduli and poorly defined thermal transitions have been regarded as imposing inevitable limitations upon the use of lignin derivatives for such purposes. Incorporation of more than 25-40% (w/w) lignin had usually resulted in materials that were brittle and weak. For the first time, however, from homogeneous blends containing 85% (w/w) underivatized industrial kraft lignin with poly(vinyl acetate) and two plasticizers, a series of thermoplastics has been fabricated with promising mechanical properties. The tensile behavior of these new polymeric materials depends directly upon the degree of association between the intrinsic kraft lignin components. In extending to values about 25 MPa and 1.5 GPa, respectively, the tensile strengths and Young's moduli vary linearly with the effective M̄w for the kraft lignin species, under conditions where the proportions of the individual molecular components, both associated and discrete, do not change. Moreover, melt-flow index measurements indicate that these polymeric materials are amenable to thermal processing by extrusion molding. Thus a significant step has been taken toward developing a new generation of thermoplastics that are lignin-based in a very fundamental way. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1899-1910, 1997
    Additional Material: 5 Ill.
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  • 94
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1933-1942 
    ISSN: 0887-6266
    Keywords: self-diffusion ; viscosity ; polymer melt ; entanglement ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dynamic properties in the melt state for two saturated hydrocarbon polymers, poly(ethylene-alt-propylene) (PEP) and head-to-head polypropylene (HHPP), were investigated by viscoelastic and diffusion measurements. Several nearly monodisperse linear samples of each species were used. Zero-shear viscosity η0 and self-diffusion coefficient D varied with temperature in accord with the WLF equation, and they also varied with molecular weight M in a manner that was consistent with the behavior of other species. The product η0D was of particular interest because extensive previous results for two other species, polystyrene and polyethylene, had led Pearson et al. to suggest that η0D/(η0D)Rouse is a universal function of the number of entanglements per molecule M/Me. With values for the Rouse model product for each species calculated from chain dimensions, and entanglement molecular weight from the plateau modulus, we show that the data for PEP and HHPP also support the Pearson universal form. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1933-1942, 1997
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  • 95
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1963-1971 
    ISSN: 0887-6266
    Keywords: dynamic mechanical analysis ; fluorinated poly(ethers) ; intermolecular cooperativity ; relaxation behavior ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The relaxation behavior of six fluorinated aromatic poly(ethers) was investigated using dynamic mechanical analysis. The glass transition temperature was found to increase as the size and rigidity of linking groups increased and varied between 168°C for a dimethyl linking group and 300°C for a bicyclic benzoate ether-linking group. For the α-relaxation the steepness of time/temperature plots and broadness of the loss curves could be qualitatively correlated with chemical structure in a manner predicted by the coupling model of relaxation. Well-separated sub-Tg transitions were also observed, as a shoulder on the low temperature side of the α-peak, and as a broad, low loss transition around -100°C. The higher temperature process was similar to the structural relaxation often found in quenched glassy polymers, while the position, intensity, and breadth of the subambient process was sensitive to chemical structure. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1963-1971, 1997
    Additional Material: 7 Ill.
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  • 96
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 507-515 
    ISSN: 0887-6266
    Keywords: poly(acrylic acid) ; FTIR ; polyelectrolyte ; conformation ; conformers ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Fourier transform infrared (FTIR) spectroscopic measurements have been undertaken to estimate the conformational energies of poly(acrylic acid) (PAA) cast films in the temperature range of 40-130°C. The temperature dependence of the IR spectra in the C=O stretching region has been analyzed to yield the side-chain and backbone conformational energies. The estimated energies are close to those previously obtained by polarized Raman spectroscopic measurements for PAA solutions. Combining the FTIR value of conformational energy with the simplified rotational isomeric state (RIS) model proposed in the Raman analysis provides a persistence length in accordance with earlier SAXS experiments. The data also agree with the Gibbs-DiMarzio predictions, further substantiating the validity of the analysis. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys, 35: 507-515, 1997
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  • 97
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 2195-2200 
    ISSN: 0887-6266
    Keywords: ESR ; mechanoradicals ; PMMA ; drilling apparatus ; computer simulation ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In this study, initially, we tried to obtain the mechanoradicals of PMMA (poly(methyl methacrylate)). For this purpose, we designed a simple drilling apparatus. Using this apparatus, we prepared some PMMA samples at 77 K in vacuum. Later, by using an ESR (electron spin resonance spectrometer), we observed ESR signals for these samples at 77 K. This means that mechanoradicals have been successfully produced by mechanical fracture in PMMA using our drilling apparatus. Secondly, we tried to identify the radicals from these spectra through using theoretical analyses and, some computer simulations have been done by suggesting two different theoretical models for these ESR signals. Finally, by using experimental and theoretical data, we showed that our simple apparatus could be used to obtain mechanoradicals from polymers. Results were seen to be in very good agreement with the literature. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2195-2200, 1997
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  • 98
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 2219-2231 
    ISSN: 0887-6266
    Keywords: nylons ; crystallinity ; DSC ; x-ray diffraction ; complications ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Differential scanning calorimetry (DSC) is one of the most widely used technique for measuring crystallinity in the polymer industry. The major source of error in the crystalline index (CIDSC) of low crystallinity polymeric articles, is the development of further crystallinity during the DSC scan. Although, this type of cold crystallization is obvious, and thus accounted for in polymers like polyethylene terephthalate, nylons are a difficult class of materials in that respect. The major contributing factors to the failure of DSC in measuring low levels of crystallinity in nylons are identified to be (1) silent crystallization between the glass (Tg) and melting (Tm) transitions, (2) extreme difficulties in packing a moisture-free nylon in the sample pan (the response due to traces of moisture being a broad endotherm competing with a broad exothermic crystallization), and (3) a sub-Tm exotherm, especially in low crystallinity nylons, due to relaxation of the processing-induced stresses. These factors, specific to nylons, mask the observation of cold crystallization and lead to substantially higher than real crystallinities. This manuscript deals with such complications and corrective actions using commercial nylon 6 films of CIDSC = 0-40%. X-ray diffraction measurements have been included to support the validity of our improved DSC methodology. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2219-2231, 1997
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  • 99
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 2281-2292 
    ISSN: 0887-6266
    Keywords: conformation ; phonon dispersion ; α-helix ; normal modes ; poly(L-leucine) ; density of states ; heat capacity ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(L-methionine) (PMet) is one of the two sulfur containing polyamino acids. Raman, FTIR spectra, and heat capacity measurements of PMet have been well interpreted through the normal mode analysis and the density of states derived therefrom. Earlier interpretation of heat capacity data is limited because it is based on the Tarasov model, wherein the concept of group frequency and skeletal similarity are used. A special feature of some dispersion curves is their tendency to bunch in the neighborhood of the helix angle. This has been attributed to the presence of strong intramolecular interactions. Repulsion between the dispersion curves is also observed. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2281-2292, 1997
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  • 100
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 2297-2307 
    ISSN: 0887-6266
    Keywords: crosslinked polymers ; photopolymerizations ; living radical polymerizations ; mechanical properties ; dynamic mechanical analysis ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Crosslinked polymer networks are used in a wide variety of applications. To use these materials effectively, a fundamental understanding of their structural evolution and the relationship between material properties and structure is essential. In this article, a novel technique employing “iniferters,” i.e., living radical polymerizations, to photopolymerize these networks is utilized to study the property and structural evolution of these highly desirable materials. Living radical polymerizations are used in this work since this technique avoids the problem of carbon radical trapping encountered while using conventional initiators. Dynamic mechanical measurements are performed on highly crosslinked methacrylate networks to glean information regarding their structural heterogeneity. By performing these measurements on homopolymerized samples at various stages of the reaction and on copolymerized samples of multifunctional methacrylates, the mechanical properties are characterized as a function of double bond conversion and comonomer composition. From such analyses, with respect to both temperature and frequency, quantitative conclusions regarding the structure of the networks are drawn. This effort is aimed at exploiting the living radical polymerizations initiated by p-xylylene bis(N,N-diethyl dithiocarbamate) (XDT), to study the mechanical property evolution and structural heterogeneity of crosslinked polymers which is nearly impossible otherwise. Polymers examined in this study include networks formed by homopolymerization of diethylene glycol dimethacrylate (DEGDMA) and polyethylene glycol 600 dimethacrylate (PEG600DMA) as well as copolymers of DEGDMA and PEG600DMA. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2297-2307, 1997
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