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  • Articles  (229)
  • Column liquid chromatography  (158)
  • Gas chromatography  (73)
  • Springer  (229)
  • 2015-2019
  • 1985-1989  (229)
  • 1988  (127)
  • 1986  (102)
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  • Articles  (229)
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  • 2015-2019
  • 1985-1989  (229)
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  • 1
    ISSN: 1432-1432
    Keywords: Primordial terrestrial atmospheres ; CH4, C2H2, CO2 ; Prebiotic synthesis ; High-frequency discharge ; Hydrocarbons ; Gas chromatography ; Mass Spectrometry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Various hydrocarbons were synthesized by high-frequency discharge in a primordial terrestrial model atmosphere. The products were extracted by benzene or methanol and analyzed by GC-MS. The mean carbon chain length of the hydrocarbons formed by the discharge through pure CH4 gas was less than 6. Benzene was also obtained. Some isomers were obtained for each of the hydrocarbons containing a given number of carbons. When a small amount of C2H2 was added to the CH4, longer chain compounds were formed, as compared with discharge in CH4 only. However, when the amount of C2H2 was increased, unextractable high molecular weight compounds were produced. The amounts of products decreased as the mixing ratio of CO2 to CH4 increased. No hydrocarbons were detected when the ratio of CO2/CH4 exceeded 1.
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  • 2
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Electrochemical detection ; Cysteinyldopamine ; Tyrosinase ; Autoxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary 5-S-Cysteinyldopamine, a new metabolite of dopamine, was determined in urine by high-performance liquid chromatography with electrochemical detection. The catechol was detected in 14 of 21 melanoma patients and 7 of 21 normal subjects; the highest values were 657 μg/day for melanoma patients and 44 μg/day for normal subjects. These results suggest that the cysteine conjugate may arise from autoxidation of dopamine but tyrosinase may also participate in the oxidation.
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  • 3
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    Chromatographia 21 (1986), S. 136-142 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Chemical reaction detector ; Carbamate insecticides ; Quantitation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary For the determination of trace amounts of carbamate insecticides in vegetables the combination of liquid chromatography with post column chemical derivatization (chemical reaction detector) is used. In a two step reaction detector the carbamates are firstly saponified in 0.01 M sodium hydroxide at 80°C with a reaction time of 30sec. To this mixture OPA reagent is added to detect the methylamine generated in the saponification. Optimization strategies for this reaction are demonstrated. At a temperature of 80 °C a reaction time of 80 sec is sufficient for quantitative transformation of the methylamine. The peak dispersion can be reduced and hence the detection limit improved by decreasing the diameter of the tubes and by diminishing dilution through the addition of reagent. A 1∶24 ratio of reagent to column (reactor) effluent is possible with cyclone-type mixers. The quantitation of carbamates in different vegetables is demonstrated. The detection limit is 20ppb at a signal to noise ratio of 10∶1.
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  • 4
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Flame ionisation detection ; Cyanogen ; Cyanogen chloride
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The response of a flame ionisation detector (FID) to cyanogen ((CN)2) and cyanogen chloride (CNCI) has been studied. The lower limits of detection for (CN)2 and CNCl were 6×10−12 moles and 2×10−11 moles respectively. In a comparative study a thermal conductivity detector gave as its lower limit of detection for both (CN)2 and CNCl 4×10−11 moles. Both detectors showed excellent linearity over the range 0 to 10 micromoles. The ratio of the gradients of the FID calibrations (CN)2/CNCI were found to be approximately two suggesting the response depended on the cyanide group. The response and stability of the FID was investigated as a function of air and hydrogen flow-rates. The response increased with increasing air flow-rate for both (CN)2 and CNCI up to 300cm3min−1, thereafter no significant increase was observed. On raising the hydrogen flow from 10 to 25cm3min−1 only a slight increase in the sensitivity of the FID towards both (CN)2 and CNCI was observed. At higher flow rates the response for (CN)2 increased markedly whereas at the same flow rates the response for CNCI increased only slightly.
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  • 5
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    Chromatographia 21 (1986), S. 205-213 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Chiral phases ; Optimization of separation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The preparation and properties of chiral bonded phases with amino acid groups are described. These phases were used in non-polar eluents and in aqueous systems in the presence of Cu2+ ions in the ligand-exchange mode. The optimization of chiral resolution is demonstrated for both cases. With non-polar eluents similarity between bonded groups and solutes is required. The elution could be accelerated by non-protonic moderators. Ligand-exchange separation is influenced by the copper content of the eluent and the stationary phase, the organic moderator concentration, the pH and ionic strength of the buffer and by the temperature. Structural requirements of both the bonded groups and of the solutes for chiral separation are discussed.
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  • 6
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    Chromatographia 21 (1986), S. 214-218 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Behaviour of metal acetylacetonates ; Adsorption isotherms ; Heat of solution
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Specific retention volumes, adsorption isotherms, molar heats of solution and changes of the entropy were determined from chromatographic data, which was obtained by the gas chromatographic separation of metal acetylacetonates. The retention data for Cr(III), Co(III) and Al(III) acetylacetonates were measured at different temperatures and different flow rates. From the retention data other values associated with adsorption and solution phenomena were calculated.
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  • 7
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Capillary columns ; Immobilized stationary phase ; Carbowax-type stationary phase ; Cross-linked polyurethane
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The preparation of an immobilized stationary phase based on Carbowax 20M is described. The stationary phase cross-linking was carried out with Desmodur N 75 or Desmodur L 75, pluriisocyanates. The properties of the prepared stationary phases are compared.
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  • 8
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Reversed-phase capacity factors ; Cavity term ; Molar volumes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Reversed-phase liquid chromatographic capacity factors are well correlated by an equation of the form: $$logk' = (logk')_0 + mV/100 + s\pi ^* + b\beta + a\alpha $$ wheremV/100 measures the cavity term and π*, β, and α are the solvatochromic parameters that measure solute dipolarity/polarizability, hydrogen bond acceptor basicity, and hydrogen bond donor acidity respectively. Liquid molar volume (molecular weight divided by liquid density at 20°C) $$\bar V$$ , and computer-calculated intrinsic (van der Waals) molecular volume, $$\underset{\raise0.3em\hbox{$\smash{\scriptscriptstyle-}$}}{V} _I $$ , are compared as measures of the cavity term in a number of correlations. $$\underset{\raise0.3em\hbox{$\smash{\scriptscriptstyle-}$}}{V} _I $$ leads to more precise correlations as well as to a “cleaner” dissection of the multiple solute/solvent interactions. The opposing exoergic effect of solvent donor/solute acceptor hydrogen bonding, and endoergic cavity term are the main factors influencing HPLC capacity factors.
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  • 9
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    Chromatographia 22 (1986), S. 40-42 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Pyridate ; CL-9673 ; Reversed phase
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The application of a simple reversed-phase, HPLC-UV method for the determination of the contact herbicide pyridate and its main metabolite 3-phenyl-4-hydroxy-6-chloropyridazine-known as CL-9673-in green cereals, grains and straw is described. The method is based on a simple extraction, separation of pyridate from its metabolite, hydrolysis of pyridate to CL-9673, high-performance liquid chromatographic separation of CL-9673 in both fractions using only one reversed phase column and UV-detection. The method is sensitive down to 3 ngg−1 CL-9673 in green plants and grain and 5ngg−1 in straw. In the range 0.05–1.0mgkg−1 recoveries are between 73.7% and 109% from green plants, between 77.7% and 102% from grains and between 77.3% and 87.5% from straw.
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  • 10
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Betablocker drugs ; Lipophilicity ; Capacity factors ; Distribution coefficients
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The reverse-phase, high-pressure liquid chromatographic capacity factors (k') of a series of 18 betablocking agents were determined in order to establish correlations with their distribution coefficient values (D), obtained from four bibliographic sources. Under the three pH conditions studied (3.5, 6.2 and 7.5) statistically significant linear correlations (p〈 0.002) between log k' and log D values were obtained for the four series studied. In this series it is concluded that the k' factor is a useful and reliable relative lipophilicity parameter.
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  • 11
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    Chromatographia 22 (1986), S. 81-87 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Recycle chromatography ; Pressure dependence ; Capacity factor
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary It was found experimentally that the potential for routine, rapid high-efficiency separations by alternate column, recycle, reversed-phase chromatography is limited by the increase of capacity factors with pressure.
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  • 12
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Metalloporphyrins ; 5,10,15,20-Tetraphenylporphine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The Co(II), Ni(II), Fe(III) and V(IV) complexes of tetraphenylporphine (TPP) can be eluted at short retention times from a LiChrosorb RP-18 column with pure ethanol. However, both Mn(III) and Co(III) complexes of metal TPP chloride type are so strongly retained on the column that they cannot be eluted. While the retention of other metal teraphenylporphine complexes was not affected, that of the metal(III) complexes of the TPP chloride type especially MnTPPCl and CoTPPCl, decreases dramatically with an increase in the concentration of NH4Cl added into the mobile phase; a linear relationship between logk' and log[NH4Cl], with the slope of about−1, has been observed for these two metal(III) complexes in the NH4Cl concentration range from 2.5×10−4 to 1.3×10−2 mol/l. Thus, the specific control of the retention of the metal(III) complexes is enabled by conditioning the NH4Cl content of the mobile phase, and the chromatographic separation is demonstrated.
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  • 13
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    Chromatographia 22 (1986), S. 55-58 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; 1-Octanol/water partition coefficient ; Cellulose acetate ; Reverse osmosis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The adsorption properties of esters, aldehydes, ethers and amides on cellulose acetate, which is commonly used as a reverse osmosis membrane material, in an aqueous solution system were measured by high-performance liquid chromatography. The adsorption property was characterized with the specific retention volume. For a noncyclic homologous series the logarithm of the specific retention volume was linearly correlated with the logarithm of the partition coefficient between 1-octanol and water. The fact that the slopes of these regression lines are almost identical confirms that the dominant effect on adsorption is the hydrophobic interaction between cellulose acetate and the solute molecule. The intercept represents the effect of the polar groups on adsorption. The effect of the polar group decreases as follows: ―C(O)O―, ―CO―, HCON〈 〉 CH3CON〈 〉 ―OH, ―O―.
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  • 14
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Volatile nitrosamines ; Fused silica capillary columns ; Linear indices
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Fused silica capillary columns of different diameters and polarities are linked to a thermal energy analyzer and a flame ionisation detector for comparison. Extra column effects are discussed. Unsymmetrical homologue nitrosamines are applied in order to assign the volatile nitrosamines most often to be determined by their linear indices rather than by their overall retention times.
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  • 15
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Dihydroartemisine ; Interconversion equilibrium ; Multiple-peaks
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The interconversion between the α- and β-isomers and the multiple-peaks of dihydroartemisinine (dihydroqinghaosu) were investigated in reversed-phase, highperformance liquid chromatography. A convenient method using the Gaussian distribution function instead of the Schmidt graphical method for the theoretical calculation of the “diffuse” probability curves versus the fraction of the dead time on column as β form was introduced. Based on the theoretical probability curves and the experimental multiple-peak chomatograms, the effects of temperature and flow velocity on the accuracy and precision of analysis of dihydroartemisinine are indicated and the activation energy of the interconversion between α- and β-isomers of dihydroartemisinine is estimated.
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  • 16
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Thermionic detector ; Flame-forming agents ; CO2 and water gas
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The use of carbon monoxide were suggested as the flame-forming agent in the thermionic detector (TID). The main characteristics of this detector were studied. It was shown that the optimum flow rate of carbon monoxide is 40 ml/min at an air flow rate of 400–550 ml/min. The response increases twice with the positive potential on the collector. Molar responses of TID were compared with those obtained when using carbon monoxide and hydrogen. For instance, for phosphorus containing compounds they are approximately the same (∼102), while for nitrogen containing compounds in the case of carbon monoxide, there is a 2–5 fold increase in the response. The linear dynamic range for methaphose and azobenzene is 103.
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  • 17
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Nucleotides ; Mytilus edulis ; Smooth muscle
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A method is described for the analysis of the 5′ mono-, di- and triphosphates of adenosine, guanosine, uridine and cytidine, as well as uridinediphosphate-glucose and cyclic AMP. Separation is achieved by reversed-phase ion-pair chromatography with linear gradient elution. Application of this method to the analysis of nucleotides in smooth molluscan muscles is described, including the determination of cAMP-levels and the calculation of energy charges for all of the four nucleotide systems.
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  • 18
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Porphyrin ; Metalloporphyrin ; Hematoporphyrin IX
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The feasibility of reversed-phase high-performance liquid chromatography for the separation of metal complexes of hematoporphyrin IX (Hp) is described. The retention order, Zn-complex〈Hp (free acid)〈 Ni-complex〈Cu-complex, is regular on an octadecylbonded stationary phase with different compositions of an aqueous methanol mobile phase. These four compounds can be successfully separated within about 8 min on a LiChrosorb RP-18 column (250×4-mm i.d.) with a 85:15 (vol/vol) mixture of methanol and phosphate buffer (pH 3) at a flow rate of 1 ml/min.
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  • 19
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Metal complexes ; Chemically bonded phase ; Specific interactions
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Packings consisting of chemically bonded diphenylphosphine complexes with CuCl2 and CuBr2 were synthesized and their retention parameters determined. The packings investigated are capable of specific interactions with electron-donating compounds and are characterized by particularly high selectivity in relation to cis and trans isomers allowing their complete separation.
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  • 20
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    Chromatographia 22 (1986), S. 157-159 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Flavonol aglycones ; Isocratic elution ; Wine phenolics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary An HPLC isocratic elution procedure which allows the separation of flavonol aglycones in wine without interference from other phenolics of low molecular weight is described. The method has been applied to the separation, identification and quantitative estimation of flavonol aglycones in ether extracts of different Spanish wines (red and white table wines and Sherry finos). The results suggest that these determinations, associated with other analyses, would permit the chemical characterization of wines.
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  • 21
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Micropacked columns ; Quantitation ; Fermentation products
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A new method is proposed for the analysis by gas chromatography of volatile compounds found in alcoholic and acetic fermentation samples. The method represents a suitable choice for the accurate and precise determination of 19 compounds (including Methanol) by direct injection onto a single column. Chromatograms of synthetic mixtures as well as actual samples show the capabilities of the micropacked column used.
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  • 22
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    Chromatographia 25 (1988), S. 31-36 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Radioactivity detector ; Solid scintillator ; Fibre-packed flow cells
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A new type of flow-cell radiation detector for use in liquid chromatography which is packed with aligned scintillator fibers is described. A primary advantage of the fiber packed cell is that light generated by the scintillator is absorbed to a much less extent by the fibers than by the powder scintillator used in conventional flow cells. A detection efficiency of 55% has been obtained for carbon-14 using 0.1-mm diameter hand-pulled glass fibers. Computer modeling has shown that even better results can be obtained by using smaller and more uniform diameter fibers which will allow better packing. The fiber cell also demonstrates back pressures which are a factor of 50 less than the conventional cell and much less susceptibility to absorption of compounds because of its lower surface area.
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  • 23
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    Chromatographia 25 (1988), S. 854-860 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Polystyrene ; Gradient elution ; Turbidimetry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Polystyrene samples of narrow molecular-weight distribution have been eluted according to their molecular weight from columns packed with bare silica Si50, phenyl, or C18 bonded phase by gradients of methanol and tetrahydrofuran (THF) or ofiso-octane and THF. Among the six combinations investigated,iso-octane/THF with a silica column formed a proper normal-phase system whereas methanol/THF with a C18 column formed a proper reversed-phase system. The combinations of C18 column andiso-octane/THF or of Si50 column and methanol/THF gradient did not correspond to the approved polarity rules in high-performance liquid chromatography but were nevertheless effective in separating polystyrene mixtures by molecular weight. Methanol andiso-octane are nonsolvents for polystyrene whereas THF is a solvent. The solubility of polystyrene as a function of molecular weight and concentration was determined by means of turbidimetric titration of solutions in THF with the nonsolvents used in the gradients. The solubility and elution characteristics were almost identical on C18 columns or in methanol/THF combinations. The elution from phenyl bonded phase and Si50 columns usingiso-octane/THF gradients required more THF than the solubility experiments. Information is also given on the occurrence of multimodal elution patterns.
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  • 24
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Polycyclic aromatic compounds ; Alkylated PAC ; Retention characteristics ; Normal phase
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Retention characteristics of series of polymethyl and mono-n-alkyl derivatives of benzene and pyrene, and also of parent polycyclic aromatic hydrocarbons (PAH), were studied using silica and aminopropyl- and cyanopropyl-modified silica. Differences in the selectivities for the studied compound groups were found between the three phases. Deviations from linear behaviour in plots of log (k′)vs. carbon number were observed for the methyl series. These are explained in terms of differences in π-electron delocalisation within the aromatic ring systems. Further, the effect of methyl substitution on selectivity decreased with an increasing number of aromatic rings. Results were obtained which indicated that the primary adsorption site in a cyano column used in normal phase mode, at least for PAH molecules, is the cyano group.
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  • 25
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    Chromatographia 25 (1988), S. 43-50 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Reversed phase ; Void volume ; Adsorption isotherms
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary In reversed-phase liquid chromatography with n-alkyl bonded silica, the dead volume (V0) of the column is theoretically indeterminate owing to adsorption of organic modifier on n-alkyl chains and of water on silanol groups. With binary mobile phases, retention volumes of the mobile phase components and of their deuterated species are relaeed to the adsorption isotherms and V0 by equations which can be solved with some assumptions on the adsorbed layer composition. Methanol-water and acetonitrile-water systems are studied. As the experimental excess isotherm shows a linear part in the concentration range 50–80% in organic modifier, the hypothesis of an adsorbed layer of constant composition in this range is possible. When increasing the water content of the mobile phase, adsorption of water occurs up to saturation of silanol groups. Then the assumption of a constant water content for a mobile phase having more than 50% of water is applied. With the hypothesis of a constant adsorbed content of organic modifier when the eluent has more than 80% of organic modifier, V0 and the absolute isotherms are calculated over the entire range of mobile phase composition. Experimental retention behavior of the mobile phase components are totally explained by these V0 determinations. The retention times of commonly used V0 markers are compared with V0 values. It is shown that, when buffering the eluent, no visible effect on the distribution equilibrium is observed, so that injection of concentrated potassium nitrate is a convenient method to measure V0. With a few solutes with are UV detectable it is possible to measure V0 whatever the mobile phase composition in methanol-water and acetonitrile-water systems.
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  • 26
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Stationary phase solubility parameters ; Cyano-silica ; Amino-silica ; Diol-silica
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Extended solubility parameters have been determined for aminopropyl, cyanopropyl and 1,2-dihydroxypropyl propyl ether (diol) normal bonded-phase HPLC columns. Parameters were calculated from both the retention data of solutes (partition model) and empirically determined solvent strengths (adsorption-displacement model). The use of solvent strengths to calculate solubility parameters for these silica-based bonded stationary phases appears to be superior, since this technique avoids many of the problems that arise from their inherent heterogeneity. Normalized solubility parameters were also used to position these columns on a stationary phase selectivity triangle. The amino and cyano phases appear in regions of the tringle expected based on the properties of the pure liquids, but an ether linkage in the diol apparently neutralizes some of the acidity expected from this phase.
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  • 27
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Simultaneous distillation-extraction ; Cheese volatiles
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A simultaneous distillation-extraction apparatus proposed by Godefroot has been used for the GC study of volatile components of cheese. 5–10 g of cheese provide a fraction that can be directly injected into a GC or a GC/MS. Two capillary columns (SE-30 and SP-1000) were evaluated, the second one being adequate for quantitative determinations. Camphor was used as internal standard. The coefficients of variation ranged from 1.4 to 11.8. The technique can be used as a fast method for the characterization of cheeses from their volatile component concentrations.
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  • 28
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    Chromatographia 25 (1988), S. 1087-1088 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Log plot ; Homologous series
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The slope of the log plot of the adjusted retention time of a homologous series usually varies from that of the n-alkane series by no more than 2%, though with unusual interactions between the functional group and the stationary phase the difference may be as high as 7%.
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  • 29
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Preparative scale separations ; Plate model
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Two close-boiling materials, diethyl ether (DEE) and dichloromethane (DCM), were separated to investigate the effects of the pure components and the mixture on elution in preparative gas-liquid chromatography. Nitrogen was used as the carrier gas, and the chromatographic column (1 cm I.D. and 0.75m length) was packed with Chromosorb A with different quantities of dinonyl phthalate stationary phase and particle sizes. Below ca. 7% (by wt.) of feed concentration, the experimental elution curves of pure DEE and DCM were almost the same as those of the mixture, and the theoretical plate model can be used successfully to predict the elution curves.
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  • 30
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Macrolide antibiotic azithromycin ; Intermediates of azithromycin ; Optimization of separation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary HPLC is the most convenient method for the assay of the azithromycin (10-dihydro-10-deoxo-11-methyl-11-azaerythromycin A), a semisynthetic macrolide antibiotic and its reaction intermediates. Data concerning the effects of pH, temperature and column type are presented. The analytical procedures enabling the reliable assay of azithromycin and its intermediates, as well as other impurities are defined. Use of a reversed-phase octadecyl column, a pH of 9.3–9.5, and isocratic mode at ambient temperature are the best conditions of analysis.
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  • 31
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Metabolic disorders ; Xanthine and 2,8-dihydroxyadenine ; Urine analysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary 2,8-Dihydroxyadeninuria and xanthinuria are inborn enzyme disorders which must be under lifelong therapeutic control. Quantitative determination of 2,8-DHA and xanthine using reversed phase HPLC was performed. A new application for the separation of purines shortens analysis-time. Examples of the determination of 2,8-DHA and xanthine before and under certain therapies are shown. Long term monitoring of the patients offers the possibility of a reliable prophylaxis against stone recurrence.
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  • 32
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Indirect detection of non-electrolytes ; Simulation of induced peaks ; RP systems
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Induced peaks observed in indirect detection of nonelectrolytes in high-performance liquid chromatography are simulated. The equation representing the signal intensity of the induced peaks is derived, and it is verified by the experimental results. The peak area is proportional to (K b ′ +1) k a ′ /| a ′ —k b ′ |, where k a ′ ad k b ′ are the capacity factors of the visualization agent and the analyte, respectively.
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  • 33
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    Chromatographia 25 (1988), S. 162-166 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Ion chromatography ; Analysis of metal ions ; Post column derivatisation ; Amperometric detection
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A method for determination of metal ions subsequent to separation by ion chromatography has previously been developed. The method is based on Indirect Amperometric Detection whereby the decrease in the oxidation current, due to a dithiocarbamate ligand added post column, is monitored. Upon elution from the chromatographic column the metal ions are complexed by the ligand. As the complexes formed are electroinactive at the applied potential, the background current decreases according to the metal ion concentration. The method developed in this work involves addition to the reagent of Zn(II) as a auxiliary metal ion to displace the analyte metals from the chromatographic eluent ligand complexes after separation. Sodium bis(2-hydroxy-ethyl) dithiocarbamate was used as the postcolumn derivatising reagent. The addition of Zn(II) to the reagent causes some unforeseen behaviour in the chromatographic system.
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  • 34
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    Chromatographia 25 (1988), S. 199-204 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Column switching ; Catecholamines ; Urine ; Serum
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    Topics: Chemistry and Pharmacology
    Notes: Summary We developed an automated, two-column HPLC-method that can be used routinely to quantify the catecholamines norepinephrine and epinephrine in body fluids. The method is based on a new, laboratory-prepared SEC-HPAC column material, on the application of a microprocessor-controlled column-switching technique, and on the use of an integrated reaction system for postcolumn derivatization and trihydroxyindol-fluorescence monitoring. It allows the direct injection (upto 500 μl) of an appropriate biological fluid and distinguishes on its integrated sample-processing mode, its practicability, its chemoselectivity and-specivity, its detection limit (2 pg), its within- and between-run precision and its speed of analysis.
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  • 35
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    Chromatographia 25 (1988), S. 404-408 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Silica surface modification ; Hexamethylcyclotrisilazane ; Hexamethyldisilazane ; Support materials
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    Topics: Chemistry and Pharmacology
    Notes: Summary The paper is concerned with the structure of an organic layer bonded to the silica surface modified with silazanes. The changes of the retention volumes of hydrocarbons is studied for the silicas modified with hexamethylcyclotrisilazane, hexamethyldisilazane and their mixtures. It is shown that most of the carbon in the layer after hexamethylcyclotrisilazane modification is bonded to the surface by Si−O−Si bonds. This fact supports the assumption of a fragmentation of the cyclosilane used for modification.
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  • 36
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Pheophytinatonicke(II) ; Chlorophyll ; Pheophytin
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    Topics: Chemistry and Pharmacology
    Notes: Summary HPLC determination of pheophytinatonicke(II) (Pheo-Ni) prepared by the replacement of magnesium(II) in chlorophyll with nicke(II) is described. The good separation of PheoNi was obtained by using chemically bonded C18 as the stationary phase and acetone-methanol (50∶50, vol/vol) as the mobile phase. Conventional spectrophotometric method was also used for the determination of PheoNi. For the synthetic samples prepared by mixing (pheophytinato a) nicke(II) [(Pheo-a) Ni] and (pheophytinato b) nicke(II) [(Pheo-b) Ni], analytical values obtained by the spectrophotometric method were very high compared to those obtained by HPLC. In the proposed HPLC method, (Pheo-a) Ni and (Pheo-b). Ni could be determined in the concentration range of 0.028–30μg/ml and 0.038–30μg/ml with relative standard deviations (n=10) of 3.1% and 0.8%, respectively.
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  • 37
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Statistical criteria ; Non-linear models ; Constants for n-alkane retention curve ; Multiparametric least-squares adjustment
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    Topics: Chemistry and Pharmacology
    Notes: Summary Multiparametric, least-squares, regression treatment of G.C. data is extended to describe deviations from the usual linear model. Through statistical evaluation of results, four parameters models are generally found adequate and the use of higher degree empirical models is discouraged.
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  • 38
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Flavonoid compounds ; Structure-retention relationships ; Reversed-phase systems
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    Topics: Chemistry and Pharmacology
    Notes: Summary Reversed-phase HPLC retention behaviour of different flavonoid compounds in different columns and with a range of methanol-buffer eluents was examined. Repeatibility and reproducibility of logk′ and Δlogk′ values were analyzed. Sharp group contributions, expressed as Δlogk′, were observed. These did not depend significantly on acid modifier type, column packing characteristics (C8 and C18) and dimensions (5,7 and 10μm) or the percentage of methanol in the mobile phase. A list of twelve group contributions is presented which is in agreement with literature data.
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  • 39
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    Chromatographia 25 (1988), S. 443-446 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Large scale separations ; Dissolution of silica ; Metallic contaminants
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    Topics: Chemistry and Pharmacology
    Notes: Summary Possible contamination of purified product by the silica matrix is of considerable importance when considering process scale high-performance liquid chromatography (HPLC) as a separation methodology. The stability of silica supports in normal phase, reversed phase and affinity chromatography modes has been examined with organic solvents and water. Both inorganic and organic components were found, contributed by the support, and the chromatographic and distillation equipment. In all cases, based on assumed values of production, they were found to contribute less than 0.01% of impurities. In critical cases crystallisation or dialysis may be considered as a last stage of purification, with re-chromatography to maximise yields.
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  • 40
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Fast atom bombardment mass spectrometry ; Nonionic detergents
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    Topics: Chemistry and Pharmacology
    Notes: Summary Microcolumn liquid chromatography (LC) combined with fast-atom-bombardment mass spectrometry (FABMS) was applied to the analysis of nonionic detergents. The porous silver filter attached to the top of the capillary fused-silica tubing worked as the interface for coupling of micro LC and FABMS.
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  • 41
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    Chromatographia 25 (1988), S. 539-542 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Temperature programming ; Retention index
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    Topics: Chemistry and Pharmacology
    Notes: Summary A method is presented for the calculation of retention indices at an assigned temperature from temperature-programmed data. If the retention times at two different program rates for the solutes and the n-alkanes are known, the retention indices at an assigned temperature can be calculated directly.
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  • 42
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    Chromatographia 25 (1988), S. 577-581 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Process scale ; Examples of separations
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    Topics: Chemistry and Pharmacology
    Notes: Summary The flexibility of process scale high performance liquid chromatography is demonstrated by three examples of reversed-phase separations (a) a standard purification (b) isolation of trace compounds, and (c) recovery from crystallisation mother liquors. It was shown that a material, thought to be acceptably pure, contained a toxic impurity, and a remaining impurity, a previously unseen component of potential therapeutic interest. Favourable cost data were indicated for example (3).
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  • 43
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Benzidine+diaminodiphenyl methane derivatives ; Preconcentration from urine ; UV and electrochemical detection
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    Topics: Chemistry and Pharmacology
    Notes: Summary For the title compounds 4,4′-DADPM, MOCA, 3,3′-DCB, 4-ADP and 4-ADPA listing on the EPA priority pollutant list, an analytical practicable, reliable, reproducible and sensitive procedure is required. Therefore a new method has been developed for the routine determination of these toxic aromatic amines in urine at the ppb level. The quantitative determination of amines is a suitable procedure of occupationally exposed persons. Urine sample preparation is done using simple liquid-liquid extraction followed by a precolumn enrichment (PRP1-material; Hamilton). Breakthrough measurements were done using an enrichment column packed with PRP1 material. The capacities of the studied amines ranged from 21.9mg/g to 96.6mg/g, while influent concentrations differed from 28.3mg/l to 332.0mg/l. The advantages of electrochemical detection regarding to selectivity and sensitivity are clearly indicated in this paper. Separation has been achieved applying reversed-phase-high-performance-liquid chromatography (LiChrosorb RP 18/5μm) followed by electrochemical or UV-detection. The detection limits employing an electrochemical detector at a potential of 1 V range from 2.2ng to 12.1ng. UV detection at 254 nm and 280 nm is about 10–100 times less sensitive. Recoveries from spiked water samples at the 5ppb levels were 75% to 96% respectively. The standard deviation of the developed procedure varies from 5.3% to 14%. Day-to-day repeatability is good.
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  • 44
    ISSN: 1612-1112
    Keywords: Thin layer chromatography ; Column liquid chromatography ; 21H, 23H-Porphine ; Metalloporphyrin complexes
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    Topics: Chemistry and Pharmacology
    Notes: Summary The chromatographic mobility of 21H, 23H-porphine and its Ni(II), Cu(II), Zn(II) and Pd(II) complexes were investigated by high-performance thin-layer chromatography on an octadecyl-bonded, silica gel plate with various polar organic solvents including alcohols, acetonitrile, dimethylsulfoxide and propylenecarbonate. The mobility generally decreases according to the central metal ion of the complex as follows: Zn(II)〉(free porphine)〉Ni(II)〉Pd(II)〉Cu(II). Methanol is a good choice of solvent for the separation of these metal porphine complexes. Successful separation of porphine and the four metal complexes is accomplished within 13 min on a LiChrosorb RP-18 column with methanol eluent.
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  • 45
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    Chromatographia 22 (1986), S. 183-186 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; C2−C5 hydrocarbons ; Pre-Concentration on silica gel ; Sorption efficiency
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    Topics: Chemistry and Pharmacology
    Notes: Summary A short stainless steel column packed with silica gel is cooled to −78°C and atmospheric hydrocarbons are preconcentrated from 3 I of air on it. Desorption to the analytical column is by heating for 10 min to 200°C. Analysis is by GC on OPN-Poracil C at 27°C. The sorption efficiencies were nearly 100% for most of the light hydrocarbons.
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  • 46
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    Chromatographia 25 (1988), S. 717-720 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Reversed-phase chromtography ; Antifungla agent ; Pharmacokinetics
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    Topics: Chemistry and Pharmacology
    Notes: Summary A high-performance liqid chromatographic method is reported for the measurement of miconazole in systemic, fungal infectious patients. Pharmacokinetic data are presented for a single patient receiving miconazole therapy. Sample preparation involves protein precipitation by acetonitrile (1:1, vol/vol). Analyses are carried out on a reversed-phae chromatographic system using octadecylsilane stationary phase: a mobile phase consisting of 0.05 M acetate buffer (pH 7.4)acetonitrile (20:80, vol/vol) is used to elaute miconazole is quantified on the basis of ultraviolet absorption at 220 nm. The precision of the method ranged from 3.21% at 0.5 mg/L to 0.85% at 2.0 mg/L. The limit of quantification was established as 0.1 mg/L. Interference from other drugs that are co-adimistered such as amphotericin B, 5-fluorocytosine of ketoconazole and most other comonly encountered drugs was not observed.
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  • 47
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Mobile phase composition and column temperature ; Retention prediction ; Polycyclic aromatic hydrocarbons
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    Topics: Chemistry and Pharmacology
    Notes: Summary The relationship between the logarithmic capacity factor measured in reversed-phase liquid chromatography and the operating conditions including the mobile phase composition and the column temperature is investigated. The strategy described herein can offer the possibility to predict the retention of polycyclic aromatic hydrocarbons without any experiments and standard materials, by utilizing equations describing the relationships between retention, temperature, mobile phase composition and physicochemical properties of the solutes previously stored in the program of the microcomputer-assisted retention prediction system. This concept is one of the most promising techniques for the optimization of the separation conditions in reversed-phase liquid chromatography.
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  • 48
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Fractional factorial experimental designs ; Ruggedness test ; Method validation
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    Topics: Chemistry and Pharmacology
    Notes: Summary Recently much attention has been directed to the validation of analytical methods. The level of validation will depend on the method application. If a method is developed for general use, for instance by different analysts, instruments or laboratories, then the effect of these changes need evaluation. This is normally referred to as ruggedness testing, where the limitations of the method to changes in the specified conditions are examined. This paper examines the use of Plackett-Burman fractional factorial experiment designs for ruggedness testing in high performance liquid chromatography (HPLC). The ability of these designs to identify confounding effects is applied to the stability indicating analysis of Salbutamol and its major degradation product, AH4045. The results show that confounding effects, proving extremely pertinent to HPLC, can be identified. The assay proved rugged to most tested changes although not to the use of column packing material from different manufacturers.
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  • 49
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    Chromatographia 26 (1988), S. 125-132 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Non-equilibrium frontal chromatography ; Nonlinear isotherms ; Variable velocity ; Multicomponent mixtures
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    Topics: Chemistry and Pharmacology
    Notes: Summary The paper presents a classification of various theoretical models for multicomponent gas chromatography at u=var for high concentrations of the mixture components with consideration of the major distinctive features of the interphase mass exchange inside the porous grains of the adsorbent and outside them within the porous medium of the chromatographic column. It has been shown that the conditions determining a given front behaviour of multicomponent gas mixture at u=var depend on: theoretical models for the kinetics and dynamics of adsorption; the values of mass exchange parameters inside the porous grains and in the porous medium. Formulae have been derived for calculating the values of the quantities characterising the frontal behaviour in the stage of adsorption and desorption of multicomponent mixture at u=var.
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  • 50
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    Chromatographia 22 (1986), S. 231-234 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Post-column reactor ; Crosheted PTFE construction ; Photochemical reaction detection
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    Topics: Chemistry and Pharmacology
    Notes: Summary Construction of crocheted photochemical reactors for use in high performance liquid chromatography is described. The design of these reactors is optimal for low intensity light sources because of their cylindrical configuration. Band broadening is minimized by the use of tightly crocheted narrow bore tubing and fittings modified to reduce dead volume. These reactors are suitable for most post-column photochemical reactions with the additional possibility of serving as mixing/delay coils, deoxygenation devices for electrochemical detectors, and as low dispersion detector cells for chemiluminesckent reactions.
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  • 51
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Alkyl-bonded phases ; Retention behaviour ; Ligand density ; n-alkyl chain length
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    Topics: Chemistry and Pharmacology
    Notes: Summary Two series of bonded phases were synthesized employing LiChrospher Si 100, 10 μm and n-alkyldimethylmonochlorosilanes as silanizing reagents. In series A the n-alkyl chain length, n, of the bonded phase was varied between 1 and 20 at a constant ligand density of 3.5±0.2μmol·m−2. In series B the ligand density, d, was gradually changed from 0 to 4.1μmol·m−2 on the C1, C4, C6, C8 and C18 bonded phases, respectively. The capacity factors of benzoic acid esters and anilines as solutes were found to increase linearly with the n-alkyl chain length of packings at constant eluent composition (series A) up to a so-called critical chain length, ncrit, where the capacity factor remained constant. ncrit was in the range from 11 to 14. The same pattern was observed when plotting the solute capacity factor against the ligand density of the packing at constant n and constant eluent composition (series B). The critical ligand density, αcrit, varied between 2.3 and 3.2 μmol·m−2 depending on n and the solute. Furthermore, solute retention was slightly higher on RP packings with an even number of carbon atoms in the alkyl chain than on those with an odd number. These findings are consistent with the results of Berendsen and de Galan (J. Chromatogr., 196, 21 (1980)), Dill (J. Phys. Chem., 91, 1980 (1987)) and Simpson and Lau (to be published). The observed phenomena reflect the dynamic structure of RP silicas which are related to the mobility of solvated n-alkyl chains. Due to the lack of a precise conformational analysis of the surface of RP silicas, a semiquantitative model was applied to interprete the described dependencies.
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  • 52
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    Chromatographia 25 (1988), S. 21-24 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Sample concentration ; Chromatographic evaporation ; Solvent effect
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    Topics: Chemistry and Pharmacology
    Notes: Summary Several micro-techniques for the removal of solvent from dilute solutions of volatile compounds have been compared. Large solute losses were experienced when the conventional blow-down technique was applied. Better yields could be obtained with static evaporation procedures, as long as an effective reflux was maintained. However, careful optimization of the vessel design and operating conditions is necessary. The most efficient volume reduction technique was shown to be chromatographic evaporation. Quantitative recoveries were obtained for the compounds tested and the process was significantly faster than static concentration. Moreover, operating conditions (gas flow, temperature) are less critical. With modifications, the principle can be used for the concentration of large sample volumes down to a few microliters.
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  • 53
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Stationary phase polarity ; Polarity parameters ; Structure-retention relationships
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    Topics: Chemistry and Pharmacology
    Notes: Summary The new stationary phase polarity parameters BN and BS evaluated from the concept of the electric intermolecular interactions are used to describe the polarity of polyoxyethylene glycol dialkyl ethers and their sulphur analogs. Relations between the discussed parameters and accepted measures of surfactants' polarity are presented and discussed. The considered parameters are correlated with the compound structures. Structural increments for characteristic fragments of the molecule are calculated and use to predict BN and BS values.
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  • 54
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    Chromatographia 25 (1988), S. 134-138 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Sulfur ; n-Octane adsorption
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    Topics: Chemistry and Pharmacology
    Notes: Summary From the adsorption isotherms of n-octane on the surface of sulfur at 29.8°C and 40.6°C some thermodynamic functions were determined. On the basis of these data the structure of the adsorbed layer of n-octane is postulated. The molecular interactions and adsorption mechanism are also discussed. It is stated that both quasi-liquid and quasi-sold layers may be formed on the surface of sulfur depending on the surface coverage with n-octane.
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  • 55
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    Chromatographia 25 (1988), S. 265-271 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Chiral phases ; Polymer coating ; Quinine substituted polysiloxanes
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    Topics: Chemistry and Pharmacology
    Notes: Summary Stationary phases for chiral separations have been synthesized by chemical modification of porous small particle silica using new procedures of fixation of the chiral moiety. So called pre-polymers of the methylpolysiloxane polysiloxane type are immobilized on silica surfaces by different procedures. These pre-polymers are substituted by chiral groups. Their synthesis is done externally i.e. not in-situ on the support surface. The immobilization on the silica surface is achieved by crosslinking and/or by chemical bonding. Anchor groups within the pre-polymer (e.g. SiH) as well as on the silica surface (SiOH) give rise to the chemical bonding therewith. Chiral phases with quinine as the chiral moiety were obtained which show high separation efficiency as well as chemical stability, in addition to the enantiomeric selectivity required for the separation of certain types of aliphatic and aromatic alcohols.
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  • 56
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    Chromatographia 25 (1988), S. 288-294 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Mobile phase volume ; Ionic solutes ; Eluent electrolyte
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    Topics: Chemistry and Pharmacology
    Notes: Summary A new method for the determination of the mobile phase volume (V m) in liquid chromatography is presented based on the model regarding the retention of ionic solutes in the presence of eluent electrolytes. TheV m value can be determined by measuring the retention volumes of two ions that have the same charge in two eluent electrolyte systems. Compared with the methods using isotopically labelled eluent components or inorganic salts asV m markers, the method presented is proved to give more reasonableV m values for both normal and reversed-phase liquid chromatography. As well as in binary mixed solvent systems, theV m values in single solvent systems can be determined by this method.
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  • 57
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    Chromatographia 25 (1988), S. 313-318 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Retention index ; Slope of log plot ; Homologous series ; Partition coefficient
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    Topics: Chemistry and Pharmacology
    Notes: Summary The slope of the n-alkane log plot dt′R/dnc (t′R=adjusted retention time; nc=carbon number) for a stationary phase can be used to obtain the retention index of an unidentified substance in a chromatogram containing only one peak with a known retention index, or to predict the retention time of a substance from that of a different homolog in the same series. It can also be used to translate retention indices into relative retention time, partition coefficient or specific retention volume. Published values of the slope are collected and critically evaluated. Equations are deduced that predict its approximate value at a specified temperature given the value at only one other temperature.
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  • 58
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    Chromatographia 25 (1988), S. 339-342 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Gradient elution ; Prediction of retention
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    Topics: Chemistry and Pharmacology
    Notes: Summary A general equation for the final retention of a solute chromatographed under conditions of stepwise gradient elution has been derived. The elution process and the distances travelled by solutes as a function of eluent volume were simulated by computer for the optimization of stepwise gradient prorams from isocratic HPLC data. The validity of the equations was experimentally veritied.
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  • 59
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    Chromatographia 25 (1988), S. 272-278 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Polyaromatic hydrocarbons ; Molecular parameters ; Retention prediction
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    Topics: Chemistry and Pharmacology
    Notes: Summary The present research studies the possibility of using the correlation dependence between molecular parameters of unsubstituted polyaromatic hydrocarbons (PAH) and their retention in reversed-phase liquid chromatography to optimize the conditions for the separation and identification of unknown peaks on the chromatograms of multicomponent mixtures. A linear correlation equation, that takes the number and environment of the carbon atom in the PAH molecule into account as well as the differences in the specific interactions of isomeric molecules with polar eluent, has been proposed. The adequacy of the proposed PAH retention model was verified by comparing the calculated retention values with the experimental data. The possibility of identifying unsubstituted PAH according to the number of carbon atoms of various types and according to the values of the molecules lengths (calculated on the basis of the retention of these substances under different eluent compositions) was exemplified by various chromatographic systems (reversed phase-eluent-PAH molecules).
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  • 60
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    Chromatographia 25 (1988), S. 327-331 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Olefin group selectivity ; Methylene group selectivity ; Non-aqueous reversed-phase
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    Topics: Chemistry and Pharmacology
    Notes: Summary The effects of mobile phase composition upon olefin group selectivity (the ratio of the retention factor of a n-alkane to 1-olefin of equal carbon number) has been examined for non-aqueous reversed-phase liquid chromatorphy. Under time-normalized conditions, large variations in olefin group selectivities were noted as the mobile phase constitutents were changes. However, methylene group selectivities were found to be insensitive to the nature of the mobile phase under these conditions. Mobile phases containing alcohols demonstrated low olefin group selectivities compared to those containing acetonitrile as weak solvent. The results of this study explain variations previously observed in the LC separation of olive oil triglycerides that differ in the number of methylene groups and double bonds.
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  • 61
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Cyano bonded phases ; Residual silanol groups ; Diethyldithiocarbamates
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    Topics: Chemistry and Pharmacology
    Notes: Summary When a cyano bonded phase is used together with a nonaqueous eluent, it is universal that the silanol groups which remain at the surface of the silica gel after bonding affect the retention of solutes. With solutes containing such atoms as N, S and O, hydrogen bond may form between the solute and the residual silanol group, leading to dual retention mechanism. Based on the understanding of retention mechanism, methods were developed to separate metal-diethyldithiocarbamate (DDTC) chelates and crown ethers on cyano bonded phase, the mobile phase being a nonaqueous solvent containing triethylamine (TEA).
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  • 62
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    Chromatographia 25 (1988), S. 393-396 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Separation of optical isomers ; Chirasil-Val capillary columns ; Amino acid esters
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    Topics: Chemistry and Pharmacology
    Notes: Summary D,L-amino acids were derivatized with (+), (±)-2-butanol or N-trifluoroacetyl-L-prolyl chloride (L-TPC) and then chromatographed. Four optical isomers were separated on a Chirasil-Val capillary column. By this method, the concentration of optical impurities arising from the commercial optically active reagents can be determined. The observed abnormal elution orders of enantiomeric amino acid esters may be caused by a selective intermolecular force.
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  • 63
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    Chromatographia 25 (1988), S. 409-412 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Separation of proteins ; Biological activity after separation
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    Topics: Chemistry and Pharmacology
    Notes: Summary The proteins of the large ribosomal subunit fromEscherichia coli have been separated by size-exclusion, ion-exchange and reversed-phase high-performance-liquid chromatography (HPLC) using various buffer systems. The biological activity of the isolated proteins was tested via their ability to assemble into active 50S subunits (total reconstitution). The activity of the reconstituted subunits was measured with poly(U)-dependent poly-(Phe) synthesis. Reversed-phase HPLC techniques yielded active proteins (80–100%) by application of 2-propanol or acetonitrile. Proteins prepared by size-exclusion chromatography employing ammonium acetate as buffer also gave highly active proteins (70%). On the other hand, separation of the proteins on ion-exchange columns, using urea containing buffers, resulted in reduced activity (up to 50%).
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  • 64
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Phospholipids ; Amniotic fluid ; Fetal lung maturity
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    Topics: Chemistry and Pharmacology
    Notes: Summary A new quantitative analytical method for the determination of phospholipids in amniotic fluid by high performance liquid chromatography (HPLC) is described. In addition to the main compounds, phosphatidylcholine (lecithin) and sphingomyelin, the so-called minor phospholipids, phosphatidylglycerol, phosphatidylinositol and phosphatidylethanolamine can also be determined. Separation is achieved using a guard-column of Lichrosorb Si 60 and an analytical column of Lichrosorb DIOL. Acetonitrile/water is used as mobile phase at an elevated temperature. By determining the recovery rates, the within-run and the between-run precision, it was shown that sufficient accuracy and precision could be achieved for all the parameters examined. The method is highly sensitive, the detection limit for sphingomyelin is 0.2 μg and 0.1 μg for all the other components. A single determination of 5 phospholipids in an amniotic fluid sample takes about two hours. By performing simultaneous extractions it is possible to analyse 5 samples per day.
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  • 65
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Reversed-phase diphenyl and naphtylethyl bonded phases ; Retention/molecular polarizability relationships ; Peropyrene aromatics
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    Topics: Chemistry and Pharmacology
    Notes: Summary The retention behavior of 15 peropyrene-type polycyclic aromatic hydrocarbons was investigated on various bonded stationary phases in reversed-phase liquid chromatography. On diphenyl and naphthylethyl bonded phases, high correlations were obtained between the molecular polarizability of solutes and their retention. However, very low or no correlations were found on various octadecyl bonded phases. These facts are discussed by using the electrostatic interaction concept between the solutes and the stationary phase. We conclude that these observations are due to two reasons: the difference in the degree of planarity of polycyclic aromatic hydrocarbons and the high ability of planarity recognition of octadecyl bonded phases.
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  • 66
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    Chromatographia 25 (1988), S. 504-506 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Porous polymeric sorbent ; Solid-phase extraction ; Chlorophenols
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    Topics: Chemistry and Pharmacology
    Notes: Summary A new porous polymer obtained by the copolymerization of two cross-linking agents: 1,4-di(methacryloyloxymethyl) naphthalene and divinylbenzene was used for the off-line preconcentration of chlorophenols from water solutions by solid-phase extraction. In order to establish its applicability to preconcentration the recoveries and breakthrough volumes of phenol, 2-; 3-chlorophenols; 2,3-; 2,4-dichlorophenols and 2,4,6-trichlorophenols were studied. The recoveries of the studied compounds were compared with those obtained for chemically bonded phases containing hexyl and octadecyl groups.
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  • 67
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Essential oils ; Evaporation rate ; Perfume composition
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    Topics: Chemistry and Pharmacology
    Notes: Summary A simple method was developed for the determination of the evaporation rate of essential oils and perfumery composition using gas chromatography with temperature programming. The volatility of 19 essential oils and 17 perfumery composition was evaluated. The method is useful for different comparative measurements.
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  • 68
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    Chromatographia 25 (1988), S. 515-519 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Retention/structure relationships ; Retention prediction ; Substituted phenols
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    Topics: Chemistry and Pharmacology
    Notes: Summary A retention prediction system (RPS) for substituted phenols in reversed-phase HPLC using a ternary mobile phase was investigated. The RPS was used to predict the retention times of the phenols, and then evaluated by comparing measured and predicted retention data. Excellent agreement between both values was obtained. In addition, the retention mechanism of the phenols was investigated by means of a correlation analysis relating the parameters of the RPS to the physicochemical properties of the phenols. The three properties investigated (partition coefficient, hydrophobic substituent constant and Hammett's constant) were used to describe quantitatively the structure-retention relationship. Significant correlating equations between these descriptors and the retention data were obtained.
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  • 69
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; NAD analogs ; NAD glycohydrolase
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    Topics: Chemistry and Pharmacology
    Notes: Summary Pig brain NAD glycohydrolase immobilized on Affi-Gel 10 or nylon 6 was used for the conversion of NAD into 3-acetylpyridine adenine dinucleotide (APAD) or 3-aminopyridine adenine dinucleotide (AAD). A reversed-phase chromatographic system consisting of a C18 Resolve column and phosphate buffer (pH 6.2)-methanol as the mobile phase was used to monitor the production of APAD and AAD.
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  • 70
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    Chromatographia 25 (1988), S. 598-602 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Capillary columns ; Steroid profiles
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    Topics: Chemistry and Pharmacology
    Notes: Summary Steroid conjugates are hydrolysed enzymatically using β-glucuronidase after extraction from urine using a solid phase extraction cartridge. After hydrolysis the free steroids are removed from the matrix, again utilising solid phase extraction. Derivatisation of the free hydroxyl groups using Hydrox-Sil AQ produces the respective TMS ethers which are extracted into hexane, in which solvent they are stable for many days. Capillary GC analysis with flame ionisation detection produces a profile of the steroids present in the sample. This technique is suitable for following changes in the urinary excretion profiles of patients undergoing investigation for a variety of steroid production-related diseases.
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  • 71
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    Chromatographia 25 (1988), S. 603-608 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Ion interaction reagent HPLC ; Separation of amines
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    Topics: Chemistry and Pharmacology
    Notes: Summary Ion interaction reagent RP-HPLC has been employed for the separation of some typical aliphatic and aromatic amines. The effects on retention of the alkyl chain length of the eluent, and of the eluent flow-rate have been studied. The use of solutions of hexylaminium-, octylaminium-and decylaminium-salicylate has been tested and compared, employing both conductometric and spectrophotometric detection. On the basis of the results obtained, the optimal experimental conditions can be chosen for each separation. Aliphatic and aromatic mono and diamines can be separated and detected, with an average sensitivity of the order of 40 ng without any pretreatment or derivatization. The retention data obtained for amines, compared with those obtained with the same ion interaction reagents for anions, help in the interpretation of the mechanism involved in the technique.
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  • 72
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    Chromatographia 25 (1988), S. 609-612 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Gas chromatography ; Triglyceride composition of grapes ; Identification system
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    Topics: Chemistry and Pharmacology
    Notes: Summary The triglyceride composition of the Tempranillo grape (Vitis vinifera) has been examined by a combination of HPLC and GLC. To identify the triglycerides, equations were applied relating log k′ with the molecular variables: equivalent carbon number, chain length and number of double bonds in each of the fatty acids in the glycerides. Ten triglycerides were found, the principal ones being trilinolein (35.75%), dilinoleyl-olein (21.03%) and dilinoleyl-palmitin (17.02%).
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  • 73
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Collagenase ; Enzyme activity
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    Topics: Chemistry and Pharmacology
    Notes: Summary The activity of bacterial collagenase Clostridiopeptidase A was estimated using a labelled synthetic peptide, 4-phenylazobenzyloxycarbonyl-L-Pro-L-Leu-Gly-L-Pro-D-Arg, as substrate. The N-protected dipeptide obtained after enzymatic hydrolysis of Leu-Gly peptide bond was quantified by reversed-phase, high-performance liquid chromatography using 4-phenylazobenzyloxycarbonyl-L-Pro-L-Phe as internal standard. The time dependence of the appearance of the hydrolysis product and the dependence of rates of hydrolysis on collagenase concentration were linear. Kinetic parameters for collagenase were determined to test the suitability of the described procedure.
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  • 74
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Racemic resolution ; Effect of temperature
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    Topics: Chemistry and Pharmacology
    Notes: Summary The effect of temperature on the resolution of racemates was investigated with respect to the resolution of racemic mixtures of aminoacid esters and 2,2,2-trifluoro-1-(9 anthryl) ethanol. Generally the capacity factor (k′) was found to increase with decreasing temperature. The values of the difference in the standard change of molar Gibbs energy, (ΔΔG), between the more retained and the less retained enantiomer do not appear to vary in a particular fashion. The sign of the enthalpic (ΔΔH) and the entropic, (ΔΔS) quantities for all the mixtures also depend upon the nature of the solute mixture.
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  • 75
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    Chromatographia 25 (1988), S. 655-658 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Structure-retention relationships ; Connectivity indices, topological indices ; Alkenes
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    Topics: Chemistry and Pharmacology
    Notes: Summary Retention indices of different alkenes are correlated with connectivity and topological parameters. The appropriate statistically valid relations hips are derived and discussed.
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  • 76
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    Chromatographia 25 (1988), S. 735-736 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; α,ω-diiodoperfluoroalkanes ; Separation ; identification
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    Topics: Chemistry and Pharmacology
    Notes: Summary The separation of α,ω-diiodoperfluoralkanes on a glass capillary column coated with OV-101 methylsilicone was investigated. Retention indices were determined at three temperatures (140, 150 and 160°C). The correlation between the retention indices and the boiling points of the investigated compounds was studied.
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  • 77
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    Chromatographia 25 (1988), S. 731-734 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Retention Index (l) ; Temperature dependence of Retention Index
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    Topics: Chemistry and Pharmacology
    Notes: Summary A linear dependence of (T−T1)/[1(T)−1(T1)] on temperature (considering the retention index 1(T1) at temperature T1 as a standard value) is derived. Both ther retention index at an assigned temperature and the temperature dependence of the retention index can be calculated from retention data measured at two temperature-programing rates.
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  • 78
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    Chromatographia 25 (1988), S. 791-796 
    ISSN: 1612-1112
    Keywords: Gel permeation ; Column liquid chromatography ; Column switching ; Additives in cellulose acetate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The capability of elution-elution multi-dimensional liquid chromatography was investigated. A “column scaling” approach was evaluated for the quantification of low-molecular-weight additives in cellulose acetate. A small-bore (1-mm i.d.) gel-permeation column was used to separate the higher-molecular-weight polymer from the lower-molecular-weight components. Once separated these additives were transferred to a C18 reversed-phase column via a switching valve. The reversed-phase system successfully separated and quantified individual additives. Analysis time for an ultraviolet inhibitor, Tinuvin®P, in cellulose acetate, including re-equilibration, was approximately 30 minutes. Both accuracy and precision were good. Precision over a three day period was about 1.5%.
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  • 79
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    Chromatographia 25 (1988), S. 811-814 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Separation of trimedlure isomers ; Medfly ; Ceratitis capitata
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    Topics: Chemistry and Pharmacology
    Notes: Summary Semi-preparative high-performance liquid chromatographic procedures on 5 μm silica were developed for the isolation of gram quantities of eight trimedlure isomers (trans: A, B1, B2, and C;cis: V, W, X, and Y) for comparative biological evaluation and NMR studies. Isolations were made from an eight-component 2∶1cis: trans-trimedlure mixture, a four-componentcis-trimedlure mixture, trimedlure-B2:X and trimedlure-C:W epimerization merization mixtures, a trimedlure-B1:Y:B2 mixture, and a trimedlure-A concentrate.
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  • 80
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    Chromatographia 22 (1986), S. 319-328 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Mass transfer coefficients ; Diffusion inside packing materials ; Comparison of liquid-solid and liquid-liquid systems
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The stationary zone mass transfer coefficient (C5) in the reduced plate height equation has been determined experimentally for an adsorption and a partition system generated on the same column. Longitudinal diffusion terms (B-terms) were measured on these systems by applying the arrested elution method. The experimentally determined C5 terms for the LLC system are 4–6 times lower than for the LSC system. B-terms for the LLC system were found to be dependent on capacity ratios and were substantially larger than the B-term for the LSC system, which turned out to be independent of capacity ratios. The obstruction factor (γip) for the intraparticle pore space was estimated by fitting the experimentally determined effective diffusion coefficients according to a mass transfer equation for packed beds. This equation was obtained by transforming a known expression for heat transfer in packed beds. Knowledge of γp allows the prediction of the magnitude of the stationary zone mass transfer (C5-term) and the comparison between the experimental and predicted values. The agreement is good in the LSC system. In the LLC system the predicted and experimental C5 values for capacity ratios up to k′=2.00 are well matched, whereas the difference becomes larger from k′=3 on. This paper explains why the efficiency of straight phase LSC systems is often substantially surpassed by analogous LLC systems.
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  • 81
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    Chromatographia 22 (1986), S. 381-387 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Precolumn derivatisation ; Amino acid analysis ; Fluorenylmethyloxycarbonylchloride (FMOC)
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    Topics: Chemistry and Pharmacology
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  • 82
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    Chromatographia 26 (1988), S. 133-138 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Electrochemical detection ; Flavonoids ; Metal-complexes
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    Topics: Chemistry and Pharmacology
    Notes: Summary The electrochemical and chromatographic behaviour of flavonoid standards and of flavonoids extracted from food (green tea, black tea and onions) is investigated with respect to metalbinding properties. It is shown that metals such as iron, copper or aluminium are complexed by flavonoids, preferrably by those having an aromatic o-dihydroxy structure. This is confirmed by cyclic voltammetry on HPLC fractions (stopped flow) and by AAS measurement of metals. As the complexing sites of flavonoids are closely related to electrochemical properties, this is used for an indirect detection of metal species at low oxidation potentials. For iron species in particular a sensitive and selective detection is possible. For copper reductive detection can also be used.
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  • 83
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Electrochemical detection ; Morphine ; Polymeric column
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A simple, sensitive, accurate and reliable method for morphine determination in biological samples has been developed. It uses reverse-phase HPLC on a polymeric column with an eluent (0.05 mol/L dibasic sodium phosphate: acetonitrile, 85∶15) at pH 9.5, allowing both the suppression of ionization of morphine amine and the promotion of oxidation of the phenolic group. Amperometric detection at mild oxidizing potential (350 mV) proves very selective, and, therefore, only a simple and rapid one-step liquid-liquid sample preparation is required. Under these conditions “clean” chromatograms are obtained even with complex biological matrices such as cadaveric blood, urine and hair. Minimum detectable amount of morphine is about 200 pg injected. A calibration line with a correlation coefficient of 0.99996 has been produced over the range 7.5–250 ng/mL. Precision results comparable to other HPLC methods.
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  • 84
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    Chromatographia 26 (1988), S. 171-177 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; GC/MS analysis ; Polycyclic aromatic hydrocarbons ; Bituminous coal ; Brown coal ; Plant waxes ; Thermodesorption
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Polycyclic aromatic hydrocarbons (PAH) today are ubiquitous detectable constituents of recent sediments. The compounds are adsorbed on particulate emissions and are thus transferred to the environment. To date the analysis of PAH in sediments, dust samples and plant material is based mainly on the application of solvent-extraction methods followed by liquid chromatography and/or gas chromatographic separation of the extracts. An alternative approach for the analysis of PAH in solid samples such as coal, sediments, dust samples and plant waxes is shown in this contribution. A commercially available device for the analysis of volatile compounds present in solid matter is connected on-line to a GC/MS system. The device enables the thermal desorption of hydrocarbons at a temperature of 320°C. Subsequently, the hydrocarbons trapped on the initial part of the capillary column are analyzed by GC/MS. The application of mass chromatography provides the possibility of detection and quantitation of PAH in complex mixtures even when they coelute with other compounds. The sample amount required varies between 1 and 10 mg depending on the hydrocarbon content.
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  • 85
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Electrochemical detector ; Phenolics ; Lignocellulosic materials
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The application of HPLC with an electrochemical detector for the determination of phenolics in lignocellulosic materials is reported. The separation of phenolic acids and aldehydes (gallic acid, p-hydroxybenzoic acid, vanillic acid, p-coumaric acid, syringic acid, ferulic acid, vanillin, syringaldehyde and p-hydroxybenzaldehyde) on two different columns (reversed phase C6 and styrene-divinylbenzene PLRP-S) is shown. Chromatograms of phenolic compounds in neutral, basic and oxidative extracts of wheat straw treated with NaOH and white rot fungusStropharia rugosoannulata are reported along with quantitative results.
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  • 86
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    Chromatographia 26 (1988), S. 234-236 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Preparative-scale separations ; Teicoplanin ; Structure determination
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    Topics: Chemistry and Pharmacology
    Notes: Summary Teicoplanin, a lipoglycopeptide antibiotic active against gram-positive bacteria, is produced as a complex mixture consisting of six major components and four chemically related minor cmmponents. Preparative HPLC was used to isolate small amounts of the pure minor components, in order to determine their structures. In the present paper the isolation procedures are presented, as well as the analytical HPLC conditions. The retention times of the minor components with respect to those of the more abundant compounds, permittedus to make hypotheses on their structures, which were then confirmed by NMR and FAB-MS investigations.
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  • 87
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Phase-transfer catalysis ; On-line derivatization ; Phenolic steroids
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    Topics: Chemistry and Pharmacology
    Notes: Summary Commercially available equipment from two manufacturers served to set up an automated system for the precolumn phase-transfer-catalyzed dansylation of phenolic steroids, using ethynyl estradiol (EE) and estradiol (E) as model compounds. Using different mixing techniques, the on-line determination of EE and E in 200μl untreated urine samples was achieved at a rate of 3–8 analyses per hour. Detection limits were calculated to be 3–5 ng/ml. Calibration curves in urine were linear over two orders of magnitude with r=0.999 (n=5) for EE and r=0.999 (n=6) for E. The repeatability of the determination of EE in urine (1μg/ml) was 3.9% (RSD; n=20) and of E (1.5μl/ml) 3.8% (RDS; n=10). The use of plasma instead of urine in the on-line procedures was not possible due to rapid formation of emulsions, but E and EE were determined in 100μl plasma samples using a mild off-line mixing procedure in 10min. Detection limits were calculated to be ca 10ng/ml. A reaction detector, based on a solvent-segmented system, was developed for the on-line post-column dansylation of phenols and was coupled with a reversed-phase LC system. The highly selective system showed excellent linearity over at least two orders of magnitude with r=0.9999 (n=6) for both phenol and 2,5-dimethylphenol. The reproducibility was good with RSD values of around 2%. Detection limits for loop injections from standard solutions were calculated to be between 4 and 11ng.
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  • 88
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Enantiomeric purity ; Chiral HPLC ; Oxyphenonium ; Post-column extraction detection
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A method is described for the determination of the enantiomeric purity (enantiomeric excess) of the anticholinergic drug oxyphenonium. The method for this quaternary ammonium compound is based on the direct HPLC analysis with a chiral stationary phase. Two kinds of α1-acid glycoprotein-bonded phases were used. For the detection a post-column extraction with fluorescence detection of the ion-pair counter ion dimethoxyantracene sulphonate was used.
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    Chromatographia 26 (1988), S. 297-299 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Electrochemical detection ; 2-Mercaptobenzothiazole ; River water
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A method is proposed for the determination of 2-mercaptobenzothiazole in river waters using multi-electrode electrochemical detection HPLC. 2-mercaptobenzothiazole determination is unsatisfactory by gas chromatography as it degrades readily on the column. Multielectrode electrochemical detection HPLC combines sensitivity and the ability to ‘screen out’ other electrochemically active species. The development work leading up to the proposed method is discussed. The method has a limit of detection of 0.798μgl−1 2-mercaptobenzothiazole and a total standard deviation of 2.06μgl−1 2-mercaptobenzothiazole at a concentration of 7.97μgl−1 2-mercaptobenzothiazole in river water.
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    Chromatographia 26 (1988), S. 229-233 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Glass capillaries ; Chirasil-Val ; Immobilisation ; Enantiomeric separation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Immobilisation methods of the chiral silicone stationary phase Chirasil-L-Val have been studied. In addition to the standard techniques of radical-induced immobilisation with dicumyl peroxide and azo tert-butane, immobilisation was solely achieved by thermal treatment: conditioning at low flow-rates or under stop-flow conditions led to unexpectedly high immobilisation despite mild temperatures. The presence of water vapor in the carrier gas accelerated the immobilisation process. While up to 75% immobilisation was attainable with both ATB and thermal methods, immobilisation with DCUP did not exceed 50%, despite relatively high DCUP concentrations. Whilst all immobilisation methods were accompanied by varying degrees of racemisation at the chiral centre, it was possible to establish conditions that yielded a high immobilisation (in excess of 70%) with a negligible loss in enantiomeric selctivity. The immobilisation reactions also slightly affected the polarity of the stationary phase, reflected in a shift of the Kovats-Indices of amino acid derivatives and in the accompanying “Squalane-Effect”. With respect to immobilisation, racemisation and polarity shift, thermal immobilisation with water-saturated carrier gas proved to be the optimum method.
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    Chromatographia 26 (1988), S. 369-371 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Urinary trypsin inhibitors
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    Topics: Chemistry and Pharmacology
    Notes: Summary Human urine contains a family of trypsin inhibitors. Procedures for their purification and characterization involve laborious techniques and the conclusions are different in the identification of the separated compounds. We report results obtained by applying our RP-HPLC method to some procedures adopted by different authors.
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  • 92
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Determination of S-Carboxymethyl-L-cysteine ; Precolumn derivatization ; HPLC on-line clean-up
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary In order to follow levels of S-Carboxymethyl-L-cysteine in biological fluids for a period as long as three half-lives after drug administration during pharmacokinetic studies, an improved method for its determination had to be developed. Like the previous one, this method uses a protein precipitation step followed by an O-Phthalaldehyde derivatization step and then an HPLC on-line clean-up. This latter was obtained by means of a switching valve system, including a Nucleosil CN 5 μm (3 cm × 4.6 mm i.d.) precolumn and a Spherisorb ODS 5 μm (15 cm×4.6 mm i.d.) analytical column. The sensitivity limit was improved to 0.1 μg/ml in plasma samples and 0.2 μg/ml in urine samples. This method was applied in studies comparing single (0.75 g) and repeated (0.75 g tid) oral administration of the drug to 30 elderly patients and 20 healthy volunteers. Results showed that the half-life was 40% longer in elderly patients than in healthy volunteers, and that area under the plasma concentration versus time curve (AUC) values in elderly patients were twice those obtained with young subjects.
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  • 93
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Anion-exchange ; Biological standard reference materials ; Anion-exchange preconcentration ; Thiocyanate system
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    Topics: Chemistry and Pharmacology
    Notes: Summary A preconcentration technique involving anion-exchange in thiocyanate media has been developed for the determination of traces of bio-significant and biofunctional elements. The procedure is applied to the analyses of NBS standard reference materials as well as environmental reference materials of NIES (The National Institute of Environmental Studies, Japan Environmental Agency). The results are quoted for vanadium, cobalt, copper, zinc, and cadmium.
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  • 94
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Preparation of methyl esters ; Tetramethylammonium hydroxide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Tetramethylammonium hydroxide in methanol has been proposed as a catalyst for preparing methyl esters of both free fatty acids and glycerides of fats. Nevertheless, procedures normally recognized as suitable can be inadequate when the fat under study contains noticeable amounts of low relative molecular mass esters. The method using tetramethylammonium hydroxide has been examined and modified in order to analyze milk fats by capillary GC. The pyrolysis methylation of free fatty acids in capillary injectors has been also studied. The modified method was satisfactory for both neutral and acid milk fats.
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  • 95
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Multi-chromatography ; Selectivity tuning ; Column combination ; Theory
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The evolution of the use of mixed phases or serial column combinations is outlined, leading to systems with fixed-length columns to be used in selectivity tuning (“multi-chromatography”). The difference between multi-chromatography and multi-dimensional gas chromatography is outlined. After discussing the system used in subsequent work, the fundamental relationships of multi-chromatography are detailed. Among the basic relationships the additivity of retention data, the relationship between the individual and composite capacity factors and the relative retentivity serving as the fundamental parameter of a multi-chromatography system are discussed. The relative retentivity is derived as a function of gas holdup times, pressures, and average velocities or flow rates. Finally, the relationships between individual vs. composite relative retention, efficiency, and resolution values are deduced.
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  • 96
    Electronic Resource
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    Springer
    Chromatographia 21 (1986), S. 29-36 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Single component mobile phase ; Temperature gradients ; RI-detection ; Triglyceride analysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Three new methods of improving triglyceride separation by RP-HPLC using propionitrile as eluent and an RI detector are described. First the baseline was stabilized by indirect thermostating of the detector. Relatively high sensitivity adjustments (4×10−5 RI units full scale deflection) were possible allowing small fat samples to be injected (down to 200 μg). Second the increase of selectivity with decreasing temperature and the increasing sharpness of peaks at higher temperatures are shown. A high temperature is indispensible for saturated long chain compounds which tend to crystallize on the column. To fulfill this requirement and avoid loss of selectivity temperature programming has been investigated. Third at higher temperatures an additional axial temperature gradient up to 0.05 K/cm was applied to enhance peak symmetry. All chromatograms achieved by those temperature gradients show higher resolution than those obtained at constant temperatures. Butterfat could be separated into more peaks than has previously been possible. The chromatogram of soybean oil, besides showing excellent selectivity for more polar components shows a series of ten long chain compounds following POP.
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  • 97
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Coated porous polymers ; Partition coefficients
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Following previous work on the solute-stationary phase-adsorbent interaction phenomena associated with the use of Chromosorb 101 support in gas chromatography, the retention of different polarity compounds on columns of Ethofat, squalane and Fractonitril VI on Chromosorb 102 has been studied. The experimental partition coefficients in these three liquid phases have been compared with those ones obtained earlier on Chromosorb 101 and Chromosorb P. The values have been related to the geometry of the support surface and the different coating of the liquid phases by scanning electron microscopy.
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  • 98
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    Springer
    Chromatographia 21 (1986), S. 149-151 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Retention indices ; Comparison of data ; Alkenes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Gas chromatographic retention indices for 47 C5 to C8 alkenes on OV-101 dimethylsilicone at 50 and 70 °C were determined within a standard deviation of 0.3i.u. Data obtained on OV-101 are compared with those measured on squalane. The comparison of the retention index and dl/dT values from both columns is presented as linear regression equations with correlation coefficients greater than 0.98.
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  • 99
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    Springer
    Chromatographia 21 (1986), S. 157-160 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Alkylation ; Carboxylic acids ; Urine analysis ; Micelles
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Carboxylic acids can be converted to their methyl esters in an aqueous sample which contains no organic solvent. The reaction appears to be assisted by the presence of a quaternary ammonium salt surfactant. The procedure is best described as a pseudo-organic phase, or micelle-like, reaction. The important experimental variables have been optimized by Simplex procedures. The reaction proceeds in 80–100% yield, for common carboxylic acids, at room temperature in less than one hour. This reaction is superior to existing two-phase extractive alkylation procedures.
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  • 100
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Polar stationary phases ; Chemically-modified silicas ; Alkyl-substituted phenols
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Stationary phases containing bonded nitrile groups have been synthesized. The effect of the n-alkyl chain length connecting the nitrile groups to the surface and of the end-capping on the chromatographic properties was studied. The synthesized material was compared with commercial nitrile phases in the separation of isomeric cresols and xylenols.
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