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  • Gas chromatography  (36)
  • kinetics
  • Springer  (50)
  • American Meteorological Society
  • 1995-1999
  • 1985-1989  (50)
  • 1965-1969
  • 1955-1959
  • 1950-1954
  • 1987  (50)
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  • 1995-1999
  • 1985-1989  (50)
  • 1965-1969
  • 1955-1959
  • 1950-1954
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  • 1
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    Electronic Resource
    Springer
    European journal of nutrition 26 (1987), S. 125-137 
    ISSN: 1436-6215
    Keywords: vitamin C ; functions ; kinetics ; pool ; saturation ; requirements ; RDA
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Medicine
    Description / Table of Contents: Zusammenfassung Die Bedeutung von Vitamin C für den menschlichen Organismus wird aus den wichtigen Funktionen ersichtlich, an denen das Vitamin beteiligt ist, wie zum Beispiel Kollagen- und Karnitinsynthesen. In neuerer Zeit entdeckt wurde seine Rolle bei der Noradrenalinsynthese, der Inaktivierung von freien Radikalen sowie der Verhinderung der Nitrosaminbildung. Die Vielfalt dieser Vitamin-C-abhängigen Funktionen läßt erkennen, daß die Bedarfsfestsetzung für Vitamin C nicht nur die Verhütung der Mangelkrankheit Skorbut anvisieren, sondern auch berücksichtigen sollte, daß alle diese Funktionen jederzeit genügend Vitamin C zur Verfügung haben müßten, um optimal reagieren zu können. Das Konzept der Gewebesättigung kommt diesem Ziel am nächsten. Studien mit einem kinetischen Modell haben ergeben, daß eine Sättigung mit täglicher Einnahme von 100 mg Vitamin C bei Nichtrauchern und von 140 mg bei Rauchern eintritt, Mengen, die als optimale Werte gelten können. Bei verschiedenen Krankheiten dürfte der Bedarf höher sein; die genauen Mengen müssen jedoch erst noch ermittelt werden.
    Notes: Summary The importance of vitamin C is reflected in its multifunctional roles which include participation in collagen and carnitine syntheses, promotion of iron absorption and the more recently discovered participation in noradrenaline synthesis, inactivation of free radical chain reactions, prevention of N-nitroso compound formation and more. Given the many extra-antiscorbutic functions of the vitamin, the Recommended Dietary Allowances (RDA) should not just prevent deficiency disease but should aim at providing sufficient amounts for all vitamin C-dependent functions to operate at full capacity. The concept of vitamin C tissue saturation is best able to meet this demand. The use of kinetic models has shown that the body pool is saturated with a daily intake of 100 mg vitamin C in non-smokers and 140 mg in smokers, amounts that may be regarded as optimal RDA values. Certain disease states may be accompanied by still higher vitamin C requirements but the exact amounts are not yet known.
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  • 2
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    Colloid & polymer science 265 (1987), S. 58-64 
    ISSN: 1435-1536
    Keywords: Polymerisation ; emulsion ; styrene ; methylmethacrylate ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The dependence of emulsion polymerisation rates on a number of important parameters is considered. Attention is paid to the use of seeded emulsion systems for the evaluation of radical desorption coefficients (k o). Experimental conditions are shown to be important. When the average number of radicals per particle is low, large changes in the rate coefficient for chain termination do not have a large effect on the kinetics. With styrene and methylmethacrylate, radical re-absorption by the polymer particles is shown to be important and radical capture efficiences can be high. Consistency is established between the results of a number of workers and values fork o are shown to be lower than those calculated from chain transfer rates.
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  • 3
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    Trees 1 (1987), S. 94-101 
    ISSN: 1432-2285
    Keywords: Monoterpenes ; Abies alba Mill ; Resin ; Seeds ; Gas chromatography
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Summary Using gas-chromatographic methods, the variability of the contents of monoterpene hydrocarbons (α-pinene, β-pinene, Δ3carene and limonene) in the resin of silver fir seeds (Abies alba Mill.) was studied. Resin cavities were characterized according to their position on the seed surface. It was estabilished that the terpene content of the resin of cavities localized on the abaxialadaxial surfaces of the seed differs significantly, creating a gradient of resin composition around the circumference of the seed. The differences between various resin cavities of single seeds were greater than the differences between different seeds of a single cone and between seeds of various cones on a single tree. An accurate definition of the resin cavity location on the seeds appears to be a fundamental condition for the collection of a sample representing the resin composition of individual trees. Resin biosynthesis in the course of organogenesis and the control of terpene contents in the resin of various locations on the seed and the cone are discussed.
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  • 4
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    Molecular and cellular biochemistry 76 (1987), S. 45-54 
    ISSN: 1573-4919
    Keywords: DNA methyltransferase ; hemimethylated DNA ; kinetics ; affinity chromatography ; (rat liver)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract DNA substrate analogs were constructed from poly(dC-dG), M13, and XP12 DNA which do not contain a mixture of types of methylation sites. These were used to distinguish different kinetic mechanisms for maintenance and de novo methylation using a highly purified rat liver DNA (cytosine-5)-methyltransferase (DMase−) preparation. De novo methylation on single (ss) and double-stranded (ds) DNA was found to obey Michaelis-Menten kinetics while methylation of hemimethylated sites showed differences depending on size of the hemimethylated region. On long stretches analogous to maintenance methylation of newly replicated DNA, saturation could not be achieved and the kinetics showed non-ideal positive cooperative kinetics, while short stretches showed non-Michaelis-Menten kinetics and rapid saturation. Two types of DMase-DNA complexes could be distinguished by means of affinity chromatography on DNA-agarose matrices and in preincubation assays. The later complex, which is engaged in methyl group turnover, exhibited enhanced stability. The competitiveness of variously configured DNAs was found to parallel the stability of complex formation, e.g., ss, hemi- and ds DNA, respectively. In studies utilizing 5-bromodeoxyuridine, the thymine analog left the basic reaction mechanisms unchanged but increased the km and S0.5 while reducing the velocity of these reactions.
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  • 5
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    Oxidation of metals 28 (1987), S. 237-258 
    ISSN: 1573-4889
    Keywords: Steel oxidation ; duplex scale ; steam ; activation energy ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The kinetics of the oxidation of ferrous alloys in steam (10–60 kPa) at 450–550°C have been studied by measuring both the rate of hydrogen emission and the amount of metal oxidized. Excellent agreement has been found between the amount of metal oxidized calculated from both the total mass of hydrogen produced in the reaction and the thickness of the oxide layer formed; rate constants calculated from the rate of hydrogen emission, the mass of hydrogen produced as the reaction proceeds, and the oxide formed agree within experimental error. The rate of oxidation of a 9%Cr-1%Mo alloy at 501°C was found to be independent of the partial pressure of the steam. For this alloy, the activation energy agreed with literature values obtained at higher temperatures and pressures. The effect of the chromium and silicon content on the oxidation rates is compared. The rate constants are compared with theoretical calculations, assuming that the rate is determined by diffusion of iron in the magnetite lattice. For the 9%Cr-1%Mo alloy, the parabolic rate constant and activation energy are in excellent agreement with values calculated using Wagner's theory. The experimental rate constants are greater for the alloys containing smaller amounts of chromium; diffusion of iron along magnetite grain boundaries may be the dominant mechanism.
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  • 6
    ISSN: 1573-4943
    Keywords: lactate dehydrogenase isoenzymes ; lactate-to-pyruvate reaction ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract In order to evaluate the functional differences that may exist in human lactate dehydrogenase (LDH) isoenzymes widely used for clinical examination the kinetic and thermodynamic properties of the lactate to pyruvate reaction that they catalize were examined. Small but significant differences in the kinetic properties of the three isoenzymes were observed. The difference in the rate constants might affect the activity measurement of the individual isoenzyme as the initial velocity for the L-P reaction catalyzed will not be the same for an equal amount of enzyme. Equilibrium constants for the overall reaction in the presence and absence of pyruvate have been determined. On the basis of transition-state theory, the standard enthalpy and free-energy changes for formation of ternary activated complex were positive, while the standard entropy change was negative. Although the standard free-energy change was the same for activation by the three isoenzymes, the enthalpy and entropy changes for the LDH-3-catalyzed reaction were different from the respective values for others. A large positive value for the free-energy change and a negative value for the entropy change indicated unfavorable production of the activated complex (K infeq. sup╪ =1.89×10-16). The enzyme appears to stabilize and retain the activated complex until it dissociates into the products.
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  • 7
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    Chromatographia 23 (1987), S. 818-824 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Selective sampling ; On-line fractionation ; Essential oil analysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The paper describes the possibilities of on-line selective sampling as an on-line fraction technique for the analysis of essential oils. Selective sampling is a micro-separation method, on-line with on-column injection, carried out directly in the syringe body by means of a selective elution of the sample through a fraction cartridge. The paper reports a method of both preparing and standardizing silica gel cartridges, and illustrates through some examples the results of some elution series of solvents on different essential oils.
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  • 8
    ISSN: 1612-1112
    Keywords: Organic pollutants determination ; Gas chromatography ; Thermal desorption
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The problem of the separation of 34 volatile organic chlorinated compounds is solved by using three different GC columns selected according to the needs of the particular separation required. The effect of water vapor contained as moisture in the trapped air on the retention of some characteristic compounds is studied. The influence of dead volumes on trap injection is also studied.
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  • 9
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    Chromatographia 23 (1987), S. 888-892 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Calculation of temperature programmed ; Retention indices
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A new method is presented for the calculation of the retention indices under linear temperature programming with or without an initial isothermal period. The data calculated by the method are in good agreement with the isothermal retention indices.
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  • 10
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Esterification in aqueous solution ; n-Propyl esters of aromatic polycarboxylic acids
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The direct esterification and gas chromatographic analysis of aromatic carboxylic acids as n-propyl esters is described. Derivatization is performed in aqueous solution with n-propanol in the presence of sulfuric acid. The n-propyl esters of benzoic, phthalic, trimellitic and pyromellitic acids permit their gas chromatographic separation from each other and from fatty acids and aliphatic dicarboxylic acids. At mode ratios of [H2O]/[n-PrOH]≤0.03 the water present does not interfere with the esterification reaction. At mole ratios above 0.03 anhydrous sodium sulfate is used for binding the water, at mole ratios of [Na2SO4anh.]/[H2O]=0.51–1.52 and of [H2SO4]/[Na2SO4anh.]=0.43–1.28, respectively.
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  • 11
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    Chromatographia 23 (1987), S. 195-198 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Structure-retention relationships ; Polarity parameters ; Retention index
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The possibility of evaluation of the parameters representing the dispersive solute-solvent interactions is presented. BN and Bs values can be used to describe the liquid phase polarity and to predict the retention indices of alcohols when the model polyxyethylene glycol dialkyl ethers and their sulphur analogs are used as stationary phases. The possibility of the first ionization potentials estimation is also presented.
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  • 12
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Prediction of retention volume ; Porous polymers coated with liquid phases
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A new expression which permits the prediction of the net retention volumes in gas chromatography with column packings of coated porous polymers is reported. The porous polymers Chromosorb 101 and Chromosorb 102 were used as supports and squalane, Ethofat and Carbowax 20M as stationary phases at three different column temperatures of 80°C, 100°C and 150°C. Several organic compounds of various polarity were used as test compounds and the net retention volumes, VNtheor, have been calculated according to this new expression. The VNtheor values were compared with the experimental net retention volumes, VNexp, and it was found that the difference between these two values is dependent on the type of compound and column packing. Nevertheless, the elution order could be predicted in most cases.
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  • 13
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    Chromatographia 23 (1987), S. 499-501 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Packed+capillary GC switching system ; Precolumn construction, oven and connector
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The constractional details of precolumns, its oven and connector have been given with two types of multiflow control modules. Two types of phases made in China, a silanized pellicular beads and a non silanized pellicular silica beads, with an optimum particle size of 20μm to 30μm were packed in the precolumn 20mm in length with the column efficiency of 4620 plates/meter at column temperature of 49°C. A 25m×0.22mm i.d. capillary column coated with bonded methylsilicone phase from Chrompack connected with the precolumn (250°C) has an efficiency of 5376 plates/meter for n-octane. But it decreased to 3149 plates/meter by decreasing the precolumn temperature to 130°C.
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  • 14
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Capillary columns ; Immobilized Carbowax-type stationary phases ; Free fatty acids analysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Capillary columns coated with acid-modified poly-(ethylene glycol)-type immobilized stationary phases have been studied. The thermostability and chromatographic behaviour of the columns and the stability of the coated films after washing with different solvents were investigated.
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  • 15
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Fourier transform IR detection ; Headspace sampling ; Solvents of abuse
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary After experimental intoxication of rats, gas chromatography — Fourier transform infrared spectrometry with headspace sampling (HS/GC/FT-IR) was used to identify solvents of abuse in biological material (blood, liver, lungs and brain). Limits of detection were measured for acetone, 2-butanone, ether, toluene and trichlorethylene with standard solutions. All the solvents have been identified in the organs of the intoxicated rats. For blood samples a salting-out effect was obtained with potassium carbonate. HS/GC/FT-IR allowed the identification of metabolites of acetone (isopropanol) and of 2-butanone (2-butanol) in blood and organs.
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  • 16
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Physico-chemical properties ; Retention indices ; Cycloolefins
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The retention indices of mono and polycycloolefins with endo or exo double bonds, on squalane or polypropylenglycol 425 are related to their physico-chemical properties such as boiling point, molar volume, molar refraction, and refractive index. Equations have been empirically obtained, from which accurate retention indices of these compounds can be predicted. Unknown boiling points of some of these compounds can also be calculated from their lineal relation with the retention index on squalane.
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  • 17
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    Chromatographia 23 (1987), S. 839-843 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Stationary phases ; Porous polymer beads ; Polarity ; Adsorbents ; Breakthrough volume
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The breakthrough volume of ådsorbent traps made with porous polymer beads Porapak N, P. Q, R, S was evaluated by analysis of polarity reference substances proposed by Rohrschneider (ethanol, methyl ethyl ketone, nitrometane, benzene, pyridine) by McReynolds (butanol, methyl propyl ketone) and of the first term of some homologous series: alcohols, aldehides, carboxilic acids, nitrocompounds, iodoalkanes and nitriles. Adjusted retention times of the compounds were measured at 200°C and correlated with the physical properties and with polarity class according to Ewell. Trapping efficiency of the various Porapak types was evaluated and the theoretical breakthrough volumes at 25°C was calculated for the used test substances.
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  • 18
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    Chromatographia 23 (1987), S. 850-855 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Capillary columns ; Bacterial cellular fatty acids ; Stationary phase selectivity ; Solid phase preseparation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The importance of selectivity in the capillary gas chromatographic analysis of the cellular fatty acids of micro-organisms is underestimated. The analysis on apolar silicone phases can lead to erratic elucidation of the fatty acid structure. Qualitative errors have been detected in commercially available standards on which computer matching identification techniques are based. Using highly polar capillary columns of the cyanopropyl silicone type, the errors could be elucidated. The exact identification of the hydrolysis products of bacteria is a must for chemotaxonomic studies applying chromatographic techniques. The fatty acid methyl ester profiles can also contain other chemical components which are very important taxonomic markers. Fatty aldehydes, for example, are main components in someClostridium species. Fractionation techniques are described for selective enrichment of fatty aldehydes and hydroxy fatty acids.
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  • 19
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    Chromatographia 23 (1987), S. 215-219 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Liquid chromatography ; Thermodynamic equilibria ; Solution and adsorption thermodynamics ; Gas adsorption isotherms
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary After a brief recall of the chromatographic principles, the different applications of gas chromatographic measurements of thermodynamic equilibria were reviewed. Gas and liquid chromatographies are now well known and elegant methods for measuring the physicochemical properties and phase equilibrium thermodynamic constants. Although fundamentally a dynamical method and mostly known as a powerful separation technique, chromatography can be schematized by a sucession of equilbria of a chemical species partitioning between a mobile phase and a fixed liquid or solid stationary phase. It can be operated in either infinite dilution or finite concentration conditions and permits to collect a large number of data for calculating molecular interactions for solutes which are either rare or available at the trace level. Gas chromatography permits the measurement of gas adsorption isotherm, gas-liquid equilibria, molecular diffusion and interaction virials. The modelization of successive partition equuilibria occuring in the chromatographic column leads to rather simple expression of differential enthalpy, entropy, free energy of adsorption or solution, variation of heat capacity, complexation constant, second virial coefficients, gas-solid and gasliquid isotherm and also binary or ternary equilibria. The possibilities of High Performance-Liquid Chromatography to investigate adsorption from solutions and chemical equilibria are also discussed.
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  • 20
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    Bulletin of experimental biology and medicine 103 (1987), S. 660-662 
    ISSN: 1573-8221
    Keywords: hydrogenated phenazepam analog ; metabolism ; kinetics ; excretion ; differences
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
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  • 21
    ISSN: 1573-904X
    Keywords: angiotensin-converting enzyme (ACE) inhibitor ; RS-10085 ; degradation ; kinetics ; products ; diketopiperazine ; peptides
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The degradation kinetics, products, and mechanisms of RS-10085(1), 2-[2-(l-ethoxycarbonyl)-3-phenylpropyl]amino-l-oxopropyl]-6,7-dimethoxy-l,2,3,4-tetrahydroisoquinoline-3-carboxylic acid(S,S,S), in aqueous solution were investigated at 40, 60, and 80°C from pH 1 to pH 13. Pseudo-first-order kinetics were observed throughout the pH range studied and the log(rate)−pH profiles reflected four kinetic processes (k o, k′o, k″o, and k OH) as well as the two pKa's of 1. Excellent (〉98%) mass balance was obtained through products 2–5. At pH 4 or below, intramolecular cyclization leading to diketopiperazine 5 accounted for greater than 93% of the observed neutral- or water-catalyzed processes (k o and k′o). At pH levels greater than 5, hydrolysis giving 2 predominated and was responsible for the observed neutral- or water-catalyzed (k″o) and specific base-catalyzed (k OH) kinetic processes. Some epimerization leading to the S,S,R drug isomer (4) was also observed at pH levels greater than 7. The relative acidity of the protons at the three chiral centers of 1 was qualitatively compared and was used to explain the observed specificity in epimerization.
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  • 22
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    Pharmaceutical research 4 (1987), S. 379-384 
    ISSN: 1573-904X
    Keywords: acute tolerance ; bumetanide ; kinetics ; dynamics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Bumetanide was administered intravenously to four mongrel dogs, in a random crossover fashion, at doses of 0.05 mg/kg (I), 0.15 mg/kg (II), and 0.5 mg/kg (III) where urinary losses were replaced with lactated Ringer's solution at 1.5 ml/min (hydropenic conditions) or at a dose of 0.5 mg/kg (IV) where urinary losses were replaced with lactated Ringer's solution isovolumetrically (euvolemic conditions). Serial plasma and urine samples were assayed for bumetanide by high-performance liquid chromatography (HPLC) and for sodium by flame photometry. There were no significant differences in the pharmacokinetic parameters of bumetanide among Treatments I–IV. The dynamic parameters E max (maximum effect attributable to the drug) and s (slope factor) were not different between treatments. However, a consistent, demonstrable increase in ER50 (urinary excretion rate of drug producing 50% of E max) was observed among Treatments I (2.34 µg/min), II (3.92 µg/min), and III (6.54 µg/min); also, a significant decrease in ER50 was observed between Treatment III (6.54 µg/min) and Treatment IV (2.66 µg/min). These results show that hydration status has a marked effect on natriuretic and diuretic response and that tolerance can rapidly develop within a single intravenous dose of bumetanide.
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  • 23
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    Colloid & polymer science 265 (1987), S. 193-205 
    ISSN: 1435-1536
    Keywords: Poly(TMPS) ; in situ ; SAXS ; crystallization ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The isothermal crystallization kinetics of poly(TMPS) has been measured by ISSAXS and results obtained for a molecular weight fraction (21,000) below the critical entanglement molecular weight (25,000) and another one above it (371,000). The SAXS intensity vs. time curves suggest that a single transformation mechanism exists. The SAXS long period is independent of crystallization time for both poly(TMPS) fractions. However the interlamellar thickness contribution to the long period is dependent upon molecular weight and crystallization temperature, increasing with temperature and molecular weight. The crystallite contribution also increases over the range studied. Both fractions exhibit a significant, but reversible decrease in thickness on cooling the sample from the crystallization temperature to room temperature and recyling again. The change is more pronounced for 371,000 specimen in keeping with its lower crystallinity. The path dependence of lamellar dimensions has significant implications in the morphological characterization of polymers annealed or crystallized at one temperature and then measured at another one.
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  • 24
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    Colloid & polymer science 74 (1987), S. 55-63 
    ISSN: 1435-1536
    Keywords: Triplet energy transfer ; micelle ; solubilization ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Triplet energy transfer from 9-methylanthracene to azulene or guajazulene has been used to probe the migration of azulenes between micelles in aqueous solution. The migration of the hydrophobic solutes between small ionic and nonionic micelles had the temperature dependence expected for a process controlled by diffusion through the intermicellar solution, although the rate in some cases was substantially less than calculated from the Smoluchowski equation. Under conditions in which the micelles grow into large, probably rod-like structures, there are severe difficulties in separating the inter- and intramicellar deactivation processes. The intermicellar migration was enhanced under these conditions, in cetyltrimethylammonium surfactants on addition of chlorate ions, and in hexaethylene glycol dodecylether at temperatures approaching the cloud-point. The mechanism of this migration is discussed and compared with pertinent results from micelle relaxation kinetics and surfactant self-diffusion measurements.
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  • 25
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    Plant and soil 104 (1987), S. 13-21 
    ISSN: 1573-5036
    Keywords: ammonification ; kinetics ; nitrification ; osmotic potentials ; soluble salts
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Studies were conducted to compare N mineralization rates in salt-amended nonsaline soils to naturally-occurring saline soils. NaCl, CaCl2, and Na2SO4 were added to nonsaline soils at rates that produced electrical conductivities of the saturation extracts (ECe) of 5, 10, 15, and 20 dS m−1. Saline soils with similar properties were leached to the same ECc levels. N mineralization in the Chino soil was inhibited by salt addition, particularly with sodium and calcium chlorides. In the Domino soil there was some inhibition of N mineralization with the chloride salts, but enhancement with Na2SO4 was observed. Nitrification in both soils was more sensitive to salt addition than ammonification. N mineralization occurred more slowly in both leached saline soils compared to the salt-amended soils. Leached saline soils often accumulated greater amounts of inorganic N compared to their native saline counterparts, particularly with the 5 dS m−1 Chino soil (native, 44 dS m−1) and with the 5, 10, 15 and 20 dS m−1 Domino soils (native, 32 dS m−1). Kinetic parameters were estimated by the linear least squares (LLS) and the nonlinear least squares (NLLS) methods. Generally, the LLS transformation estimated greater values of potentially mineralizable N (No) and lower rate constants (k). With the NLLS equation, No values for the leached saline soils were usually lower, and k values usually higher than in the salt-amended soils. The nonsaline controls generally had the highest No and lowest k estimates. Average LLS rate constants for the salt-amended and leached saline soils were 0.055 and 0.083 for the Chino, and 0.104 and 0.137 week−1, respectively, for the Domino soils. With the NLLS equation, average k values for the salt-amended and leached saline soils were 0.087 and 0.089 for the Chino, and 0.181 and 0.387 week−1, respectively, for the Domino soils. These results suggest that N mineralization rates obtained in salt-amended nonsaline soils may not be representative of those in naturally-occurring saline soils.
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  • 26
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    Journal of inclusion phenomena and macrocyclic chemistry 5 (1987), S. 385-395 
    ISSN: 1573-1111
    Keywords: Nitrogen monoxide ; ESR spectroscopy ; disproportionation reaction ; CaHY-type zeclite ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract An ESR spectroscopic study of adsorbed NO on CaHY-type zeolite was carried out and the kinetics are discussed on the basis of a mechanistic model of the disproportionation reaction. An amount of NO less than the amount of Ca2+ distributed in Site II of the faujasite structure was admitted onto the sample maintained at 373 K. ESR spectra were recorded at room temperature. The spectra consisted of well-resolved signals. It is proposed that NO molecules on CaHY-type zeolite have two kinds of adsorption patterns. The initial formation of N2O may be expressed by the following reactions: $$[ ] + NO\mathop \rightleftharpoons \limits_{}^{K_1 } [NO],[NO] + NO\mathop \rightleftarrows \limits_{\overset{\lower0.5em\hbox{$\smash{\scriptscriptstyle\leftharpoonup}$}} {k} _2 }^{\overset{\lower0.5em\hbox{$\smash{\scriptscriptstyle\rightharpoonup}$}} {K} _2 } [N_2 O_2 ],[N_2 O_2 ] + NO\mathop \to \limits_{}^{\overset{\lower0.5em\hbox{$\smash{\scriptscriptstyle\rightharpoonup}$}} {K} _3 } [NO_2 ] + N_2 O,$$ where [], [NO] and [N2O2] denote vacant adsorption, NO adsorption, and N2O2 adsorption sites, respectively. A rate equation for N2O appearance (α) has been derived by a steady state approximation: $$\alpha = \frac{{\overset{\lower0.5em\hbox{$\smash{\scriptscriptstyle\rightharpoonup}$}} {k} _3 K_1 K_2 P^3 }}{{1 + (K_1 + \overset{\lower0.5em\hbox{$\smash{\scriptscriptstyle\rightharpoonup}$}} {k} _3 /\overset{\lower0.5em\hbox{$\smash{\scriptscriptstyle\leftharpoonup}$}} {k} _2 )P + K_1 (K_2 + \overset{\lower0.5em\hbox{$\smash{\scriptscriptstyle\rightharpoonup}$}} {k} _3 /\overset{\lower0.5em\hbox{$\smash{\scriptscriptstyle\leftharpoonup}$}} {k} _2 )P^2 }},$$ WhereP is the pressure of NO. The rate equation was used to explain the kinetic results of the disproportionation of NO.
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    Journal of inclusion phenomena and macrocyclic chemistry 5 (1987), S. 709-716 
    ISSN: 1573-1111
    Keywords: Cyclodextrin ; rhodamine B ; equilibrium ; kinetics ; temperature-jump
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    Topics: Chemistry and Pharmacology
    Notes: Abstract A UV/visible spectrophotometric temperature-jump study of the inclusion of the rhodamine B zwitterion (RB) by β-cyclodextrin (βCD) to form a 1:1 complex (RB·βCD) in aqueous 1.00 mol dm−3 NaCl at pH 6.40 and 298.2 K yields:k 1=(1.3±0.2)×108 dm3 mol−1 s−1,k −1=(2.2±0.5)×104 s−1, andK 1=(5.9±2.3)×103 dm3 mol−1 for the equilibrium: $${\text{RB + }}\beta {\text{CD}}{\text{RB}} \cdot \beta {\text{CD}} K_1 $$ Under the same conditions the dimerization of RB: $${\text{2}} {\text{RB}}({\text{RB}})_2 K_d $$ is characterized byK d =(1.8±1.0)×103 dm3 mol−1. The interaction of RB with αCD and γCD is weaker than with βCD, and is discussed in terms of the relative sizes of RB and the cyclodextrin annulus. Comparisons are made with the inclusions of other dyes by cyclodextrins.
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  • 28
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Aqueous samples ; Direct injection ; Traces of ketones and halogenated hydrocarbons ; Environmental analysis
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    Topics: Chemistry and Pharmacology
    Notes: Summary Procedures for the quantitative analysis of industrial effluents which involve concentration by solvent extraction or the purge-and-trap method are time-consuming, labor-intensive, and prone to error. Direct aqueous injection gas chromatography using an electron-capture detector for the analysis of volatile halocarbons at the ppb level is in routine use in many laboratories. We now discuss the development of a similar protocol for the analysis of volatile polar organics such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and tretrahydrofuran using a flame-ionization detector.
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  • 29
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Nitrogen-specific detector ; Flash methylation ; Barbital and pentobarbital ; Blood analysis
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    Topics: Chemistry and Pharmacology
    Notes: Summary A sensitive and simplified method is described for the determination of barbital (B) and pentobarbital (PB) in blood using gas chromatography with a nitrogen-specific flame ionization detector. After a simple one-step extraction, B and PB were reconstituted in trimethylanilinium hydroxide and introduced directly into the gas chromatograph. Lower limits of detection was 0.14 μg/ml for B and PB in either water or blood solutions. The recoveries for B from water and blood were 90 and 88%, respectively; for PB they were essentially complete. The average between-run and within-run coefficients of variation for B from water and blood were lower than 7.8%, whereas those of PB were lower than 3.0%. The scale and sensitivity of detection for B and PB were found to be suitable for use in pharmacokinetic studies in the rat.
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  • 30
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    Chromatographia 23 (1987), S. 423-426 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Complexation ; Mercaptosilane chemically bonded phase ; Transition metal complexes ; Olefinic π-complexes
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    Topics: Chemistry and Pharmacology
    Notes: Summary A column packing containing thiol groups chemically bonded to the silica surface was synthesized. The thiol functional groups were used as ligands capable of forming stable complexes with Cu(II). The prepared material was characterized by gas chromatography using unsaturated linear and branched hydrocarbons as well as cyclic and aromatic hydrocarbons. The occurrence of specific metal—olefin interactions resulting from the formation of π-complexes during the chromatographic process was observed.
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  • 31
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Backflushing, peak-cutting technique ; Trace analysis
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    Topics: Chemistry and Pharmacology
    Notes: Summary A backflusing, peak-cutting method was developed for the analysis of trace components present in the tail of a major component peak. Using a helium-ionization detector, the minimum detectable concentration (MDC) was: oxygen in hydrogen, 0.5ppm; nitrogen in oxygen or argon, 1ppm; and methane and carbon monoxide in nitrogen, 1ppm. The corresponding MDC values for the conventional single-column method were 7.2ppm, 8.3ppm, and 14 and 5ppm, respectively. Equations used to predict the retention time are given. The accuracy of the predicted retention time is about two percent compared to experimental results.
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  • 32
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Alkylthiazoles ; Energy contributions of the alkyl groups ; Retention indices
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    Topics: Chemistry and Pharmacology
    Notes: Summary Retention indices and their energy equivalents were determined for ten alkylthiazoles analysed on the stationary phases Apiezon L, Triton X-305 and Carbowax 1000. It was found that the energy contributions of identical alkyl groups to the partial molar free energy of sorption of a molecule are not equivalent. Smaller energy contribututions are due to the α-position of alkyl groups with respect to the heteroatoms in the thiazole ring (α-effect). This effect was most pronounced for 2-alkylthiazoles. Higher sorption energies were found for dimethylthiazoles with two methylgroups in a vicinal position. The retention indices were predicted for ten other di- and tri-substituted methyl, ethyl and propyl thiazoles on the basis of the so-called α- and ortho-effects. The predicted values are in good agreement with the experimentally determined values.
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  • 33
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Carbohydrate TMS-ethers ; Tautomeric equilibrium mixtures of aldoses ; MS and NMR identification
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Equilibrium tautomers of aldopentoses (arabinose, ribose, xylose and lyxose) and aldohexones (allose, altrose, gulose, idose and talose) have been analyzed as their trimethyl-silyl ethers by capillary GC. Pentoses were separated on SE-54 and hexoses on OV-225. The four components of the tautomer equilibrium mixture have been identified using GC/MS and NMR data.
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  • 34
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    Chromatographia 23 (1987), S. 722-726 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Adsorbents for gas chromatography ; Strong adsorption sites ; Heterogeneity of silica surface
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    Topics: Chemistry and Pharmacology
    Notes: Summary A simple gas chromatographic method is presented for the determination of the quantity of the strongest adsorption sites on an adsorbent's surface. The method consists of the blockage of the sites with quasi-irreversibly adsorbed, known amount of a strongly interacting compound and subsequent measuring of the retention of a hydrocarbon during the presence of the blocking compound in the column. Heterogeneity of chromatographic grade silicas is investigated with this method.
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  • 35
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Esterification in aqueous solution ; n-Propyl esters of aliphatic hydroxy acids
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    Topics: Chemistry and Pharmacology
    Notes: Summary Aliphatic hydroxy acids were esterified in aqueous solution in the presence of different amounts of sulfuric acid. Esterification of lactic, tartronic, malic and citric acids in water/n-propanol mixtures with mole ratios between 0.03 and 2.15 can be utilized for the determination of these acids by gas chromatography. Water does not interfere at water/n-propanol mole ratios below 0.03. For mole ratios above 0.03 anhydrous sodium sulfate is used for the binding of water. The mole ratio range was 0.24–2.13 for anhydrous sodium sulfate/water, and 0.16–1.28 for sulfuric acid/anhydrous sodium sulfate.
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  • 36
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Gas chromatography ; Bonded silica ; Residual silanol groups
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    Topics: Chemistry and Pharmacology
    Notes: Summary Silanol groups of chromatographic material surfaces were determined by chemical reaction with methyl-lithium. Evolved methane was measured by a gas chromatographic method using a column packed with molecular sieves. This chromatographic technique leads to very reproducible results, particularly for the control of the hydroxylation of a silica gel and for the analysis of residual groups at the surface of bonded silica.
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  • 37
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    Chromatographia 23 (1987), S. 790-795 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Capillary columns in series ; Variable polarity columns ; Essential oils analysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary By connecting capillary columns of different polarity in series and by changing the temperature program gradient, a system of variable polarity is obtained. The working conditions can be adjusted to optimize separations of complex mixtures. Application to the analysis of essential oils of: lavender, thyme, lemon petit grain, bergamot, and tangerine, are reported.
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  • 38
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    Chromatographia 23 (1987), S. 240-242 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Stillingia oil ; Quantitative lipid analysis ; Chinese tallow,Sapium sebiferum
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    Topics: Chemistry and Pharmacology
    Notes: Summary Contemporary stillingia oil from China is qualitatively similar to the oil described earlier, but it exhibits significant quantitative differences reflecting a degree of autoxidation of the unsaturated fatty acids either before or after crushing of the seeds.
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  • 39
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Chemically bonded phases ; Specific interactions ; Chloroderivatives of alkanes and alkenes
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    Topics: Chemistry and Pharmacology
    Notes: Summary Interactions of Cu(II) complexes chemically bonded to the surface of silica with chloro-derivatives of alkanes and alkenes were investigated. It was found that chlorine as a substituent exerts a considerable influence on the retention of the individual chloro-derivatives. In the case of chloroalkenes this influence is negative while in the case of chloroalkanes it is positive. The magnitude of the observed effect depends on the number of substituents and on the way of their distribution within the molecule.
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  • 40
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    Chromatographia 23 (1987), S. 286-288 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Macroporous copolymers of 2-hydroxyethyl ; methacrylate ; Graft polymers ; Polar sorbent for gas chromatography
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The gas chromatographic behaviour of crosslinked macroporous 2-hydroxyethyl methacrylate grafted with 2-methyloxazoline was investigated and the range of applicability of the copolymer was assessed. Retention index values were measured on this copolymer and compared with those obtained on the terpolymer 2-hydroxyethyl methacrylate-ethylene dimethacrylate-acrylonitrile. Rohrschneider constants and efficiency data for selected sorbates are given. The use of this type of polymer in the separation of various types of compounds is documented by various examples.
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  • 41
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    Chromatographia 23 (1987), S. 50-52 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Retention indices ; C6 alkanols ; OV-101 ; Carbowax 20M
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    Topics: Chemistry and Pharmacology
    Notes: Summary Gas chromatographic retention indices for 16 C6 alkanols measured on capillary columns coated with OV-101 methylsilicone and Carbowax 20M propylethyleneglycol liquid phases at 80° and 90°C were determined. The respective standard deviation values were 0.5 and 0.8 i.u. The correlation between the retention indices measured on non-polar and polar stationary phases and the boiling points of the alkanols was studied.
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  • 42
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    Chromatographia 23 (1987), S. 53-54 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Dual-column system ; Thermal conductivity detector ; Anesthetic gas mixtures
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    Topics: Chemistry and Pharmacology
    Notes: Summary A simple dual-column system with a thermal conductivity detector is described, that can be used for the quantitative analysis of anesthetic gas mixtures of halothane (2-bromo-2-chloro-1,1,1-trifluoroethane), nitrous oxide and oxygen. The separation was performed on a Carbopack (SP 1000) column and a Porapak Q column arranged in series across the detector.
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  • 43
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    Chromatographia 23 (1987), S. 132-136 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Column liquid chromatography ; Thin-layer chromatography ; Analysis of lactulose in carbohydrate mixtures
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    Topics: Chemistry and Pharmacology
    Notes: Summary Lactulose is a disaccharide with important implications in medicine, nutrition and dairy technology. It has to be determined usually as a minor component in complex matrices containing many other sugars. This paper describes the different chromatographic techniques (planar, liquid and gas chromatography) which have been proposed for the separation and quantification of lactulose in mixtures with other carbohydrates; the advantages of each technique are compared and some features where more research is necessary are outlined.
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  • 44
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    Chromatographia 23 (1987), S. 169-170 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Packed column ; Immobilized silicone stationary phases ; Ozonization
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    Topics: Chemistry and Pharmacology
    Notes: Summary Immobilization of silicone stationary phases, OV-1701 vinyl and OV-225 vinyl, on Chromosorb W-AW support was achieved in a simple procedure using ozone as an initiator. A column efficiency of 2400 theoretical plates/meter was obtained.
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  • 45
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    Chromatographia 23 (1987), S. 3-6 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Allyl bonded phases ; Addition Reactions ; Synthesis of new bonded phases
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    Topics: Chemistry and Pharmacology
    Notes: Summary The presence of the double bond on the allyl moiety has been utilized as a site for addition reactions which could produce new stationary phases. Bromination and hydrobromination reactions have been employed to prove the feasibility of making modifications to the allyl bonded phase. Both retention volumes and thermodynamic parameters for the solutes studied change upon conversion to one of the brominated phases. Sample size studies are consistent with a bonded phase adsorption mechanism. FTIR spectra also confirm the modifications which have occurred on the allyl bonded material.
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  • 46
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    Chromatographia 23 (1987), S. 265-268 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Dicarboxylic acid analysis ; n-Propyl esters of C2−C16 dicarboxylic acids ; Esterification in aqueous solution
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    Topics: Chemistry and Pharmacology
    Notes: Summary C2−C16 dicarboxylic acids were esterified in aqueous solution in the presence of sulfuric acid. Esterification in water/n-propanol mixtures with mole ratios between 0.03 and 2.21 can be utilized for the quantitative determination of dicarboxylic acids by gas chromatography. The presence of water does not interfere at water/n-propanol mole ratios below 0.45. For mole ratios above 0.45 anhydrous sodium sulfate has been used for binding the water. The mole ratio range tested was 0.12–0.99 for anhydrous sodium sulfate/water, and 0.16–2.55 for sulfuric acid/anhydrous sodium sulfate.
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  • 47
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    Chromatographia 23 (1987), S. 487-491 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Packed+capillary GC switching system ; Column efficiency utilization ratio ; New packed precolumn
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary To match the need of high efficiency capillary column (plate number N2, Plate height H2 and carrier gas linear velocity U2), a new high efficiency packed column (N1, H1 and U1) at high carrier gas velocity with small capacity factor has been developed in the light of theoretical discussion of factors effecting the column efficiency utilization ratio.
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  • 48
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    Chromatographia 23 (1987), S. 492-498 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Packed+capillary GC switching system ; Accurate system quantitation ; Analysis of complex samples or dilute solution
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A packed column containing immobilized SE-54 liquid phase on pellicular silica beads ZIPAX and having a high efficiency and high mass transfer rate has been successfully used in a two-dimensional packed+capillary column system without a cold trap. The application of this system is demonstrated by the analysis of C6-C8 aromatic hydrocarbons and lowboiling hydrocarbons present in natural oils, and of highboiling components present in low concentrations in a low-boiling solvent.
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  • 49
    ISSN: 1612-1112
    Keywords: Gas chromatography ; FT-IR detection ; γ- and δ-Haloesters
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    Topics: Chemistry and Pharmacology
    Notes: Summary The decomposition of γ- and δ-haloesters has previously been observed to take place within a commercial GC/FT-IR light-pipe system. Using a home-built light-pipe interface, an analysis of this same class of compounds was conducted from which the source of the decomposition was determined to be a brass fitting central to the commercial system's assembly. It is proposed that the reaction is due to a weakening of the carbon-halogen bond by metal interaction thereby allowing lactonization to occur.
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    Mycopathologia 98 (1987), S. 179-184 
    ISSN: 1573-0832
    Keywords: adhesion ; C. albicans ; kinetics ; concanavalin A
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract The early in vitro kinetics of Candida albicans attachment to human buccal epithelial cells was studied with the aid of an adhesion assay and solutions of concanavalin A (Con A), a lectin which is capable of inhibiting yeast adhesion. Various saccharides and putative receptor analogues were also tested. Solutions of each single reagent were added to tubes containing aliquots of mucosal cells and germinated yeasts at the beginning of a 1-hour incubation period (time O) or at 10 minute intervals during the assay. The number of yeasts attached to 200 mucosal cells was subsequently determined microscopically. Yeast adhesion remained constant following addition of phosphate-buffered saline (PBS) at time 0 or at any time thereafter. However, addition of Con A at 0, 10 or 20 minutes of incubation decreased adhesion significantly to 38%, 45% and 63% of control values. This inhibitory effect dwindled as time of incubation prior to lectin addition increased and Con A could not inhibit adhesion significantly after twenty minutes. Results obtained with Con A using live germinated yeasts were similar to those obtained with formalin-killed C. albicans. The other reagents tested failed to decrease adhesion significantly. These included the putative receptor analogues fibronectin, N-acetyl-d-glucosamine and d-galactose, and several non-specific saccharides such as α-d-methylglucopyranoside, d-ribose and d-xylose. It is suggested that in vitro attachment to human mucosal cells by C. albicans is inhibitable up to a defined point in time by a lectin with affinity for mannosecontaining surface moieties, but becomes non-reversible thereafter. This experimentally-observed irreversibility is independent of yeast cell viability.
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