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  • 1
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Sphärische makroporöse Partikel, die als Trägermaterialen für verschiedene Säulen-Operationen eingesetzt werden sollen, wurden mittels Suspensions- und Mikrosuspensionspolymerisation von Trimethylolpropan-trimethacrylat (TRIM) in Gegenwart verschiedener Mengen porogener Reagenzien (Toluol bzw. Mischungen von Toluol und Isooktan) hergestellt. Textur und Eigenschaften der Partikel variierten deutlich mit dem Anteil und der Zusammensetzung des porogenen Reagens und wurden zusätzlich durch die Wahl des Suspensionstabilisators beeinflußt. Die makroporösen Partikel wiesen ein Gesamtporenvolumen von 0,4 bis 3,6 cm3/g und eine spezifische Oberfläche von 7 bis 〉 450 m2/g auf. Alle Partikel enthielten Makroporen und, außer den Teilchen mit sehr niedriger spezifischer Oberfläche, einen gewissen Anteil an Mikroporen (Durchmesser 〈 60 Å). Durch Erniedrigung der Monomerkonzentration und Erhöhung des Isooktan-Gehaltes im porogenen Reagens auf 50 Gew.-% konnte das Auftreten von Mikroporen vollständig unterdrückt werden. Das Erhöhen des Isooktan-Gehaltes führte zu einem vergrößerten Gesamtporenvolumen und zu einem verringerten Quellvermögen der Polymermatrix in Toluol. Der Einfluß einer Hitzebehandlung bei 130°C und eines Aufpfropfens von Polymethylmethacrylat auf die Partikeleigenschaften wurde ebenfalls untersucht.Die Menge an nicht umgesetzten Doppelbindungen in den Partikeln konnte durch Variation der Polymerisationstemperatur verändert werden. Das Vorhandensein leicht zugänglicher Doppelbindungen ist wichtig, da sie zur Funktionalisierung der festen makroporösen Partikel verwendet werden können.
    Notes: Spherical macroporous particles, intended for use as carrier particles in various types of column operations, were prepared by suspension and microsuspension polymerization of trimethylolpropane trimethacrylate (TRIM), in the presence of various amounts of porogenic agents (toluene or mixtures of toluene and isooctane). The texture and properties of the particles varied markedly with the amount and composition of the porogenic agent, and were also affected by the choice of suspension stabilizer. Macroporous particles were prepared, ranging in total pore volume from 0.4 to 3.6 cm3/g, and in specific surface area from 7 to 〉450 m2/g. All of the particles contained macropores, and except for those with very low specific surface area, contained a certain fraction of micropores (diameter 〈60 Å). The presence of micropores could be eliminated completely by decreasing the monomer concentration and increasing the isooctane content of the porogenic agent to 50 wt.-%. Increasing the isooctane content also resulted in an increase in the total pore volume and a decrease in the tendency of the polymer matrix to swell in toluene. The effect on properties of particles by heat treatment at 130°C and by grafting poly(methyl methacrylate) onto the particles was also studied.The amount of unreacted double bonds of the particles could be varied by varying the polymerization temperature. The presence of easily accessible double bonds is important as they can be utilized for functionalization of the rigid macroporous particles.
    Additional Material: 11 Ill.
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  • 2
    ISSN: 0899-0042
    Keywords: semipreparative separation ; enantiomers ; chromatography ; tri-acetylcellulose ; melatonin ; 2-amidotetralins ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to obtain milligram amounts of the enantiomers of a series of compounds to be tested for binding to the melatonin binding site, a system for semipreparative enantiomeric separation was set up using tri-acetylcellulose as the chiral stationary phase. Interactions of this class of compounds with tri-acetylcellulose were examined on an analytical scale with a series of 20 compounds. Apparently, both steric and electrostatic interactions determine retention behavior on tri-acetylcellulose. Semipreparative separations were carried out for a subset of seven compounds. The purity of the first eluting enantiomer usually was around 99%, whereas the purity of the second eluting enantiomer was slightly less. The system described is easy to use and has the major advantage that a series of compounds can be separated with one technique. The purities obtained are sufficient for a first screen of their affinity. © 1994 Wiley-Liss, Inc.
    Additional Material: 2 Ill.
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  • 3
    ISSN: 0899-0042
    Keywords: CBH I ; cellulase ; cation ; sodium ; potassium ; enantioselectivity and temperature ; ionic strength ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An increase in both retention and enantioselectivity for some β-blocking agents was observed when exchanging potassium to sodium ion in the buffer used as mobile phase. A large effect of ionic strength on retention was observed, while the enantioselectivity was constant. Chirality 10:513-518, 1998. © 1998 Wiley-Liss, Inc.
    Additional Material: 5 Ill.
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  • 4
    ISSN: 0899-0042
    Keywords: cellulase ; CBH I-silica ; temperature dependent enantioselectivity ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 4 Ill.
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  • 5
    ISSN: 0899-0042
    Keywords: cellulase ; cellobiohydrolase I ; cellobiohydrolase II ; Trichoderma reesei ; chiral stationary phase ; chiral separation ; enantiomer ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Intact and fragmented cellobiohydrolase II (CBH II) were immobilized to silica and used as chiral stationary phases (CSPs) for liquid chromatographic separations of enantiomers. Both acidic and basic chiral compounds could be resolved into their enantiomers on these phases. The enantioselectivities obtained on intact CBH II and its core were almost equivalent. Comparisons were also made with CBH I silica. It was found that the new materials show quite different chiral and chromatographic properties. The enzymatic activity of the CBH II in free solution was influenced by alprenolol and mexiletine, both separated on the corresponding CSP. It indicates that the sites for catalysis and for chiral recognition overlap. © 1995 Wiley-Liss, Inc.
    Additional Material: 7 Ill.
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  • 6
    ISSN: 0899-0042
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to elucidate the chiral recognition mechanisms of the enzyme cellobiohydrolase I (CBH I), its carboxylic groups were covalently modified. The synthetic modification was carried out either in the presence or absence of cellobiose, which has proven to inhibit the enzymatic activity and if present in the mobile phase impairs enantioselectivity of amino alcohols. Compared to the reference CSP (unmodified CBH-I silica and CBH-I core silica), the synthetically modified phases show differences both in enantioselectivity and retention. The enzymatic differences between the CSPs were also in line with the chromatographic results. The selectivity factors of propranolol are almost unchanged during the reaction periods in the presence of cellobiose, while they decreased rapidly without the inhibitor. In one case, even a slight improvement in enantioselectivity was obtained, indicating that non-stereospecific carboxylic groups were ruled out. Chirality 10:760-769, 1998. © 1998 Wiley-Liss, Inc.
    Additional Material: 6 Ill.
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  • 7
    ISSN: 0173-0835
    Keywords: Capillary zone electrophoresis ; Amino-coated capillaries ; Reversed electroosmosis ; Brij 35 ; Taurodeoxycholic acid micelles ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Enkephalin-related peptides were separated at low pH in a capillary with covalently bonded aminopropyl groups. The peptides are electrostatically repelled from the capillary surface and much higher efficiencies and faster separations were achieved compared to separations using uncoated capillaries. At low pH the amino groups are protonated, which results in reversed electroosmosis. The influence of voltage and ionic strength on the mobility and the separation efficiency was studied. The repeatability of migration times within one day was very good with relative standard deviations of 0.3-0.7%. Increasing the pH decreased the electroosmosis, eventually turning towards the cathode in the pH range 5-6; the separation performance, however, was lower at higher pH. Neutral and anionic micellar agents were added to the background electrolyte at different concentrations; the enkephalins had weak association with the neutral micellar agents but were distributed to the anionic taurodeoxycholic acid (TDC) micelles, giving rise to changes in separation selectivities. Very high efficiencies were obtained for peptides with a low distribution to the TDC micelles, while the efficiencies were impaired for those with a strong association with the micelles, which may indicate a slow mass transfer in the association process.
    Additional Material: 8 Ill.
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