FLAVIN-PHOTOSENSITIZED MONOMERIZATION OF DIMETHYLTHYMINE CYCLOBUTANE DIMER IN THE PRESENCE OF MAGNESIUM PERCHLORATE

We have investigated the photosensitized monomerization of the cis,syn -cyclobutane dimer of 1,3-di-methylthymine using riboflavin tetraacetate and a 5-deazaflavin derivative as photosensitizer. Although little monomerization of the dimer is induced by photoexcitation of the flavins in the absence of any additives, the flavins can function as an efficient photosensitizer in the presence of magnesium perchlorate. Mechanistic studies involving spectroscopic, quantum-yield and flash-photolysis measurements demonstrated that the photosensitized monomerization exclusively proceeds through electron transfer from the dimer to the triplet flavins complexed with Mg²⁺. The effects of magnesium perchlorate are compared with those on the chloranil-photosensitized monomerization and also with the effects of HClO₄ on the flavin-photosensitized reaction.     

Topographical properties of polymer films deposited in capillaries for electrophoretic separations of large organic molecules

Topography and thickness of hydrophilic polymer coatings of fused-silica capillaries for capillary electrophoresis (CE) were investigated using atomic force microscopy (AFM), scanning electron microscopy (SEM), and profilometry. Three hydrogels, poly(2-hydroxyethyl methacrylate) [poly(HEMA)], poly(diethylene glycol monomethacrylate) [poly(DEGMA)], and poly(triethylene glycol monomethacrylate) [poly(TEGMA)], were deposited using two procedures, either by simple physical sorption of the polymers, or by derivatization of the capillary wall surface with glycidyl methacrylate (EPMA) followed by polymerization of the appropriate monomers. The performance of the modified capillaries was tested under CE conditions (decrease in the electroosmotic flow, EOF dependence on pH, separation of milk and standard proteins). It has been found that the most important property of the polymer coating is its thickness, whereas its topography and the degree of its hydrophobicity are less significant. Film deposition by physical adsorption is preferable to polymerization on the derivatized surface.     

Ausnützung der Sorptionseigenschaften von Trägern in der Graschromatographie

Zusammenfassung Die Möglichkeit der Anwendung fester Stoffe mit kleinen Oberflächen als Sorbentien in der Gaschromatographie wurde untersucht. Die Sorptionseigenschaften von Trägern auf Kieseiguhrbasis, Rysorb BLK, LM und P wurde geprüft. Rysorb BLK wurde mit Saccharose in verschiedener gewichtsmäßiger Bedeckung modifiziert und der Einfluß des Bedeckungsgrades auf die Trennwirkung des Trägers untersucht. Ferner wurde die analytische Anwendung solcher Träger bewertet.

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Summary The possibility of employing solid materials with small surfaces as sorbents in gas chromatography was investigated. The sorption properties of carriers with a kieselguhr base, Rysorb BLK, LM and P were tested. Rysorb BLK was modified with saccharose in various coatings by weight and the influence of the degree of coating on the separation action of the carrier was studied. An appraisal was also made of the analytical application of such carriers.

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Résumé On a étudié la possibilité d'utiliser des corps solides de petites surfaces comme sorbants en Chromatographie en phase gazeuse. On a expérimenté les propriétés de sorption des supports sur base de kieselguhr, de Rysorb BLK, LM et P. Le Rysorb BLK a été modifié avec le saccharose avec un revêtement différent et équivalent et Ton a étudié l'influence du degré de revêtement sur l'action séparatrice du support. On a apprécié de plus l'emploi de ces supports en analyse.

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Herrn Prof. Dr. Ing.M. Jureek zum 60. Geburtstag gewidmet.     

Knowledge Discovery from Medical Data and Development of an Expert System in Immunology

Artificial intelligence is one of the fastest-developing areas of science that covers a remarkably wide range of problems to be solved. It has found practical application in many areas of human activity, also in medicine. One of the directions of cooperation between computer science and medicine is to assist in diagnosing and proposing treatment methods with the use of IT tools. This study is the result of collaboration with the Children’s Memorial Health Institute in Warsaw, from where a database containing information about patients suffering from Bruton’s disease was made available. This is a rare disorder, difficult to detect in the first months of life. It is estimated that one in 70,000 to 90,000 children will develop Bruton’s disease. But even these few cases need detailed attention from doctors. Based on the data contained in the database, data mining was performed. During this process, knowledge was discovered that was presented in a way that is understandable to the user, in the form of decision trees. The best models obtained were used for the implementation of expert systems. Based on the data introduced by the user, the system conducts expertise and determines the severity of the course of the disease or the severity of the mutation. The CLIPS language was used for developing the expert system. Then, using this language, software was developed producing six expert systems. In the next step, experimental verification was performed, which confirmed the correctness of the developed systems.     

The effect of the structure and structural changes of the stationary phase on the retention characteristics of solutes. I. The study of interactions in solutions

Summary Interactions between n-octadecane and its monofunctional derivatives (1-chloro-, 1-hydroxy-), used as stationary phases, and solutes of various structural types have been studied. Using open tubular columns, ensuring a high separation efficiency and relative inertness of the inner surface, the retention data were measured and from them the specific retention volumes, the retention indexes, and the differential solution heats were calculated. Correlations between the measured quantities and the structures of both the stationary phases and the solutes are discussed.     

Operational parameters of voltammetric high-performance liquid chromatographic detectors with copper electrodes and application to a determination of some fodder biofactors

Two versions of an amperometric detector with a copper working electrode have been constructed and tested for high-performance liquid chromatography (HPLC). The performance of the detectors was studied using selected amino acids. The dependence of the detector response on the mobile phase flow-rate was studied in the range common in both macro- and microcolumn HPLC (5 microliter/min to 1.0 ml/min). It has been found that the detection sensitivity generally increases with decreasing flow-rate, i.e., the detector response is governed by the rate of the complexation reaction between the cupric ions and the solutes. This fact makes amperometric detection with a copper electrode especially useful for microcolumn separations. For all 20 amino acids studied, calibration curve parameters and detection limits have been determined; the latter vary from 0.4 to 18 ng in the injected volume. The amino acids can also be sensitively detected in a medium of 0.1-1.0 M ammonia, which is promising for the use of strong anion exchangers in amino acid separations. Choline can also be detected at a copper electrode, with a detection limit of 40 ng. An HPLC method with amperometric detection at a copper electrode has been developed for the determination of lysine, methionine and choline in fodder biofactors.     

EXAFS studies on the reaction of gold (III) chloride complex ions with sodium hydroxide and glucose

EXAFS and QEXAFS experiments were carried out at Hasylab laboratory in DESY center (X1 beamline, Hamburg, Germany) to monitor the course of the hydrolysis reactions of [AuCl(4)](-) complex ions as well as their reduction using glucose. As a result, changes in the spectra of [AuCl(4)](-) ions and disappearance of absorption Au-L(3) edge were registered. From the results of the experiments we have carried out, the changes in bond lengths between Au(3+) central ion and Cl(-) ligands as well as the reduction of Au(3+) to metallic form (colloidal gold was formed in the system) are evident. Good quality spectra obtained before and after the reactions gave a chance to determine the bond length characteristic of Au-Cl, Au-OH and Au-Au pairs. Additionally, the obtained results were compared with the simulated spectra of different gold (III) complex ions, possibly present in the solution. Finally, the mechanism of these reactions was suggested. Unfortunately, it was not possible to detect the changes in the structure of gold (III) complex ions within the time of reaction, because of too high rates of both processes (hydrolysis and reduction) as compared with the detection time.     

Desoxyzucker, 4. Mitt.: Verbesserung der Darstellung von 3-Desoxy-d-ribohexose (3-Desoxy-d-glucose) und ihres 3-Mercaptoderivats aus 1,2-5,6-Di-O-isopropyliden-α-d-glucofuranose

Zusammenfassung Das 3-O-(S-Methyl-dithiocarbonat) der 1,2-5,6-Di-O-isopropyliden--d-glucofuranose wurde bei einer Temperatur von 490–510° und im Vakuum 20–30 mm Hg in einer Ausbeute von 60% in das 3-S-(S-Methyl-dithiocarbonat) der 1,2-5,6-Di-O-isopropyliden-3-mercapto-3-desoxy--d-ribohexofuranose umgelagert, wodurch die angeführte Verbindung zur Darstellung von 3-Desoxy-d-ribohexose (3-Desoxy-d-glucose) und ihrer Isopropylidenderivate, ggf. zur Darstellung von 3-Mercapto-3-desoxy-d-glucose und ihrer Derivate sehr geeignet wird.Mit 1 Abbildung3. Mitt.: Coll. Czechoslov. Chem. Comm.27, 94 (1962).     

Affinity liquid chromatography and capillary electrophoresis of seminal plasma proteins

Interactions of boar, bull, and human seminal plasma proteins with heparin and phosphorylcholine were studied by affinity LC using heparin immobilized to a Toyopearl support. A step gradient elution from 0.15 to 1.50 M NaCl was employed to elute the seminal plasma proteins. Relative amounts of the heparin-binding fraction of seminal plasma proteins (H+) in seminal plasma of three species were determined. Further on, the fraction of seminal plasma proteins interacting with phosphorylcholine-binding proteins (P+) was evaluated. P+ proteins were not found in human seminal plasma and their highest amount was present in bull seminal plasma. A CE method was developed for separation of seminal plasma proteins. Various capillaries and separation conditions were tested; the best resolution was obtained in a bare-silica capillary, with a micellar system consisting of a 0.02 M borate buffer and 0.05 M SDS pH 10.0. The optimized conditions were applied to the identification of the components in boar plasma.