High-performance liquid chromatographic determination of glycogen in sea urchin gonads with refractive index detection

A high-performance liquid chromatographic method using refractive index detection for the determination of glycogen in sea urchin (Paracentrotus lividus) gonads is developed. After alkaline digestion with sodium carbonate, samples are adjusted to pH 4.6 with citric acid and incubated with amyloglucosidase to hydrolyze the glycogen. The resulting glucose is determined using a Spherisorb NH2 column as the stationary phase and an acetonitrile-water mixture (80:20, v/v) as the mobile phase. The relative standard deviation (%) was 3.57, the limit of detection was 40.1 microg/mL, and the recovery percentage was 97.2%.     

Synthesis,crystal structure and luminescent property of a novel H<Subscript>2</Subscript>O-bridged cobalt(II) polymer with one-dimensional chain structure

The coordination compound [Co(C₁₀H₇COO)₂(H₂O)₃]_2n · 4nH₂O was prepared by the reaction of 1-naphthoic acid and cobalt(II) acetate tetrahydrate in basic solution, and was fully characterized by X-ray diffraction, element analysis, FTIR, TG-DTA and luminescent spectra. In the crystal the six-coordinated Co(II) centers are linked into one-dimensional zigzag chains by water molecules, which are further assembled into a two-dimensional network through weak inter-chain C–H···π interactions. The solid complex exhibits favorable fluorescent properties similar to those of free ligand at room temperature, which can be assigned to the intraligand electronic transfer.     

Sorption of binary liquid mixtures on polymer networks Part I. Determination of surface excess isotherms and free energy functions

Two groups of polymer networks (polymer resins) are investigated by selective liquid sorption fromn-propanol-water mixtures. Group 1 consists of gel polymerized polar (hydrophilic) ion exchangers which swell in the binary liquid mixture. Group 2 consists of non-polar, non-swelling, macroporous resins. The free energy isotherms accompanying the sorption processes are calculated from the excess isotherms and the bulk activities. The adsorption excess free energies reveal the differences in polarity of the polymer network.     

A new selective cleavage of n,n-dicarbamoyl-protected amines using lithium bromide

A mild and new procedure for the selective cleavage of an alkoxycarbonyl group (Boc, CBz) in N,N-dicarbamoyl-protected amino compounds is described. The method is based on the use of lithium bromide in acetonitrile and is compatible with a large range of other functionalities present in the substrates. Compared with other reported methodologies, the procedure is particularly useful for the Cbz-selective cleavage in N,N-Ts,Cbz-diprotected amines. A rationalization of the selectivity supported by ab initio calculations is also presented.     

Characteristic features of intra- and intermolecular interactions in crystals of pyrrole-2-carbaldehyde isonicotinoylhydrazone and its hydrate

Pyrrole-2-carbaldehyde isonicotinoylhydrazone (1) and its hydrate [1·H₂O] (2) were studied by single-crystal X-ray diffraction analysis. The introduction of the pyrrole substituent into N"-substituted isonicotinic hydrazide (INH) causes the intramolecular redistribution of the electron density compared to those in INHs studied earlier, which increases the basicity of the hydrazone nitrogen atom (N") involved in intermolecular hydrogen bonding. This effect has not been observed in the structures of N"-substituted INHs and benzhydrazides studied previously. Intermolecular hydrogen bonds play a decisive role in the formation of the crystal structures of 1 and 2.     

Corrosion studies of a chromium steel in imitated seawater

A series of in-door experiments was performed to get some insight into the corrosion behavior of a commercial alloy Fe-12% Cr (3CR12) exposed to imitated seawater. Applying different analytical methods, the main corrosion process was found to be the formation of flakes on the surface which, peel off after they have reached a certain size. Some Cr is dissolved in the solution, its relative concentration with respect to Fe is higher than in the bulk material. The flakes consist mainly of mixed oxihydroxides of the type FeOOH containing some Cr and Mg. The oxidic layer on the interface is very thin, behaves essentially stationary with a slight growth of about 0.05 nm/day. It consists of Cr oxide with some inclusions of Fe and Mg and is not of a chromite type. Immediately below this oxidic layer, the metallic substrate exhibits a thin layer depleted in Cr and behaving like a-Fe (bcc). As compared with stainless steel, potentiostatic current vs. time records at anodic potentials below the pitting potential indicate a very different stability of the surface films for 3CR12. The kinetics of the passive layer formation on 3CR12 was found to follow a parabolic law initially and to change later (after 10...100 seconds in deaerated solution and even earlier in aerated solution) to a linear law. After some time, pitting corrosion and/or cracks due to internal stresses play the dominant role. Cr does not form a protective oxidic layer. The surface morphology of samples exposed at -200 mV for 20 and 80 minutes has been studied by scanning electron microscopy and scanning Auger microprobe. The results reflect the competing formation of oxidic layers and pitting, the participation of Cr in the dissolution process. They also suggest that Mg, which is a component of the solution was incorporated into the rust and some Mg was also found on the metallic surface.     

Effect of dicyclopentadiene-and diindenezirconocene dichlorides on free-radical polymerization of methyl methacrylate

The effect of zirconocene dichloride and its indene-containing derivative on the radical polymerization of methyl methacrylate initiated by benzoyl peroxide has been studied. The influence of the metallocenes on the kinetic parameters of the process and the average degree of polymerization has been established. Concentration and temperature dependences have been measured for the initial rate of reaction and the average degree of polymerization in relation to the content of the components in the systems. The microstructure of poly(methylmethacrylate) prepared in the presence of the used initiation systems has been determined.     

N-isopropenylazoles: III. Quantum-chemical analysis of the reaction of azoles with allene and propyne in the gas phase

Reactions of pyrrole, imidazole, pyrazole, and 1,2,4-triazole with allene and propyne in the gas phase with formation of the corresponding N-isopropenylazoles were simulated at the RHF/6-31G**, B3LYP/6-31G**, and MP2(full)/6-31G** levels. Dissociation of the N-H bond to give azolate ion is the main constituent of the reaction coordinate. All the examined azoles react preferentially with allene rather than with propyne; their reactivity decreases in the series pyrrole > imidazole > pyrazole > 1,2,4-triazole due to participation of the pyridine type nitrogen atoms in the prototropic propyne-allene rearrangement.     

Dampfraumanalyse mehrkomponentiger Systeme. VIII

Zusammenfassung Die Verfasser bestimmten mit Hilfe ihres Dampfraumanalysenverfahrens die Alkoholtension über Äthanol-Wasser-Zinkchlorid-Lösungen. Auch die Viskosität der flüssigen Phase wurde gemessen. Die Meß-ergebnisse werden mit den beim Calciumchlorid in einer früheren Arbeit erhaltenen verglichen.

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Summary With the aid of their vapor space analytical procedure the authors determined the alcohol tension above ethanol-water-zinc chloride solutions. The viscosity of the liquid phase was also measured. The findings were compared with those obtained with calcium chloride in a previous study.

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Résumé Les auteurs ont déterminé la tension de vapeur de l'alcool sur des solutions éthanol-eau-chlorure de zinc par leur méthode d'analyse à chambre de vaporisation. Ils ont également déterminé la viscosité de la phase liquide. Les résultats des mesures sont comparés à ceux qui ont été obtenus antérieurement avec le chlorure de calcium.

     

Analysis of gas chromatography—mass spectrometry data by reverse library search and the detection of substances not in the library

Computer least-squares methods are used to conduct an automatic reverse search of a library of complete mass spectra for the analysis of the output data matrix from a g.c.—m.s. system. The search is limited to those mass spectra falling within a narrow retention index window about the retention index corresponding to each scan in the datamatrix. The least-squares estimated parameters obtained are proportional to the concentrations of the substances present at each scan and are displayed graphically as the profiles of resolved overlapping g.c. peaks. The precision of the parameters is estimated. The root mean square Values of the residuals of the least-squares fits are used successfully to indicate the presence of substances not in the library. Examples are given of the results produced with data from this laboratory. Possible elaborations and improvements of this computer program are discussed.