Mit der papierchromatographischen Untersuchung der Filix-Phloroglucide und der Rohfilicine

Ohne Zusammenfassung     

The extraction of elements with cyclic solvents and its application to geochemical analysis

The extraction of the elements Zn, Cd, Hg, Ga, In, Tl, Sn, Pb, As, Sb and Bi into the solvents cyclohexanone, cyclohexanol, and cyclohexane from hydrochloric acid solutions, has been studied. Cyclohexanone is a more efficient but less selective extracting agent than cyclohexanol while cyclohexane has little extracting power. Solvent extraction of hydrochloric acid solutions of materials of geochemical interest into cyclohexanone has been used to enrich trace elements prior to spectrochemical analysis.     

Mechanism and scope of salen bifunctional catalysts in asymmetric aldehyde and α-ketoester alkylation

Metal complexes of C₂-symmetric Lewis acid/Lewis base salen ligands provide bifunctional activation resulting in rapid rates in the enantioselective addition of diethylzinc to aldehydes (up to 92% ee). Further experiments probed the reactivity of the individual Lewis acid and Lewis base components of the catalyst and established that both moieties are essential for asymmetric catalysis. These catalysts are also effective in the asymmetric addition of diethylzinc to α-ketoesters. This finding is significant because α-ketoesters alone serve as their own ligands to accelerate racemic 1,2-carbonyl addition of Et₂Zn and racemic carbonyl reduction. The latter proceeds via a metalloene pathway, and often accounts for the predominant product. Singular Lewis acid catalysts do not accelerate enantioselective 1,2-addition over these two competing paths. The bifunctional amino salen catalysts, however, rapidly provide enantioenriched 1,2-addition products in excellent yield, complete chemoselectivity, and good enantioselectivity (up to 88% ee). A library of the bifunctional amino salens was synthesized and evaluated in this reaction. The utility of the α-ketoester method has been demonstrated in the synthesis of an opiate antagonist.     

Screening for metal ligands by liquid chromatography--ligand-exchange--electrospray mass spectrometry

Electrospray ionization mass spectrometry is applied for the selective detection of metal ligands after a post-column continuous-flow ligand-exchange reaction. The detection is based on the specific release of a reporter ligand from a metal-reporter ligand complex by a high affinity ligand. Constant infusion and direct-injection experiments are performed to optimize the method. The on-line coupling of a liquid chromatographic separation prior to the continuous flow ligand-exchange reaction enables the screening for high affinity ligands in complex samples. The feasibility of the method is demonstrated by using several ligands with a different affinity for either Cu(II) or Zn(II) ions. The selectivity of the ligand-exchange detection method can be tuned by the choice of the reporter ligand. This is demonstrated by using either 2,2'-bipyridyl or 5-methyl-1,10-phenanthroline as reporter ligands.     

Acid-base properties of 1-acyl-5-hydroxypyrazolidines in a hydrogen bond

In solutions, 1-acyl-5-hydroxypyrazolidines form only intermolecular hydrogen bonds in which the proton acceptor is the oxygen atom of the hydroxyl group. These compounds are similar to phenols with respect to the acidity in a hydrogen bond.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 936–939, July, 1989.     

Application of high-performance liquid chromatography of some antibiotics in clinical microbiology

During recent years high-performance liquid chromatography has become an excellent tool for the determination of antibiotics in biological fluids. Compared with biological assays, the major benefits of this method are specificity and rapidity. In particular, the determination of biologically inactive metabolites emphasizes that this technique plays an outstanding role for the analysis of antibiotics. This paper describes how the method can be used in the analysis of several antibiotics and demonstrates the efficacy of this method for clinical microbiology. Methods for the determination in biological fluids of acylaminopenicillins (azlocillin, mezlocillin, piperacillin and aspoxicillin), quinolones (ciprofloxacine, norfloxacine and ofloxacine), a penem (imipenem) and a cephalosporin (cefixime) are summarized. Furthermore, their application to in vitro studies and their trial in clinical studies are described.     

Dual analyte flow injection fluorescence immunoassays using thiophilic gel reactors and synchronous scanning detection

Heterogeneous fluorescence immunoassays have been automated using flow injection manifolds incorporating thiophilic gel solid phase reactors to separate antibody-bound and unbound analyte molecules. Antibody elution is achieved by changes in ionic strength, thus allowing the use of pH sensitive fluorescent labels. This facilitates the development of dual analyte systems, in which two competitive immunoassays with separate labels are monitored in parallel. Detection of the fluorophores by high speed synchronous fluorescence scanning while the flow is briefly stopped utilises either one synchronous interval which detects both fluorophores, or two separate scans at different wavelength intervals, one for each fluorophore. Simultaneous analyses of serum albumin and transferrin exemplify these novel approaches. Spectroscopic interferences are very small, analyte recoveries are close to 100%, with a relative standard deviation of 5-6% and a sampling rate of 20 h-1.     

Pd-catalyzed selective addition of heteroaromatic C-H bonds to C-C triple bonds under mild conditions

Simple heteroarenes such as pyrroles and indoles undergo addition reactions to C-C triple bonds in the presence of a catalytic amount of Pd(OAc)(2) under very mild conditions, affording cis-heteroarylalkenes in most cases. The cleavage of aromatic C-H bonds is the possible rate-determining step in CH(2)Cl(2), and the addition of heteroaromatic C-H bonds to C-C triple bonds is in a trans-fashion.     

Instrumental neutron activation analysis of tree rings for dendrochemical studies

Instrumental neutron activation analysis (INAA) was employed to determine zinc, cadmium and potassium concentrations in the growth rings of ponderosa pine (Pinus ponderosa Dougl.) trees growing along the shores of Lake Roosevelt in Washington State, U.S.A. where mineral processing activities have resulted in high burdens of zinc and cadmium in the lake sediments. The tree growing along the contaminated waterway display elevated concentrations of zinc in its growth rings relative to a tree growing along an uncontaminated tributary of Lake Roosevelt. Cadmium concentrations in the growth rings from both sites are similar from 1988 to 1993. Water quality data indicate an increased concentration of cadmium in the lake from 1984 to 1988. The increased concentrations of cadmium in the lake water were reflected in apparent increases in concentrations of cadmium in individual rings of the tree sampled at the contaminated site. This suggests that translocation of cadmium in the sapwood of heartwood-forming species does not occur in the short term, and thus may not be a limiting factor in using trees as environmental monitors for cadmium. In addition, five-year tree ring segments were analyzed and subsequently reanalyzed as individual single-year ring segments. The analytical data obtained for the pooled individual rings are essentially the same as for the five-year segments, demonstrating the utility of NAA for dendrochemical studies.