Regio- and stereoselective C-2 and C-3 cleavage of 2-(1-aminoalkyl)aziridines with alcohols, carboxylic acids, and sodium iodide

Ring opening of nonactivated aziridines 1 using several nucleophiles, such as alcohols, carboxylic acids, and sodium iodide, is described. Depending on the nucleophile used, aziridines 1 are cleaved at C-3 or C-2 with total regio- and stereoselectivity, affording chiral 2-alkoxy-1,3-diamines 2 with alcohols, or O-acylated-1-hydroxy-2,3-diamines 6 with carboxylic acids in moderate or high yield. In the case of the aziridines derived from phenylalanine, treatment with NaI afford trans-4-phenylbut-3-en-1,2-diamines 9, generating the alkene with total diastereoselectivity. Mechanisms have been proposed to explain these reactions.     

Interfacing in-line gas-diffusion separation with optrode sorptive preconcentration exploiting multisyringe flow injection analysis

An automatic multisyringe flow injection analysis (MSFIA) system coupling a flow-through optical fiber diffuse reflectance sensor with in-line gas-diffusion (GD) separation is proposed for the isolation, preconcentration and determination of traces of volatile and gas-evolving compounds in samples containing suspended solids, with no need for any preliminary batch sample treatment. The flowing methodology overcomes the lost of sensitivity of the in-line separation technique, when performed in a uni-directional continuous-flow mode, through the implementation of disk-based solid-phase extraction schemes. The high selectivity and sensitivity, the low reagent consumption and the miniaturization of the whole assembly are the outstanding features of the automated set-up. The proposed combination of techniques for separation, flow analysis, preconcentration and detection was applied satisfactorily to sulfide determination in environmental complex matrixes. The method based on multicommutation flow analysis involves the stripping of the analyte as hydrogen sulfide from the donor channel of the GD-module into an alkaline receiver segment, whereupon the enriched plug merges with well-defined zones of the chormogenic reagents (viz., N,N-dimethyl-p-phenylenediamine (DMPD) and Fe(III)). The in-line generated methylene blue dye is subsequently delivered downstream to the dedicated optrode cell furnished with a C₁₈ disk, while recording continuously the diffuse reflectance spectrum of the pre-concentrated compound. This procedure provides a linear working range of 20-500 μg l⁻¹ sulfide with a relative standard deviation of 2.2% (n = 10) at the 200 μg l⁻¹ level, and a detection limit of 1.3 μg l⁻¹.     

Simultaneous spectrophotometric determination of metal ions with 4-(pyridyl-2-azo)resorcinol (PAR)

Summary A new method for the simultaneous determination of the divalent ions of cadmium, cobalt, copper, lead, manganese, nickel and zinc in binary, ternary and quaternary mixtures based on the application of a multiple linear regression programme to the spectra of the complexes of these ions with 4-(pyridyl-2-azo)resorcinol (PAR) was developed. The detection limits afforded by the proposed method range from 0.02 g/ml for Co(II), Mn(II), Ni(II) and Zn(II) to 0.10 g/ml for Pb(II). The method is rapid and quite simple as it entails no prior separation, and was successfully applied to the analysis for the above-mentioned ions in synthetic samples and real alloys.     

Effect of variables influencing S 1/2 in sequential injection analysis. Extrapolability of S 1/2 based results between SIA designs

The influence of variables including ionic strength, propulsion rate and instrumental design parameters on dispersion in a sequential injection analysis system was studied via S(1/2) and several other parameters related to the dispersion profile. The influence of such parameters on a real system was evaluated in the reaction of Fe(II) with o-phenanthroline by optimizing various instrumental designs using the simplex method and comparing the results.     

Kinetic thermometric determination of traces of manganese by its catalytic effect on the reaction between Tiron and hydrogen peroxide

We have developed a highly sensitive kinetic thermometric method for the determination of traces of Mn(II) by its catalytic effect on the oxidation of Tiron by hydrogen peroxide. The reaction is monitored by the initial-rate method, which is applied to temperature-time curves. Under the optimum conditions established in preliminary experiments, manganese can determined over the range 1–120 ng/mL, with an rsd of 5.8% and 1.3% for S ng/mL and 40 ng/mL Mn(II), respectively. The proposed method is subjected to few interferences, the most serious of which is posed by Pb(II), with a tolerated ratio of 201. The method was satisfactorily applied to the determination of Mn(II) in various types of sample (water, beer and wine).

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Zusammenfassung Es wurde eine hochempfindliche kinetische thermometrische Methode zur Bestimmung von Spuren an Mn(II) anhand dessen katalytischen Effektes auf die Oxidation von Tiron mit Wasserstoffperoxid entwickelt. Der Verlauf der Reaktion wurde über die Anfangsgeschwindigkeiten bei den Temperatur-Zeit-Kurven verfolgt. Unter in Vorexperimenten ermittelten optimalen Bedingungen kann Mangan im Bereich 1–120 ng/ml mit einer relativen Standardabweichnung von 5.8% bzw. 1.3% für 5 ng/ml bzw. 40 ng/ml Mn(II) bestimmt werden. Das Verfahren wird von einigen Kreuzwirkungen beeinflußt, von denen die intensivste der Einfluß von Pb(II) mit einem zulässigen Verhältnis von 201 ist. Diese Technik konnte zur Bestimmung von Mn(II) in den verschiedenartigsten Proben (Wasser, Bier, Wein) zufriedenstellend angewendet werden.

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The financial support of DGIC.I (Grant PS 89-0146) is grealfully acknowledged.     

The potential of mass spectrometry to study iron-containing proteins used in clinical diagnosis

Many proteins contain iron as metal ion either within their own structures or bound to their active sites. These iron-containing proteins are involved in numerous biological processes and some of them serve as biomarkers of clinical pathologies, not only related to iron homeostasis but also to other physiological disorders. Thus, a variety of analytical strategies have been developed over the last years in order to conduct studies on Fe-containing proteins. Among them, mass spectrometric (MS) methods still remain as preferred tools since they provide the capabilities of structure elucidation together with quantitative possibilities. Therefore, in this work we have tried to summarize the most recent applications of elemental and molecular mass spectrometric-based methods for the characterization (mostly qualitative but quantitative in some cases) of the high abundant Fe-containing proteins used for clinical diagnosis.     

ADHD candidate gene (DRD4 exon III) affects inhibitory control in a healthy sample

Background  

Dopamine is believed to be a key neurotransmitter in the development of attention-deficit/hyperactivity disorder (ADHD). Several recent studies point to an association of the dopamine D4 receptor (DRD4) gene and this condition. More specifically, the 7 repeat variant of a variable number of tandem repeats (VNTR) polymorphism in exon III of this gene is suggested to bear a higher risk for ADHD. In the present study, we investigated the role of this polymorphism in the modulation of neurophysiological correlates of response inhibition (Go/Nogo task) in a healthy, high-functioning sample.