Square-wave adsorptive stripping voltammetry of menadione (vitamin K(3))

Menadione (vitamin K₃) undergoes a reversible two-electron transfer involving the quinone structure in acidic medium. As demonstrated by using cyclic voltammetry, the reduced form is more strongly adsorbed than the oxidized one. Stripping voltammetry of an adsorbed layer has been applied to the determination of this molecule after preconcentration of the reduced compound and scanning the potential towards less negative values. Adsorption, which is highly effective when stirring is used, approaches an equilibrium process in quiescent solution, as evidenced by a loss of part of the adsorbed material when stirring is stopped. A square-wave mode has been selected owing to its high sensitivity (the current is 20 times that for the differential pulse mode), but also to its high scan-rate, which minimizes the slow desorption process occurring during the scan. A concentration range from 2 × 10⁻¹⁰ to 5 × 10⁻⁷ M is easily investigated, the detection limit being 1.3 × 10⁻¹⁰ M. The influence of several operational parameters has also been considered.     

Isotherms of adsorption of aromatic compounds on cellulose from heptane-isopropanol solutions

The isotherms of adsorption of benzene, anisole, benzyl alcohol, and benzaldehyde on the surface of microspherical mesoporous crosslinked cellulose were calculated from the chromatographic peaks of these compounds with consideration given to the longitudinal smearing of the analyte zone under the action of adsorption forces. The solvents were n-heptane-isopropanol mixtures containing various amounts of isopropanol (up to 2 vol %). The adsorption isotherms were described using equations of the displacement adsorption theory. The mechanism of the sorption of aromatic compounds and the physical meaning of the constants entering into the adsorption isotherm equation were discussed.     

Utility of N‐[4‐(N‐Substituted Sulfamoyl)Phenyl] Cyanothioformamides in the Synthesis of Heterocyclic Compounds

The novel cyanothioformamides 2a‐d were prepared by treatment of isothiocyanatosulfonamides 1a‐d with potassium cyanide at room temperature. Cyclocondensation of compounds 2b,c with phenyl isocyanate as electrophile furnished the corresponding imidazolidines 3a,b . The reactivity of compound 3a towards some nitrogen nucleophiles was investigated. Thus, the thiosemicarbazone 4 and imidazo[4,5‐b]quinoxaline 6 were synthesized by condensation of compound 3a with thiosemicarbazide and o‐phenylenediamine, respectively. Treatment of 3a with hydrochloric acid afforded compound 7 . Our investigation was extended to include the reactivity of cyanothioformamide 2 towards o‐aminophenol, anthranilic acid, and o‐phenylenediamine and yielded the corresponding heterocycles 9 , 11 and 13 derivatives, respectively. Structures of the synthesized compounds were established by their elemental analysis and spectral data.     

In situ assembled ZIF superstructures via an emulsion-free soft-templating approach

Assembling well-defined MOF superstructures remains challenging as it requires easily removable hard templates or readily available immiscible solutions for an emulsion-based soft-template approach. In this work, a single-step emulsion-free soft templating approach is reported to spontaneously prepare hollow ZIF-8 and ZIF-67 colloidosomes with no further purification. These superstructures can load different enzymes regardless of the size and charge with a high encapsulation efficiency of 99%. We envisage that this work will expand the repertoires of MOF superstructures by the judicious selection of precursors and the reaction medium.

An emulsion-free approach for the preparation of hollow ZIF-8 superstructures in a single step is established based on metal sulfate hydrates in methanol.     

Erratum to: The Wigner—Ville distribution associated with the quaternion offset linear canonical transform

Analysis Mathematica -     

Electrochemical behaviour of an indium electrode in concentrated KOH solutions at different temperatures

Summary The electrochemical behaviour of pure indium in KOH solutions (1–4M) was studied at different temperatures (25–70°C) by potentiostatic techniques. Two anodic peaks corresponding to the formation of In(OH)₃ and In₂O₃ were observed. The heights of the two peaks increased with the increase of alkali concentration. An increase of temperature increased the peak currents and shifted their corresponding potentials to more negative values. The variation of the peak currents and peak potentials with scan rate suggested that the anodic dissolution of indium was a diffusion controlled process. In cyclic voltammetry, the reverse scan consistently showed one peak which was attributed to the reduction of anodic oxidation products into indium. X-ray diffraction analysis confirmed the presence of In(OH)₃ at the first anodic peak, In(OH)₃ and In₂O₃ at the second anodic peak and In₂O₃ in the permanent passive region.

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Zum elektrochemischen Verhalten einer Indium-Elektrode in konzentrierter Kalilauge bei verschiedenen Temperaturen

Zusammenfassung Es wurde das Verhalten von reinem Indium in 1 – 4M KOH-Lösungen bei Temperaturen zwischen 25 und 70°C mittels potentiostatischer Methoden untersucht. Zwei anodische Peaks, entsprechend der Bildung von In(OH)₃ und In₂O₃, traten auf. Die Höhe der beiden Peaks wurde mit zunehmender Alkalikonzentration gesteigert. Eine Temperaturerhöhung verstärkte die Peakströme und verschob die entsprechenden Potentiale zu negativeren Werten. Die Abhängigkeit der Peakströme und Peakpotentiale von der Scangeschwindigkeit legte den Schluß nahe, daß die anodische Lösung von Indium in einem diffusionskontrollierten Prozeß stattfindet. Bei der cyclischen Voltammetrie zeigte der reverse Scan einheitlich einen Peak, der der Reduktion der anodischen Oxidationsprodukte zu Indium zugeschrieben wurde. Röntgendiffraktionsanalyse bestätigte die Präsenz von In(OH)₃ beim ersten anodischen Peak, In(OH)₃ beim zweiten Peak und In₂O₃ im permanent passiven Bereich.

     

On the Synthesis of Some 2-Arylhydrazono-3-oxothieno[2,3-<Emphasis Type="Italic">b</Emphasis>]pyridines by Reaction of Nitrilimines with 2-Mercaptonicotinic Acid

Summary. Nitrilimines prepared from N-arylhydrazono chlorides reacted with 2-mercaptonicotinic acid yielding the corresponding addition products, 2-[(2-oxo-1-arylhydrazonopropan-1-yl)mercapto] nicotinic acids, which were treated with 1,1-carbonyldiimidazole in THF affording by cyclocondensation the corresponding hitherto unknown 2-arylhydrazono-3-oxothieno[2,3-b]pyridines.     

Studies on extraction of beryllium by di-(2-ethyl hexyl)-phosphoric acid from hydrochloric acid solutions

The distribution of Be between aqueous HCl solutions and organic phases of di-(2-ethyl hexyl)-phosphoric acid, has been described. The dependence of extraction on aqueous acidity, metal and extractant concentration as also on the diluent type, was thoroughly examined. The possible mechanism of extraction has been discussed in the light of results obtained.     

Resistance of zinc thermal sprayed coatings on different corrosive environments

Zinc coatings on ferrous substrates are possible to be applied with thermal spraying. In the present work the corrosion behavior of zinc thermal sprayed coatings deposited on low carbon steel St-37 was examined in a simulated marine atmosphere (salt spray chamber-SSC) and in a dry atmosphere at elevated temperature (400°C). The corrosion progress was examined by means of optical microscopy, scanning electron microscopy, X-ray diffraction and thermogravimetric analysis. From this investigation it was deduced that in the SSC the coating is uniformly corroded, while the main corrosion products are hydrated zinc oxides and chlorides. By contrast at 400°C only a thin, compact and continuous film of ZnO is formed on top of the coating, which remains adherent to the ferrous substrate.     

Efficient desulfurization of 2-thiopyrimidine nucleosides to the corresponding 4-pyrimidinone analogues using trans-2-(phenylsulfonyl)-3-phenyloxaziridine

A brief treatment of 2-thiopyrimidine nucleosides (s²U^∗) with trans-2-phenylsulfonyl-3-phenyloxaziridine (PSO) results in efficient substrate desulfurization leading to the corresponding 4-pyrimidinone analogues (H²U^∗). The key transformation proceeds through oxidation of the 2-thiocarbonyl group to a sulfur oxyacid derivative and subsequent elimination of sulfur dioxide. 4-Pyrimidinone 1-β-d-riboside (H²U) has been transformed into the respective phosphoramidite, a ready-to-use monomer for the introduction of a modified nucleoside into an oligonucleotide chain. Moreover, the effective desulfurization of the 2-thiouridine nucleotide could be achieved directly at the oligonucleotide level, by treatment of the TdA(s²U)dGdC oligonucleotide with PSO, as verified by MALDI-TOF mass spectrometry.