Rietveld refinement and vibrational spectroscopic study of alunite from el Gnater, central Tunisia

The crystal structure of alunite (K_0.72,Na_0.28) Al₃(SO₄)₂(OH)₆ from El Gnater, central Tunisia, is refined by the Rietveld method. Raman and infrared data of this mineral are also given in order to provide some further information about the mineralogy and chemistry of this alunite. The crystal system is trigonal, space group R $ \bar 3 The crystal structure of alunite (K_0.72,Na_0.28) Al₃(SO₄)₂(OH)₆ from El Gnater, central Tunisia, is refined by the Rietveld method. Raman and infrared data of this mineral are also given in order to provide some further information about the mineralogy and chemistry of this alunite. The crystal system is trigonal, space group R m, with a = 6.9834(4) ? and c = 17.0899(11) ?. Final Rietveld refinement converges to R _p = 0.16, R _wp = 0.16, and R _Bragg = 0.07. In the alkalic site, the occupancy of potassium and sodium is refined to 72 and 28%, respectively. The Raman and infrared spectra are investigated in order to improve previous assignments of the observed frequencies, especially for tetrahedral and octahedral vibration and OH group, which are discussed on the basis of unit-cell group analysis and by comparison with previously observed wavenumbers of natrojarosite and synthetic alunite. The text was submitted by the authors in English.     

Bioactive Electroconductive Hydrogels: The Effects of Electropolymerization Charge Density on the Storage Stability of an Enzyme-Based Biosensor

Electrode-supported hydrogels were conferred with the biospecificity of enzymes during the process of electropolymerization to give rise to a class of bioactive, stimuli-responsive co-joined interpenetrating networks of inherently conductive polymers and highly hydrated hydrogels. Glucose responsive biotransducers were prepared by potentiostatic electropolymerization [750 mV vs. Ag/AgCl (3 M KCl)] of pyrrole at Poly(hydoxyethyl methacrylate)-based hydrogel-coated Pt micro-electrodes (Φ = 100 μm) from aqueous solutions of pyrrole and glucose oxidase (GOx; 0.4 M pyrrole, 1.0 mg/ml GOx) to 1.0 and 10.0 mC/cm². Polypyrrole was them over-oxidized by cyclic voltammetry (0–1.2 V vs. Ag/AgCl, 40 cycles in PBKCl, pH = 7.0). Biotransducers were stored at 4 °C in PBKCl for up to 18 days. Amperometric dose–response at 0.4 V vs. Ag/AgCl followed by Lineweaver–Burk analysis produced enzyme kinetic parameters as a function of electropolymerization charge density and storage time. Apparent Michaelis constant (K _Mapp) increased from 18.6–152.0 mM (1.0 mC/cm²) and from 2.7–6.1 mM (10.0 mC/cm²). Biotransducer sensitivity increased to 21.2 nA/mM after 18 days and to 12.8 pA/mM after 10 days for the 1.0 and 10.0 mC/cm² membranes, respectively. Maximum current, I _max, also increased over time to 2.7 nA (1.0 mC/cm²) and to 170 pA (10.0 mC/cm²). Electropolymerization of polypyrrole is shown to be an effective means for imparting bioactivity to a hydrogel-coated microelectrode. GOx was shown to be stabilized and to increase activity over time within the electroconductive hydrogel.     

Organophotocatalyzed Synthesis of Vinyl-SCF3 and Benzoyl-SCF3 Using a New N-(SCF3)(CF3)-Shelf-Stable Reagent

We report the photocatalyzed C−SCF₃ bond formation using a new shelf-stable PhPh-N-(SCF₃)(CF₃) reagent I in combination with 4CzIPN as organophotocatalyst under blue LED irradiation. While the synthesis of vinyl-SCF₃ is performed in the presence of bromide salts as an activator of reagent I , the synthesis of trifluoromethylthioesters was undertaken using aldehydes as starting material in the presence of a hydrogen atom transfer catalyst (HAT). Preliminary mechanistic investigations including EPR spectroscopy and cyclic voltammetry analysis shed the light on the reaction mechanisms.