Conformationally controlled intramolecular heterocyclization of 2,4-diaminoperfluoro-4-methyl-2-pentenethiocyanate-3

Perfluoro-2-methyl-2-pentene-thiocyanate-3 reacts with ammonia to give 2,4-diaminoperfluoro-4-methyl-2-pentenethiocyanate-3 ( 4 ) and 2-aminoperfluoro-4, 4-dimethyl-4,5-dihydro-5-ethylidene-1,3-thiazole ( 5 ). Compound 4 is kinetically stable and at 150°C under-goes rotational isomerization to afford the cyclic isomer 2-amino-4,4-bis(trifluoromethyl)-4,5-dihydro-5-(1-aminoperfluoroethylidene) -1,3-thiazole ( 6 ). Intramolecular cyclizations, resulting in the thiazolines 5 and 6 , proceed likewise via the Thorpe reaction. For compounds 4–6 , X-ray diffraction analyses were undertaken and IR spectra in solution and in solid state were investigated. It is supposed that a high kinetic preference for formation of 4 and the fact that it does not undergo spontaneous cyclization in ammonolysis stem from the NH …︁ N intramolecular hydrogen bonding between two amino groups.     

Selective Synthesis of 2,5‐Diformylfuran by Sustainable 4‐acetamido‐TEMPO/Halogen‐Mediated Electrooxidation of 5‐Hydroxymethylfurfural

A new method was developed for the selective gram‐scale synthesis of 2,5‐diformylfuran (DFF), which is an important chemical with a high application potential, via oxidation of biomass‐derived 5‐hydroxylmethylfurfural (HMF) catalyzed by 4‐acetylamino‐2,2,6,6‐tetramethylpiperidine‐1‐oxyl (4‐AcNH‐TEMPO) in a two‐phase system consisting of a methylene chloride and aqueous solution containing sodium hydrogen carbonate and potassium iodide. The key feature of this method is the generation of the I₂ (co‐)oxidant by anodic oxidation of iodide anions during pulse electrolysis. In addition, the electrolyte can be successfully recycled five times while maintaining a 62–65 % yield of DFF. This novel method provides a sustainable pathway for waste‐free production of DFF without the use of metal catalysts and expensive oxidants. An advantage of electrooxidation is utilized in the preparation of demanding chemical.     

Stabilization of mixture of two rigid solids modeling temperature and porosity

In this paper we investigate the asymptotic behavior of solutions to the initial boundary value problem for a mixture of two rigid solids modeling temperature and porosity. Our main result is to establish conditions which ensure the analyticity and the exponential stability of the corresponding semigroup.     

Implanted biofuel cell operating in a living snail

Implantable biofuel cells have been suggested as sustainable micropower sources operating in living organisms, but such bioelectronic systems are still exotic and very challenging to design. Very few examples of abiotic and enzyme-based biofuel cells operating in animals in vivo have been reported. Implantation of biocatalytic electrodes and extraction of electrical power from small living creatures is even more difficult and has not been achieved to date. Here we report on the first implanted biofuel cell continuously operating in a snail and producing electrical power over a long period of time using physiologically produced glucose as a fuel. The "electrified" snail, being a biotechnological living "device", was able to regenerate glucose consumed by biocatalytic electrodes, upon appropriate feeding and relaxing, and then produce a new "portion" of electrical energy. The snail with the implanted biofuel cell will be able to operate in a natural environment, producing sustainable electrical micropower for activating various bioelectronic devices.     

Theoretical evaluation of structural models of the S2 state in the oxygen evolving complex of Photosystem II: protonation states and magnetic interactions

Protonation states of water ligands and oxo bridges are intimately involved in tuning the electronic structures and oxidation potentials of the oxygen evolving complex (OEC) in Photosystem II, steering the mechanistic pathway, which involves at least five redox state intermediates S(n) (n = 0-4) resulting in the oxidation of water to molecular oxygen. Although protons are practically invisible in protein crystallography, their effects on the electronic structure and magnetic properties of metal active sites can be probed using spectroscopy. With the twin purpose of aiding the interpretation of the complex electron paramagnetic resonance (EPR) spectroscopic data of the OEC and of improving the view of the cluster at the atomic level, a complete set of protonation configurations for the S(2) state of the OEC were investigated, and their distinctive effects on magnetic properties of the cluster were evaluated. The most recent X-ray structure of Photosystem II at 1.9 ? resolution was used and refined to obtain the optimum structure for the Mn(4)O(5)Ca core within the protein pocket. Employing this model, a set of 26 structures was constructed that tested various protonation scenarios of the water ligands and oxo bridges. Our results suggest that one of the two water molecules that are proposed to coordinate the outer Mn ion (Mn(A)) of the cluster is deprotonated in the S(2) state, as this leads to optimal experimental agreement, reproducing the correct ground state spin multiplicity (S = 1/2), spin expectation values, and EXAFS-derived metal-metal distances. Deprotonation of Ca(2+)-bound water molecules is strongly disfavored in the S(2) state, but dissociation of one of the two water ligands appears to be facile. The computed isotropic hyperfine couplings presented here allow distinctions between models to be made and call into question the assumption that the largest coupling is always attributable to Mn(III). The present results impose limits for the total charge and the proton configuration of the OEC in the S(2) state, with implications for the cascade of events in the Kok cycle and for the water splitting mechanism.     

Free-flow isoelectric focusing of proteins remaining in cell fragments following sonication of thyroid carcinoma cells

The method of preparing protein mixtures for electrophoretic analysis of membrane-associated cell proteins was improved. By sonication, about one-half of the proteins of thyroid cells were released into the supernatant, while the other half preferentially comprising membrane proteins still remained in cell fragments, which could be sedimented by centrifugation. After sonication, even those proteins which remained in cell fragments, could completely be dissolved by free-flow isoelectric focusing media. They migrated through the free-flow electrophoresis chamber without forming precipitates. Because of these improvements, it was possible to show that the two thyroid cancer cell lines ML-1 and ONCO-DG1 express cytokeratin 8 at similar rates, but cytokeratins 7 and 18 differently. In addition, the presence of inorganic pyrophosphatase, tubulin-beta-5, and tubulin-beta-1 chains in human thyroid cells was proved for the first time.     

Determination of the micelle-solute association constants of some benzene and naphthalene derivatives by micellar high performance liquid chromatograph

Summary The interaction of some benzene and naphthalene derivatives with sodium dodecyl sulphate, hexadecyltrimethylmmonium bromide and polyoxyethylene [23] dodecanol micelles has been evaluated by high operformance liquid chromatography using micellar mobile phases. The micelle-solute association constants have been obtained for the compounds investigated. Good correlation between free energy of transfer for water-micelles and for octanol-water has been observed.