BV periodic solutions of an evolution problem associated with continuous moving convex sets

This paper is concerned with BV periodic solutions for multivalued perturbations of an evolution equation governed by the sweeping process (or Moreau's process). The perturbed equation has the form –DuN _C (t)(u(t))+F(t,u(t)), whereC is a closed convex valued continuousT-periodic multifunction from [0,T] to ^d ,N ^C (t)(u(t)) is the normal cone ofC(t) atu(t),F: [0,T]× ^{d d} is a compact convex valued multifunction and Du is the differential measure of the periodic BV solutionu. Several existence results for this differential inclusion are stated under various assumptions on the perturbationF.     

Spectroscopic properties of the photoproducts of pyridoxal-5′-P irradiation: Catalytic site recognition of ribonuclease A

Photoproducts of pyridoxal-5-P, i.e., 4-pyridoxic-5-P and bis-pyridoxal-5-P, have been studied by spectroscopic methods. The spectroscopic properties of bis-pyridoxal-5-P (bis-PLP) resemble those of pyridoxal-5-P (PLP) under similar experimental conditions. The coupling of methylen hydrogens to the phosphorus atom has been shown by NMR spectroscopy. The singlet in the³¹P-NMR spectra and the triplet in¹H-undecoupled experiments confirm the presence of the phosphate group in the 5 position of the structure of the vitamin. The effect of pH and solvent composition on the relative distribution of species of bis-pyridoxine-5-P (bis-PNP) has been investigated by absorption and fluorescence spectroscopy. The acid-base dissociation of the phosphate group is easily detected by emission spectroscopy. Bis-PNP and bis-PLP bind to the enzyme RNase A and they behave as competitive inhibitors with respect to the substrate cytidine-2-3-cyclic phosphate. The natural forms of vitamin B₆, pyridoxine, and pyridoxine-5-P have no effect on the catalytic activity of the protein. Experimental evidence derived from fluorescence and inhibition experiments is consistent with the hypothesis that bis-PNP recognizes the catalytic site of RNase A.     

Synthesis, crystal structure, and properties of MnNCN, the first carbodiimide of a magnetic transition metal

Synthesis, single-crystal structure determination, and magnetic properties are reported for manganese carbodiimide, MnNCN. The presumably unstable but inert phase adopts the trigonal system (R3m) with a = 3.3583(4) A, c = 14.347(2) A, V = 140.13(3) A3, and Z = 3. Divalent manganese is octahedrally coordinated by nitrogen atoms at 2.26 A, and the NCN(2-) unit adopts the linear [N=C=N](2-) carbodiimide shape with two C=N double bonds of 1.23 A. MnNCN contains high-spin Mn(II) with five unpaired electrons and behaves like an antiferromagnet with an ordering temperature below 30 K.     

Flow-through optical fiber sensor for automatic sulfide determination in waters by multisyringe flow injection analysis using solid-phase reflectometry

A software-controlled flow-through optical fiber diffuse reflectance sensor capitalized on the implementation of disk-based solid-phase pre-concentration schemes in a multisyringe flow injection analysis (MSFIA) set-up is proposed for the trace determination of sulfide in environmental waters and wastewaters. The fully automated flowing methodology is based on Fischer's coupling reaction of sulfide with N,N-dimethyl-p-phenylenediamine (DMPD) in the presence of Fe(iii) as oxidizing reagent in a 0.5 M HCl medium. The on-line generated methylene blue dye is subsequently delivered downstream to a dedicated optode cell furnished with an octadecyl-chemically modified (C(18)) disk, while continuously recording the diffuse reflectance spectrum of the pre-concentrated compound. A double regeneration protocol is finally executed to warrant minimum background noise and negligible baseline. Under the optimized chemical and hydrodynamic conditions, the optosensing MSFIA method features coefficients of variation better than 0.7%(n= 10) at 50 microg l(-1) concentration, a linear working range of 20-200 microg l(-1) sulfide, a 3sigma(blank) detection limit of 2.9 microg l(-1) sulfide and an injection throughput of 8 h(-1) for a pre-concentration sample volume of 2.9 ml. The interfacing of the robust and versatile multisyringe flow injection-based optode with a plug-in spectrophotometer furnished with a light emitting diode assures the miniaturization of the overall flow analyzer, which is, thus, readily adaptable to real-time monitoring schemes. The potential of the multisyringe flow method was assessed via the determination of sulfide traces in water samples of different complexity (namely, freshwater, seawater and wastewater).     

A simple and very sensitive spectrophotometric method for the direct determination of copper ions

A sensitive spectrophotometric method for the direct determination of copper in aqueous samples without a preconcentration step has been developed. It is based on the formation of a yellow complex with the chromogenic reagent di-2-pyridyl ketone benzoylhydrazone (dPKBH) in an alkaline medium. The complex stoichiometry was 1:2 (Cu:dPKBH) and presents maximum absorbance at 370 nm. The influence of chemical variables affecting the behaviour of the system such as pH, concentration of dPKBH, buffer solution and ethanol, order of addition of the reagents and stability of the complex, were evaluated. The molar absorptivity (epsilon) was 3.92x10(4) L mol(-1) cm(-1), and Beer's law was obeyed up to 3 mg L(-1) of copper. The relative standard deviation was 0.46% (n=11) for a sample containing 1 mg L(-1) Cu(II). The limit of detection was 2.5 micro g L(-1) and was therefore more sensitive than the direct methods reported previously. Finally, the method was successfully validated by analysing several real samples with different matrices, such as tap water, natural water or copper alloys, with an average relative error of 2.46%.     

The Reaction of Singlet Oxygen with Adamantylideneadamantane Mediated by Rose Bengal

The photo-oxygenation of adamantylideneadamantane ( 1 ) on siliceous supports using admixed granules of ion-exchange resin fixed to methylene blue (MB) and rose bengal (RB) gave exclusively the corresponding dioxetane derivative 2 for the former sensitizer, while the latter gave 2 and traces of the epoxide 3. RB and the charge-transfer complex produced from N-ethylcarbazole and 2,4,5,6-tetranitrofluoren-9-one both reacted with chemically generated singlet oxygen to give superoxide radical anion. Trapping of the latter with 5,5-dimethyl-1-pyrroline 1-oxide gave an adduct exhibiting a characteristic ESR spectrum. The treatment of 1 in MeOH with 30% aqueous H₂O₂ for 22 h at 60° gave 3 in 100% yield. Repetition of this experiment in the presence of 2,6-di(tert-butyl)-p-cresol caused no significant change. These results indicate that singlet oxygen reacts with 1 , in the presence of RB, by two different processes. The first leads to dioxetane formation. The second process involves conversion of singlet oxygen by RB to superoxide radical anion which subsequently gives H₂O₂ so producing epoxide 3 from 1 .     

A thieno-2H-chromene alpha-amino acid derivative: synthesis and photochromic properties

[structure: see text] A new photochromic thieno-2H-chromene alpha-amino acid derivative was prepared by C-N palladium-catalyzed cross-coupling of a bromothieno-2H-chromene with the aminated aromatic side chain of the methyl ester of a N,N-diprotected amino acid. Its good photochromic properties demonstrated by flash photolysis and continuous irradiation indicate a possible application in ophthalmic lenses. It may also be inserted into peptides to give photoinduced reversible structural changes.     

Clean osmium-catalyzed asymmetric dihydroxylation of olefins in ionic liquids and supercritical CO2 product recovery

The combination of ionic liquids (ILs) as solvents in the asymmetric Sharpless dihydroxylation (AD) with the use of scCO(2) in the separation process allows a very simple, efficient, clean and robust system for the reuse of the AD catalytic system, which also does not need the use of organic solvents either for the reaction or for the separation of products and allows the isolation of the diol, in high yield and enantiomeric excess and basically without contamination with osmium.     

Synthesis of 5-glycopyranosylamino-pyrano[2,3-d]pyrimidin-2-one derivatives

Summary Three series of 3-substituted 5-glycopyranosylamino pyrano[2,3-d]pyrimidin-2-one derivatives,3 a–c,4 a–c, and5 a–c have been prepared by treatment of the corresponding 1,4-dihydro-6-glycopyranosylamino pyrimidin-4-ones1 a–c with malonic, methyl malonic and ethyl malonic acids, respectively.

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Synthese von Derivaten des 5-Glucopyranosylaminopyrano[2,3-d]pyrimidin-2-on

Zusammenfassung Es wurden drei Serien von 3-substituierten 5-Glucopyranosylaminopyrano[2,3-d]pyrimidin-2-onen (3 a–c,4 a–c und5 a–c) mittels Behandlung der entsprechenden 1,4-Dihydro-6-glucopyranosylamino-pyrimidin-4-one (1 a–c) mit Malon-, Methylmalon- bzw. Ethylmalonsäure dargestellt.