Fluorescence and Time-Resolved Delayed Luminescence of Porphyrins in Organic Solvents and Polymer Matrices

Porphyrin dyes fulfill an essential function in photosynthesis and are important in photodynamic therapy and in a range of electronic devices. Their spectroscopic characteristics may play a crucial role in these processes. The spectral properties of two porphyrin dyes: tetraphenylporphyrin and tetraphenysulfporphyrin in organic solvents (acetone, chloroform, methyl alcohol, and dimethyl-sulfoxide) and in polyvinyl alcohol and poly(methylmethacrylate) films have been investigated. Absorption, fluorescence, and microsecond time-resolved delayed luminescence spectra have been measured at room temperature. The existence of different aggregated dye forms in the ground and excited states has been demonstrated. The manifold of dye species depends on the solvent/polymer. In the case of the polymers, it also depends on the solvent used to coat the polymer film. Delayed luminescence spectra and decay times of the two porphyrins in the different solutions and in polymeric matrices suggest that different mechanisms of deexcitation of the singlet excited states may be responsible for their generation in these and other porphyrin dyes.     

Noncommutative Berezin transforms and multivariable operator model theory

In this paper, we initiate the study of a class of noncommutative domains of n-tuples of bounded linear operators on a Hilbert space H, where m?2, n?2, and p is a positive regular polynomial in n noncommutative indeterminates. These domains are defined by certain positivity conditions on p, i.e.,

     

Thermal behaviour of some dibenzobicyclo[2.2.2]octane derivatives

A number of dibenzobicyclo[2.2.2]octane derivatives have been studied due to the interest of such compounds as ligands for coordination compounds with potential biological activity. Their thermal behaviour has been analyzed in order to find out more information about their fragmentation. A connection between the bridge substituents and the fragmentation process has been observed.     

Amine oxidase amperometric biosensor coupled to liquid chromatography for biogenic amines determination

A selective and sensitive method is presented for biogenic amines (BA) determination. The novelty consists in coupling a highly selective electrochemical biosensor to a weak acid cation-exchange column for online detection of amines. A bienzyme design, based on a recently isolated amine oxidase from grass pea and commercial horseradish peroxidase, was used for the biosensor construction. The enzymes were co-immobilized on the surface of a graphite electrode together with the electrochemical mediator (Os-redox polymer). The electrochemical detection was performed at a low applied potential (?50 mV vs. Ag/AgCl, KCl_0.1 M), where biases from interferences are minimal. The separation and determination of six BA, with relevance in food analysis (tyramine, putrescine, cadaverine, histamine, agmatine and spermidine), were investigated. Irrespective of the BA nature, the amine oxidase-based biosensor showed a linear response up to 5 mM, and its sensitivity decreases in the following order: cadaverine, putrescine, spermidine, agmatine, histamine and tyramine. The approach was used to estimate the BA content in fish samples, after their extraction with methanesulfonic acid.     

Assessment of collagen-based materials which are supports of cultural and historical objects

The thermal degradation of collagen-based materials, viz. collagen, recently manufactured parchments and tanned leathers, a heritage parchment and patrimonial (historical) leathers, was investigated by thermal analysis methods. With progressive heating, all these materials exhibit three main successive processes, associated with dehydration, protein denaturation and pyrolysis/oxidation. The analysis of both denaturation and thermo-oxidation revealed significant differences between aged leather, collagen, recently manufactured parchments and tanned leathers in terms of the number of overlapping processes (reflected in the number of peaks recorded at denaturation) and of the oxidative degradation rates, given by the normalised curves of differential thermal gravimetry (DTG). The various observations are proposed as qualitative indices for assessing the age and storage conditions of leather. A three-phase model was used for explaining the results. This consists of crystalline collagen filaments that are embedded in an amorphous matrix with an interface zone between the crystalline and amorphous regions. Solid-state ¹H NMR investigations corroborate the thermal analysis results and enhance the understanding of the ageing processes.     

Theoretical studies of carbocations in ion pairs. 8. Search for anchimeric assistance in the ionization of 2-butyl cation precursors

The structures of carbocations formed in the ionization of 2-butyl precursors were investigated by high level ab initio MO calculations on the reaction of 2-butyl fluoride (1) with borane, which gives a C4H9+ cation paired with trihydrofluoroborate (FBH3-, A). Two conformations of the "open," secondary cation (2) in the ion pair resulted from two conformations of 1, with F gauche and trans to C4 (2-g and 2-t, respectively). No anchimeric assistance by hydrogen (in 1-g) or methyl (in 1-t) was evidenced. In fact, attempts at optimizing the geometry of the H-bridged (3) and methyl-bridged (6) cations at short interionic distances (d) led to the corresponding conformations of 2. Upon ion separation, proton transfer from 2 to the anion occurred at intermediate interionic distances, consonant with experimental observations in trifluoroacetic acid. Elimination was prevented by addition of a lithium cation to the ion pair, i.e., running computations on triple ions (2.A.Li+). Cation 6 became an energy minimum beyond d = 2.5 A and 3 beyond 2.8 A. Cation 2-g was still the most stable isomer at d = 3.2 A, which was greater than the interionic distance in the crystals of the isomeric tert-butyl cation salts (3-3.1 A). Thus, spectral determinations of 2-butyl cations in the solid state should be interpreted with 2-g as the main component of the ion mixture. When the ions became separated (d >/= 4 A), only the bridged ions were energy minima. In this process, bridging did not occur opposite to the leaving group to assist the ionization, but on the same side with it, being controlled by the electrostatic interaction with the anion, as it departed from the vicinity of the cation. Such behavior was also noted in the ionization of the 3-methyl-2-butyl homolog.     

Metal-Free Arylation of Benzothiophenes at C4 by Activation as their Benzothiophene S-Oxides

Benzothiophenes, activated by oxidation to the corresponding S-oxides, undergo C−H/C−H-type coupling with phenols to give C4 arylation products. While an electron-withdrawing group at C3 of the benzothiophene is important, the process operates without a directing group and a metal catalyst, thus rendering it compatible with sensitive functionalities—e.g. halides and formyl groups. Quantum chemical calculations suggest a formal stepwise mechanism involving heterolytic cleavage of an aryloxysulfur species to give a π-complex of the corresponding benzothiophene and a phenoxonium cation. Subsequent addition of the phenoxonium cation to the C4 position of the benzothiophene is favored over the addition to C3; Fukui functions predict that the major regioisomer is formed at the more electron-rich position between C3 and C4. Varied selective manipulation of the benzothiophene products showcase the synthetic utility of the metal-free arylation process.     

Mechanistically inspired design of Fe(III)-TAML peroxide-activating catalysts

Recent broad-ranging mechanistic studies of FeIII-TAML peroxide activators enable a strategy for designing catalysts with improved (i) hydrolytic and (ii) operational stabilities, (iii) faster activation of H2O2 and other peroxides, and (iv) a pH of highest activity closer to 7. Combining all items of insight leads to [Fe{1-NO2C6H3-3,4-(NCOCMe2NCO)2CF2}(OH2)]- (1a) which exhibits the most desirable technical performance in its class.     

Precision of Raman depolarization and optical attenuation measurements of sound tooth enamel

The demineralization of enamel that is associated with early caries formation affects the optical properties of the enamel. Polarized Raman spectroscopy and optical coherence tomography have been used to detect these changes and potentially offer a means to detect and monitor early caries development. The total optical attenuation coefficient as measured by optical coherence tomography and the polarization anisotropy of the Raman peak arising from the symmetric ν₁ vibration of at approximately 959 cm⁻¹ have been demonstrated as being sensitive markers of early caries. This ex vivo study on extracted human teeth demonstrates that these measurements can be made with reasonable precision with concomitantly good repeatability and reproducibility in sound enamel. Such reliability is crucial for these techniques to have a practical clinical value.     

Per-O-methylation of neutral carbohydrates directly from aqueous samples for gas chromatography and mass spectrometry analysis

Per-O-methylation of neutral carbohydrates in one step by adding dimethyl sulfoxide, powdered sodium hydroxide, and methyl iodide directly to aqueous sample is described. The influence of the water on the methylation reaction is investigated. Solid powdered sodium hydroxide is very hygroscopic and can scavenge the water from sample if an additional excess of sodium hydroxide is added. The degree of per-O-methylation of carbohydrates is checked by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Gas chromatography-mass spectrometry analysis of mono- and disaccharides from grape juice is presented.