SU(3) Polyakov Linear-Sigma Model: Magnetic Properties of QCD Matter in Thermal and Dense Medium

The linear-sigma model, in which information about confining gluons is included through the Polyakov-loop potential (PLSM), is considered in order to perform a systematic study for various magnetic properties of QCD matter under extreme conditions of high temperatures and densities and finite magnetic field strengths. The introduction of magnetic field to the PLSM Lagrangian requires suitable utilization of Landau quantization, modification in the dispersion relations, and momentum-space dimension-reduction. We observed that increasing the magnetic field leads to filling-up lower Landau levels first and decreasing the number of occupied levels. We conclude that the population of Landau levels is most sensitive to the magnetic field and to the quark charges. The influences of finite magnetic field on the temperature dependence of chiral and deconfinement order-parameter(s) are studied. We present estimations for the magnetization, the magnetic susceptibility, the permeability, and the catalytic properties of QCD matter as functions of temperature. The dependences of the resulting freeze-out parameters, temperatures, and baryon chemical potentials on the corresponding magnetic field strengths have been analyzed, as well. These calculations are compared with recent lattice QCD simulations, whenever available. We conclude that the QCD matter seems to have paramagnetic property at temperatures greater than the critical one. There is an evidence for weak diamagnetic property at low temperatures. Last but not least, we observe that the magnetic catalysis is inverse, namely, the critical temperatures decrease with increasing the magnetic field.     

Oxygen isotope effects on electron transfer to O2 probed using chemically modified flavins bound to glucose oxidase

Apo-glucose oxidase has been reconstituted with flavins modified in the 7 and 8 positions and characterized with regard to the catalytic rate of O(2) reduction and oxygen-18 isotope effects on this process. Kinetic studies as a function of driving force indicate a reorganization energy for electron transfer to O(2) of lambda = 28 kcal mol(-)(1) at optimal pH, which is similar to the value obtained earlier from temperature dependencies of rates (Roth, J. P.; Klinman, J. P. Proc. Natl. Acad. Sci. U.S.A. 2003, 100, 62-67). For the various enzyme-bound flavins, competitive oxygen-18 kinetic isotope effects fall within the narrow range of 1.0266(5) to 1.0279(6), apparently because of the dominant contribution of outer-sphere reorganization to the activation barrier; within the context of semiclassical and quantum mechanical electron transfer theories, the magnitude of the isotope effects reveals the importance of nuclear tunneling.     

Functionalised electrode array for the detection of nitric oxide released by endothelial cells using different NO-sensing chemistries

In a preliminary study aimed at developing strategies for the simultaneous detection of various biologically important molecules, a procedure is described that allows the electrochemical detection of nitric oxide (NO) released by a population of human umbilical vein endothelial cells (HUVEC) by using an array of electrodes comprising three individually addressable electrodes. Each electrode in the array was modified with a different NO-sensitive electrocatalyst, thereby demonstrating the possibility of modifying the individual electrodes in an array with different sensing chemistries. This study opens a doorway to the development of arrays of electrodes for the simultaneous detection of multiple analytes in a complex environment by suitably tailoring the sensitivity and selectivity of each electrode in the array to a specific analyte in the test medium.     

Thermal stability of poly(vinyl bromide) and vinyl bromide-methyl acrylate copolymers. I

The thermal stability of PVB and five VB-MA copolymers with different compositions was studied by thermogravimetric analysis in dynamic nitrogen. The reactivity ratios of the copolymers were determined by using NMR techniques. It was found that r₁(VB) = 0.5 ± 0.1 and r₂(MA) = 7.3 ± 0.3. The stability of VB increases as the MA concentration in the copolymer compositions increases. Apparently, the formation of lactone and anhydride structures has a stabilizing effect. The stability imparted to the degrading copolymers by lactone and anhydride structures is insufficient to produce stability comparable to that of PMA itself.     

Synthese d'aziridine alcool a fonction aziridine secondaire

The reactions of Grignard reagents with α-keto oximes 1 and α-hydroximino alcohols 3, give secondary aziridine alcohols 2 or 4, which with SOCL₂ (or COCl₂)give azabicyclo[3.1.0]oxo-2 oxaisothiazolidine-1, 5 or azabicyclo[3.1.0]carbamate-1,2,3 6. The determination of configuration of 2,4 and 5 was achieved by an NOE study.     

Thermal stability of poly(β-bromostyrene) and copolymers of β-bromostyrene with methyl methacrylate

The thermal stabilities of poly(-bromostyrene), poly-(methyl methacrylate) homopolymers and copolymers of-bromostyrene-methyl methacrylate covering the entire composition range were studied using TG analysis. At each extreme of the composition range, incorporation of comonomer units results in a copolymer more stable than the brominated homopolymer. Maximum stability occurs for compositions of approximately 62 mole percent-bromostyrene. The formation of the anhydride structure among the degradation products leads to the stability of the copolymers.

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Zusammenfassung Die thermische Stabilität von-Bromstyrol- und Methylmethacrylat-Homopolymeren sowie von sich über den ganzen Zusammensetzungsbereich erstreckenden-Bromstyrol/Methylmethacrylat-Kopolymeren wurde thermogravimetrisch untersucht. An beiden Enden des Zusammensetzungsbereichs führt der Einbau von Komonomereinheiten zu einem Kopolymer, das stabiler als das bromierte Homopolymer ist. Maximale Stabilität wird bei einem Gehalt von etwa 62 Mol-%-Bromstyrol erreicht. Die Bildung der Anhydridstruktur führt zur Stabilität des Kopolymers.

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Presented at the World Conference of Thermal Analysis, held in Bad Hofgastein (Austria), 1985.     

Time-resolved measurements of the photolysis and recombination of adenosylcobalamin bound to glutamate mutase

Femtosecond to nanosecond transient absorption spectroscopy is used to investigate the photolysis of 5'-deoxyadenosylcobalamin (coenzyme B12, AdoCbl) bound to glutamate mutase. The photochemistry of AdoCbl is found to be inherently dependent upon the environment of the cofactor. Excitation of AdoCbl bound to glutamate mutase results in formation of a metal-to-ligand charge transfer intermediate state which decays to form cob(II)alamin with a time constant of 105 ps. This observation is in contrast to earlier measurements in water where the photohomolysis proceeds through an intermediate state in which the axial dimethylbenzimidazole ligand appears to have dissociated, and measurements in ethylene glycol where prompt bond homolysis is observed (Yoder, L. M.; Cole, A. G.; Walker, L. A., II; Sension, R. J. J. Phys. Chem. B 2001, 105, 12180-12188). The quantum yield for formation of stable radical pairs in the enzyme is found to be phi = 0.05 +/- 0.03, and the resulting intrinsic rate constants for geminate recombination and "cage escape" are 1.0 +/- 0.1 and 0.05 +/- 0.03 ns(-1), respectively. The rate constant for geminate recombination is 30% less than that observed for AdoCbl in water or ethylene glycol. This reduction is insufficient to account for the 10(12)-fold increase in the homolysis rate observed when substrate is bound to the protein. Finally, the protein provides a cage to prevent diffusive loss of the adenosyl radical; however, the ultimate yield for long-lived radicals is determined by the evolution from a singlet to a triplet radical pair as proposed for AdoCbl in ethylene glycol.     

Diphosphine sulfides derived from 2,2'-biphosphole: novel chiral S,S ligands for palladium-catalyzed asymmetric allylic substitution

Diphosphine sulfides derived from 2,2'-biphosphole have been efficiently synthesized in an enantiomerically pure form by a four step synthetic sequence. These S,S-ligands were used for the first time in Pd-catalyzed asymmetric allylic alkylation. Good yields and enantiomeric excess up to 73% were obtained.     

Efficient synthesis of fluorophosphonylated alkyles by ring-opening reaction of cyclic sulfates

Ring-opening reactions of functionalized 1,2-cyclic sulfates and oxetanes with the phosphonodifluoromethyl carbanion are reported. This approach allows an easy access to fluorinated beta-hydroxyphosphonates that are building blocks in the synthesis of acyclic nucleosides. Synthesis of precursors of nucleoside phosphorylase inhibitors from these alcohols is described.     

Multiphoton control of the 1,3-cyclohexadiene ring-opening reaction in the presence of competing solvent reactions

Although physical chemistry has often concentrated on the observation and understanding of chemical systems, the defining characteristic of chemistry remains the direction and control of chemical reactivity. Optical control of molecular dynamics, and thus of chemical reactivity provides a path to use photon energy as a smart reagent in a chemical system. In this paper, we discuss recent research in this field in the context of our studies of the multiphoton optical control of the photo-initiated ring-opening reaction of 1,3-cyclohexadiene (CHD) to form 1,3,5- cis-hexatriene (Z-HT). Closed-loop feedback and learning algorithms are able to identify pulses that increase the desired target state by as much as a factor of two. Mechanisms for control are discussed through the influence of the intensity dependence, the nonlinear power spectrum, and the projection of the pulses onto low orders of polynomial phase. Control measurements in neat solvents demonstrate that competing solvent fragmentation reactions must also be considered. In particular, multiphoton excitation of cyclohexane alone is capable of producing hexatriene. Statistical analyses of data sets obtained in learning algorithm searches in neat cyclohexane and for CHD in hexane and cyclohexane highlight the importance of linear and quadratic chirp, while demonstrating that the control features are not so easily defined. Higher order phase components are also important. On the basis of these results the involvement of low-frequency ground-state vibrational modes is proposed. When the population is transferred to the excited state, momentum along the torsional coordinate may keep the wave packet localized as it moves toward the conical intersections controlling the yield of Z-HT.