Co-C bond dissociation energy and reaction volume change of 2',5'-dideoxyadenosylcobalamin studied by laser-induced time-resolved photoacoustic calorimetry

Time resolved photoacoustic calorimetry (PAC) was applied to a study of the photolysis of a coenzyme B(12) analog 2',5'-dideoxyadenosylcobalamin, which lacks an -OH group at the 2' position of ribofuranose ring. In aqueous solution, we report for the first time the quantum yield Phi(d) (0.25+/-0.02), Co-C bond dissociation energy (BDE; 31.8+/-2.5 kcal mol(-1)) and reaction volume change deltaV(R) (6.5+/-0.5 ml mol(-1)) due to conformation changes of the corrin ring and its side chains accompanying the cleavage of the Co-C bond. These values for the analog are very similar to those for the natural cofactor. Based our results and previous studies, a possible explanation for the similarity in their structure and properties versus the large difference in their enzymatic activity is discussed.     

Hydrogen bond directed synthesis of pyridazine and naphthyridine containing macrocycles

This work describes a high-yielding, one-step synthesis of pyrizadine and naphthyridine containing macrocycles directed by intramolecular H-bonding.     

Quark-diagram estimates ofCP violation in two-body baryonicB_d^0 - \bar B_d^0 decays

CP violation in partial-decay-rate asymmetries are examined for some two-body baryonic decays of \(B_d^0 - \bar B_d^0 \) system. We discuss two feasible experimental circumstances: the symmetrice ⁺ e ^? collisions (i) on theZ ⁰ resonance to produce incoherent \(B_d^0 \bar B_d^0 \) states, and (ii) just above the ?(4S) resonance to produceC=even \(B_d^0 \bar B_d^0 \) states. Using the quark-diagram scheme, we estimate the branching ratios of those decays, and the numbers ofb \(\bar b\) pairs needed for testing theCP-violating effects for 3σ signature. We find that the promising channels may beB _d ⁰ , \(\bar B_d^0 \to p\bar p\) , \(\Delta ^ + \bar \Delta ^ - \) , \(p\bar \Delta ^ - \) , \(\Delta ^ + \bar p\) , \(n\bar n\) , \(\Delta ^0 \bar \Delta ^0 \) , \(n\bar \Delta ^0 \) , \(\Delta ^0 \bar n\) , \(\Sigma _c^ + \bar \Sigma _c^ - \) , \(\Lambda _c^ + \bar \Lambda _c^ - \) , \(\Sigma _c^ + \bar \Lambda _c^ - \) , \(\Lambda _c^ + \bar \Sigma _c^ - \) , \(\Sigma _c^0 \bar \Sigma _c^0 \) , \(\Xi _c^0 \bar \Xi _c^0 \) , which should be interesting for experimental observation.     

A note on approximate controllability for semilinear one-dimensional heat equation

The one-dimensional semilinear heat equation is considered. It is shown that if the nonlinear functionF(y) is uniformly bounded then the system is approximately controllable for every given terminal timeT>0 under some ordinary condition onb. The results may be extended to the general one-dimensional semilinear heat equation with one-dimensional control or to a boundary control heat system with semilinear boundary condition.     

Chiral separation of amino acids derivatized with fluoresceine-5isothiocyanate by capillary electrophoresis and laser-induced fluorescence detection using mixed selectors of beta-cyclodextrin and sodium taurocholate

Chiral separation of 20 pairs of amino acids derivatized with fluoresceine-5-isothiocyanate (FITC) by capillary electrophoresis and laser-induced fluorescence detection was studied using the mixture of beta-cyclodextrin (beta-CD) and sodium taurocholate (STC) as selector. Resolution was considerably superior to that obtained by using either beta-CD or STC alone. The molar ratio of beta-CD to STC of about 2:3 was found to be critical to achieve maximum separation. At this beta-CD-to-STC ratio, chiral separation occurred at really low total concentration of beta-CD and STC (<0.1 mM). Other impacting factors were investigated including the total concentration of beta-CD and STC, pH, and capillary conditioning procedure between two successive runs. Using a running buffer of 80 mM borate containing 20 mM beta-CD and 30 mM STC at pH 9.3, all of the 20 pairs of FITC-amino acid enantiomers were baseline resolved. The resolutions of the most pairs of the amino acid enantiomers (17 of 20) were higher than 3.0, only three pairs gave a resolution lower than 3.0 but higher than 1.90 (beta-phenylserine, pSer). The highest resolution reached 14.58 (Glu). Two derivatives of beta-CD, 2-hydroxypropyl-beta-CD (HP-beta-CD) and heptakis(2,6-di-O-methyl)-beta-CD (DM-beta-CD) were also explored. HP-beta-CD showed similar cooperative effect with STC, while DM-beta-CD together with STC led to poorer chiral separation.