Studies on Polymerization of Vinyl Compounds Initiated by Metal Chelate III. Accelerating Effect of Aniline on the Polymerization of Methyl Methacrylate Initiated by Nickel Chelate of β-Diketone

Aniline markedly accelerated polymerization of methyl methacrylate initiated by metal chelates of β-diketones. The kinetic studies of the polymerizaion of methyl methacrylate initiated by Ni (II) acetyl acetonate in the presence of aniline yielded R_p=[I]^0.55 [A]^0.66 [M]^1.87. The polymerization was of free radical in character. The accelerating effect of aniline was attributed to its reduction activation of the chelate. The activation energy for the overall polymerization was 21.3Kcal/mole, which yielded 33.4Kcal/mole for the activation energy for the initiation.     

Mass spectrometric detection of protein, lipid and heme components of cytochrome c oxidase from R. sphaeroides and the stabilization of non-covalent complexes from the enzyme

The cytochrome c oxidase enzyme from the Rhodobacter sphaeroides bacteria exists as a complex of four peptide subunits, two hemes, and a variety of lipids and metal ions held together by non-covalent forces. While the native enzyme functions as an associated unit, this complex usually dissociates during MALDI- TOF analysis. Through the use of matrix additives such as sucrose, the complete complex and partial complexes can be stabilized in the MALDI-TOF experiment. The dissociation of the complex allows for the detection of the components of the enzyme. The direct detection of associated lipids from an aqueous solution of the intact enzyme may eliminate the need for enzyme disruption and lipid extraction. The partial dissociation of multisubunit enzymes in such experiments may allow for the determination of subunit-subunit and subunit-lipid interactions     

Cycloadditions dipolaires-1,3—XXIV: Addition d'esters nitroniques aux olefines monoactivees

The orientation of the cycloaddition of the geometrical isomers of nitronic esters to monoactivated olefines is unique. Depending on the nature of the olefinic substituent, a competition between two modes of approach of the dipolarophile by the 1,3-dipole is observed. All these cycloadditions lead to stable invertomers of N-alkoxyisoxazolidines.     

A theoretical study of potassium cation binding to glycylglycine (GG) and alanylalanine (AA) dipeptides

By combining Monte Carlo conformational search technique with high-level density functional calculations, the geometry and energetics of K(+) interaction with glycylglycine (GG) and alanylalanine (AA) were obtained for the first time. The most stable K(+)-GG and K(+)-AA complexes are in the charge-solvated (CS) form with K(+) bound to the carbonyl oxygens of the peptide backbone, and the estimated 0 K binding affinities (DeltaH(0)) are 152 and 157 kJ mol(-1), respectively. The K(+) ion is in close alignment with the molecular dipole moment vector of the bound ligand, that is, electrostatic ion-dipole interaction is the key stabilizing factor in these complexes. Furthermore, the strong ion-dipole interaction between K(+) and the amide carbonyl oxygen atom of the peptide bond is important in determining the relative stabilities of different CS binding modes. The most stable zwitterionic (ZW) complex involves protonation at the amide carbonyl oxygen atom and is approximately 48 kJ mol(-1) less stable than the most stable CS form. The usefulness of proton affinity (PA) as a criterion for estimating the relative stability of ZW versus CS binding modes is examined. The effect of chain length and the nature of metal cations on cation-dipeptide interactions are discussed. Based on results of this study, the interaction of K(+) with longer peptides consisting of aliphatic amino acids are rationalized.     

Synthesis, relaxometric and photophysical properties of a new pH-responsive MRI contrast agent: the effect of other ligating groups on dissociation of a p-nitrophenolic pendant arm

Two gadolinium(III) chelates, GdNP-DO3A (1-methlyene-(p-NitroPhenol)-1,4,7,10-tetraazacycloDOdecane-4,7,10-triAcetate) and GdNP-DO3AM (1-methlyene(p-NitroPhenol)-1,4,7,10-tetraazacycloDOdecane-4,7,10-triacetAMide), containing a single nitrophenolic pendant arm plus either three acetate or three amide pendant arms were synthesized and characterized. The properties of the gadolinium, terbium, and dysprosium complexes of these ligands were examined as a function of pH. The extent and mechanism of the changes in water relaxivity with pH of each gadolinium complex was found to differ substantially for the two complexes. The water relaxivity of Gd(NP-DO3A) increases from 4.1 mM(-1) s(-1) at pH 9 to 7.0 mM(-1) s(-1) at pH 5 as a result of acid-catalyzed dissociation of the nitrophenol from the lanthanide. The nitrophenol group in Gd(NP-DO3AM) does not dissociate from the metal center even at pH 5; therefore, the very modest increase in relaxivity in this complex must be ascribed to an increase in prototropic exchange rate of the bound water and/or phenolic protons.     

Photochemistry and photobiology of cryptochrome blue-light photopigments: the search for a photocycle

Cryptochromes are flavoproteins that exhibit high sequence and structural similarity to the light-dependent DNA-repair enzyme, photolyase. Cryptochromes have lost the ability to repair DNA; instead, they use the energy from near-UV/blue light to regulate a variety of growth and adaptive processes in organisms ranging from bacteria to humans. The photocycle of cryptochrome is not yet known, although it is hypothesized that it may share some similarity to that of photolyase, which utilizes light-driven electron transfer from the catalytic flavin chromophore. In this review, we present genetic evidence for the photoreceptive role of cryptochromes and discuss recent biochemical studies that have furthered our understanding of the cryptochrome photocycle. In particular, the role of the unique C-terminal domain in cryptochrome phototransduction is discussed.     

Dual catalyst control in the enantioselective intramolecular Morita-Baylis-Hillman reaction

The intramolecular Morita-Baylis-Hillman (MBH) reaction has been achieved with unprecedented levels of enantioselectivity. Using a co-catalyst system involving pipecolinic acid and N-methylimidazole, cyclic MBH products have been obtained with enantiomer ratios of 92:8 (84% ee). In addition, reactions may be carried out with a "kinetic resolution quench" involving acetic anhydride and an asymmetric acylation catalyst such that ee enhancement occurs to deliver products with >98% ee with an isolated yield of 50%. [reaction: see text]     

Design and Performance Evaluation of Optical Ethernet Switching Architecture with Liquid Crystal on Silicon-Based Beam-Steering Technology

A non-blocking optical Ethernet switching architecture with liquid crystal on a silicon-based beam-steering switch and optical output buffer strategies are proposed. For preserving service packet sequencing and fairness of routing sequence, priority and round-robin algorithms are adopted at the optical output buffer in this research. Four methods were used to implement tunable fiber delay modules for the optical output buffers to handle Ethernet packets with variable bit-rates. The results reported are based on the simulations performed to evaluate the proposed switching architecture with traffic analysis under a traffic model captured from a real-core network.     

Error bounds for monotone linear complementarity problems

We give a bound on the distance between an arbitrary point and the solution set of a monotone linear complementarity problem in terms of a condition constant that depends on the problem data only and a residual function of the violations of the complementary problem conditions by the point considered. When the point satisfies the linear inequalities of the complementarity problem, the residual consists of the complementarity condition plus its square root. This latter term is essential and without it the error bound cannot hold. We also show that another natural residual that has been employed to bound errors for strictly monotone linear complementarity problems fails to bound errors for the monotone case considered here. Sponsored by the United States Army under contract No. DAAG29-80-C-0041. This material is based on research sponsored by National Foundation Grant DCR-8420963 and Air Force Office of Scientific Research Grant AFOSR-ISSA-85-00080.