Antibody-catalyzed benzoin oxidation as a mechanistic probe for nucleophilic catalysis by an active site lysine

Aldolase antibody 24H6, which was obtained by reactive immunization against a 1,3-diketone hapten, is shown to catalyze additional reactions, including H/D exchange and oxidation reactions. Comparison of the H/D exchange reaction at the alpha-position of a wide range of aldehydes and ketones by 24H6 and by other aldolase antibodies, such as 38C2, pointed at the significantly larger size of the 24H6 active site. This property allowed for the catalysis of the oxidation of substituted benzoins to benzils by potassium ferricyanide. This reaction was used as a mechanistic probe to learn about the initial steps of the 24H6-catalyzed aldol condensation reaction. The Hammett correlation (rho=4.7) of log(k(cat)) versus the substituent constant, sigma, revealed that the reaction involves rapid formation of a Schiff base intermediate from the ketone and an active site lysine residue. The rate-limiting step in this oxidation reaction is the conversion of the Schiff base to an enamine intermediate. In addition, linear correlation (rho=3.13) was found between log(K(M)) and sigma, indicating that electronic rather than steric factors are dominant in the antibody-substrate binding phenomenon and confirming that the reversible formation of a Schiff base intermediate comprises part of the substrate-binding mechanism.     

Competitive reactions among three monomers over a catalytic surface

We studied in this work a three-monomer reaction model on one- and two-dimensional lattices. We have taken different reactivity rates among pairs of monomers and the reaction between two selected monomers was forbidden. We have employed the mean field and the pair approximation to decouple the equations of motion for the densities of single and pairs of monomers. We found the stationary states and the phase diagram of the model. We have shown that, in two dimensions and within the pair approximation, there is a first-order transition line between active and poisoned steady states.     

New multicomponent approach for the creation of chiral quaternary centers in the carbonyl allylation reactions

The combined regio- and stereo-controlled carbometalation reaction of alkynyl sulfoxide followed by a zinc homologation and finally an allylation reaction led, in a single-pot operation, to chiral homoallylic alcohols in excellent yields and diastereoselectivities for the creation of chiral quaternary and tertiary centers. The key features in all of the reactions that are described in this article are the high degree of stereocontrol, the level of predictability, and "the ease of execution" which ensures success in the application of such methods. The chiral sulfinyl moiety can be finally removed by simple treatment with alkyllithiums, which allows further functionalizations of the carbon skeleton. By using one of these methods, the creation of chiral quaternary centers with the smallest possible difference, namely CD3 versus CH3 and 13CH3 versus CH3, was easily performed.     

Orientation of diamagnetic layered transition metal oxide particles in 1-tesla magnetic fields

The magnetic field-driven orientation of microcrystals of six diamagnetic layered transition metal oxides (HLaNb(2)O(7), HCa(2)Nb(3)O(10)·0.5H(2)O, KNaCa(2)Nb(4)O(13), KTiTaO(5), KTiNbO(5), and H(2.2)K(1.8)Nb(6)O(17)·nH(2)O) suspended in epoxy resins was studied by X-ray diffraction using permanent magnets producing a 0.8 T field. Although the degree of orientation, quantified as the Hermans order parameter, was strongly affected by the particle size distribution, in all cases microcrystals with ～1-2 μm lateral dimensions were found to orient with the magnetic field vector in the layer plane. Control of the orientation of ionically conducting layered oxides is of interest for practical applications in batteries and fuel cells. The consistent direction of orientation of the lamellar oxides studied can be rationalized in the framework of a quantitative bond anisotropy model developed by Uyeda (Phys. Chem. Miner.1993, 20, 77-80). The asymmetry of metal-oxygen bonding at the faces of the octahedral layers results in long and short M-O bonds perpendicular to the plane of the sheets. This distortion of the M-O octahedra, which is a structural feature of almost all layered materials that contain octahedral bonding frameworks, gives rise to the diamagnetic anisotropy and results in an easy axis or plane of magnetization in the plane of the sheets.     

4-Cyanopyridine and amide-N and amide-O linkage isomers of 4-pyridinecarboxamide on trans-chloro(1,4,8,11-tetraazacyclotetradecane)ruthenium(II/III)

The synthesis, UV-vis spectra, and electrochemical behavior of the nitrile-bonded trans-[Ru(II)Cl(cyclam)(4-NCpyH(+))](BF(4))(2) (4-Ncpy = 4-cyanopyridine; cyclam = 1,4,8,11-tetraazacyclotetradecane) and of trans-[Ru(III)Cl(cyclam)(NHC(O)-4-pyH(+))](2+) are described. The UV-vis spectrum of the Ru(II) nitrile complex shows a MLCT band at 548 nm at pH 1, which is shifted to 440 nm at pH approximately 6, for the unprotonated species. trans-[Ru(II)Cl(cyclam)(4-NCpyH(+))](2+) was electrolytically oxidized (+600 mV vs Ag/AgCl) at pH 1 to Ru(III), followed by hydrolysis (k = 0.25 s(-1)) of the coordinated nitrile to give trans-[Ru(III)Cl(cyclam)(NHC(O)-4-pyH(+))](2+), in which the amide is deprotonated and coordinated through nitrogen. The identity of the species is pH dependent, the nitrogen-bonded amide prevailing at low pH (< 7), but the oxygen-bonded amide is formed through linkage isomerization at higher pH (>8). Reduction of trans-[Ru(III)Cl(cyclam)(NHC(O)-4-pyH)](2+) in acidic media does not result in fast aquation (k = approximately 2.4 x 10(-5) s(-1)) as for other amides on ruthenium(II) pentaammine, but instead linkage isomerization occurs, resulting in the oxygen-bonded species, with an estimated rate constant of approximately 2 x 10(-2) s(-1), smaller than in the pentaammine analogues.