Application of circular dichroism spectroscopy in the study of mixed-valence asymmetric ruthenium polypyridyl complexes

Circular dichroism (CD) spectroelectrochemistry is used to determine the extent of singly occupied molecular orbital delocalization in mixed-valence multinuclear complexes, specifically the mixed-valence Ru(II)Ru(III) states of the four diastereoisomers of [(Ru(bpy)(2))(2)(bpt)](3+) [1; bpy = 2,2'-bipyridyl and bpt = 3,5-bis(pyrid-2'-yl)-1,2,4-triazolato anion]. The complex was found to be stable to thermal racemization in the three oxidation states, but photoracemization in the Ru(II)Ru(II) state was observed.     

SANS and SAXS analysis of charged nanoparticle adsorption at oil-water interfaces

A systematic study of the adsorption of charged nanoparticles at dispersed oil-in-water emulsion interfaces is presented. The interaction potentials for negatively charged hexadecane droplets with anionic polystyrene latex particles or cationic gold particles are calculated using DLVO theory. Calculations demonstrate that increased ionic strength decreases the decay length of the electrostatic repulsion leading to enhanced particle adsorption. For the case of anionic PS latex particles, the energy barrier for particle adsorption is also reduced when the surface charge is neutralized through changes in pH. Complementary small-angle scattering experiments show that the highest particle adsorption for PS latex occurs at moderate ionic strength and low pH. For cationic gold particles, simple DLVO calculations also explain scattering results showing that the highest particle adsorption occurs at neutral pH due to the electrostatic attraction between oppositely charged surfaces. This work demonstrates that surface charges of particles and oil droplets are critical parameters to consider when engineering particle-stabilized emulsions.     

Cationic and neutral phenylmercury(II) complexes with heterocyclic thione ligands. X-ray structures of [HgPh(dmpymtH)][BF4] · H2O and [{HgPh}2(μ-dtu)]

The neutral complex [HgPh(dmpymt)] 1 (dmpymtH = 4,6-dimethylpyrimidine-2(1H)-thione) reacts with HBF₄ to give the cationic complex [HgPh(dmpymtH)][BF₄] 2. The X-ray molecular structure of the later revealed a [2+1] coordination sphere about the mercury(II) atom (C−Hg−S and Hg?N). In the dinuclear complex [(HgPh)₂(μ-dtu)] 3 [dtuH₂ = 2,4(1H,3H)-pyrimidinedithione or dithiouracil] the coordination spheres are also [2+1] although dissimilar regarding the Hg?N secondary bonds. NMR spectroscopy (¹H, ¹³C and ¹⁹⁹Hg) studies were undertaken in solution and the results discussed in the light of the X-ray structures.     

Conversion of pyruvate decarboxylase into an enantioselective carboligase with biosynthetic potential

Pyruvate decarboxylase (PDC) catalyzes the decarboxylation of pyruvate into acetaldehyde and CO(2) and requires the cofactors thiamin diphosphate and Mg(2+) for activity. Owing to its catalytic promiscuity and relaxed substrate specificity, PDC catalyzes carboligation side reactions and is exploited for the asymmetric synthesis of 2-hydroxy ketones such as (R)-phenylacetyl carbinol, the precursor of (-)-ephedrine. Although PDC variants with enhanced carboligation efficiency were generated in the past, the native reaction, i.e., formation of aldehydes, is heavily favored over carboligation side reactions in all these biocatalysts. We characterized an active site variant (Glu473Gln) in which partitioning between aldehyde release versus carboligation is inverted with an up to 100-fold preference for the latter pathway. Due to a defective protonation of the central carbanion/enamine intermediate, substrate turnover stalls at this catalytic stage and addition of external aldehydes leads to quantitative and enantioselective formation of 2-hydroxy ketones as shown for (R)-phenylacetyl carbinol, which is afforded with unmatched yields, rates, and purity. This protein variant thus constitutes an example for the rational design of biocatalysts with greatly enhanced accidental catalytic promiscuity by selective blockage of the native reaction and accumulation of reactive intermediates under steady-state turnover conditions.     

Structure and dynamics of 1,2-dimethoxyethane and 1,2-dimethoxypropane in aqueous and non-aqueous solutions: a molecular dynamics study

Herein, we report a comparative modelling study of 1,2-dimethoxyethane (DME) and 1,2-dimethoxypropane (DMP) at 298 K and 318 K in the liquid state, water mixtures, and at infinite dilution condition in water, methanol, carbon tetrachloride, and n-heptane. Both DME and DMP are united-atom models compatible with GROMOS∕OPLS force fields. Calculated thermodynamic and structural properties of the pure DME and DMP liquids resulted in excellent agreement with the experimental data. In aqueous solutions, densities, diffusion coefficients, and concentration dependent conformers of DME, were in agreement with experimental data. The calculated free energy of solvation (ΔG(hyd)) at 298 K is equal to -22.1 ± 0.8 kJ mol(-1) in good agreement with the experimental value of 20.2 kJ mol(-1). In addition, the free energy of solvation of DME in non-aqueous solvents follows the trend methanol ≈ water < carbon tetrachloride < n-heptane, consistently with the dielectric constant of the solvents. On contrary, the presence of an extra methyl group on chiral carbon makes DMP less soluble than DME in water (ΔG(hyd) = -16.0 ± 1.1 kJ mol(-1)) but more soluble in non-polar solvents as n-heptane. Finally, for the DMP the chiral discrimination of the two enantiomers was calculated as solvation free energy difference of one DMP isomer in the solution of the other. The obtained value of ΔΔG(RS) = -3.7 ± 1.4 kJ mol(-1) indicates a net chiral discrimination of the two enantiomers.     

Nonlinear transmission of a tetrabrominated naphthalocyaninato indium chloride

The axially substituted complex chloro indium(III) 2-tetrabromo-3-tetra-(3,5-di-tert-butylphenyloxy)naphthalocyanine [Br4(tBu2PhO)4NcInCl (1); MW = 1996] has been synthesized for the first time, and its nonlinear transmission properties have been evaluated with the Z-scan technique in both open and closed aperture configurations at 532 nm for nanosecond pulsed radiation. The tetrabrominated complex 1 displayed a larger positive nonlinear absorption coefficient when compared to an analogous nonbrominated naphthalocyanine [(tBu2PhO)8NcInCl (2); MW = 2498]. The effect of the four Br atoms on the nonlinear optical behavior of 1 is evaluated, discussed, and compared with the nonlinear optical behavior of 2. It is shown that the bromination of the naphthalocyanine ring considerably improves the limiting properties of such a system when high-intensity radiations are produced by nanosecond laser pulses at 532 nm.