Mononuclear nitrogen/sulfur-ligated zinc methoxide and hydroxide complexes: investigating ligand effects on the hydrolytic stability of zinc alkoxide species

The synthesis and properties of mononuclear zinc methoxide ([(ebnpa)Zn-OCH3]ClO4) (1) and hydroxide ([(ebnpa)Zn-OH]ClO4) (2) complexes of a new mixed nitrogen/sulfur ligand (ebnpa = N-2-(ethylthio)ethyl-N,N-bis(6-neopentylamino-2-pyridylmethyl)amine) are reported. The structures of 1 and 2 were determined by X-ray diffraction. Each possesses a single zinc-coordinated anion (methoxide or hydroxide) and exhibits an overall trigonal bipyramidal geometry. Structural and spectroscopic studies indicate the presence of two hydrogen-bonding interactions involving the oxygen atom of the zinc-bound anion in each complex. Treatment of [(ebnpa)Zn-OH]ClO4 with CH3OH results in the formation of an equilibrium mixture of 1 and 2. 1H NMR spectroscopic methods were used to examine the equilibrium as a function of temperature, yielding KMe (304 K) = 0.30(8), DeltaHMe = -0.9(1) kcal/mol, and DeltaSMe = -5(1) eu. The negative enthalpy indicates that spontaneous zinc alkoxide formation from a hydroxide precursor occurs in this system at low temperature. Using the experimentally determined DeltaHMe value, we found the homolytic Zn-O bond dissociation energy (BDE) in the Zn-OCH3 unit to be approximately -14 kcal/mol relative to the Zn-O BDE in the Zn-OH unit.     

Structure of microparticles in solid-stabilized emulsions

Emulsions of oil and water stabilized by adsorbed solid particles are known as solid-stabilized emulsions (often referred to as Pickering emulsions). Using confocal microscopy, we have studied the assembly of colloidal-sized polystyrene particles in poly(dimethylsiloxane)-in-water solid-stabilized emulsions. Monodisperse polystyrene particles, when included in the emulsions at low concentrations, were found to form small patches with local "hexagonal" order, separated by other particle-free domains. Polystyrene particles with different sizes (1 and 4 microm) and different wettability could simultaneously segregate to the emulsion interface; even mixtures of hydrophobic and hydrophilic solid particles were found to simultaneously segregate to the same interface.     

Papieruntersuchung

Analytical and Bioanalytical Chemistry -     

Genetic variants in novel pathways influence blood pressure and cardiovascular disease risk

Blood pressure is a heritable trait influenced by several biological pathways and responsive to environmental stimuli. Over one billion people worldwide have hypertension (≥140?mm?Hg systolic blood pressure or ≥90?mm?Hg diastolic blood pressure). Even small increments in blood pressure are associated with an increased risk of cardiovascular events. This genome-wide association study of systolic and diastolic blood pressure, which used a multi-stage design in 200,000 individuals of European descent, identified sixteen novel loci: six of these loci contain genes previously known or suspected to regulate blood pressure (GUCY1A3-GUCY1B3, NPR3-C5orf23, ADM, FURIN-FES, GOSR2, GNAS-EDN3); the other ten provide new clues to blood pressure physiology. A genetic risk score based on 29 genome-wide significant variants was associated with hypertension, left ventricular wall thickness, stroke and coronary artery disease, but not kidney disease or kidney function. We also observed associations with blood pressure in East Asian, South Asian and African ancestry individuals. Our findings provide new insights into the genetics and biology of blood pressure, and suggest potential novel therapeutic pathways for cardiovascular disease prevention.     

Gaussian sum rules in quantum chromodynamics and local duality

A new type of hadronic sum rules are studied in QCD. They correspond to the Gauss-Weierstrass transform of hadronic spectral functions. There is an interesting analogy between these sum rules and the theory of the heat equation which provides a useful framework for formulating quantitatively the notion of local duality. In particular, finite energy sum rules are shown to follow within this framework from the principle of conservation of total heat. Explicit calculations of these sum rules in QCD - from both perturbative and non-perturbative contributions à la Shifman, Vainshtein and Zakharov [1] - have been made in a rather general way which should cover all the practical cases involving light quark systems. A particular case of the -spectral function and its duality to QCD is discussed in detail as an illustration of this new approach.     

Factors affecting the loudness of modulated sounds.

Loudness matches were obtained between unmodulated carriers and carriers that were amplitude modulated either periodically (rates between 2 and 32 Hz, modulation sinusoidal either on a linear amplitude scale or on a dB scale; the latter is called dB modulation) or with the envelope of the speech of a single talker. The carrier was a 4-kHz sinusoid, white noise, or speech-shaped noise. Both normally hearing subjects and subjects with cochlear hearing loss were tested. Results were expressed as the root-mean-square (rms) level of the modulated carrier minus the level of the unmodulated carrier at the point of equal loudness. If this difference is positive, this indicates that the modulated carrier has a higher rms level at the point of equal loudness. For normally hearing subjects, the results show: (1) For a 4000-Hz sinusoidal carrier, the difference was slightly positive (averaging about 0.7 dB). There was no significant effect of modulation rate or level over the range 20-80 dB SL. (2) For a speech-shaped noise or white noise carrier, the difference was close to zero, although for large modulation depths it tended to be negative. There was no clear effect of level (over the range 35-75 dB SPL) or modulation rate. For the hearing-impaired subjects, the differences were small, but tended to be slightly negative for both the 4000-Hz carrier and the noise carriers, when the modulation rate was above 2 Hz. Again, there was no clear effect of overall level. However, for dB modulation, the differences became more negative with increasing modulation depth. For modulation rates in the range 4-32 Hz, the results could be fitted reasonably well using the assumption that the loudness of modulated sounds is based on the rms value of the time-varying intensity of the response of the basilar membrane (taking into account the compression that occurs in the normal cochlea). The implications of the results for the fitting of multi-band compression hearing aids and for the design of loudness meters are discussed.     

Dynamics and collapse of two-dimensional colloidal lattices

One interesting aspect of colloidal particles is the formation of colloidal crystals at the 2D and 3D levels. Here we report the dynamics and collapse of colloidal lattices at liquid-liquid interfaces using Pickering emulsions as an experimental template. The colloidal particles oscillate around their equilibrium positions. The short-time diffusion constant (<10 s) of single particles increases with increasing lattice spacing; the oil-phase viscosity has an effect on diffusion only at large interparticle distances. Strikingly, we observe that the equilibrium structure can be disturbed when increasing the output laser intensity in a confocal laser scanning microscope, which leads to the collapse of colloidal lattices in the presence of small laser powers.     

Dynamics of charged microparticles at oil-water interfaces

Solid-stabilized emulsions have been used as a model system to investigate the dynamics of charged microparticles with diameters of 1.1 microm at oil-water interfaces. Using confocal microscopy, we investigated the influences of interfacial curvature, cluster size, and temperature on the diffusion of solid particles. Our work suggests that a highly curved emulsion interface slows the motion of solid particles. This qualitatively supports the theoretical work by Danov et al. (Danov, K. D.; Dimova, R.; Pouligny, B. Phys. Fluids 2000, 12, 2711); however, the interfacial curvature effect decreases with increasing oil-phase viscosity. The diffusion of multiparticle clusters at oil-water interfaces is a strong function of cluster size and oil-phase viscosity and can be quantitatively related to fractal dimension. Finally, we report the influence of temperature and quantify the diffusion activation energy and friction factor of the particles at the investigated oil-water interfaces.