Osmotic Pressure and Phase Boundary Determination of Multiphase Systems by Analytical Ultracentrifugation

We show that analytical ultracentrifugation can be applied to derive full equations of state of colloids in a single sedimentation equilibrium experiment, by determination of single‐phase boundaries as well as of osmotic pressure versus concentration at fixed temperatures. A continuous dependence of the osmotic pressure, over orders of magnitude between at least ～10¹ and 10⁴ Pa, and a wide concentration range, are determined in agreement with standard theoretical considerations. Two model experimental colloidal systems are investigated: For a well‐known synthetic clay system (laponite), it is shown that two regimes—counter‐ion ideal gas and interacting double layers—can easily be identified in the equation of state, whereas metastable glass‐ or microphase‐separated gel states previously encountered in osmotic stress measurements of laponite are circumvented. For the case of rigid, crystallized catanionic bilayers, single phase domains can be identified. Osmotic pressure results in this case disagree with results obtained using the classical osmotic stress technique, as a result of sample adhesion to the ultracentrifuge cell windows and uncertainty due to possible micromolar ion contamination.     

Orthidines A-E, tubastrine, 3,4-dimethoxyphenethyl-β-guanidine, and 1,14-sperminedihomovanillamide: potential anti-inflammatory alkaloids isolated from the New Zealand ascidian Aplidium orthium that act as inhibitors of neutrophil respiratory burst

In addition to the known dihydroxystyrylguanidine alkaloid tubastrine (1), five new dimers, orthidines A-E (2-6) and the biosynthetically unrelated 1,14-sperminedihomovanillamide (orthidine F, 7) were isolated from the New Zealand ascidian Aplidium orthium. The structures of the new compounds, elucidated by interpretation of spectroscopic data, encompass benzodioxane neolignan-type scaffolds (2-5) and a 1,2,3,4-tetrasubstituted cyclobutane (6), the latter likely having arisen via [_π2_s+_π2_s] dimerization of tubastrine. The subunit head-to-tail orientation of dimer 6 was established unambiguously by interpretation of data from a ²J,³J-HMBC NMR experiment. The structure of 7 was also confirmed by facile synthesis. Compounds 1-4, 6, and 7 inhibited the in vitro production of superoxide by PMA-stimulated human neutrophils in a dose-dependent manner with IC₅₀s of 10-36 μM and this was associated with inhibition of superoxide production by neutrophils in vivo in a murine model of gouty inflammation.     

Identification of six new photoactive yellow proteins--diversity and structure-function relationships in a bacterial blue light photoreceptor

Photoactive yellow proteins (PYP) are bacterial photoreceptors with a Per-Arnt-Sim (PAS) domain fold. We report the identification of six new PYPs, thus nearly doubling the size of this protein family. This extends the taxonomic diversity of PYP-containing bacteria from photosynthetic to nonphotosynthetic bacteria, from aquatic to soil-dwelling organisms, and from Proteobacteria to Salinibacter ruber from the phylum Bacteriodetes. The new PYPs greatly increase the sequence diversity of the PYP family, reducing the most prevalent pair-wise identity from 45% to 25%. Sequence alignments and analysis indicate that all 14 PYPs share a common structure with 13 highly conserved residues that form the chromophore binding pocket. Nevertheless, the functional properties of the PYPs vary greatly--the absorbance maximum extends from 432 to 465 nm, the pK(a) of the chromophore varies from pH 2.8 to 10.2, and the lifetime of the presumed PYP signaling state ranges from 1 ms to 1 h. Thus, the PYP family offers an excellent opportunity to investigate how functional properties are tuned over a wide range, while maintaining the same overall protein structural fold. We discuss the implications of these results for structure-function relationships in the PYP family.     

Thrombin allostery

Thrombin is a Na(+)-activated, allosteric serine protease that plays multiple functional roles in blood pathophysiology. Binding of Na(+) is the major driving force behind the procoagulant, prothrombotic and signaling functions of the enzyme. This review summarizes our current understanding of the molecular basis of thrombin allostery with special emphasis on the kinetic aspects of Na(+) activation. The molecular mechanism of thrombin allostery is a remarkable example of long-range communication that offers a paradigm for many other biological systems.     

Transmission of ultrasound through a single layer of bubbles

We investigate, both experimentally and theoretically, the effect of coupling between resonant scatterers on the transmission coefficient of a model system of isotropic scatterers. The model system consists of a monodisperse layer of bubbles, which exhibit a strong monopole scattering resonance at low ultrasonic frequencies. The layer was a true 2D structure obtained by injecting very monodisperse bubbles (with radius a ∼ 100 μm) into a yield-stress polymer gel. Even for a layer with a low concentration of bubbles (areal fraction, n a ² , of 10-20%, where n is the number of bubbles per unit area), the ultrasonic transmission was found to be significantly reduced by the presence of bubbles (-20 to -50 dB) and showed a sharp minimum at a particular frequency. Interestingly, this frequency did not correspond to the resonance frequency of the individual, isolated bubbles, but depended markedly on the concentration. This frequency shift is an indication of strong coupling between the bubbles. We propose a simple model, based on a self-consistent relation, which takes into account the coupling between the bubbles and gives good agreement with the measured transmission coefficient.     

Voltammetric Antioxidant Analysis in Mineral Oil Samples Immobilized into Boron‐Doped Diamond Micropore Array Electrodes

Mineral oil microdroplets containing the model antioxidant N,N‐didodecyl‐N′,N′‐diethyl‐phenylene‐diamine (DDPD) are immobilized into a 100×100 pore‐array (ca. 10 μm individual pore diameter, 100 μm pitch) in a boron‐doped diamond electrode surface. The robust diamond surface allows pore filling, cleaning, and reuse without damage to the electrode surface. The electrode is immersed into aqueous electrolyte media, and voltammetric responses for the oxidation of DDPD are obtained. In order to further improve the current responses, 20 wt% of carbon nanofibers are co‐deposited with the oil into the pore array. Voltammetric signals are consistent with the oxidation of DDPD and the associated transfer of perchlorate anions (in aqueous 0.1 M NaClO₄) or the transfer of protons (in aqueous 0.1 M HClO₄). From the magnitude of the current response, the DDPD content in the mineral oil can be determined down to less than 1 wt% levels. Perhaps surprisingly, the reversible (or midpoint) potential for the DDPD oxidation in mineral oil (when immersed in 0.1 NaClO₄) is shown to be concentration‐dependent and to shift to more positive potential values for more dilute DDPD in mineral oil solutions. An extraction mechanism and the formation of a separate organic product phase are proposed to explain this behavior.     

Convergence of adaptive FEM for elliptic obstacle problems

We treat the convergence of adaptive lowest-order FEM for some elliptic obstacle problem with affine obstacle. For error estimation, we use a residual error estimator which is an extended version of the estimator from [2] and additionally controls the data oscillations. The main result states that an appropriately weighted sum of energy error, edge residuals, and data oscillations satisfies a contraction property that leads to convergence. In addition, we discuss the generalization to the case of inhomogeneous Dirichlet data and non-affine obstacles χ ∈ H²(Ω) for which similar results are obtained. (© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Proton Emission——-Recent Results and Future Prospects

Considerable progress has been made in the study of proton-emitting nuclei since the first observation of direct proton emission nearly half a century ago. This has led to improvements in our understanding of this rare decay process and provided invaluable nuclear structure data far from the valley of beta stability. This paper reviews the implications of some recent results for exotic iridium, rhenium and tantalum isotopes and considers prospects for future experimental studies of proton-emitting nuclei located at and above the N =82 neutron shell closure.     

Insight into the local structure of barium indate oxide-ion conductors: an X-ray total scattering study

In this paper we presented the X-ray PDF investigation of orthorhombic Ba(2)In(2)O(5) and cubic Ba(2)In(1.7)P(0.3)O(5.3) and Ba(2)In(1.7)S(0.3)O(5.45) samples. Pure Ba(2)In(2)O(5) was found to be properly described-at the local scale-by the orthorhombic average structure. Ba(2)In(1.7)P(0.3)O(5.3) and Ba(2)In(1.7)S(0.3)O(5.45) cannot be described, at the local scale, by a cubic symmetry. The PDFs of these two samples clearly showed a distorted atom arrangement in the short-range which can be described again with the orthorhombic symmetry found in pure barium indate.     

Addition of aluminum and gallium species to aromatic and alkyl-substituted 1,4-diaza-1,3-butadiene ligands

In this report, we investigate the interactions of Me(x)MCl(3-x) (x = 0-3, M = Al, Ga) with various aromatic and alkyl-substituted 1,4-diaza-1,3-butadiene (R)DAB ligands (or α-diimine ligands) to give a variety of structures in solution and in the solid state. In combination with other previously reported structures, certain general trends of reactivity of these species can be deduced, although there are still some unexplained modes of reactivity. The methylated Al species react with aromatic-substituted (R)DAB ligands to provide final products that result from C═N insertion into the Al-CH(3) group followed by rearrangement reactions. The addition of methyl groups onto the backbone of the (R)DAB ligand is insufficient to stop the insertion and rearrangement processes from occurring. In the case of MeAlCl(2) with the bulky (DiPP)DAB ligand, the reaction could be followed spectroscopically from the monoadduct through the inserted/rearranged final product. Methylated Ga species, however, are much less predictable in their behavior with aromatic-substituted (R)DAB ligands. Depending on the exact species and ratios used, coordinated adducts can be formed and identified, or inserted/rearranged products similar to the aluminum reactions can be obtained. Quite interestingly, cation/anion pairs can also be formed in which GaCl(3) or MeGaCl(2) act as a chloride acceptors. This behavior was unique and substantially different from the analogous Al reactions which formed either a dicoordinated adduct or an inserted/rearranged complex. When the stronger-donating alkyl-substituted (R)DAB ligands were used with Me(2)GaCl, only cation/anion pairs were obtained. Surprisingly, when the same reactions were performed using Me(2)AlCl as a reagent, irreproducible results were obtained.