Salt concentration and particle density dependence of electrophoretic mobilities of spherical colloids in aqueous suspension

Using laser Doppler velocimetry in the superheterodyne mode, we conducted a systematic study of the electrophoretic mobility of dispersions of small silica spheres (a=18 nm) suspended in water at different salinities and particle concentrations. The concentration of NaCl was varied from 40 microM up to 16 mM, while the particle concentrations were varied between 4.2x10(18) and 2.1x10(20) m-3. We find a decrease of mobility with increasing salt concentrations and an increase with increased particle number densities. The latter observation is not backed by the standard cell model of electrophoresis with Shilov-Zharkikh boundary conditions. Rather, if the experimental data are interpreted within that model, an unexpected change of the zeta potential at constant added salt concentration results. Interestingly, all experimental data collapse onto a single master curve, if plotted versus the ratio C* of particle counterions to added salt ions. We obtain a logarithmic increase of mobility for C*<1 and a plateau for C*>1. This may indicate a change of the Stern layer structure not yet included in the theoretical model.     

Michael addition of amine derivatives to conjugate phosphinyl and phosphonyl nitrosoalkenes. Preparation of alpha-amino phosphine oxide and phosphonate derivatives

The synthesis of nitrosoalkenes derived from phosphine oxides and phosphonates generated through base-mediated dehydrohalogenations of readily available alpha-halooximes is reported. These highly reactive intermediates act as Michael acceptors toward nucleophilic reagents such as ammonia, amines, and optically active amino esters, furnishing alpha-amino phosphine oxides and phosphonates in a highly regioselective fashion.     

Highly efficient retro-cycloaddition reaction of isoxazolino[4,5:1,2][60]- and -[70]fullerenes

Isoxazolino[4,5:1,2][60]- and -[70]fullerenes undergo an efficient retro-cycloaddition reaction to pristine fullerene by thermal treatment in the presence of an excess of a dienophile and Cu(II) catalysis, which can be selectively used in the presence of malonate or pyrrolidine cycloadducts. Trapping experiments using N-phenylmaleimide as dipolarophile have shown that the reaction mechanism occurs by thermal removal of the nitrile oxide 1,3-dipole, in a process which is favored by the presence of Cu(II) as the catalyst. The ESI-MS study supports the observed retro-cycloaddition process for both C60 and C70 derivatives. In contrast to previous electrochemical retro-cycloaddition processes observed in fulleropyrrolidines, isoxazolinofullerenes were stable under oxidative conditions.     

Imaging photoelectron transmission through self-assembled monolayers: the work-function of alkanethiols coated gold

In this paper, we present a new approach for studying the electronic properties of self-assembled monolayers and their interaction with a conductive substrate, the low-energy photoelectron imaging spectroscopy (LEPIS). LEPIS relies on imaging of photoelectrons ejected from a conductive substrate and subsequently transmitted through organic monolayers. Using this method, we measure the relative work-function of alkanethiols of different length on gold substrate, and we are able to follow the changes occurring when the surface coverage is varied. We also computed the work-function of model alkanethiols using a plane-wave density functional theory approach, in order to demonstrate the correlation between changes in the work-function with the monolayer organization and density.     

Efficient hydrogen-evolving cathodes based on proton and electron reservoir behaviors of the phosphotungstate [H7P8W48O184](33-) and the Co(II)-Containing Silicotungstates [Co(6)H2O)(30){Co(9)Cl(2)(OH)(3)(H(2)O)(9)(beta-SiW(8)O(31))(3)}](5-) and [{Co(3)(B-beta-SiW(9)O(33)(OH))(B-beta-SiW(8)O(29)OH)(2)}(2)](22-)

Original and simple procedures for glassy carbon electrode modification with polyoxometalates (POMs), phosphotungstate [H7P8W48O184]33-, and Co(II)-containing silicotungstates [Co6(H2O)30{Co9Cl2(OH)3(H2O)9(beta-SiW8O31)3}]5- and [{Co3(B-beta-SiW9O33(OH))(B-beta-SiW8O29OH)2}2]22- give stable and very active surfaces for the hydrogen-evolution reaction (HER). For this purpose, the selected POMs fixed on Vulcan XC-72 were adsorbed on the electrode surface or were directly entrapped in polyvinylpyridine films on the electrode. Cyclic voltammetry and confocal microscopy results converge to indicate that the activation is related to the proton and electron reservoir-like behaviors of these molecular oxides and not to any electrode surface area increase. However, the Tafel parameters of the HER process, which are different from one POM to the next, are in the range of those of the best metallic electrodes.     

Eta(1)-2-pyrone metal carbonyl complexes as CO-releasing molecules (CO-RMs): a delicate balance between stability and CO liberation

An evaluation of the CO releasing ability of iron(II) and molybdenum(II) complexes has facilitated the discovery of the most rapid CO releaser, namely [Mo(CO)(3)(eta(5)-C(5)H(5))(eta(1)-{O}-C{=O}-O-CMe=CH-COMe=CBr)]BF(4) (CORM-F10), reported to date. The rate of CO release is related to the overall solution phase stability of the transition metal carbonyl complex. The cytotoxicity and vasodilatory properties of CORM-F10 have been determined.     

Photoinduced electron transfer between the cationic complexes Ru(NH3)5pz2+ and trans-RuCl([15]aneN4)NO2+ mediated by phosphate ion: visible light generation of nitric oxide for biological targets

The photochemical behavior of the tetraazamacrocyclic complex trans-RuCl([15]ane)(NO)2+ (RuNO2+) in a 10 mM phosphate buffer solution, pH 7.4, and in the presence of Ru(NH3)5pz2+ (Rupz2+) is reported. Irradiation (436 nm) of an aqueous solution containing both cationic complexes as PF6- salts labilizes NO from RuNO2+ with a quantum yield (phiNO) dependent on the concentration of Rupz2+ with a maximum value of phiNO (1.03(11)x10(-3) einstein mol-1) found for a solution with equimolar concentrations (5x10(-5) M) of the two complexes in phosphate buffer solution. The quantitative behavior of this system suggests that the two cations undergo preassociation such that photoexcitation of the visible absorbing Rupz2+ is followed by electron or energy transfer to RuNO2+, which does not absorb appreciably at the excitation wavelength, and this leads to NO release from the reduced nitrosyl complex. Notably, the NO release was not seen in the absence of phosphate buffer; thus, it appears that phosphate ions mediate NO generation, perhaps by facilitating formation of a supramolecular complex between the two ruthenium cations. Reexamination of the cyclic voltammetry of Rupz2+ showed that the electrochemical behavior of this species is also affected by the presence of the phosphate buffer.     

Molecular modeling simulations of the morphology of polyphenylene dendrimers

Three polyphenylene dendrimers were studied by molecular modeling techniques with the goal of better defining the notion of shape persistence often associated with these molecules. We show that despite the rigidity of the monomers, a large variety of dendrimer morphologies is accessible, in large part due to the asymmetrical branching pattern of the monomers (they have nodes in meta and para positions with respect to their anchor point). The folding ability of a branch depends on the number and sequence of the meta and para nodes it contains: while some of the branches are always straight, others can fold back, and the amplitude of that folding increases with generation. As a result, the range of accessible morphologies increases with the generation, from a dense-shell model in low generation to a model intermediate between a dense shell and a dense core in high generation. When the typical A2B monomer is replaced by an A4B monomer, the dense packing limit is reached as early as the second generation because of a higher density and the presence of nodes in the ortho position, which are oriented backward.     

A Look at BMOϕ(ω) through Carleson Measures

As Fefferman and Stein showed, there is a tight connection between Carleson measures and BMO functions. In this work we extend this type of results to the more general scope of the BMO_ϕ(ω) spaces. As a byproduct a weighted version of the Triebel-Lizorkin space is introduced, which turns out to be isomorphic to BMO(ω) as in the unweighted case.     

Nuclearity and Thermal States in Conformal Field Theory

We introduce a new type of spectral density condition, that we call L ²- nuclearity. One formulation concerns lowest weight unitary representations of and turns out to be equivalent to the existence of characters. A second formulation concerns inclusions of local observable von Neumann algebras in Quantum Field Theory. We show the two formulations to agree in chiral Conformal QFT and, starting from the trace class condition for the conformal Hamiltonian L ₀, we infer and naturally estimate the Buchholz-Wichmann nuclearity condition and the (distal) split property. As a corollary, if L ₀ is log-elliptic, the Buchholz-Junglas set up is realized and so there exists a β-KMS state for the translation dynamics on the net of C^*-algebras for every inverse temperature β > 0. We include further discussions on higher dimensional spacetimes. In particular, we verify that L ²-nuclearity is satisfied for the scalar, massless Klein-Gordon field. Dedicated to László Zsidó on the occasion of his sixtieth birthday Supported by MIUR, GNAMPA-INDAM and EU network “Quantum Spaces–Non Commutative Geometry” HPRN-CT-2002-00280