pH-mediated interactions between poly(acrylic acid) and methylcellulose in the formation of ultrathin multilayered hydrogels and spherical nanoparticles

Poly(acrylic acid) forms insoluble hydrogen-bonded interpolymer complexes with methylcellulose in aqueous solutions under acidic conditions. In this work the reaction heats and binding constants were determined for the complexation between poly(acrylic acid) and methylcellulose by isothermal titration calorimetry at different pH and findings are correlated with the aggregation processes occurring in this system. The principal contribution to the complexation heat results from primary polycomplex particle aggregation. Transmission electron microscopy of nanoparticles produced at pH 1.4 and 2.4 demonstrated that they are spherical and dense structures. The nanoparticles ranged from 80 to 200 nm, whereas particles formed at pH 3.2 were 20-30 nm and were stabilized against aggregation by a network of uncomplexed macromolecules. For the first time, multilayered materials were developed on the basis of hydrogen-bonded complexes of poly(acrylic acid) and methylcellulose using layer-by-layer deposition on a glass surface. The thickness of these films was a linear function of the number of deposition cycles. The materials were subsequently cross-linked by thermal treatment, resulting in ultrathin hydrogels which detached from the glass substrate upon swelling. The swelling capacity of ultrathin hydrogels differed from the swelling of the thicker films of a similar chemical composition.

The surface geometry of carbonmonoxide and hydrogen co-adsorbed on Ni 111

A combination of photoelectron spectroscopy, temperature programmed desorption and low energy electron diffraction structure determinations have been applied to study the p(2 x 2) structures of pure hydrogen and co-adsorbed hydrogen and CO on Ni {111}. In agreement with earlier work atomic hydrogen is found to adsorb on fcc and hcp sites in the pure layer with H-Ni bond lengths of 1.74Angstrom. The substrate interlayer distances, d(12) = 2.05Angstrom and d(23) = 2.06Angstrom, are expanded with respect to clean Ni {111} with buckling of 0.04Angstrom in the first layer. In the co-adsorbed phase Co occupies hcp sites and only the hydrogen atoms on fcc sites remain on the surface. d(12) is even further expanded to 2.08Angstrom with buckling in the first and second layer of 0.06 and 0.02Angstrom, respectively. The C-O, C-Ni, and H-Ni bond lengths are within the range of values also found for the pure adsorbates.

Multiple hydrogen bonds induce formation of nanoparticles with internal microemulsion structure by an amphiphilic copolymer

A particulate microemulsion is generated in a simple two-component system comprising an amphiphilic copolymer (Pluronic P123) in mixtures with tannic acid. This is correlated to complexation between the poly(ethylene oxide) in the Pluronic copolymer and the multiple hydrogen bonding units in tannic acid which leads to the breakup of the ordered structure formed in gels of Pluronic copolymers, and the formation of dispersed nanospheres containing a bicontinuous internal structure. These novel nanoparticles termed ‘‘emulsomes’’ are self-stabilized by a coating layer of Pluronic copolymer. The microemulsion exhibits a pearlescent appearance due to selective light scattering from the emulsion droplets. This simple formulation based on a commercial copolymer and a biofunctional and biodegradable additive is expected to find applications in the fast moving consumer goods sector.

Spectroscopic Investigation on the Formation of a Dinuclear Me(2)SO-Ru(2)-Mercaptopyridine Bridged Complex: [Ru(2)Cl(3)(mu-pyS)(mu-dmso)(dmso)(4)]center dot 2H(2)O

A dinuclear ruthenium(II) complex double-bridged by an N-aromatic ligand 2-mercaptopyridine (2-pyridinethiol or 2-pyridyl mercaptan) and a methyl sulfoxide (dmso) have been characterized by X-ray crystallography. The reported compound with formula [Ru(2)Cl(3) (mu-pyS)(mu-dmso)(dmso)(4)] center dot 2H(2)O, [C(15)H(36)Cl(3)NO(7)S(6)Ru(2)] (P2/c, a = 13.8175(2) angstrom, b = 10.5608(2) angstrom, c = 21.3544 (3) angstrom, beta = 106.090(1)degrees, V = 2,994.05(8) angstrom(3), Z = 4) represents a seven-membered ring system with both rutheniums in an octahedral geometry. All the hydrogen bonds (C-H-Cl) and the van der Waals contacts give rise to three-dimensional network in the structure and add stability to the dinuclear compound. To our knowledge, this is the first time that the formation of a dinuclear ruthenium(II) complex double-bridged by an N-aromatic ligand 2-mercaptopyridine and dmso have been reported. The study also provided valuable insight into bioinorganic chemistry as continuing efforts are being made to develop metal-based cancer chemotherapeutics. A major feature of this paper is the resolution of a double bridged ruthenium structure which contributes to a better understanding of ruthenium reactivity.

Fluorimetric study of the pro-oxidant activity of EUK8 in the presence of hydrogen peroxide

The catalase mimetic complex Mn(III)-salen chloride (EUK8) was found to be pro-oxidant under low hydrogen peroxide concentrations. The increase in the fluorescence rate of the probe 1,2,3-dihydrorhodamine (DHR) in solution, as well as the carbonyl content of human serum albumin were found to be maximum at H(2)O(2):EUK8 molar ratios ranging from 0 to 2, supporting previous findings regarding the mechanism of EUK8 catalase activity and the formation of highly oxidative Mn(V)-O(2-) species. This pro-oxidant effect is precluded by the presence of glutathione. Cytotoxicity to HeLa cells, as probed by increased rate of oxidation of intracellular DHR, was not observed. Our findings suggest that the combination of H(2)O(2) and EUK8 at specific molar ratios, in the absence of reductants/antioxidants, induces the oxidation of organic molecules. It is shown that the fluorimetric determination of pro-oxidant activity of metal complexes is more sensitive than the colorimetric quantification of protein carbonyl content. The implications of our findings with respect to the somewhat confusing results arising from in vivo studies of EUK8 and other Mn(III) anti-oxidant metal complexes are discussed.

Investigating the formation and the properties of monoalkyl carbonates in aqueous medium using capillary electrophoresis with capacitively coupled contactless conductivity detection

Although alkyl carbonic acids (ACAs) and their salts are referred to as instable species in aqueous medium, we demonstrate that a monoalkyl carbonate (MAC) can in fact be easily formed from bicarbonate and an alcohol even in the presence of a high amount of water. A CE system with two capacitively coupled contactless conductivity detectors (C(4)Ds) was used to obtain different parameters about these species and their reactions. Based on the mobilities obtained for a series of alcohols ranging from 1 to 5 carbons, the coefficients of diffusion and the hydrodynamic radii were calculated. When compared with the equivalent carboxylates, MACs have radii systematically smaller. Although the precise pK(a) values of the ACAs could not be obtained, because of the fast decomposition in acid medium, it was possible, for the first time, to show that they are below 4.0. This result suggests that the acidity of an ACA is quite similar to the first hydrogen of H(2)CO(3). Using a new approach to indirectly calibrate the C(4)D, the kinetic constants and the equilibrium constants of formation were also obtained. The results suggest that the increase in the chain length makes the MACs less stable and more inert.

Numerical solution of the two-dimensional Gross-Pitaevskii equation for trapped interacting atoms

We present a numerical scheme for solving the time-independent nonlinear Gross-Pitaevskii equation in two dimensions describing the Bose-Einstein condensate of trapped interacting neutral atoms at zero temperature. The trap potential is taken to be of the harmonic-oscillator type and the interaction both attractive and repulsive. The Gross-Pitaevskii equation is numerically integrated consistent with the correct boundary conditions at the origin and in the asymptotic region. Rapid convergence is obtained in all cases studied. In the attractive case there is a limit Co the maximum number of atoms in the condensate. (C) 2000 Published by Elsevier B.V. B.V. All rights reserved.

The formation of CN and CN+ by direct radiative association

Rate coefficients for direct radiative association of carbon and nitrogen atoms to form CN, and of carbon ions and nitrogen atoms to form CN+ ions, are calculated for temperatures in the range of 300 to 14,700 K. For the CN molecule, the rate coefficients can be represented by the standard expression, k(CN)(T) = 7.87 x 10(-19)(T/300)(0.056) exp (-96.0/T) cm(3) s(-1) for temperatures between 300 and 2700 K and k(CN)(T) = 1.37 x 10(-18)(T/300)-0.128 exp (-520.1/T) cm(-3) s(-1) at T > 2700 K. For the CN+ ion, the corresponding expression is k(CN+)(T) = 1.08 x 10(-18)(T/300)(0.071) exp (-57.5/T) cm(-3) s(-1) for the temperature range studied. Calculated rate coefficients k(CN) are about 2 orders of magnitude lower than the canonical value used in the modeling of the chemistry of various astrophysical environments.

Dinitrosyl iron complexes with cysteine. kinetics studies of the formation and reactions of dnics in aqueous solution

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

A combined experimental and theoretical study on the formation of ag filaments on beta-Ag2MoO4 induced by electron irradiation

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Base-Paired and Base-Stacked Structures of the Anti-HIV Drug Lamivudine: A Nucleoside DNA-Mimicry with Unprecedented Topology

We have prepared a DNA-mimicry of nucleosides in which the anti-HIV drug lamivudine (beta-L-2',3'-dideoxy-3'-thiacytidine, 3TC) self-assembles into a base-paired and helically base-stacked hexagonal structure. Face-to-face and face-to-tail stacked 3TC=3TC dimers base-paired through two hydrogen bonds between neutral cytosines by either N-H center dot center dot center dot O or N-H center dot center dot center dot N atoms give rise to a right-handed DNA-mimicry of lamivudine with an unusual highly symmetric hexagonal lattice and topology. In addition, a base-paired and base-stacked supramolecular architecture of lamivudine hemihydrochloride hemihydrate was also obtained as a result of our crystal screenings. This structure is formed through partially face-to-face stacked lamivudine pairs held together by protonated and neutral fragments. However, no helical stacking occurs in this structure in which lamivudine also adopts unusual conformations as the C1'-endo and C1'-exo sugar puckers and cytosine orientations intermediate between the anti and syn conformations. As a conclusion drawn from the nucleoside duplex, the hexagonal DNA-mimicry of lamivudine reveals that such double-stranded helices can be assembled without counterions and organic solvents but with higher crystallographic symmetry instead, because only water crystallizes together with lamivudine in this structure.

Computational Study of the Hydration of Sulfuric Acid Dimers: Implications for Acid Dissociation and Aerosol Formation

We have investigated the thermodynamics of sulfuric acid dimer hydration using ab initio quantum mechanical methods. For (H2SO4)2(H2O)n where n = 0−6, we employed high-level ab initio calculations to locate the most stable minima for each cluster size. The results presented herein yield a detailed understanding of the first deprotonation of sulfuric acid as a function of temperature for a system consisting of two sulfuric acid molecules and up to six waters. At 0 K, a cluster of two sulfuric acid molecules and one water remains undissociated. Addition of a second water begins the deprotonation of the first sulfuric acid leading to the di-ionic species (the bisulfate anion HSO4−, the hydronium cation H3O+, an undissociated sulfuric acid molecule, and a water). Upon the addition of a third water molecule, the second sulfuric acid molecule begins to dissociate. For the (H2SO4)2(H2O)3 cluster, the di-ionic cluster is a few kcal mol−1 more stable than the neutral cluster, which is just slightly more stable than the tetra-ionic cluster (two bisulfate anions, two hydronium cations, and one water). With four water molecules, the tetra-ionic cluster, (HSO4−)2(H3O+)2(H2O)2, becomes as favorable as the di-ionic cluster H2SO4(HSO4−)(H3O+)(H2O)3 at 0 K. Increasing the temperature favors the undissociated clusters, and at room temperature we predict that the di-ionic species is slightly more favorable than the neutral cluster once three waters have been added to the cluster. The tetra-ionic species competes with the di-ionic species once five waters have been added to the cluster. The thermodynamics of stepwise hydration of sulfuric acid dimer is similar to that of the monomer; it is favorable up to n = 4−5 at 298 K. A much more thermodynamically favorable pathway forming sulfuric acid dimer hydrates is through the combination of sulfuric acid monomer hydrates, but the low concentration of sulfuric acid relative to water vapor at ambient conditions limits that process.

Interaction of the solar wind with them Moon: An overview on the results from the SARA experiment aboard Chandrayaan-1

The results from the Sub-keV Atom Reflecting Analyzer (SARA) experiment onboard Chandrayaan-1 have revealed several hitherto unknown and interesting aspects about the interaction of solar wind with the Moon. The SARA experiment had two sensors — CENA and SWIM. The Chandrayaan-1 energetic neutrals analyzer (CENA), detected energetic neutral atoms (ENAs), and the Solar Wind Monitor (SWIM) measured ions of solar wind origin. In this review, we summarize the observations made by the SARA experiment, which are: (1) substantial (~20%) and sustained backscattering of solar wind protons from lunar surface as energetic neutral hydrogen,1 (2) minimagnetosphere around magnetic anomalies on Moon using the backscattered ENAs,2 (3) reflection of solar wind protons from the Moon surface,3 (4) huge (~50%) deflection of solar wind protons over strong magnetic anomalies,4 and (5) presence of protons in the near-lunar plasma wake.5 These results have implications on the lunar plasma environment, implantation of solar wind hydrogen on lunar surface, and behavior of small scale magnetic anomalies on planetary bodies. The SARA observations suggest that similar processes may happen on other airless bodies covered with regolith in the solar system as well as in extra-solar system. This paper presents a review of the results obtained from the SARA observation.

Extraction of the s-wave pi N scattering lengths from data on pionic atoms

For many years a combined analysis of pionic hydrogen and deuterium atoms has been known as a good tool to extract information on the isovector and especially on the isoscalar s-wave pN scattering length. However, given the smallness of the isoscalar scattering length, the analysis becomes useful only if the pion–deuteron scattering length is controlled theoretically to a high accuracy comparable to the experimental precision. To achieve the required few-percent accuracy one needs theoretical control over all isospin-conserving three-body pNN !pNN operators up to one order before the contribution of the dominant unknown (N†N)2pp contact term. This term appears at next-to-next-to-leading order in Weinberg counting. In addition, one needs to include isospin-violating effects in both two-body (pN) and three-body (pNN) operators. In this talk we discuss the results of the recent analysis where these isospin-conserving and -violating effects have been carefully taken into account. Based on this analysis, we present the up-to-date values of the s-wave pN scattering lengths.

HELIOSPHERIC ENERGETIC NEUTRAL HYDROGEN MEASURED WITH ASPERA-3 AND ASPERA-4

We re-analyze the signal of non-planetary energetic neutral atoms (ENAs) in the 0.4-5.0 keV range measured with the Neutral Particle Detector (NPD) of the ASPERA-3 and ASPERA-4 experiments on board the Mars and Venus Express satellites. Due to improved knowledge of sensor characteristics and exclusion of data sets affected by instrument effects, the typical intensity of the ENA signal obtained by ASPERA-3 is an order of magnitude lower than in earlier reports. The ENA intensities measured with ASPERA-3 and ASPERA-4 now agree with each other. In the present analysis, we also correct the ENA signal for Compton-Getting and for ionization loss processes under the assumption of a heliospheric origin. We find spectral shapes and intensities consistent with those measured by the Interstellar Boundary Explorer (IBEX). The principal advantage of ASPERA with respect to the IBEX sensors is the two times better spectral resolution. In this study, we discuss the physical significance of the spectral shapes and their potential variation across the sky. At present, these observations are the only independent test of the heliospheric ENA signal measured with IBEX in this energy range. The ASPERA measurements also allow us to check for a temporal variation of the heliospheric signal as they were obtained between 2003 and 2007, whereas IBEX has been operational since the end of 2008.