Synthesis and characterization of 3-[(thiourea)-propyl]-functionalized silica gel and its application in adsorption and catalysis

The objective of this research was the preparation of a silica gel functionalized successively with 3-chloropropyltrimethoxysilane (SG-PrCl) and thiourea (SG-Pr-THIO), and its application in adsorption and catalysis. The materials were characterized by 13C and 29Si NMR, FTIR, scanning electron micrographs (SEM), analysis of nitrogen and elemental analysis. Aiming at its application in adsorption, the [3-(thiourea)-propyl] silica gel (SG-Pr-THIO) was tested as an adsorbent for transition-metal ions using a batchwise process. The organofunctionalized surface showed the ability to adsorb the metal ions Cd(ii), Cu(ii), Ni(ii), Pb(ii) and Co(ii) from water, ethanol and acetone. The adsorption isotherms were fitted by Langmuir, Freundlich, Temkin and Dubinin-Radushkevich (D-R) models. The kinetics of adsorption of metals were performed using three models such as pseudo-first order, pseudo-second order and Elovich. The Langmuir and pseudo-first order models were the most appropriate to describe the adsorption and kinetic data, respectively. With the purpose of application in catalysis, the SG-Pr-THIO was reacted with a Mo(ii) organometallic complex, forming the new material SG-Pr-THIO-Mo. Only a few works in the literature have reported this type of reaction, and none dealt with thiourea and Mo(ii) complexes. The new Mo-silica gel organometallic material was tested as catalyst in the epoxidation of cyclooctene and styrene. © 2013 The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.

Macauba palm (acrocomia aculeata) cake from biodiesel processing: an efficient and low cost substrate for the adsorption of dyes

The potential of natural and heat-treated Macauba palm cake as adsorbent for the removal of Methylene Blue (MB) and Congo Red (CR) from solution has been investigated. Equilibrium adsorption was attained in <7 h and the process was favored at pH 5.0 for MB and pH 6.5 for CR with an adsorbent (g):adsorbate (mL) ratio of 1:200 and an initial concentration of adsorbate of 25 mg L−1. The maximum adsorption capacities of the natural and heat-treated materials were, respectively, 25.80 and 32.30 mg g−1 for MB, and 32.00 and 20.30 mg g−1 for CR. The isotherm model proposed by Sips represented most adequately the adsorption of MB and CR. The adsorptions of the dyes were best described in terms of a pseudo second-order reaction. Thermodynamic parameters such as ΔHo, ΔSo and ΔGo were calculated. The adsorption process was found to be endothermic and spontaneous. Macauba palm cake is adequate for the removal of waste dye from industrial effluents by virtue of its abundance, low cost and efficiency of adsorption.

Effect of pH on boron adsorption in some soils of Parana, Brazil

Temporary B deficiency can be triggered by liming of acid soils because of increased B adsorption at higher soil pH. Plants respond directly to the activity of B in soil solution and only indirectly to B adsorbed on soil constituents. Because the range between deficient and toxic B concentration is relatively narrow, this poses difficulty in maintaining appropriate B levels in soil solution. Thus, knowledge of the chemical behavior of B in the soil is particularly important. The present study investigated the effect of soil pH on B adsorption in four soils of Parana State, and to correlate these values with the physical and chemical properties of the soils. Surface samples were taken from a Rhodic Hapludox, Arenic Hapludalf, Arenic Hapludult, and one Typic Usthorthent. To evaluate the effect of pH on B adsorption, subsamples soil received the application of increasing rates of calcium carbonate. Boron adsorption was accomplished by shaking 2.0 g soil, for 24 h, with 20 mL of 0.01 mol L-1 NaCl solution containing different concentrations (0.0, 0.1, 0.2, 0.4, 0.8, 1.2, 1.6, 2.0, and 4.0 mg B L-1). Sorption was fitted to non-linear form of the Langmuir adsorption isotherm. Boron adsorption increased as concentration increased. Boron adsorption was dependent on soil pH, increasing as a function of pH in the range between 4.6 and 7.4, although the bonding energy has decreased. Maximum adsorption capacity (MAC) of B was observed in the Arenic Hapludalf (49.8 mg B kg(-1) soil) followed by Arenic Hapludult (22.5 mg kg(-1)), Rhodic Hapludox (17.4 mg kg(-1)), and Typic Usthorthent (7.0 mg kg(-1)). The organic matter content, clay content, and aluminum oxide content (Al2O3) were the soils properties that affecting the B adsorption on Parana soils.

Critical adsorption of polyelectrolytes onto charged Janus nanospheres

Based on extensive Monte Carlo simulations and analytical considerations we study the electrostatically driven adsorption of flexible polyelectrolyte chains onto charged Janus nanospheres. These net-neutral colloids are composed of two equally but oppositely charged hemispheres. The critical binding conditions for polyelectrolyte chains are analysed as function of the radius of the Janus particle and its surface charge density, as well as the salt concentration in the ambient solution. Specifically for the adsorption of finite-length polyelectrolyte chains onto Janus nanoparticles, we demonstrate that the critical adsorption conditions drastically differ when the size of the Janus particle or the screening length of the electrolyte are varied. We compare the scaling laws obtained for the adsorption-desorption threshold to the known results for uniformly charged spherical particles, observing significant disparities. We also contrast the changes to the polyelectrolyte chain conformations close to the surface of the Janus nanoparticles as compared to those for simple spherical particles. Finally, we discuss experimentally relevant physicochemical systems for which our simulations results may become important. In particular, we observe similar trends with polyelectrolyte complexation with oppositely but heterogeneously charged proteins.

Study of pK Values and Effective Dielectric Constants of Ionizable Residues in Pentapeptides and in Staphylococcal Nuclease (SNase) Using a Mean-Field Approach

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

Enrichment of Tropical Peat with Micronutrients for Agricultural Applications: Evaluation of Adsorption and Desorption Processes

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

Chitosan and alginate biopolymer membranes for remediation of contaminated water with herbicides

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

Effect of the aspartic acid D2 on the affinity of Polybia-MP1 to anionic lipid vesicles

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

Monotonicity, interlacing and electrostatic interpretation of zeros of exceptional Jacobi polynomials

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Enhancement of voltammetric determination of quinizarine based on the adsorption at surfactant-adsorbed-layer in disposable electrodes

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

Stretching of BDT-gold molecular junctions: thiol or thiolate termination?

It is often assumed that the hydrogen atoms in the thiol groups of a benzene-1,4-dithiol dissociate when Au-benzene-1,4-dithiol-Au junctions are formed. We demonstrate, by stability and transport property calculations, that this assumption cannot be made. We show that the dissociative adsorption of methanethiol and benzene-1,4-dithiol molecules on a flat Au(111) surface is energetically unfavorable and that the activation barrier for this reaction is as high as 1 eV. For the molecule in the junction, our results show, for all electrode geometries studied, that the thiol junctions are energetically more stable than their thiolate counterparts. Due to the fact that density functional theory (DFT) within the local density approximation (LDA) underestimates the energy difference between the lowest unoccupied molecular orbital and the highest occupied molecular orbital by several electron-volts, and that it does not capture the renormalization of the energy levels due to the image charge effect, the conductance of the Au-benzene-1,4-dithiol-Au junctions is overestimated. After taking into account corrections due to image charge effects by means of constrained-DFT calculations and electrostatic classical models, we apply a scissor operator to correct the DFT energy level positions, and calculate the transport properties of the thiol and thiolate molecular junctions as a function of the electrode separation. For the thiol junctions, we show that the conductance decreases as the electrode separation increases, whereas the opposite trend is found for the thiolate junctions. Both behaviors have been observed in experiments, therefore pointing to the possible coexistence of both thiol and thiolate junctions. Moreover, the corrected conductance values, for both thiol and thiolate, are up to two orders of magnitude smaller than those calculated with DFT-LDA. This brings the theoretical results in quantitatively good agreement with experimental data.

Adsorption/desorption of arsenic by tropical peat: influence of organic matter, iron and aluminium

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Adsorption of pH-responsive polyelectrolyte chains onto spherical macroions

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Experimental and Theoretical Studies of Volatile Corrosion Inhibitors Adsorption on Zinc Electrode

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Zero-valent iron mediated degradation of ciprofloxacin - Assessment of adsorption, operational parameters and degradation products

The zero-valent iron (ZVI) mediated degradation of the antibiotic ciprofloxacin (CIP) was studied under oxic condition. Operational parameters such as ZVI concentration and initial pH value were evaluated. Increase of the ZVI concentration from 1 to 5 g L−1 resulted in a sharp increase of the observed pseudo-first order rate constant of CIP degradation, reaching a plateau at around 10 g L−1. The contribution of adsorption to the overall removal of CIP and dissolved organic carbon (DOC) was evaluated after a procedure of acidification to pH 2.5 with sulfuric acid and sonication for 2 min. Adsorption increased as pH increased, while degradation decreased, showing that adsorption is not important for degradation. Contribution of adsorption was much more important for DOC removal than for CIP. Degradation of CIP resulted in partial defluorination since the fluoride measured corresponded to 34% of the theoretical value after 120 min of reaction. Analysis by liquid chromatography coupled to mass spectrometry showed the presence of products of hydroxylation on both piperazine and quinolonic rings generating fluorinated and defluorinated compounds as well as a product of the piperazine ring cleavage.