Understanding the Effect of Adsorption Geometry over Substrate Selectivity in the Surface-Enhanced Raman Scattering Spectra of Simazine and Atrazine

This paper studies the selectivity of Well-defined Au and Ag nanostructures as substrates for the SERS, (surface-enhanced Raman scattering) detection of simazine (6-chloro-N,N`-diethyl-1,3,5-triazine-2,4-diamine) and atrazine (6-chloro-N-ethyl-N`-isopropyl-1,3,5-triazine-2,4-diamine). Our data showed that simazine and atrazine displayed similar SERS spectra when the Au was employed as substrate. Conversely, distinct SERS signatures were obtained upon the utilization of Ag substrates. Density functional theory (DFT) calculations and vibrational assignments suggested that, while simazine and atrazine adsorbed on Au via the N3 position of the triazine ring, simazine adsorbed on Ag via N3 and atrazine via N5. The results presented herein demonstrated that the adsorption geometry of analyte molecules can play a central role over substrate selectivity in SERS, which is particularly important in applications involving ultrasensitive analysis of mixtures containing structurally similar molecules.

Adsorption of 4-aminopyridine on Co and Ag electrodes probed by SERS

The adsorption of 4-aminopyridine (4-AP) on Co and Ag electrodes in acid or alkaline solutions of KCl and KI electrolyte salts were monitored by the Surface-enhanced Raman Spectroscopy (SERS) technique. The SERS intensity for the Ag electrode was in 2 orders of magnitude higher than for the Co electrode, due to the enhancement of the Raman cross-section on Ag by the surface-plasmon excitation. In acidic chloride medium (pH 4), the SERS results for Ag electrodes indicate that the protonated form of 4-AP (4-APH(+)) adsorbs in the potential range of -0.1 to -0.6 V (Ag broken vertical bar AgCl broken vertical bar KCl sat) through hydrogen-bonding between 4-APH(+) and Cl(-) adsorbed on the electrode surface: at more negative potentials the neutral form 4-AP is the predominant adsorbed species. For Co electrode in the same medium, only bands due to neutral 4-AP were observed in the spectra at -0.8 and -0.9 V. For more negative potentials bands assigned to both 4-AP and 4-AP surface complex are observed, with the lasts being enhanced, as the potentials are turned more negative. In alkaline chloride medium (pH 13), for less negative potentials the bands assigned to free 4-AP were observed in the spectra of both Ag and Co surfaces. For more negative potentials, only bands assigned to the 4-AP surface complex were observed. For 0.1 mol L(-1) KI acidic or alkaline solutions, bands assigned to 4-AP and 4-APH(+) were observed in a wider potential range than in chloride solutions. An adsorption scheme of 4-AP on Ag and Co is proposed for acidic and alkaline solutions. (C) 2010 Elsevier B.V. All rights reserved.

Boron adsorption in lowland soils from Parana State, Brazil

Boron adsorption by soil is the main phenomenon that affects its availability to plants. This, the present study investigated the effect of liming on B adsorption by lowland soils of Parana State, and to correlate these values with the physical and chemical properties of the soils. Surface samples of three lowland soils [Gleissolo Haplico (GX), Plintossolo Haplico (FX) and Cambissolo Haplico (CX)], with different origin material and physicochemical properties were used. Samples with or without liming application were incubated during 60 days. Boron adsorption was accomplished by shaking 4.0g soil samples, for 24 h, with 20 mL of 0.01 mol L-1 CaCl2 solution containing different concentrations of B (0, 1, 2, 4, 8 and 16 mg L-1). Sorption was fitted to non-linear form of the Langmuir adsorption isotherm. The adsorption isotherms indicated that the B adsorption increased with its increasing concentration in the equilibrium solution. Maximum adsorption capacity of B ranged from 3.0 to 13.9 mg kg(-1) (without liming) and 14.7 to 35.7 mg kg(-1) (with liming). Liming increased the amount of adsorbed B in Gleissolo Haplico and Plintossolo Haplico soils, although the bonding energy has decreased. The amount of adsorbed B by Cambissolo Haplico soil was not affected by liming application. The most important soil properties affecting the B adsorption in lowland soils were pH, clay content, exchangeable aluminum and iron oxide contents.

Mass fractal characteristics of silica sonogels as determined by small-angle x-ray scattering and nitrogen adsorption

A sample series of silica sonogels was prepared using different water-tetraethoxysilane molar ratio (r(w)) in the gelation step of the process in order to obtain aerogels with different bulk densities after the supercritical drying. The samples were analyzed by means of small-angle x-ray-scattering (SAXS) and nitrogen-adsorption techniques. Wet sonogels exhibit mass fractal structure with fractal dimension D increasing from similar to2.1 to similar to2.4 and mass-fractal correlation length xi diminishing from similar to13 nm to similar to2 nm, as r(w) is changed in the nominal range from 66 to 6. The process of obtaining aerogels from sonogels and heat treatment at 500degreesC, in general, increases the mass-fractal dimension D, diminishes the characteristic length xi of the fractal structure, and shortens the fractal range at the micropore side for the formation of a secondary structured particle, apparently evolved from the original wet structure at a high resolution level. The overall mass-fractal dimension D of aerogels was evaluated as similar to2.4 and similar to2.5, as determined from SAXS and from pore-size distribution by nitrogen adsorption, respectively. The fine structure of the secondary particle developed in the obtaining of aerogels could be described as a surface-mass fractal, with the correlated surface and mass-fractal dimensions decreasing from similar to2.4 to similar to2.0 and from similar to2.7 to similar to2.5, respectively, as the aerogel bulk density increases from 0.25 (r(w)=66) up to 0.91 g/cm(3) (r(w)=6).

The role of organic matter on the adsorption of mercury in sediments from Amazon lakes, Brazil

Gold has been exploited intensively in the Brazilian Amazon during the past 20 years, and the elemental mercury (Hg) used in amalgamating the gold has caused abnormal Hg concentrations in waterways. Since 1986 particular attention has been given to the Madeira River because it is the largest tributary of the Amazon River and gold mining was officially allowed on a 350-km sector of the river. In this paper, samples of sediments from nine lakes located in the Madeira River basin, Rondonia State, Brazil, were analysed for mercury and organic matter. The average Hg content ranged between 33 and 157 ppb, which is about 8-40 times higher than the average value corresponding to 4.4 ppb for rocks occurring in the area (regional background). Significant correlation was found between the Hg content and organic matter in the sediments, indicating its importance on the retention of this heavy metal.

Influence of solution treatment on the adsorption and morphology of poly(o-methoxyaniline) layer-by-layer films

It is shown that the adsorption and morphological properties of layer-by-layer films of poly(o-methoxyaniline) (POMA) alternated with poly(vinyl sulfonic acid) (PVS) are affected dramatically by different treatments of the POMA solutions employed to prepare the films. Whereas the dimension of the globular structures seen by atomic force microscopy increases non monotonically during film growth in parent POMA solution, owing to a competition of adsorption/desorption processes, it changes monotonically for the fractionated POMA. The roughness of the latter films depends on the concentration of the solution and saturates at a given size of the scan window. This allowed us to apply scaling laws that indicated a self-affine mechanism for adsorption of the treated POMA.

Use of Biopolymeric Membranes for Adsorption of Paraquat Herbicide from Water

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

Adsorption of various ions from acetone and ethanol on silica gel modified with 2-, 3-, and 4-aminobenzoate

Chemically bonded phases were obtained by reaction of 2-, 3-, and 4-aminobenzoate with 3-chloropropyl-silica gel. These phases were employed for metal cation adsorption in a batch method and applied to the separation of transition metal cations by chromatographic analysis.

Induction of physical paramorphogenesis in Aspergillus sp

A simple and easily reproducible method to obtain little fungical pellets from mycelial fractionization, completely under control with respect to development, size and homogeneity without genetic compromise, is described. The method has been successully employed with Aspergillus niger and also showed similar results with Aspergillus oryzae.

Comparative study using small-angle x-ray scattering and nitrogen adsorption in the characterization of silica xerogels and aerogels

A comparative study using small-angle x-ray scattering (SAXS) and nitrogen adsorption has been carried out in the structural characterization of silica xerogels and aerogels, obtained from tetraethoxysilane sonohydrolysis. The specific surface and the mean pore size as measured by both the techniques were found to be in notable agreement in all cases for aerogels and xerogels. According to the SAXS data, aerogels at 500 °C exhibit a mass fractal structure with fractal dimension D∼2.4 in the range between the correlation length ξ∼5.3 nm and a∼0.75 nm. An experimental method to probe the mass fractal structure of aerogels from exclusively nitrogen adsorption isotherms has been presented. For aerogels at 500 °C, we have found D∼2.4 in the range between the pore width 2rξ∼33 nm and 2ra∼4.5 nm, which is in notable agreement with the SAXS results (D ∼2.4, ξ∼5.3 nm, a∼0.75 nm) if we assign the pore width 2r probed by the Kelvin equation in the adsorption method to the Bragg distance 2π/q associated to the correlation length 1/q probed by SAXS.

CO 2 adsorption on polar surfaces of ZnO

Physical and chemical adsorption of CO 2 on ZnO surfaces were studied by means of two different implementations of periodic density functional theory. Adsorption energies were computed and compared to values in the literature. In particular, it was found that the calculated equilibrium structure and internuclear distances are in agreement with previous work. CO 2 adsorption was analyzed by inspection of the density of states and electron localization function. Valence bands, band gap and final states of adsorbed CO 2 were investigated and the effect of atomic displacements analyzed. The partial density of states (PDOS) of chemical adsorption of CO 2 on the ZnO(0001) surface show that the p orbitals of CO 2 were mixed with the ZnO valence band state appearing at the top of the valence band and in regions of low-energy conduction band. [Figure not available: see fulltext.] © 2012 Springer-Verlag Berlin Heidelberg.

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.

Adsorption of pH-responsive polyelectrolyte chains onto spherical macroions

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Kinetic and Thermodynamic Studies on the Adsorption of Reactive Red 239 by Carra Sawdust Treated with Formaldehyde

In this study, carra sawdust pre-treated with formaldehyde was used to adsorb reactive red 239 (RR239). The effects of several experimental conditions, including the concentration of dye, sorbent dosage, temperature, ionic strength, stirring speed and solution pH, on the kinetics of the adsorption process have been studied, and the experimental data were fitted to pseudo-second-order model. A study of the intra-particle diffusion model indicates that the mechanism of dye adsorption using carra sawdust is rather complex and is most likely a combination of external mass transfer and intra-particle diffusion. The experimental data obtained at equilibrium were analyzed using the Langmuir and Freundlich isotherm models, and the results indicated that at this concentration range, both models can be applied for obtaining the equilibrium parameters. The maximum dye uptake obtained at 298 K was found to be 15.1 mg g(-1). In contrast to the usual systems, the reactive dye studied in the present work is strongly attached to the sawdust even after several washes with water, allowing it to be discarded as a solid waste.