Surface modification of alumina nanofibres for the selective adsorption of alachlor and imazaquin herbicides

The effective removal of pollutants using a thermally and chemically stable substrate that has controllable absorption properties is a goal of water treatment. In this study, the surfaces of thin alumina (γ-Al2O3) nanofibres were modified by the grafting either of two organosilane agents, 3-chloro-propyl-triethoxysilane (CPTES) and octyl-triethoxysilane (OTES). These modified materials were then trialed as absorbents for the removal of two herbicides, alachlor and imazaquin from water. The formation of organic groups during the functionalisation process established super hydrophobic sites on the surfaces of the nanofibres. This super hydrophobic group is a kind of protruding adsorption site which facilitates the intimate contact with the pollutants. OTES grafted substrate were shown to be more selective for alachlor while imazaquin selectivity is shown by the CPTES grafted substrate. Kinetics studies revealed that imazaquin was rapidly adsorbed on CPTES-modified surfaces. However, the adsorption of alachlor by OTES grafted surface was achieved more slowly.

Study of an organically modified clay: Selective adsorption of heavy metal ions and voltammetric determination of mercury(II)

In this work, a hydrophilic clay, Na-montmorillonite from Wyoming, USA, was rendered organophilic by exchanging the inorganic interlayer cations for hexaclecyltrimethylammonium ions (HDTA), with the formulae of [(CH3)(3)N(C16H33)](+) ion. Based on fact that organo-clay has high affinities for non-ionic organic molecules, 1,3,4-thiadiazole-2,5-dithiol was loaded oil the HDTA-montmorillonite surface, resulting in the 1,3,4-thiadiazole-2,5-dithiol-HDTA-montmorillonite complex (TDD-organo-clay).The following properties of TDD-organo-clay are discussed: selective adsorption of heavy metal ions measured by batch and chromatographic column techniques, and utilization as preconcentration agent in a chemically modified carbon paste electrode (CMCPE) for determination of mercury(II).The main point of this paper is the construction of a selective sensor, a carbon paste electrode modified with TDD-organo-clay, its properties and its application to the determination of mercury(II) ions, as this element belongs to the most toxic metals. The chemical selectivity of this functional group and the selectivity of voltammetry were combined for preconcentration and determination. (c) 2005 Elsevier B.V. All rights reserved.

Selective adsorption of l- and d-amino acids on calcite: Implications for biochemical homochirality

The emergence of biochemical homochirality was a key step in the origin of life, yet prebiotic mechanisms for chiral separation are not well constrained. Here we demonstrate a geochemically plausible scenario for chiral separation of amino acids by adsorption on mineral surfaces. Crystals of the common rock-forming mineral calcite (CaCO3), when immersed in a racemic aspartic acid solution, display significant adsorption and chiral selectivity of d- and l-enantiomers on pairs of mirror-related crystal-growth surfaces. This selective adsorption is greater on crystals with terraced surface textures, which indicates that d- and l-aspartic acid concentrate along step-like linear growth features. Thus, selective adsorption of linear arrays of d- and l-amino acids on calcite, with subsequent condensation polymerization, represents a plausible geochemical mechanism for the production of homochiral polypeptides on the prebiotic Earth.

Separation of n-paraffins by selective adsorption

A study has been undertaken of the vapor-phase adsorptive separation of n-alkanes from Kuwait kerosene (Kuwait National Petroleum Company, heavy kerosene) using zeolite molecular sieves. Due to the shortage of information on the adsorption of multicomponent systems in the open literature, the present investigation was initiated to study the effect of feed flowrate, temperature, and zeolite particle size on the height of mass transfer zone (MTZ) and the dynamic capacity of the adsorbent for multicomponent n-alkanes adsorption on a fixed-bed of zeolite type-5A. The optimum operating conditions for separation of the n-alkanes has been identified so that the effluent would also be of marketable quality. The effect of multicycle adsorption-desorption stages on the dynamic behaviour of zeolite using steam as a desorbing agent has been studied and compared with n-pentane and n-hexane as desorbing agents. The separation process comprised one cycle of adsorption using a fixed-bed of zeolite type-5A. The bed was fed with vaporized kerosene until saturation had been achieved whereby the n-alkanes were adsorbed and the denormalized material eluted. The process of adsorption-desorption was carried out isobarically at one atmosphere. A mathematical model has been developed to predict the breakthrough time using the method of characteristics. The results were in a reasonable agreement with the experimental values. This model has also been utilized to develop the equilibrium isotherm. Optimum operating conditions were achieved at a feed flowrate of 33.33 x 10-9 m3/s, a temperature of 643 K, and a particle size of (1.0 - 2.0) x 10-3 m. This yielded an HMTZ value and a dynamic capacity of 0.206 m and 9.6S3 x 10-2 kg n-alkanes/kg of zeolite respectively. These data will serve as a basis for design of a commercial plant. The purity of liquid-paraffin product desorbed using steam was 83.24 wt%. The dynamic capacity was noticed to decrease sharply with the cycle number, without intermediate reactivation of zeolite, while it was kept unchanged by intermediate reactivation. Normal hexane was found to be the best desorbing agent, the efficiency of which was mounted to 88.2%.

2-Mercaptoimidazole covalently bonded to a silica gel surface for the selective separation of mercury(II) from an aqueous solution

Silica gel with a specific surface area of 365 m(2).g(-1) and an average pore diameter of 60 Angstrom was chemically modified with 2-mercaptoimidazole. The degree of functionalization of the covalently attached molecule, (drop SiO)(3)(CH2)(3) - MI, where MI is the 2-mercaptoimidazole bound to the silica surface by a propyl group, was 0.58 mmolg.(-1). In individual metal adsorption experiments from aqueous solutions by the batch procedure, the affinity order was Hg(II)much greater than Cd-II > Cu-II approximate to Zn-II approximate to Pb-II > Mn-II at solution pHs between 4 and 7. Due to the high affinity by the sulfur atom, Hg-II is strongly bound to the functional groups. When solution containing a mixture of Hg-II, Cd-II, Cu-II, Zn-II, Pb-II, and Mn-II ions was passed through a column packed with the adsorbent, Hg-II was the only one whose adsorption and elution was not affected by the presence of other ions.

Preparation of a silica gel modified with 2-amino-1,3,4-thiadiazole for adsorption of metal ions and electroanalytical application

Silica gel with a specific area of 382 m2 g-1 and an average pore diameter of 60 Å was chemically modified with 2-amino-1,3,4-thiadiazole, for the purpose of selective adsorption of heavy metals ions and possible use as a chemically modified carbon paste electrode (CMCPE). The following properties of this functionalized silica gel are discussed: selective adsorption of heavy metal ions measured by batch and chromatographic column techniques, and utilization as preconcentration agent in a chemically modified carbon paste electrode (CMCPE) for determination of mercury(II). The chemical selectivity of this functional group and the selectivity of voltammetry were combined for preconcentration and determination. ©2006 Sociedade Brasileira de Química.

Characterization of corn (Zea mays) leaf powder and Its adsorption properties regarding Cu(II) and Cd(II) from aqueous samples

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

Use of Eutectic Mixtures for Preparation of Monolithic Carbons with CO2-Adsorption and Gas-Separation Capabilities

With global warming becoming one of the main problems our society is facing nowadays, there is an urgent demand to develop materials suitable for CO2 storage as well as for gas separation. Within this context, hierarchical porous structures are of great interest for in-flow applications because of the desirable combination of an extensive internal reactive surface along narrow nanopores with facile molecular transport through broad “highways” leading to and from these pores. Deep eutectic solvents (DESs) have been recently used in the synthesis of carbon monoliths exhibiting a bicontinuous porous structure composed of continuous macroporous channels and a continuous carbon network that contains a certain microporosity and provides considerable surface area. In this work, we have prepared two DESs for the preparation of two hierarchical carbon monoliths with different compositions (e.g., either nitrogen-doped or not) and structure. It is worth noting that DESs played a capital role in the synthesis of hierarchical carbon monoliths not only promoting the spinodal decomposition that governs the formation of the bicontinuous porous structure but also providing the precursors required to tailor the composition and the molecular sieve structure of the resulting carbons. We have studied the performance of these two carbons for CO2, N2, and CH4 adsorption in both monolithic and powdered form. We have also studied the selective adsorption of CO2 versus CH4 in equilibrium and dynamic conditions. We found that these materials combined a high CO2-sorption capacity besides an excellent CO2/N2 and CO2/CH4 selectivity and, interestingly, this performance was preserved when processed in both monolithic and powdered form.

Electrostatically mediated specific adsorption of small molecules in metallo-organic frameworks

We investigate the interaction of ethylene and ethane with a Cu-tricarboxylate complex and show that at low loadings the lighter molecule has a higher binding energy as a result of an increased interaction with the framework Cu and stronger hydrogen bonding with the basic framework oxygens. This leads to selective adsorption of ethylene by a factor of about 2 at low pressure, which is overcome by the stronger van der Waals interaction of ethane at high loadings, explaining recent literature data. The results suggest the possibility of separation of light hydrocarbons at low pressures or in trace amounts.

Fate of potassium fertilisers applied to clay soils under rainfed grain cropping in south-east Queensland, Australia

Negative potassium (K) balances in all broadacre grain cropping systems in northern Australia are resulting in a decline in the plant-available reserves of K and necessitating a closer examination of strategies to detect and respond to developing K deficiency in clay soils. Grain growers on the Red Ferrosol soils have increasingly encountered K deficiency over the last 10 years due to lower available K reserves in these soils in their native condition. However, the problem is now increasingly evident on the medium-heavy clay soils (Black and Grey Vertosols) and is made more complicated by the widespread adoption of direct drill cropping systems and the resulting strong strati. cation of available K reserves in the top 0.05-0.1 m of the soil pro. le. This paper reports glasshouse studies examining the fate of applied K fertiliser in key cropping soils of the inland Burnett region of south-east Queensland, and uses the resultant understanding of K dynamics to interpret results of field trials assessing the effectiveness of K application strategies in terms of K availability to crop plants. At similar concentrations of exchangeable K (K-exch), soil solution K concentrations and activity of K in the soil solution (AR(K)) varied by 6-7-fold between soil types. When K-exch arising from different rates of fertiliser application was expressed as a percentage of the effective cation exchange capacity (i.e. K saturation), there was evidence of greater selective adsorption of K on the exchange complex of Red Ferrosols than Black and Grey Vertosols or Brown Dermosols. Both soil solution K and AR(K) were much less responsive to increasing K-exch in the Black Vertosols; this is indicative of these soils having a high K buffer capacity (KBC). These contrasting properties have implications for the rate of diffusive supply of K to plant roots and the likely impact of K application strategies (banding v. broadcast and incorporation) on plant K uptake. Field studies investigating K application strategies (banding v. broadcasting) and the interaction with the degree of soil disturbance/mixing of different soil types are discussed in relation to K dynamics derived from glasshouse studies. Greater propensity to accumulate luxury K in crop biomass was observed in a Brown Ferrosol with a KBC lower than that of a Black Vertosol, consistent with more efficient diffusive supply to plant roots in the Ferrosol. This luxury K uptake, when combined with crops exhibiting low proportional removal of K in the harvested product (i.e. low K harvest index coarse grains and winter cereals) and residue retention, can lead to rapid re-development of stratified K profiles. There was clear evidence that some incorporation of K fertiliser into soil was required to facilitate root access and crop uptake, although there was no evidence of a need to incorporate K fertiliser any deeper than achieved by conventional disc tillage (i.e. 0.1-0.15 m). Recovery of fertiliser K applied in deep (0.25-0.3 m) bands in combination with N and P to facilitate root proliferation was quite poor in Red Ferrosols and Grey or Black Vertosols with moderate effective cation exchange capacity (ECEC, 25-35 cmol(+)/kg), was reasonable but not enough to overcome K deficiency in a Brown Dermosol (ECEC 11 cmol(+)/kg), but was quite good on a Black Vertosol (ECEC 50-60 cmol(+)/kg). Collectively, results suggest that frequent small applications of K fertiliser, preferably with some soil mixing, is an effective fertiliser application strategy on lighter clay soils with low KBC and an effective diffusive supply mechanism. Alternately, concentrated K bands and enhanced root proliferation around them may be a more effective strategy in Vertosol soils with high KBC and limited diffusive supply. Further studies to assess this hypothesis are needed.

Facile preparation and some applications of an affinity matrix with a cleavable connector arm containing a disulfide bond

A versatile affinity matrix in which the ligand of interest is linked to the matrix through a connector arm containing a disulfide bond is described. It can be synthesized from any amino-substituted matrix by successive reaction with 2-imino-thio-lane, 5, 5'-dithiobis(2-nitrobenzoic acid), and a thiol derivative of the ligand of choice. The repertoire of ligands can be significantly increased by the appropriate use of avidin-biotin bridges. After adsorption of the material to be fractionated, elution can be effected by reducing the disulfide bond in the connector arm with dithiothreitol. Examples of the preparation and use of various affinity matrices based on amino-substituted Sepharose 6MB are given. One involves the immobilization of the Fab' fragment of a monoclonal antibody against Aspergillus oryzae β-galactosidase and the specific binding of that enzyme to the resulting immunoaffinity matrix. Another involves the immobilization of N-biotinyl-2-thioethylamine followed by complex formation with avidin. The resulting avidin-substituted matrix was used for the selective adsorption and subsequent recovery of mouse hybridoma cells producing anti-avidin antibodies. By further complexing the avidin-substituted matrix with appropriate biotinylated antigens, it should be possible to fractionate cells producing antibodies against a variety of antigens.

Dessulfurização oxidativa do dibenzotiofeno catalisada por V2O5 suportado

A necessidade de redução da emissão de poluentes, visando diminuir os sérios problemas de poluição atmosférica enfrentados atualmente, é hoje uma das principais preocupações mundiais, provocando o surgimento de leis mais rígidas, que restringem o teor de enxofre na gasolina e no diesel. Assim, o desenvolvimento de tecnologias mais eficazes na remoção de enxofre nestes combustíveis tem recebido atenção crescente. Estas tecnologias incluem a extração física com solvente, a adsorção seletiva, processos de redução/oxidação microbiológicos e a dessulfurização oxidativa (ODS). A dessulfurização oxidativa converte os compostos de enxofre em sulfonas que podem ser facilmente separadas por processos físicos. Portanto, a ODS apresenta grande potencial para tornar-se um processo complementar a processo de hidrodessulfurização tradicional na produção de combustíveis altamente dessulfurizados. Neste contexto, este trabalho visou o estudo do desempenho de catalisadores de V2O5 suportados em alumina, sílica e sílica-alumina frente à reação de ODS do dibenzotiofeno em presença do peróxido de hidrogênio, como oxidante, e da acetonitrila, como solvente polar aprótico. Os catalisadores foram preparados por impregnação ao ponto úmido e caracterizados por difração de raios-X (DRX), análise textural, redução à temperatura programada (TPR-H2), dessorção de amônia à temperatura programa (TPD-NH3) e espectroscopia Raman. O efeito de parâmetros reacionais como quantidade de solvente, relação O/S e concentração de catalisador foram investigados, utilizando a alumina como suporte, visando estabelecer as condições reacionais que levassem a maiores valores de conversão do dibenzotiofeno (DBT). Uma vez estabelecidas estas condições, foi analisado o efeito do teor de V2O5 presente no catalisador e, posteriormente, o efeito do suporte catalítico. Os resultados obtidos mostraram a 70 C razão molar H2O2/Sde 16,6, razão carga/solvente igual a 1:1 e 100 mg do catalisador 15 % V2O5/SiO2, a conversão obtida foi de 95%

Luminescence functionalization of SBA-15 by YVO4 : Eu3+ as a novel drug delivery system

Luminescence functionalization of the ordered mesoporous SBA-15 silica was realized by depositing a YVO4:Eu3+ phosphor layer on its surface via the Pechini sol-gel process, resulting in the formation of the YVO4:Eu3+@SBA-15 composite material. This material, which combines the mesoporous structure of SBA-15 and the strong red luminescence property of YVO4:Eu3+, can be used as a novel functional drug delivery system. The structure, morphology, porosity, and optical properties of the materials were well characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, N-2 adsorption, and photoluminescence spectra. As expected, the pore volume, surface area, and pore size of SBA-15 decrease in sequence after deposition of the YVO4:Eu3+ layer and the adsorption of ibuprofen (IBU, drug). The IBU-loaded YVO4:Eu3+@SBA-15 system still shows the red emission of Eu3+ (617 nm, D-5(0)-F-7(2)) under UV irradiation and the controlled drug release property. Additionally, the emission intensity of Eu3+ increases with an increase in the cumulative released amount of IBU in the system, making the extent of drug release easily identifiable, trackable, and monitorable by the change of luminescence. The system has great potential in the drug delivery and disease therapy fields.

MAS NMR studies of modified HY zeolites

The variations in structure and acidity on the internal and external surfaces of HY zeolites modified by MgO and SiO2 have been studied by MAS NMR, together with the selective adsorption of perfluorotributyl-amine. Al-27 and Si-29 MAS NMR spectra revealed that the modifications led to significant changes of the framework owing to the migration of some non-framework Si and Al into the framework in the course of the modifications. H-1 MAS NMR spectra showed that the modifications decreased the acidity of the zeolite surfaces. With an increasing of the loading of the oxides, the acidity of the surface decreased further. Both of the two kinds of Bronsted acidity of the MgO-modified HY zeolites decreased, particularly those in the supercages, while those of the SiO2-modified HY zeolites decreased less, and this result is consistent with that of NH3-TPD, from the adsorption of perfluorotributyl-amine, it was found that the acidic sites on the external surface of the HY zeolite can be completely covered by SiO2 after being modified by the chemical liquid deposition (CLD) method.

Interaction of Room Temperature Ionic Liquid Solutions with a Cholesterol Bilayer

Water solutions of representative (IC(4)mim][Cl] and [C(4)mim][Tf2N] room temperature ionic liquids (ILs) in contact with a neutral lipid bilayer made of cholesterol molecules has been investigated by molecular dynamics simulations based on an empirical force field model. The results show that both ILs display selective adsorption at the water-cholesterol interface, with partial inclusion of ions into the bilayer. In the case Of [C(4)mim][Cl], the adsorption of ions at the water-cholesterol interface is limited by a sizable bulk solubility of the IL, driven by the high water affinity of [Cl](-). The relatively low Solubility Of [C(4)mim][Tf2N], instead, gives rise to a nearly complete segregation of the IL component on the bilayer, altering its volume, compressibility, and electrostatic environment. The computational results display important similarities to the results of recent experimental measurements for ILs in contact with phospholipid model membranes (see Evans, K. O. Int. J. Mol. Sci. 2008, 9, 498-511 and references therein).