Iron oxyhydroxide nanostructured in montmorillonite clays: Preparation and characterization

Akaganeite is a very rare iron oxyhydroxide in nature. It can be obtained by many synthetic routes, but thermohydrolysis is the most common method reported in the literature. In this work, akaganeite-like materials were prepared through the thermohydrolysis of FeCl(3)center dot 6H(2)O in water and suspensions containing clay minerals. X-ray diffractometry (XRD), Fourier transform infrared (FTIR) spectroscopy, and scanning electron microscopy (SEM) data show that the clays determine the crystal phase and size of the iron oxyhydroxide crystals. According to XRD and FTIR data, beta-FeO(OH) (akaganeite) is the main metal oxyhydroxide phase. Considering the small basal spacing (d(0 0 1)) displacement observed when comparing the XRD patterns of pristine clays with the composites containing beta-FeO(OH), the iron oxyhydroxide should be mostly located on the basal and edge surfaces of the clay minerals. UV-Vis electronic absorption spectra indicate that the preferred phase of the iron oxyhydroxide is determined by the nature of the clay minerals. (C) 2010 Elsevier Inc. All rights reserved.

Effect of solvent on the adsorption behavior and on the surface properties of Sterculia striata polysaccharide

Characterization of Sterculia striate polysaccharide (SSP) films adsorbed onto Si wafers from solutions prepared in ethyl methyl imidazolium acetate (EmimAc), water or NaOH 0.01 mol/L was systematically studied by means of ellipsometry, atomic force microscopy and contact angle measurements. SSP adsorbed from EmimAc onto Si wafer as homogeneous monolayers (similar to 0.5 nm thick), while from water or NaOH 0.01 mol/L SSP formed layers of similar to 4.0 nm and similar to 1.5 nm thick, respectively. Surface energy values found for SSP adsorbed from EmimAc or water were 68 +/- 2 mJ/m(2) and 65 +/- 2 mJ/m(2), respectively, whereas from NaOH it amounted to 57 +/- 3 mJ/m(2). The immobilization of lysozyme (LYS) onto SSP films was also investigated. The mean thickness of LYS (d(LYS)) immobilized onto SSP films adsorbed from each solvent tended to increase with the decrease of gamma(P)(S) and gamma(total)(S). However, the enzymatic activity of LYS molecules was higher when they were immobilized onto SSP films with higher gamma(P)(S) and gamma(total)(S) values. (C) 2010 Elsevier Ltd. All rights reserved.

Micro/nanostructured carbon composite modified with a hybrid redox mediator and enzymes as a glucose biosensor

A carbon micro/nanostructured composite based on cup-stacked carbon nanotubes (CSCNTs) grown onto a carbon felt has been found to be an efficient matrix for enzyme immobilization and chemical signal transduction. The obtained CSCNT/felt was modified with a copper hexacyanoferrate/polypyrrole (CuHCNFe/Ppy) hybrid mediator, and the resulting composite electrode was applied to H(2)O(2) detection, achieving a sensitivity of 194 +/- 15 mu A mmol(-1) L. The results showed that the CSCNT/felt matrix significantly increased the sensitivity of CuHCNFe/Ppy-based sensors compared to those prepared on a felt unrecovered by CSCNTs. Our data revealed that the improved sensitivity of the as-prepared CuHCNFe/Ppy-CSCNT/felt composite electrode can be attributed to the electronic interactions taking place among the CuHCNFe nanocrystals, Ppy layer and CSCNTs. In addition, the presence of CSCNTs also seemed to favor the dispersion of CuHCNFe nanocrystals over the Ppy matrix, even though the CSCNTs were buried under the conducting polymer layer. The CSCNT/felt matrix also enabled the preparation of a glucose biosensor whose sensitivity could be tuned as a function of the number of glucose oxidase (GOx) layers deposited through a Layer-by-Layer technique with an sensitivity of 11 +/- 2 mu A mmol(-1) L achieved at 15 poly(diallyldimethylammoniumchloride)/GOx bilayers. (C) 2011 Elsevier Ltd. All rights reserved.

Nitric oxide sensing by cytochrome c bonded to a conducting polymer modified glassy carbon electrode

A nitric oxide biosensor based on cytochrome c (an heme protein) covalently immobilized to poly(5-amino-1-naphthol) by using cyanuric chloride as a bridge was developed. The immobilization was studied by cyclic voltammetry and quartz crystal microbalance. The nitric oxide detection as a function of poly(5-amino-1-naphthol) amount was recorded, and the best result was obtained with the electrode prepared by 70 cycles. The sensitivity and detection limit were 0.015 mu A cm(-2)/mu mol L(-1) and 2.85 mu mol L(-1), respectively. (C) 2009 Elsevier B.V. All rights reserved.

V(2)O(5) nanoparticles obtained from a synthetic bariandite-like vanadium oxide: Synthesis, characterization and electrochemical behavior in an ionic liquid

Highly stable and crystalline V(2)O(5) nanoparticles with an average diameter of 15 nm have been easily prepared by thermal treatment of a bariandite-like vanadium oxide, V(10)O(24)center dot 9H(2)O. Their characterization was carried out by powder X-ray diffractometry (XRD). Fourier transform infrared (FT-IR) and Raman spectroscopies, and transmission electron microscopy (TEM). The fibrous and nanostructured film obtained by electrophoretic deposition of the V(2)O(5) nanoparticles showed good electroactivity when submitted to cyclic voltammetry in an ionic liquid-based electrolyte. The use of this film for the preparation of a nanostructured electrode led to an improvement of about 50% in discharge capacity values when compared with similar electrodes obtained by casting of a V(2)O(5) xerogel. (C) 2009 Elsevier Inc. All rights reserved.

PVP superabsorbent nanogels

Monomer free hydrogel nanoparticles (nanogels) were prepared by crosslinking preformed poly(N-vinyl-2-pyrrolidone) (PVP) entrapped in the aqueous pool of hexadecyltrimethylammonium bromide reverse micelles using the Fenton reaction. The PVP nanoparticles were spherical with a dry diameter of 27 nm. The diameter of the swollen particles was ten times higher, i.e., a swelling ratio, Q, above 900, characterizing this preparation as superabsorbent. PVP nanogel swelling was dependent on bound Fe(3+) and varied with pH and ionic strength. Nanogel deswelling by salt followed the anions lyotropic series, i.e., SCN(-) < HSO(3)(-) < NO(3)(-) < I(-) < Cl(-) < CH(3)COO(-) < CF(3)SO(3)(-). The value of Q reached 6,000 in iron-free PVP nanoparticles at low pH, making this nanogel one of the most efficient swelling systems so far described.

Development of Highly Selective Enzymatic Devices Based on Deposition of Permselective Membranes on Aligned Nanowires

We describe a simple and efficient strategy to fabricate enzymatic devices based on the deposition of glucose oxidase on aligned and highly oriented CoNiMo metallic nanowires. CoNiMo nanowires with an average diameter of 200 nm and length of 50 mu m were electrodeposited on Au-covered alumina substrates via electrodeposition, using alumina membranes as templates. Enzyme-modified electrodes were fabricated via enzyme immobilization using a cross-linker. To minimize nonspecific reactions in the presence of interfering agents, a permselective membrane composed of poly(vinylsulfonic acid) and polyamidoamine dendrimer was deposited via electrostatic interaction. The formation of hydrogen peroxide as a product of the enzymatic reaction was monitored at low overpotential, 0.0 V (vs Ag/AgCl). The detection limit was estimated at 22 mu M under an applied potential of 0.0 V. The apparent Michaelis-Menten constant determined from the Lineweaver-Burke plot was 2 mM.

Thin films of xyloglucans for BSA adsorption

In this work. XG extracted from Tamarindus indica (XGT) and Copaifera langsdorffii (XGC) seeds were deposited onto Si wafers as thin films. The characteristics of XGT and XGC adsorbed layers were compared with a commercial XG sample (TKP, Tamarind kernel powder) by ellipsometry, and atomic force microscopy (AFM). Moreover, the adsorption of oxidized derivative of XGT (To60) onto amino-terminated Si wafers and the immobilization of bovine serum albumin (BSA) onto polysaccharides covered wafers, as a function of pH, were also investigated. The XG samples presented molar ratios Glc:Xyl:Gal of 2.4:2.1:1 (XGC) 2.8: 23: 1 (XGT) and 1.91.91 (TKP). The structure of XGT and XGC was determined by O-methy alditol acetate derivatization and showed similar features, but XGC confirmed the presence of more alpha-D-Xyl branches due to more beta-D-Gal ends. XGT deposited onto Si adsorbed as fibers and small entities uniformly distributed, as evidenced by AFM, while TPK and XGC formed larger aggregates. The thickness of To60 onto amino-terminated surface was similar to that determined for XGT onto Si wafers. A maximum in the adsorbed amount of BSA occurred close to its isoelectric point (5.5). These findings indicate that XGT and To60 are potential materials for the development of biomaterials and biotechnological devices. (C) 2008 Elsevier B.V. All rights reserved.

Lysozyme binding to poly(4-vinyl-N-alkylpyridinium bromide)

The adsorption behavior of polycations at ionic strengths (1) ranging from 0.001 to 0.1 onto silicon wafers was studied by means of ellipsometry, contact angle measurements and atomic force microscopy (AFM). Polycations chosen were bromide salts of poly(4-vinylpyridine) N-alkyl quaternized with linear aliphatic chains of 2 and 5 carbon atoms, QPVP-C2 and QPVP-C5, respectively. Under 1 0.001 the reduction of screening effects led to low adsorbed amounts of QPVP-C2 or QPVP-C5 (1.0 +/- 0.1 mg/m(2)), arising from the adsorption of extended chains. Upon increasing l to 0.1, screening effects led to conformational changes of polyelectrolyte chains ill Solution and to higher adsorbed amount values (1.9 +/- 0.2 mg/m(2)). Advancing contact angle theta(a) measurements performed with water drops onto QPVP-C2 and QPVP-C5 adsorbed layers varied from (45 +/- 2)degrees to (50 +/- 5)degrees, evidencing the exposure of both hydrophobic alkyl groups and charged moieties. The adsorption of lysozyme (LYZ) molecules to QPVP-C5 layers was more pronounced than to QPVP-C2 films. Antimicrobial effect of LYZ bound to QPVP-C2 or QPVP-C5 layers or to Si wafers was evaluated with enzymatic assays using Micrococcus luteus as Substrates. The adsorption behavior of QPVP-C2 and QPVP-C5 at the water-air interface was studied by means Of surface tension measurements. Only QPVP-C5 was able to reduce water Surface tension. Mixtures of LYZ and QPVP-C5 were more efficient in reducing Surface tension than pure LYZ solution, evidencing co-adsorption at liquid-air interface. Moreover, antimicrobial action observed for mixtures of LYZ and QPVP-C5 was more pronounced than that measured for pure LYZ. Hydrophobic interaction between LYZ and QPVP-C5 ill Solution seems to drive the binding and to preserve LYZ secondary structure. (c) 2008 Elsevier Inc. All rights reserved.

Copper hexacyanoferrate nanoparticles modified electrodes: A versatile tool for biosensors

Copper hexacyanoferrate nanoparticles of about 30 nm in size have been prepared by the sonochemical irradiation of a mixture of aqueous potassium ferricyanide and copper chloride solutions. The nanoparticles were immobilized onto fluorine doped tin oxide (FTO) electrodes by using the electrostatic deposition layer-by-layer technique (LbL), obtaining electroactive films with electrocatalytic properties towards H2O2 reduction, providing higher currents than those observed for electrodeposited bulk material, even in electrolytes containing NH4+, Na+ and K+. The nanoparticles assembly was used as mediator in a glucose biosensor by immobilizing glucose oxidase enzyme by both, cross-linking and LbL. techniques. Sensitivities obtained were dependent on the immobilization method ranging from 1.23 mu A mmol(-1) L cm(-2) for crosslinking to 0.47 mu A mmol(-1) L cm(-2) for LbL; these values being of the same order than those obtained with electrodes where the amount of enzyme used is much higher. Moreover, the linear concentration range where the biosensors can operate was 10 times higher for electrodes prepared with the LbL immobilization method than with the conventional crosslinking one. (C) 2008 Elsevier B.V. All rights reserved.

Adsorption of di-2-pyridyl ketone salicyloylhydrazone on Amberlite XAD-2 and XAD-7 resins: Characteristics and isotherms

The adsorption of DPKSH onto Amberlite XAD-2 (styrene resin) and XAD-7 (acrylic ester resin) has been investigated, at (25 +/- 1)degrees C and pH 4.7. The experimental equilibrium data were fitted to the Langmuir, Freundlich, and Dubinin-Radushkevich (D-R) models. These three models provide a very good fit for both resins and the respective constants K(L), K(F), and K(DR) were calculated. For the same DPKSH concentration interval, the minimum time of contact for adsorption maximum at XAD-7 was smaller than at XAD-2 and the maximum amount of DPKSH adsorbed per gram of XAD-2 is smaller than at XAD-7. The investigation indicates that the mean sorption energy (E) characterizes a physical adsorption and the surfaces of both resins are energetically heterogeneous. The constants obtained in these studied systems were correlated and compared with those obtained for the silica gel/DPKSH system. (C) 2008 Published by Elsevier Inc.

Electrostatic layer-by-layer deposition and electrochemical characterization of thin films composed of MnO(2) nanoparticles in a room-temperature ionic liquid

Thin films of MnO(2) nanoparticles were grown using the layer-by-layer method with poly (diallyldimetylammonium) as the intercalated layer. The film growth was followed by UV-vis, electrochemical quartz crystal microbalance (EQCM), and atomic force microscopy. Linear growth due to electrostatic immobilization of layers was observed up to 30 bilayers, but electrical connectivity was maintained only for 12 MnO(2)/PPDA bilayers. The electrochemical characterization of this film in 1-butyl-2,3-dimethyl-imidazolium (BMMI) bis(trifluoromethanesulfonyl)imide (TFSI) (BMMITFSI) with and without addition of a lithium salt indicated a higher electrochemical response of the nanostructured electrode in the lithium-containing electrolyte. On the basis of EQCM experiments, it was possible to confirm that the charge compensation process is achieved mainly by the TFSI anion at short times (<2 s) and by BMMI and lithium cations at longer times. The fact that large ions like TFSI and BMMI participate in the electroneutrality is attributed to the redox reaction that occurs at the superficial sites and to the high concentration of these species compared to that of lithium cations.

Surface active ionic liquids: Study of the micellar properties of 1-(1-alkyl)-3-methylimidazolium chlorides and comparison with structurally related surfactants

The impetus for the increasing interest in studying surface active ionic liquids (SAILs; ionic liquids with long-chain ""tails"") is the enormous potential for their applications, e.g., in nanotechnology and biomedicine. The progress in these fields rests on understanding the relationship between surfactant structure and solution properties, hence applications. This need has prompted us to extend our previous study on 1-(1-hexadecyl)-3-methylimidazolium chloride to 1-(1-alkyl)-3-methylimidazolium chlorides, with alkyl chains containing 10, 12, and 14 carbons. In addition to investigating relevant micellar properties, we have compared the solution properties of the imidazolium-based surfactants with: 1-(1-alkyl)pyridinium chlorides, and benzyl (2-acylaminoethyl)dimethylammonium chlorides. The former series carries a heterocyclic ring head-group, but does not possess a hydrogen that is as acidic as H2 of the imidazolium ring. The latter series carries an aromatic ring, a quaternary nitrogen and (a hydrogen-bond forming) amide group. The properties of the imidazolium and pyridinium surfactants were determined in the temperature range from 15 to 75 degrees C. The techniques employed were conductivity, isothermal titration calorimetry, and static light scattering. The results showed the important effects of the interactions in the interfacial region on the micellar properties over the temperature range studied. (C) 2011 Elsevier Inc. All rights reserved.

Micellar properties of surface active ionic liquids: A comparison of 1-hexadecyl-3-methylimidazolium chloride with structurally related cationic surfactants

Ionic liquids, ILs, carrying long-chain alkyl groups are surface active, SAIIs. We investigated the micellar properties of the SAIL 1-hexadecyl-3-methylimidazolium chloride, C(16)MeImCl, and compared the data with 1-hexadecylpyridinium chloride, C(16)PYCl, and benzyl (3-hexadecanoylaminoethyl)dimethylammonium chloride, C(15)AEtBzMe(2)Cl. The properties compared include critical micelle concentration, cmc; thermodynamic parameters of micellization; empirical polarity and water concentrations in the interfacial regions. In the temperature range from 15 to 75 degrees C, the order of cmc in H(2)O and in D(2)O is C(16)PYCl > C(16)MeImCl > C(15)AEtBzMe(2)Cl. The enthalpies of micellization, Delta H(mic)(degrees), were calculated indirectly from by use of the van`t Hoff treatment; directly by isothermal titration calorimetry, ITC. Calculation of the degree of counter-ion dissociation, alpha(mic), from conductivity measurements, by use of Evans equation requires knowledge of the aggregation numbers, N(agg), at different temperatures. We have introduced a reliable method for carrying out this calculation, based on the volume and length of the monomer, and the dependence of N(agg) on temperature. The N(agg) calculated for C(16)PyCl and C(16)MeImCl were corroborated by light scattering measurements. Conductivity- and ITC-based Delta H(mic)(degrees) do not agree; reasons for this discrepancy are discussed. Micelle formation is entropy driven: at all studied temperatures for C(16)MeImCl; only up to 65 degrees C for C(16)PyCl; and up to 55 degrees C for C(15)AEtBzMe(2)Cl. All these data can be rationalized by considering hydrogen-bonding between the head-ions of the monomers in the micellar aggregate. The empirical polarities and concentrations of interfacial water were found to be independent of the nature of the head-group. (C) 2010 Elsevier Inc. All rights reserved.

Effect of sonication on the particle size of montmorillonite clays

This paper reports on the effect of sonication on SAz-1 and SWy-1 montmorillonite suspensions. Changes in the size of the particles of these materials and modifications of their properties have been investigated. The variation of the particle size has been analyzed by DLS (dynamic light scattering). In all cases the clay particles show a bimodal distribution. Sonication resulted in a decrease of the larger modal diameter, as well as a reduction of its volume percentage. Simultaneously, the proportion of the smallest particles increases. After 60 min of sonication, SAz-1 presented a very broad particle size distribution with a modal diameter of 283 nm. On the other hand, the SWy-1 sonicated for 60 min presents a bimodal distribution of particles at 140 and 454 nm. Changes in the properties of the clay suspensions due to sonication were evaluated spectroscopically from dye-clay interactions, using Methylene Blue. The acidic sites present in the interlamellar region, which are responsible for dye protonation, disappeared after sonication of the clay. The changes in the size of the scattering particles and the lack of acidic sites after sonication suggest that sonication induces delamination of the clay particles. (c) 2008 Elsevier Inc. All rights reserved.