Controlled biocide release from hierarchically-structured biogenic silica: surface chemistry to tune release rate and responsiveness.

Biocides are essential for crop protection, packaging and several other biosystem applications. Therein, properties such as tailored and controlled release are paramount in the development of sustainable biocide delivery systems. We explore the self-similar nano-organized architecture of biogenic silica particles to achieve high biocide payload. The high surface area accessibility of the carrier allowed us to develop an efficient, low energy loading strategy, reaching significant dynamic loadings of up to 100 mg·g-1. The release rate and responsiveness were tuned by manipulating the interfaces, using either the native hydroxyl surfaces of the carrier or systems modified with amines or carboxylic acids in high density. We thoroughly evaluated the impact of the carrier-biocide interactions on the release rate as a function of pH, ionic strength and temperature. The amine and carboxyl functionalization strategy led to three-fold decrease in the release rate, while higher responsiveness against important agro-industrial variables. Key to our discoveries, nanostructuring thymol in the biogenic silica endowed systems with controlled, responsive release promoting remarkable, high and localized biocidal activity. The interfacial factors affecting related delivery were elucidated for an increased and localized biocidal activity, bringing a new light for the development of controlled release systems from porous materials.

Single-Step Exfoliation and Covalent Functionalization of MoS2 Nanosheets by an Organosulfur Reaction.

A simple approach to exfoliate and functionalize MoS2 in a single-step is described, which combines the dispersion of MoS2 in polybutadiene solution and ultrasonication processes. The great advantage of this process is that a colloidal stability of MoS2 in nonpolar solvent is achieved by chemically bonding polybutadiene on the perimeter edge sites of MoS2 sheets. In addition, elastomeric nanocomposite has been prepared with singular mechanical properties using functionalized MoS2 as nanofiller in a polybutadiene matrix with a subsequent vulcanization reaction.

Manganese chlorins immobilized on silica as oxidation reaction catalysts.

Synthetic strategies that comply with the principles of green chemistry represent a challenge: they will enable chemists to conduct reactions that maximize the yield of products with commercial interest while minimizing by-products formation. The search for catalysts that promote the selective oxidation of organic compounds under mild and environmentally friendly conditions constitutes one of the most important quests of organic chemistry. In this context, metalloporphyrins and analogues are excellent catalysts for oxidative transformations under mild conditions. In fact, their reduced derivatives chlorins are also able to catalyze organic compounds oxidation effectively, although they have been still little explored. In this study, we synthesized two chlorins through porphyrin cycloaddition reactions with 1.3-dipoles and prepared the corresponding manganese chlorins (MnCHL) using adequate manganese(II) salts. These MnCHL were posteriorly immobilized on silica by following the sol-gel process and the resulting solids were characterized by powder X-ray diffraction (PXRD), UVVIS spectroscopy, FTIR, XPS, and EDS. The catalytic activity of the immobilized MnCHL was investigated in the oxidation of cyclooctene, cyclohexene and cyclohexane and the results were compared with the ones obtained under homogeneous conditions.

Electrospray induced surface activation of polystyrene microbeads for diagnostic applications.

Electrospray is generally regarded as a "soft" technique due to the absence of any observable molecular fragmentation or destruction. This study reports on a novel and easy way to induce surface activation on the surface of polystyrene microbeads through electrospray deposition into a grounded aqueous electrolyte solution bath. This process, nicknamed EISA, which stands for electrospray induced surface activation, proposes that when a highly charged microbead formed by the electrospray process sinks into the aqueous electrolyte solution, it behaves like a highly charged spherical capacitor that discharges in the conductive liquid. The energy released leads to a breakup of the polystyrene surface bonds and water oxidation with oxygen. Further reactions produce a carboxylated surface that was confirmed by X-ray photoelectron spectroscopy (XPS) and protein coupling. An immunoassay based on these modified microbeads was also developed and presented for use in syphilis detection, demonstrating a reliable signal-to-noise ratio between positive and negative results.

Wettability effect of graphene-based surfaces on silicon carbide and their influence on hydrophobicity of nanocrystalline cerium oxide films.

We investigate the water-repellent ability of graphene-based surfaces stabilized on silicon carbide (SiC) and the nanocrystalline cerium oxide (CeO2) films electrodeposited on them. Water contact angle is revealed strongly dependent on the number of graphene monolayers on SiC, indicating partial permeability of graphene on SiC. Fluctuations in the roughness of textured surfaces as well as variations of oxygen vacancy content in CeO2 electrodeposits are determinant for the hydrophobicity of the interaction between water droplets and nanocrystalline CeO2 electrodeposits on monolayers graphene on SiC.

Photolysis of phenylalanine in the presence of oxidized carbon nanotubes.

Photolyses at 254 nm of phenylalanine (Phe) in aqueous solutions, were carried out in the presence of oxidized carbon nanotubes modified by the reaction with SO2 (mNTO). Kinetics of the photolyses were followed by UV spectrophotometry at 220 nm, and the products were characterized by HPLC, XPS, and (13)C-SSNMR. The ratio of the initial rates of photolysis in the presence and absence of mNTO, k*/ko*, showed a systematic decrease. The photolytic decay of Phe occurs with minor formation of tyrosine. The mass of nanotubes produced an exponential attenuation of the photolytic decomposition of Phe. Total carbon analyses (TCA) showed no inorganic carbon formation after the photolyses. The first-order rate constant of photofunctionalization of mNTO by the insertion of phenylalanine onto the nanotube matrix was calculated from TCA to be kin = 30.1 min(-1). Comparison of the XPS spectra of the mNTO before and after the photolysis, using the atom inventory technique, suggests the insertion of Phe along with the extrusion of a sulfide radical anion ((•)S(-)) which undergo subsequent oxidation to SO4(2-). The obtained results show the effects of mNTO on the photolysis of Phe and provide a new method of photofunctionalization of carbon materials, modified by the intermediates of the reduction of SO2, with an organic moiety.

Cell adhesion to plasma-coated PVC.

To produce environments suitable for cell culture, thin polymer films were deposited onto commercial PVC plates from radiofrequency acetylene-argon plasmas. The proportion of argon in the plasmas, P(Ar), was varied from 5.3 to 65.8%. The adhesion and growth of Vero cells on the coated surfaces were examined for different incubation times. Cytotoxicity tests were performed using spectroscopic methods. Carbon, O, and N were detected in all the samples using XPS. Roughness remained almost unchanged in the samples prepared with 5.3 and 28.9% but tended to increase for the films deposited with P(Ar) between 28.9 and 55.3%. Surface free energy increased with increasing P(Ar), except for the sample prepared at 28.9% of Ar, which presented the least reactive surface. Cells proliferated on all the samples, including the bare PVC. Independently of the deposition condition there was no evidence of cytotoxicity, indicating the viability of such coatings for designing biocompatible devices.

Structure and dielectric properties of electrochemically grown ZrO2 films.

The dielectric properties of electrochemically grown zirconium oxide films by anodisation of zirconium in 1.0 mol dm-3 phosphoric acid solution were investigated in a 3 to 30 V potential range with a view to inducing surface modifications for eventual use in biomedical and electronic applications. The oxide films grown at different potentials were characterised by Atomic Force Microscopy, X-ray photoelectron and Raman spectroscopies; the latter demonstrated the incorporation of phosphate ions into the passive films. Flat band potentials calculated from the Mott-Shottky analysis of the oxides semiconducting properties confirm the bilayer structure of the films. The oxide dielectric permittivity was evaluated from impedance spectroscopy measurements and the film oxide model proposed gave values independent of the oxide growth potential.

Selective insertion of sulfur dioxide reduction intermediates on graphene oxide.

Graphite microparticles (d50 6.20 µm) were oxidized by strong acids, and the resultant graphite oxide was thermally exfoliated to graphene oxide sheets (MPGO, C/O 1.53). Graphene oxide was treated with nonthermal plasma under a SO2 atmosphere at room temperature. The XPS spectrum showed that SO2 was inserted only as the oxidized intermediate at 168.7 eV in the S 2p region. Short thermal shocks at 600 and 400 °C, under an Ar atmosphere, produced reduced sulfur and carbon dioxide as shown by the XPS spectrum and TGA analysis coupled to FTIR. MPGO was also submitted to thermal reaction with SO2 at 630 °C, and the XPS spectrum in the S 2p region at 164.0 eV showed that this time only the nonoxidized episulfide intermediate was inserted. Plasma and thermal treatment produced a partial reduction of MPGO. The sequence of thermal reaction followed by plasma treatment inserted both sulfur intermediates. Because oxidized and nonoxidized intermediates have different reactivities, this selective insertion would allow the addition of selective types of organic fragments to the surface of graphene oxide.

Bioactive nanocomposites of bacterial cellulose and natural hydrocolloids.

The aim of this work was to develop bioactive films from bacterial cellulose and hydrocolloids (guar gum and hyaluronic acid), coated or not with collagen. After mechanical treatment, a suspension of cellulose nanofibres was obtained which, combined with the dispersions of hydrocolloids, was used to produce bionanocomposite films by wet casting. The materials were stable in physiological solution and presented better swelling capacity than that of the bacterial cellulose. The films were coated with collagen by dipping. Cell adhesion tests and surface analysis by tensiometry, X-ray photoelectron spectroscopy and atomic force microscopy showed that the surface properties of the films can be adjusted by changing the proportions of the components. The collagen coating presented a self-assembling pattern resembling that of living tissues. The materials developed in this work showed potential for applications in the medical field as bioactive wound dressings, scaffolds for cellular growth and sustained drug release systems. The films were obtained by simple production and purification methods, including the use of low toxicity solvents. Thus, in addition to potential cost saving, the development of these bionanocomposites is in accordance with green chemistry principles.

Effects of reprocessing on chemical and morphological properties of guide wires used in angioplasty.

OBJECTIVE: To investigate the influence of the reprocessing technique of enzymatic bath with ultrasonic cleaning and ethylene oxide sterilization on the chemical properties and morphological structure of polymeric coatings of guide wire for regular guiding catheter. METHODS: These techniques simulated the routine of guide wire reprocessing in many hemodynamic services in Brazil and other countries. Samples from three different manufacturers were verified by scanning electron microscopy and X-ray photoelectron spectroscopy. RESULTS: A single or double sterilization of the catheters with ethylene oxide was not associated with morphological or chemical changes. However, scanning electron microscopy images showed that the washing method was associated with rough morphological changes, including superficial holes and bubbles, in addition to chemical changes of external atomic layers of polymeric coating surfaces, as detected by the X-ray photoelectron spectroscopy method, which is compatible with extended chemical changes on catheter surfaces. CONCLUSION: The reprocessing of the catheters with ethylene oxide was not associated with morphological or chemical changes, and it seemed appropriate to maintain guide wire coating integrity. However, the method combining chemical cleaning with mechanical vibration resulted in rough anatomical and chemical surface deterioration, suggesting that this reprocessing method should be discouraged.

Effects of reprocessing on chemical and morphological properties of guide wires used in angioplasty / Efeitos do reprocessamento nas propriedades químicas e morfológicas de fios-guia usados em angioplastia

OBJECTIVE: To investigate the influence of the reprocessing technique of enzymatic bath with ultrasonic cleaning and ethylene oxide sterilization on the chemical properties and morphological structure of polymeric coatings of guide wire for regular guiding catheter. METHODS: These techniques simulated the routine of guide wire reprocessing in many hemodynamic services in Brazil and other countries. Samples from three different manufacturers were verified by scanning electron microscopy and X-ray photoelectron spectroscopy. RESULTS: A single or double sterilization of the catheters with ethylene oxide was not associated with morphological or chemical changes. However, scanning electron microscopy images showed that the washing method was associated with rough morphological changes, including superficial holes and bubbles, in addition to chemical changes of external atomic layers of polymeric coating surfaces, as detected by the X-ray photoelectron spectroscopy method, which is compatible with extended chemical changes on catheter surfaces. CONCLUSION: The reprocessing of the catheters with ethylene oxide was not associated with morphological or chemical changes, and it seemed appropriate to maintain guide wire coating integrity. However, the method combining chemical cleaning with mechanical vibration resulted in rough anatomical and chemical surface deterioration, suggesting that this reprocessing method should be discouraged.

OBJETIVO: Investigar a influência das técnicas de reprocessamento de banho enzimático com limpeza ultrassônica e a esterilização com óxido de etileno nas propriedades químicas e estruturas morfológicas de revestimentos poliméricos de fios-guia usados como guias em cateteres regulares. MÉTODOS: Estas técnicas simulam a rotina de processamento de fios-guia em muitos serviços de hemodinâmica do Brasil e de outros países. Amostras de três diferentes fabricantes foram verificadas por microscopia eletrônica de varredura e espectroscopia de fotoelétrons de raios-X. RESULTADOS: Uma única ou dupla esterilização dos cateteres com óxido de etileno não foi associada a mudanças químicas ou morfológicas. Contudo, imagens de microscopia eletrônica de varredura mostraram que o método de lavagem foi associado a intensas modificações morfológicas, incluindo bolhas e buracos superficiais, assim como mudanças nas ligações químicas das camadas atômicas externas do revestimento polimérico, conforme demonstrado por resultados de espectroscopia de fotoelétrons de raios-X, compatível com extensas modificações químicas induzidas por esse processo de lavagem. CONCLUSÃO: O reprocessamento dos fios-guia de cateteres com óxido de etileno não está associado a mudanças químicas e morfológicas dos mesmos e pode ser considerado adequado para manter a integridade destes materiais. Entretanto, o método que combina lavagem química com vibração mecânica resulta em intensas deteriorações anatômicas e químicas, sugerindo que esse método de processamento deve ser desencorajado.

Structure and properties of polypyrrole/bacterial cellulose nanocomposites.

An electrically conducting composite based on bacterial cellulose (BC) and polypyrrole (PPy) was prepared through in situ oxidative polymerization of pyrrole (Py) in the presence of BC membrane using ammonium persulfate (APS), as an oxidant. The electrical conductivity, morphology, mechanical properties and thermal stability of the composites obtained using APS (BC/PPy·APS) were evaluated and compared with BC/PPy composites prepared using as oxidant agent Iron III chloride hexahydrate (FeCl3·6H2O). The morphology of the BC/PPy·APS composites is characterized by spherical conducting nanoparticles uniformly distributed on the BC nanofiber surface, while the composites produced with FeCl3·6H2O (BC/PPy·FeCl3) is composed of a continuous conducting polymer layer coating the BC-nanofibers. The electrical conductivity of BC/PPy·FeCl3 was 100-fold higher than that found for BC/PPy·APS composites. In order to understand the site-specific interaction between PPy and BC functional groups, both composites were characterized by Fourier transform infrared (attenuated total reflectance mode) spectroscopy attenuation reflectance (FTIR-ATR) and X-ray photoelectron spectrometry (XPS). The affinity between functional groups of PPy·FeCl3 and BC is higher than that found for BC/PPy·APS composite. In addition, the tensile properties were also influenced by the chemical affinity of both components in the polymer composites.

AFM characterization of spin coated carboxylated polystyrene nanospheres/xyloglucan layers on mica and silicon.

Self-assembled nano-arrays have a potential application as solid-phase diagnostics in many biomedical devices. The easiness of its production is directly connected to manufacture cost reduction. In this work, we present self-assembled structures starting from spin coated thin films of carboxylated polystyrene (PSC) and xyloglucan (XG) mixtures on both mica and silicon substrates. AFM images showed PSC nanospheres on top of a homogeneous layer of XG, for both substrates. The average nanosphere diameter fluctuated for a constant speed and it was likely to be independent of the component proportions on the mixture within a range of 30-50% (v/v) PSC. It was also observed that the largest diameters were found at the center of the sample and the smallest at the border. The detected nanospheres were also more numerous at the border. This behavior presents a similarity to spin coated colloidal dispersions. We observed that the average nanosphere diameter on mica substrates was bigger than the nanosphere diameters obtained on top of silicon substrates, under the same conditions. This result seems to be possibly connected to different mixture-surface interactions.

Electronic structure and optical properties of an alternated fluorene-benzothiadiazole copolymer: interplay between experimental and theoretical data.

The donor-acceptor copolymer containing benzothiadiazole (electron acceptor), linked to functionalized fluorene (electron donor), [poly[9,9-bis(3'-(tert-butyl propanoate))fluorene-co-4,7-(2,1,3-benzothiadiazole)] (LaPPS40), was synthesized through the Suzuki route. The polymer was characterized by scanning electron microscopy, gel permeation chromatography, NMR, thermal analysis, cyclic voltammetry, X-ray photoelectron spectroscopy, UV-vis spectrometry, and photophysical measurements. Theoretical calculations (density functional theory and semiempirical methodologies) used to simulate the geometry of some oligomers and the dipole moments of molecular orbitals involved were in excellent agreement with experimental results. Using such data, the higher energy absorption band was attributed to the π-π* (S(0) → S(4)) transition of the fluorene units and the lower lying band was attributed to the intramolecular (ICT) (S(0) → S(1)) charge transfer between acceptor (benzothiadiazole) and donor groups (fluorene) (D-A structure). The ICT character of this band was confirmed by its solvatochromic properties using solvents with different dielectric properties, and this behavior could be well described by the Lippert-Mataga equation. To explain the solvatochromic behavior, both the magnitude and orientation of the dipole moments in the electronic ground state and in the excited state were analyzed using the theoretical data. According to these data, the change in magnitude of the dipole moments was very small for both transitions but the spatial orientation changed remarkably for the lower energy band ascribed to the ICT band.

Synthesis of TiO2 nanocrystals with a high affinity for amine organic compounds.

This article describes a different approach to the colloidal synthesis of TiO(2) nanocrystals using a polymer melt as a solvent. This approach allowed us to obtain a colloidal dispersion with a high degree of stability in a polymeric solvent, resulting in a transparent colloid. Using this method, it was possible to obtain the TiO(2) nanocrystal with Brønsted acid sites and polymer chains chemically anchored on the nanocrystal surface. The acid surface of those nanocrystals has the chemical property to react in the presence of amine organic compounds and to maintain the colloidal stability. In this way, TiO(2) nanocrystals were combined with a molecular probe containing amine functional groups such as polyaniline. Through the combination of the molecular probe and inorganic nanocrystals, we obtained a hybrid material with interesting chemical, optical, and electronic behavior, making it a promising material for photovoltaic, photochromic, and sensor devices.

Improving the osteointegration and bone-implant interface by incorporation of bioactive particles in sol-gel coatings of stainless steel implants.

In this study, we report a hybrid organic-inorganic TEOS-MTES (tetraethylorthosilicate-methyltriethoxysilane) sol-gel-made coating as a potential solution to improve the in vivo performance of AISI 316L stainless steel, which is used as permanent bone implant material. These coatings act as barriers for ion migration, promoting the bioactivity of the implant surface. The addition of SiO(2) colloidal particles to the TEOS-MTES sol (10 or 30 mol.%) leads to thicker films and also acts as a film reinforcement. Also, the addition of bioactive glass-ceramic particles is considered responsible for enhancing osseointegration. In vitro assays for bioactivity in simulated body fluid showed the presence of crystalline hydroxyapatite (HA) crystals on the surface of the double coating with 10mol.% SiO(2) samples on stainless steel after 30 days of immersion. The HA crystal lattice parameters are slightly different from stoichiometric HA. In vivo implantation experiments were carried out in a rat model to observe the osteointegration of the coated implants. The coatings promote the development of newly formed bone in the periphery of the implant, in both the remodellation zone and the marrow zone. The quality of the newly formed bone was assessed for mechanical and structural integrity by nanoindentation and small-angle X-ray scattering experiments. The different amount of colloidal silica present in the inner layer of the coating slightly affects the material quality of the newly formed bone but the nanoindentation results reveal that the lower amount of silica in the coating leads to mechanical properties similar to cortical bone.

Effect of protein solution components in the adsorption of Herbaspirillum seropedicae GlnB protein on mica.

The adsorption of proteins and its buffer solution on mica surfaces was investigated by atomic force microscopy (AFM). Different salt concentration of the Herbaspirillum seropedicae GlnB protein (GlnB-Hs) solution deposited on mica was investigated. This protein is a globular, soluble homotrimer (36kDa), member of PII-like proteins family involved in signal transducing in prokaryote. Supramolecular structures were formed when this protein was deposited onto bare mica surface. The topographic AFM images of the GlnB-Hs films showed that at high salt concentration the supramolecular structures are spherical-like, instead of the typical doughnut-like shape for low salt concentration. AFM images of NaCl and Tris from the buffer solution showed structures with the same pattern as those observed for high salt protein solution, misleading the image interpretation. XPS experiments showed that GlnB protein film covers the mica surface without chemical reaction.

Dewetting pattern and stability of thin xyloglucan films adsorbed on silicon and mica.

Thin polysaccharide films prepared with xyloglucan (XG), a neutral polysaccharide extracted from the seeds of Guibourtia hymenifolia were prepared by spin-coating and drop deposition under pH3, pH5 and pH12, on silicon and mica substrates. Atomic force microscopy (AFM) images show flat nanoporous matrices with additional grain-like structures on both mica and silicon for pH 3 and pH 5. However, X-ray photoelectron spectroscopy (XPS) and Auger spectra of these adsorbed biopolymers prepared under alkaline condition (pH 12) reveal that Na(+) ions from the solution interact with the mica substrate surface and with XG forming chemical bonds. Both XPS and Auger results suggest XG depolymerisation during adsorption, caused by an alkaline ss-base catalyzed degradation mechanism, which is consistent with the more basic character of the mica surface under these conditions. Thus, the polysaccharide diffusion is inhibited during dewetting due to the surface bonding. On the other hand, the interaction of Na(+) in solution with the silicon surface is weaker, favoring its interaction with the polysaccharide, conserving the overall polymer structure of XG and allowing the biopolymer to slip and diffuse during dewetting, forming the final branched fractal structure.

Intercalation of an oxalatooxoniobate complex into layered double hydroxide and layered zinc hydroxide nitrate.

A Zn/Al layered double hydroxide with molar ratio of 3 was prepared by coprecipitation in alkaline pH and used as a matrix to intercalate the ionic complex diaquadioxalatooxoniobate(V) (DDON), derived from NH(4)[NbO(C(2)O(4))(2)(H(2)O)(2)]2H(2)O. In a similar way, the layered zinc hydroxide nitrate, Zn(5)(OH)(8)(NO(3))(2)2H(2)O, was synthesized, preexpanded with azelate ions ((-)OOC(CH(2))(7)COO(-)), and then intercalated with the niobium complex. For both layered matrices, the results from X-ray powder diffractometry, Fourier transform infrared spectroscopy, and thermal analysis (TG/s-DTA) indicate the presence of the oxalate ion. In addition, results from X-ray photoelectron and Raman spectroscopy indicate the presence of the niobium center bonded to oxygen atoms. Finally, diffuse reflectance UV-vis spectroscopy suggests that the niobium centers are coordinated to oxalate ions. This is the first report of the intercalation of niobium into a layered matrix.