Biocides and techniques for their encapsulation: a review.

Biocides are compounds that are broadly used to protect products and equipment against microbiological damage. Encapsulation can effectively increase physicochemical stability and allow for controlled release of encapsulated biocides. We categorized microencapsulation into coacervation, sol-gel, and self-assembly methods. The former comprises internal phase separation, interfacial polymerization, and multiple emulsions, and the latter include polymersomes and layer-by-layer techniques. The focus of this review is the description of these categories based on their microencapsulation methods and mechanisms. We discuss the key features and potential applications of each method according to the characteristics of the biocide to be encapsulated, relating the solubility of biocides to the capsule-forming materials, the reactivity between them and the desired release rate. The role of encapsulation in the safety and toxicity of biocide applications is also discussed. Furthermore, future perspectives for biocide applications and encapsulation techniques are presented.

Industrial and agroindustrial wastes: an echotechnological approach to the production of supported photocatalysts.

Agroindustrial wastes (rice husk, exhausted bark acacia, and tobacco dust) and foundry sands from the iron foundry industry were employed as a support source for photocatalysts. TiCl4 was used as the titanium precursor in the preparation of the supported photocatalysts. The solids were characterized by scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX), diffuse reflectance spectroscopy over the ultraviolet range (DRS-UV), X-ray diffraction (XRD), small-angle X-ray scattering (SAXS), nitrogen adsorption-desorption at -196 °C and zeta potential (ZP) measurements. The systems were evaluated for the photodegradation of rhodamine B (RhB). Among the tested systems, the highest percentage of dye degradation was reached by the catalyst prepared with foundry sand supports, with values of 65% under ultraviolet and 39% under visible radiation, whereas under the same conditions, the catalyst prepared with rice husk showed the best photocatalytic performance among the samples prepared with agroindustrial wastes with values of 43% under ultraviolet and 38% under visible radiation. Strong Spearman's correlations among the photocatalytic activity, the zeta potential (ζp>0.900) and the band gap energy (ζp>0.895) were observed. Exploratory tests with tap water samples revealed that the system may be sensitive to other analytes present in these environmental samples.

Correlating the Morphological Properties and Structural Organization of Monodisperse Spherical Silica Nanoparticles Grown on a Commercial Silica Surface.

A variety of nanosilicas have been widely used to fabricate rough surfaces with superhydrophobic and superhydrophilic properties. In this context, we prepared mixed silica and mixed nanosilica that were generated by the growth and self-assembly of synthesized monodisperse silica nanospheres (11-30 nm, 363 m(2) g(-1) ) on the surface of Sylopol-948 and Dispercoll S3030 by using a base-catalyzed sol-gel route. Using this process, the interactions and hierarchical structure between the nano- and microsized synthesized silica particles were studied by changing the amount of tetraethoxysilane. The resulting materials were characterized by BET analysis, small-angle X-ray scattering (SAXS), dynamic light scattering, FTIR spectroscopy, and SEM. The mixed silica presented a higher specific surface area (326 m(2) g(-1) ), a six-fold higher percentage of (SiO)6 (44-68 %), and a higher amount of silanol groups (14.0-30.7 %) than Sylopol-948 (271 m(2) g(-1), 42.6 %, and 12.5 %, respectively). The morphological and hierarchical structural differences in the silica nanoparticles synthesized on the surface of commercial silica (micrometric or nanometric) were identified by SAXS. Mixed micrometric silica exhibited a higher degree of structural organization between particles than mixed nanosilica.

Infrared and Raman spectroscopic characterization of some organic substituted hybrid silicas.

Nine hybrid silicas bearing the organic substituent groups methyl, octyl, octadecyl, vinyl, phenyl, mercaptopropyl, isocyanatopropyl, chloropropyl and glycidoxypropyl were synthesized by an acid-catalyzed, hydrolytic sol-gel process. The resulting solid materials were characterized by their absorbance and attenuated total reflection (ATR) IR and Raman spectra. The latter technique proved to be particularly useful in the identification of the organic moieties in the hybrid silicas. The effect of the presence of the organic groups on the silica networks was also investigated - there were increases observed in both the SiOSi bond angles and bond lengths. Moreover, deconvolution of the IR-active antisymmetric SiOSi stretching bands permitted detection of the four- and six-membered siloxane rings present in the silicas. There proved to be a greater number of four-membered rings on the surfaces of the particles. Both IR and Raman spectroscopy proved to be invaluable in the characterization of these hybrid materials.

Metal and hydrocarbon behavior in sediments from Brazilian shallow waters drilling activities using nonaqueous drilling fluids (NAFs).

The impact of drilling oil activities in the Brazilian Bonito Field/Campos Basin (Rio de Janeiro) shell drilling (300 m) using nonaqueous fluids (NAFs) was investigated with respect to Al, Fe, Mn, Ba, Co, Pb, Cu, As, Hg, Cr, Ni, Zn, Cd, V, and aliphatic and polynuclear aromatic hydrocarbons concentrations in the sediment. Sampling took place in three different times during approximately 33 months. For the metals Al, As, Co, Cr, Cu, Cd, Fe, Ni, Mn, V, and Zn, no significant variation was observed after drilling activities in most of the stations. However, an increase was found in Ba concentration--due to the drilling activity--without return to the levels found 22 months after drilling. High Ba contents was already detected prior to well drilling, probably due to drilling activities in other wells nearby. Hydrocarbon contents also suggest previous anthropogenic activities. Aliphatic hydrocarbon contents were in the range usually reported in other drilling sites. The same behavior was observed in the case of polyaromatic hydrocarbons. Nevertheless, the n-alkane concentration increased sharply after drilling, returning almost to predrilling levels 22 months after drilling activities.

Combining silica-based adsorbents and SPME fibers in the extraction of the volatiles of beer: an exploratory study.

A series of silica-based materials were employed as sorbents within solid-phase microextraction vials. The aim of the study was to evaluate the effect of an additional phase on the distribution of the volatile and less volatile analytes. The adsorption of six probe molecules, namely isoamyl acetate, ethyl hexanoate (ethyl caproate), phenylethyl alcohol, ethyl octanoate (ethyl caprilate), 2-phenylethyl acetate, and ethyl decanoate, was monitored by detecting the desorbed amount on a DVD-CAR-PDMS fiber from Pilsen beer. The microextraction process involved the presence of different silica-based phases produced via different methods: xerogel produced by hydrolytic and non-hydrolytic routes, aerogel, pyrogenic, and precipitated silica. The resulting data are discussed in correlation with sorbent texture properties (specific area and pore diameter). The modification of silica with alkyl groups also affects the preconcentrated amount of the target molecules in the headspace. The presence of sorbents was shown to affect the analyte signal more than the addition of NaCl or the use of ultrasound.

Octadecylsilane-modified silicas in the adsorption of toluene.

A series of octadecylsilane-modified silicas were prepared by sol-gel and grafting methods. Carbon contents and octadecyl chain conformations were shown to depend on the preparative route. Grafting engenders a low carbon content and a liquid-like chain conformation, while the sol-gel method affords a much higher carbon content and a crystalline conformation. The relationships between the toluene adsorption of the hybrid silicas and their chain conformations, their carbon contents and their textural characteristics are discussed. These sorbents, when used in combination with ultraviolet diffuse reflectance spectroscopy (UV DRS), can be employed as a rapid screening method for detection of aromatic compounds in water and air environmental matrices.

Supported ionic liquid phase rhodium nanoparticle hydrogenation catalysts.

Rh(0) nanoparticles (ca. 4 nm) dispersed in an ionic liquid (1-n-butyl-3-methylimidazolium tetrafluoroborate) were immobilized within a silica network, prepared by the sol-gel method. The effect of the sol-gel catalyst (acid or base) on the encapsulated ionic liquid and Rh(0) content, on the silica morphology and texture, and on the catalyst alkene hydrogenation activity was investigated. The Rh(0) content in the resulting xerogels (ca. 0.1 wt% Rh/SiO(2)) was shown to be independent of the sol-gel process. However, acidic conditions afforded higher contents of encapsulated ionic liquid and xerogels with larger pore diameters, which in turn might be responsible for the higher catalyst activity in hydrogenation of the alkenes.

Evaluation of lead desorption from cement matrices.

Desorption of lead immobilized into cement and concrete matrices was evaluated in the pH range between 4 and 8 within a period of 2 h to 15 days. Lead-desorbed content in aqueous milieu was monitored by Graphite Furnace Atomic Absorption Spectroscopy, while matrices were directly analyzed by X-ray photoelectronic spectroscopy or Rutherford Backscattering spectrometry. For low pH, higher Pb desorption was observed, about 5-7 times higher than that measured in the case of concrete matrices. The inclusion of polyvinyl alcohol as a matrix modifier was evaluated through a factorial design. Polymer inclusion yielded a reduction in Pb desorption, but its effect cannot be justified in terms of the ability of this polymer to chelate the metal. The resulting modified matrices did not present toxicity to Daphnia magna.

Octadecylsilane hybrid silicas prepared by the sol-gel method: morphological and textural aspects.

A series of octadecylsilane-modified silicas was prepared by the sol-gel method through the hydrolysis and cocondensation of tetraethylorthosilicate (TEOS) with octadecyltriethoxysilane (ODS). The ODS:TEOS ratio was varied between 0:100 and 100:0. The resulting carbon content was between 2.5 and 53.4%. In the case of pure ODS, the resulting silica presented 68.6% of C. Hybrid silicas were characterized by scanning electron microscopy, energy dispersive X-ray spectroscopy, and (29)Si nuclear magnetic resonance spectroscopy. Spheres of ca. 0.5-1.0 microm were obtained in the case of hydrolysis of pure TEOS. The combination of ODS:TEOS ratio yielded systems combining spherical and lamellar patterns zones. Monitoring the particle growth, it seems that spherical particles grow around lamellar zones, these latter concentrating the organosilicon moieties. The degree of cross-linking of ODS moieties was shown to be dependent on the ODS addition time and stirring speed.