Niobium, in fact, is an essential element for Brazil. Their applications are so many and so special that they put it as one of the subjects treated by the wikiLeaks site as strategic and that it should be treated in the USA. It is one of the elements most exported by Brazil and is mainly used in the production of special alloys for use in gas pipelines, air turbines, among other applications. It is believed that niobium-based materials can be obtained for applications with higher added value and in equally strategic areas. Research to obtain active and selective drugs, materials to maximize the use of renewable energy, and new nanostructured materials to improve the performance of different components are ongoing and promise a revolution for the next few years.

A synthetic niobia was modified by treatment with hydrogen peroxide to be used as a catalyst for converting glycerol into petrochemical compounds. The catalytic properties of niobium oxyhydroxide were obtained by generating acidic and oxygenated groups (peroxo groups) on the solid surface. Compounds like ethers and allyl alcohol were obtained. A very active H2O2-modified catalyst showed high activity for the oxidation and dehydration of 91% of glycerol conversion using H2O2 and 46% of allyl alcohol selectivity in volatile phase. The product was analyzed by gas chromatography-mass spectrometry (GC-MS), thermogravimetry-mass spectrometry (TGA-MS) and nuclear magnetic ressonance (NMR). These results strongly suggest that the reactions involve acid and oxidizing species generated after the reaction of niobium with H2O2. 1H and 13C multidimensional NMR spectroscopy confirmed the results obtained with GC-MS and showed the production of several compounds after niobia treatment.

A magnetic catalyst (sample MCat) consisting of KI supported on a mixture of silica and maghemite (γ-Fe2O3) was prepared and used in the transesterification reaction for the synthesis of biodiesel. The energy dispersive X-ray spectrum of the catalyst showed signals due to Si, Fe, K, and I. Powder X-ray diffraction data revealed the amorphous nature of the SiO2 and the duly impregnation of the support with KI. 57Fe Mössbauer spectroscopy and magnetization measurements confirmed the ferrimagnetic iron oxide in the catalyst to be maghemite. N2 adsorption-desorption data indicated that the silica is mesoporous with a specific area of 352 m2 g-1, enabling the impregnation of 40 and 11 wt.% of KI and maghemite, respectively, according to the chemical composition obtained by the X-ray fluorescence measurements. The MCat was found to be efficient in the transesterification reaction in the macaúba and soybean oils. The MCat was easily removed from the reaction medium, with a hand magnet, and efficiently reused for more four consecutive reaction cycles. The good catalytic activity along with its magnetic behavior, high chemical stability and recyclability make the MCat a suitable material for the green synthesis of biodiesel.

Integrins are transmembrane glycoprotein receptors that regulate cell-matrix interactions, thus functioning as sensors from the environment. They also act as cell adhesion molecules that are responsible for the maintenance of the normal epithelial phenotype. Some studies have reported a correlation between carcinogenesis and changes in integrin expression, especially β1 integrin, however its role in prostate cancer (PC) is unclear. The aim of our study was to evaluate the expression of β1 integrin in localized PC and to correlate the pattern of expression with recurrence after surgical treatment. Methods For this case-control study, we retrospectively selected surgical specimens from 111 patients with localized PC who underwent radical prostatectomy. Recurrence was defined as a PSA level exceeding 0.2ng/mL after surgery, and the median follow-up was 123 months. Integrin expression was evaluated by immunohistochemistry in a tissue microarray containing two samples from each tumor. We employed a semiquantitative analysis and considered a case as positive when the expression was strong and diffusely present. Results: There was a loss of 11 cases during the tissue micro array assembling. β1 expression was positive in 79 of the 100 evaluated cases (79%). The univariate and multivariate analyses showed that the negative expression of β1 integrin was associated with biochemical recurrence (p = 0.047) and time to recurrence after radical prostatectomy (p = 0.023). When β1 was negative, the odds ratio for recurrence was 2.78 times higher than that observed in the positive cases [OR = 2.78, p = 0.047, IC 95% (1.01-7.66)]. Conclusions: The loss of β1 integrin immune expression was correlated with biochemical recurrence in patients treated with radical prostatectomy for localized PC.

A review of most of the reported studies on the use of iron oxides as catalyst in specific processes, namely Haber-Bosch reaction, Fischer-Tropsch synthesis, Fenton oxidation and photolytic molecular splitting of water to produce gaseous hydrogen, was carried out. An essential overview is thus presented, intending to address the fundamental meaning, as well as the corresponding chemical mechanisms, and perspectives on new technological potentialities of natural and synthetic iron oxides, more specifically hematite (α-Fe2O3), goethite (α-FeOOH), magnetite (Fe3O4) and maghemite (γ-Fe2O3), in heterogeneous catalysis.

Ferro é um elemento versátil que forma várias fases com diferentes estados de oxidação e estruturas, tais como Feº, FeO, Fe3O4, γ-Fe2O3, α-Fe2O3 e FeOOH. Todas estas fases têm propriedades físico-químicas únicas que podem ser usadas para diferentes aplicações. Neste trabalho, descreve-se o uso de diferentes compostos de ferro, sintéticos e também naturais ou de rejeitos, em aplicações ambientais e tecnológicas. Duas áreas principais de pesquisa são descritas. A primeira é relacionada às estratégias para aumentar a reatividade de fases de ferro pela formação de compósitos Feº/Fe óxido e pela introdução de novos metais na estrutura de óxidos de ferro para promover novas reações superficiais. A segunda área de pesquisa é o uso das propriedades magnéticas de algumas fases de ferro para produzir materiais magnéticos versáteis com aplicações focadas em adsorção, catálise e emulsões.

Iron is a versatile element forming several phases with different oxidation states and structures, such as Feº, FeO, Fe3O4, γ-Fe2O3, α-Fe2O3 and FeOOH. All these phases have unique physicochemical properties which can be used for different applications. In this work, it is described the use of different iron compounds, synthetic and also from natural and waste sources, in environmental and technological applications. Two main research areas are described. The first one is related to strategies to increase the reactivity of Fe phases, mainly by the formation of Feº/iron oxide composites and by the introduction of new metals in the iron oxide structure to promote new surface reactions. The second area is the use of the magnetic properties of some iron phases to produce versatile magnetic materials with focus in adsorption, catalysis and emulsions.

Um novo material à base de nióbia (Nb2O5) foi sintetizado e quimicamente modificado para oxidar compostos orgânicos em meio aquoso, na presença de H2O2. A nióbia foi modificada por dopagem com tungstênio e também tratamento com H2O2 com o intuito de potencializar suas propriedades oxidativas. A investigação dos produtos gerados pela oxidação do azul de metileno, usando a técnica de espectroscopia de massas com ionização por eletrospray (ESI-MS), mostrou que o corante foi sucessivamente oxidado produzindo diferentes compostos intermediários. A sucessiva hidroxilação durante o processo oxidativo indica a alta reatividade dos radicais hidroxilas que são gerados, envolvendo H2O2 sobre a superfície do grão de nióbia dopada com W. Estes resultados sugerem fortemente que o H2O2 pode regenerar in situ o grupo peróxido, permanecendo ativo no sistema.

A novel material based on niobia (Nb2O5) was synthesized to oxidize an organic compound in aqueous medium in the presence of H2O2 after chemical modifications. Niobia was modified by doping with tungsten and also treating with H2O2 in order to maximize the oxidative properties of this oxide. The analysis of the products from methylene blue dye oxidation with electrospray ionization mass spectrometry (ESI-MS) showed that the dye was successively oxidized to different intermediate compounds. The successive hydroxylation during this oxidation strongly suggests that highly reactive hydroxyl radicals are generated involving H2O2 on the W-doped niobia grain surface. These results strongly suggest that the H2O2 can regenerate in situ the peroxo group remaining active the system.

Neste estudo a celulose obtida da palha de feijão foi utilizada para produzir um material hidrofóbico (acetato de celulose) para ser avaliado como absorvente de óleo. Nas reações de acetilação foram utilizados anidrido acético e dois catalisadores, a piridina (PY) e N-bromossuccinimida (NBS). Os materiais produzidos foram caracterizados por espectroscopia na região do infravermelho médio, microscopia eletrônica de varredura, difratometria de raios-X e análise elementar. O NBS mostrou-se mais eficiente que a PY e, seu uso resultou em materiais com maiores quantidades de grupos acetatos, mais hidrofóbicos e com maiores capacidades de absorção de óleo de soja.

In this work, cellulose from beans straw was used to produce a more hydrophobic material (cellulose acetate) for use as oil absorbent. Acetic anhydride was used in the reactions with two catalysts, pyridine (PY) and N-bromosuccinimide (NBS). The materials produced were characterized by infrared spectroscopy, scanning electron microscopy, X-ray diffraction and elemental analysis. NBS proved more efficient than PY, with the resulting materials containing higher number of acetate groups, being more hydrophobic and with higher capacity to absorb soybean oil.

Currently, public policy has encouraged innovation in universities and also transference of technology to the industry. Another important stage to be considered would be the registration or filing of a patent and the economical viability study. Government programs, such as the innovation incentive program, among others, should facilitate popularization and promote interest by industry. In this work we described the steps, from the conception of the idea to the scale up going through its interest by the industry. The case study is about the glycerol conversion utilizing modified niobia as catalysts.

PURPOSE: Tumor banks have the primary responsibility for collecting, cataloging, storing and disseminating samples of tissues, cells and fluids, which are used by researchers to identify diagnostic molecular markers, prognostic indicators and therapeutic targets. The objective of this review was to describe a simple, reliable and reproducible protocol for obtaining and storing samples of urological tumors. MATERIALS AND METHODS: Urogenital tumor tissues were collected by the surgeons from the Urology Division of University of Sao Paulo Medical School. The obtained surgical specimens were immediately placed in liquid nitrogen, dry ice or in a tube containing RNAlater ®, and then stored by cryopreservation (-80°C). A mirror fragment was fixed in 10% formalin processed routinely and embedded in Paraplast®. RESULTS: We developed a protocol for the collection, cataloging, storage, conservation and use of tumor samples. During a period of one year the Urological Tumor Bank of the Urology Division stored 274 samples of prostate, bladder, kidney, penis and testicle tumors of different histological types, 74 urine and 271 serum samples. CONCLUSIONS: Having biological materials characterized and available along with the clinical patient information provides an integrated portrait of the patients and their diseases facilitating advances in molecular biology. It also promotes the development of translational research improving methods of diagnosis and cancer treatment.

A oligomerização do glicerol catalisada por ácido foi investigada por espectrometria de massas com ionização electrospray, em modo de íon positivo, i.e. ESI(+)-MS. Os dados de ESI(+)-MS revelaram que a 280 °C e em meio ácido (pH 2), glicerol sofre sucessivas condensações intermoleculares para produzir espécieis oligoméricas, i.e. [(glicerol)n - (n - 1) H2O] (n = 2-5). Esses resultados de ESI(+)-MS, em associação com as informações obtidas por análises de infravermelho e RMN de ¹H e 13C, indicaram que esses oligômeros sofrem desidratações para formar uma mistura de produtos, composta principalmente por compostos cíclicos, assim como alquenos e derivados carbonílicos (aldeídos e cetonas).

Acid-catalyzed oligomerization of glycerol was investigated by direct infusion electrospray ionization mass spectrometry in the positive ion mode, i.e. ESI(+)-MS. The ESI(+)-MS data revealed that at 280 ºC and in acidic medium (pH 2), glycerol undergoes successive intermolecular condensations to produce oligomeric species, i.e. [(glycerol)n - (n - 1) H2O] (n = 2-5). These ESI(+)-MS data, in association with the information provided by IR, ¹H and 13C NMR analyses, indicated that these oligomers undergo intramolecular dehydrations to form miscellaneous products comprised mainly by cyclic compounds as well as alkenes and carbonylic derivatives (aldehydes and ketones).

In this work, composites based on activated carbon/iron oxide (AC/Fe) were prepared in two different proportions (AC/Fe 5/1 and 1/1) and evaluated in the removal of the organic dye methylene blue (MB). Physical-chemical properties of the composites were determined by X-ray diffraction (XRD), adsorption/dessorption of N2 isotherm, temperature programmed reduction (TPR) and scanning electron microscopy (SEM). Results showed that goethite (α- FeOOH), with nanometer particle size, was formed over carbon surface for both composites. These materials showed high efficiency to remove MB from solution by combined adsorption and oxidation process. The AC/Fe 1/1 showed to be more active in (MB) oxidation then AC/Fe 5/1.

In this work synthetic niobia was used to promote the oxidation of methylene blue dye in aqueous medium. The niobia was characterized by N2 adsorption/desorption, XRD and TG measurements. The presence of reactive species on the niobia surface strongly increased the oxidation rate of the methylene blue dye. The reaction mechanism was studied by ESI-MS suggesting that the oxidation of the organic dye involve oxidizing species generated mainly after previous treatment with H2O2. It can be observed that the catalyst is a good material in the activation of gas (atmospheric oxygen) or liquid (hydrogen peroxide) oxidant agent with a total discoloration of the dye solution after only 1 h of reaction.

In this work were prepared composites of iron oxide and carbonaceous materials in two different weight proportions (Carbon/Fe 1/1 and 1/2). The physico-chemical properties of the composites were determined by temperature programmed reduction (TPR), adsorption/dessorption of N2, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and pulse titration H2. The XRD and XPS analysis showed a cubic iron oxide phase, identified as maghemite, formed over the carbon surface. The particle size of maghemite showed to be within 10-30 nm. Carbon/Fe 1/2 was the most active in MB removal kinetics and ESI-MS studies showed that MB removal by both composites leads to oxidized intermediates.

Anion adsorption/desorption dynamics was studied as individual processes on surface of particles of a gibbsitic clay. The data suggest a remarkable gibbsite role as nitrate leaching retardant in soil. The opposite behavior of gibbsite towards adsorption/desorption of silicate and phosphate suggests the need of an adequate compromise solution regarding interval and rate applications of anions in cultivated gibbsitic soils. The high P adsorption verified in pH values lower than that reported for the point of zero charge of synthetic Al-hydroxides implies that this process takes place in pedogenic gibbsites through inner sphere complexation.