Adição experimental de novos materiais às argilas da região do polo cerâmico de Santa Gertrudes (SP)

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

Aplicação de água residuária tratada de suinocultura em solo cultivado com soja

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Diagnose nutricional da goiabeira

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Influência da variação sazonal de atributos de fertilidade do solo sobre a biomassa microbiana em uma cronosseqüencia de plantio de palma de óleo (Elaeis oleifera (Kunth) Cortés) no Nordeste Paraense

O Brasil possui cerca de 32 milhões de hectares de áreas com aptidão para a expansão da cultura da palma de óleo e mais de 90% destas estão na Amazônia. Há necessidade de compreender a interação de novos plantios e de seu desenvolvimento com o meio ambiente. Este estudo foi conduzido em plantios comerciais da empresa Dendê do Pará SA (DENPASA) em Castanhal – Pará e avaliou o efeito da variação sazonal da precipitação sobre a fertilidade do solo e desta sobre a biomassa microbiana do solo em uma cronosseqüencia de plantios de palma de óleo com 5, 8 e 12 anos e floresta secundária. Foram mensurados/estimados e correlacionados os atributos do solo carbono da biomassa microbiana (C_BMS), carbono total (C_TOTAL), nitrogênio (N_TOTAL), respiração basal (RBS), quociente metabólico (qCO₂), relação carbono da biomassa microbiana/ carbono total (C_BMS:C_TOTAL), relação carbono/nitrogênio (C/N), umidade gravimétrica (Ug), fósforo (P), potássio (K), cálcio (Ca), magnésio (Mg), alumínio (Al), capacidade de troca efetiva de cátions (CTC) e saturação por alumínio (m). O C_BMS foi o atributo mais sensível para diferenciar as áreas do estudo e os períodos seco e chuvoso. Os atributos químicos de fertilidade do solo e a biomassa microbiana do solo apresentaram correlações significativas mais fortes e em maior número no período chuvoso. Os índices microbianos qCO₂ e C_BMS:C_TOTAL comprovaram que áreas de plantio convencional podem ser relativamente eficientes em relação à dinâmica do C em comparação a área de floresta secundária.

Outlining precision boundaries among areas with different variability standards using magnetic susceptibility and geomorphic surfaces

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

Liberação controlada de nutrientes e novos sistemas para avaliação de espécies químicas empregadas na fertilização

Pós-graduação em Química - IQ

Validation of a HPLC method for determination of glutamine in food additives using post-column derivatization

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Umidade na folha de amoreira (Morus sp.) em ambientes de armazenamento

Mulberry leaves (IZ 56/4 cultivar) in the pos-harvest, had been taken to the laboratory and submitted to six storage environments (8 hours in open ambient-O, 8 hours in cover ambientC, 1hO/7hC, 2hO/6hC, 3hO/5hC and 4hO/4hC), aiming to evaluate moisture exchange capacity . It was utilized the experimental design split plot with five replications (blocks), six principal treatments (parcels) and nine secondary treatments (sub parcels, weighing of hour in hour, of 08h00min. until 16h00min.). In the period of eight hours of experimentation mulberry leaves moisturedevreased in all the ambients evaluated. However, for cover leaves with wet cloth, for all periods, the water purport (74,63%) was maintained close to the original value (08h00min.- 76,07%), demonstrating the efficiency technique in the conservation of the humidity of leaves for feeding silkworm.

Determinação de vanádio em águas usando a técnica de difusão em filmes finos por gradientes de concentração

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Hb S-Sao Paulo: A new sickling hemoglobin with stable polymers and decreased oxygen affinity

Hb S-Sao Paulo (SP) [HBB:c.20A > T p.Glu6Val: c.196A > G p.Lys65Glu] is a new double-mutant hemoglobin that was found in heterozygosis in an 18-month-old Brazilian male with moderate anemia. It behaves like Hb S in acid electrophoresis, isoelectric focusing and solubility testing but shows different behavior in alkaline electrophoresis, cation-exchange HPLC and RP-HPLC. The variant is slightly unstable, showed reduced oxygen affinity and also appeared to form polymers more stable than the Hb S. Molecular dynamics simulation suggests that the polymerization is favored by interfacial electrostatic interactions. This provides a plausible explanation for some of the reported experimental observations. (C) 2012 Elsevier Inc. All rights reserved.

Isolation, enzymatic characterization and antiedematogenic activity of the first reported rattlesnake hyaluronidase from Crotalus durissus terrificus venom

A hyaluronidase (CdtHya1) from Crotalus durissus terrificus snake venom (CdtV) was isolated and showed to exhibit a high activity on hyaluronan cleavage. However, surveys on this enzyme are still limited. This study aimed at its isolation, functional/structural characterization and the evaluation of its effect on the spreading of crotoxin and phospholipase A(2) (PLA(2)). The enzyme was purified through cation exchange, gel filtration and hydrophobic chromatography. After that, it was submitted to a reverse-phase fast protein liquid chromatography (RP-FPLC) and Edman degradation sequencing, which showed the first N-terminal 44 amino acid residues whose sequence evidenced identity with other snake venom hyaluronidases. CdtHya1 is a monomeric glycoprotein of 64.5 kDa estimated by SDS-PAGE under reducing conditions. It exhibited maximum activity in the presence of 0.2 M NaCl, at 37 degrees C, pH 5.5 and a specificity to hyaluronan higher than that to chondroitin-4-sulphate, chondroitin-6-sulphate or dermatan. Divalent cations (Ca2+ and Mg2+) and 1 M NaCl significantly reduced the enzyme activity. The specific activity of CdtHya1 was 5066 turbidity reducing units (TRU)/mg, against 145 TRU/mg for the soluble venom, representing a 34.9-fold purification. The pure enzyme increased the diffusion of crotoxin and PLA (2) through mice tissues. CdtHya1 (32 TRU/40 mu L) potentiated crotoxin action, as evidenced by mice death, and it decreased the oedema caused by subplantar injections of buffer, crotoxin or PLA(2), thus evidencing the relevance of hyaluronidase in the crotalic envenoming. This work yielded a highly active antiedematogenic hyaluronidase from CdtV, the first one isolated from rattlesnake venoms. (C) 2012 Elsevier Masson SAS. All rights reserved.

Estimating subsoil resistance to nitrate leaching from easily measurable pedological properties

Leaching of nitrate (NO3-) can increase the groundwater concentration of this anion and reduce the agronomical effectiveness of nitrogen fertilizers. The main soil property inversely related to NO3- leaching is the anion exchange capacity (AEC), whose determination is however too time-consuming for being carried out in soil testing laboratories. For this reason, this study evaluated if more easily measurable soil properties could be used to estimate the resistance of subsoils to NO3- leaching. Samples from the subsurface layer (20-40 cm) of 24 representative soils of São Paulo State were characterized for particle-size distribution and for chemical and electrochemical properties. The subsoil content of adsorbed NO3- was calculated from the difference between the NO3- contents extracted with 1 mol L-1 KCl and with water; furthermore, NO3- leaching was studied in miscible displacement experiments. The results of both adsorption and leaching experiments were consistent with the well-known role exerted by AEC on the nitrate behavior in weathered soils. Multiple regression analysis indicated that in subsoils with (i) low values of remaining phosphorus (Prem), (ii) low soil pH values measured in water (pH H2O), and (iii) high pH values measured in 1 moL L-1 KCl (pH KCl), the amounts of surface positive charges tend to be greater. For this reason, NO3- leaching tends to be slower in these subsoils, even under saturated flow condition.

Processi di biorefining per l'estrazione di secondary chemical building blocks da sottoprotti dell'agro-industria

Phenol and cresols represent a good example of primary chemical building blocks of which 2.8 million tons are currently produced in Europe each year. Currently, these primary phenolic building blocks are produced by refining processes from fossil hydrocarbons: 5% of the world-wide production comes from coal (which contains 0.2% of phenols) through the distillation of the tar residue after the production of coke, while 95% of current world production of phenol is produced by the distillation and cracking of crude oil. In nature phenolic compounds are present in terrestrial higher plants and ferns in several different chemical structures while they are essentially absent in lower organisms and in animals. Biomass (which contain 3-8% of phenols) represents a substantial source of secondary chemical building blocks presently underexploited. These phenolic derivatives are currently used in tens thousand of tons to produce high cost products such as food additives and flavours (i.e. vanillin), fine chemicals (i.e. non-steroidal anti-inflammatory drugs such as ibuprofen or flurbiprofen) and polymers (i.e. poly p-vinylphenol, a photosensitive polymer for electronic and optoelectronic applications). European agrifood waste represents a low cost abundant raw material (250 millions tons per year) which does not subtract land use and processing resources from necessary sustainable food production. The class of phenolic compounds is essentially constituted by simple phenols, phenolic acids, hydroxycinnamic acid derivatives, flavonoids and lignans. As in the case of coke production, the removal of the phenolic contents from biomass upgrades also the residual biomass. Focusing on the phenolic component of agrifood wastes, huge processing and marketing opportunities open since phenols are used as chemical intermediates for a large number of applications, ranging from pharmaceuticals, agricultural chemicals, food ingredients etc. Following this approach we developed a biorefining process to recover the phenolic fraction of wheat bran based on enzymatic commercial biocatalysts in completely water based process, and polymeric resins with the aim of substituting secondary chemical building blocks with the same compounds naturally present in biomass. We characterized several industrial enzymatic product for their ability to hydrolize the different molecular features that are present in wheat bran cell walls structures, focusing on the hydrolysis of polysaccharidic chains and phenolics cross links. This industrial biocatalysts were tested on wheat bran and the optimized process allowed to liquefy up to the 60 % of the treated matter. The enzymatic treatment was also able to solubilise up to the 30 % of the alkali extractable ferulic acid. An extraction process of the phenolic fraction of the hydrolyzed wheat bran based on an adsorbtion/desorption process on styrene-polyvinyl benzene weak cation-exchange resin Amberlite IRA 95 was developed. The efficiency of the resin was tested on different model system containing ferulic acid and the adsorption and desorption working parameters optimized for the crude enzymatic hydrolyzed wheat bran. The extraction process developed had an overall yield of the 82% and allowed to obtain concentrated extracts containing up to 3000 ppm of ferulic acid. The crude enzymatic hydrolyzed wheat bran and the concentrated extract were finally used as substrate in a bioconversion process of ferulic acid into vanillin through resting cells fermentation. The bioconversion process had a yields in vanillin of 60-70% within 5-6 hours of fermentation. Our findings are the first step on the way to demonstrating the economical feasibility for the recovery of biophenols from agrifood wastes through a whole crop approach in a sustainable biorefining process.

EPR-Spektroskopie zur Untersuchung von Struktur und Dynamik in Polymer-Ton-Nanokompositen

Ziel der vorliegenden Arbeit war die Untersuchung von Struktur und Dynamik in Polymer-Ton-Nanokompositen mittels EPR-Spektroskopie; damit sollten ein Beitrag zur Analyse der Tensidschicht in solchen Systemen geleistet und die Ergebnisse anderer Messmethoden ergänzt werden. Die Tensidschicht in Polymer-Ton-Nanokompositen nimmt großen Einfluss auf das System, denn sie bestimmt die Wechselwirkung zwischen Ton und Polymer: Damit hydrophiler Ton gut mit hydrophobem Polymer (hier Polystyrol) mischbar ist, muss das Schichtsilikat zunächst mit Tensiden organisch-modifiziert werden; dies geschieht durch Kationenaustausch der Natriumionen im Ton gegen Tenside. Um mit Hilfe der EPR einen Einblick in die Tensidschicht zu gewinnen, muss etwa 1% der zur Tonmodifizierung eingesetzten Amphiphile spinmarkiert sein. So gelang es im Rahmen dieser Arbeit, Tenside mit verschiedenen Kopfgruppen, nämlich Trimethylammonium- bzw. Trimethylphosphoniumtenside, zu synthetisieren und sie an verschiedenen Positionen ihrer hydrophoben Alkylkette mit einem Nitroxidradikal zu markieren. Das Nitroxidradikal diente als Spinsonde für die EPR-Experimente. Neben der Synthese verschiedener, spinmarkierter Amphiphile, der anschließenden Darstellung organisch-modifizierten Tons (Kationenaustausch) und verschiedener Polymer-Ton-Nanokomposite (Schmelzinterkalation) wurden alle Proben mittels EPR-Spektroskopie untersucht; dabei wurden sowohl cw- als auch gepulste Messtechniken eingesetzt. Aus cw-Experimenten ging hervor, dass die Dynamik der gesamten Tensidschicht mit der Temperatur zunimmt und die Mobilität der hydrophoben Tensidalkylkette mit wachsendem Abstand zu ihrer Kopfgruppe wächst. Zugabe von Polymer behindert bei steigender Temperatur das Anschwellen des Tons bei Aufschmelzen der Tensidschicht; die Dynamik des Systems ist eingeschränkt. Mit Hilfe gepulster EPR-Messungen (ENDOR und ESEEM), die Informationen über Abstände bzw. Kontakt in den untersuchten Systemen lieferten, ließ sich ein Strukturmodell der Polymer-Ton-Nanokomposite skizzieren, das Vorstellungen anderer, älterer Methoden unterstützt: Hierbei richten sich die Tenside in Multischichten unterschiedlicher Mobilität parallel zur Tonoberfläche aus.

Radiochemical aspects of production and processing of radiometals for preparation of metalloradiopharmaceuticals

Radiometals play an important role in nuclear medicine as involved in diagnostic or therapeutic agents. In the present work the radiochemical aspects of production and processing of very promising radiometals of the third group of the periodic table, namely radiogallium and radiolanthanides are investigated. The 68Ge/68Ga generator (68Ge, T½ = 270.8 d) provides a cyclotron-independent source of positron-emitting 68Ga (T½ = 68 min), which can be used for coordinative labelling. However, for labelling of biomolecules via bifunctional chelators, particularly if legal aspects of production of radiopharmaceuticals are considered, 68Ga(III) as eluted initially needs to be pre-concentrated and purified. The first experimental chapter describes a system for simple and efficient handling of the 68Ge/68Ga generator eluates with a cation-exchange micro-chromatography column as the main component. Chemical purification and volume concentration of 68Ga(III) are carried out in hydrochloric acid – acetone media. Finally, generator produced 68Ga(III) is obtained with an excellent radiochemical and chemical purity in a minimised volume in a form applicable directly for the synthesis of 68Ga-labelled radiopharmaceuticals. For labelling with 68Ga(III), somatostatin analogue DOTA-octreotides (DOTATOC, DOTANOC) are used. 68Ga-DOTATOC and 68Ga-DOTANOC were successfully used to diagnose human somatostatin receptor-expressing tumours with PET/CT. Additionally, the proposed method was adapted for purification and medical utilisation of the cyclotron produced SPECT gallium radionuclide 67Ga(III). Second experimental chapter discusses a diagnostic radiolanthanide 140Nd, produced by irradiation of macro amounts of natural CeO2 and Pr2O3 in natCe(3He,xn)140Nd and 141Pr(p,2n)140Nd nuclear reactions, respectively. With this produced and processed 140Nd an efficient 140Nd/140Pr radionuclide generator system has been developed and evaluated. The principle of radiochemical separation of the mother and daughter radiolanthanides is based on physical-chemical transitions (hot-atom effects) of 140Pr following the electron capture process of 140Nd. The mother radionuclide 140Nd(III) is quantitatively absorbed on a solid phase matrix in the chemical form of 140Nd-DOTA-conjugated complexes, while daughter nuclide 140Pr is generated in an ionic species. With a very high elution yield and satisfactory chemical and radiolytical stability the system could able to provide the short-lived positron-emitting radiolanthanide 140Pr for PET investigations. In the third experimental chapter, analogously to physical-chemical transitions after the radioactive decay of 140Nd in 140Pr-DOTA, the rapture of the chemical bond between a radiolanthanide and the DOTA ligand, after the thermal neutron capture reaction (Szilard-Chalmers effect) was evaluated for production of the relevant radiolanthanides with high specific activity at TRIGA II Mainz nuclear reactor. The physical-chemical model was developed and first quantitative data are presented. As an example, 166Ho could be produced with a specific activity higher than its limiting value for TRIGA II Mainz, namely about 2 GBq/mg versus 0.9 GBq/mg. While free 166Ho(III) is produced in situ, it is not forming a 166Ho-DOTA complex and therefore can be separated from the inactive 165Ho-DOTA material. The analysis of the experimental data shows that radionuclides with half-life T½ < 64 h can be produced on TRIGA II Mainz nuclear reactor, with specific activity higher than any available at irradiation of simple targets e.g. oxides.