Towards to the trans-bromination of 2-styrylpyridine with a palladacycle intermediary and structure analysis for trans-1,2-dibromo-2-styrylpyridine

The simple halogenation of alkynes in conventional organic reactions gives a blend of cis and trans isomers. It is proposed then, a synthesis of stereospecific halogenation of alkynes in trans position, using palladacycle as intermediaries. The recrystallization of the compound obtained by bromination of 2-Styrylpyridine, with cyclepalladium intermediary results in a single crystal, which is subjected to X-ray diffraction. The crystal packing is established through weak interactions of three types. The first one is of the type pi x pi interactions, from symmetry operation, between the centroids. The second one is of the type C-X center dot center dot center dot pi interactions. And the last type is an anomalous intermolecular interaction between halogens, C-X center dot center dot center dot X-C, with bond distances smaller than the sum of the van der Waals radii. The conformation on the C=C bond is trans and the dihedral angle between the aromatic rings is (with esd approximate) 18.1(3)degrees. (C) 2010 Elsevier B.V. All rights reserved.

Synthesis and characterization of mono and polymeric cyclopalladated compounds: Crystal and molecular structure of [{Pd(dmba)(ONO(2))}(2)(mu-pz)] center dot H(2)O (pz = pyrazine)

In the treatment of cyclometallated dimer [Pd(dmba)(mu-Cl)](2) (dmba = N,N-dimethylbenzylamine) with AgNO(3) and acetonitrile the result was the monomeric cationic precursor [Pd(dmba)(NCMe)(2)](NO(3)) (NCMe=acetonitrile) (1). Compound 1 reacted with m-nitroaniline (m-NAN) and pirazine (pz), originating [Pd(dmba)(ONO(2))(m-NAN)] (2) and [{Pd(dmba)(ONO(2))}(2)(mu-pz)] center dot H(2)O (3), respectively. These compounds were characterized by elemental analysis, IR and NMR spectroscopy. The IR spectra of (2-3) display typical bands of monodentade O-bonded nitrate groups, whereas the NMR data of 3 are consistent with the presence of bridging pyrazine ligands. The structure of compound 3 was determined by Xray diffraction analysis. This packing consists of a supramolecular chain formed by hydrogen bonding between the water molecule and nitrato ligands of two consecutive [Pd(2)(dmba)(2)(ONO(2))2(mu-pz)] units. (c) 2008 Elsevier Ltd. All rights reserved.

A technological innovation for capsicums production in Peru: the mechatronics arms

Peru agricultural exports have increased in recent years due to (i) free trade agreements with many countries (United States, Canada, European Union, China, Thailand, Singapore, Japan, Chile, among others), (ii) an increasing international demand for healthy products, (iii) country´s economic development and (iv) more private investments in this sector (Velazco 2012). Also, if we can compare among Peru three main regions (Coast, Andean highlands and the Jungle), It is the Coast (western region) that has a developed agricultural production due to unique weather conditions, private investments, public infrastructure, transport costs and quality of land (Gomez, 2008). This country development is also related to the production of non-traditional products for export like asparagus, artichokes, capsicums, bananas, grapes, among others; produced by agro industrial companies and small farmers and that are mainly labor intensive (Gomez, 2008 and Velazco, 2012). This very successful export diversification and self-discovery process was the result of a combination of strong natural comparative advantages (mainly excellent agro climatic conditions) and a significant innovation effort. It meant the introduction and expansion of new products and markets, the entry of new firms, and experimental research and the adoption of new techniques and process technologies developed abroad (in irrigation, crop management, post-harvesting, sanitary control, storage and packing) to produce high-quality, niche (gourmet) and higher value-added products, in line with consumer trends in sophisticated food markets. In products such as asparagus, mango, organic coffee and capsicums, Peru has become a leading world exporter (OECD). For this reason one of the government main tasks for the next years is to meet urgent agriculture producer’s needs in the areas of technological Innovation and business management (MINAG). In this context, this thesis analyzes the applicability of a new technology – the mechatronic arms – specifically to capsicums production sector in Peru. We chose Capsicums production sector (paprika, chilli pepper) because is mainly labor intensive and is the sector where my family company (DIROSE SAC) operates. This innovation consists in a 40 arms mechatronic combine, and it was first created in order to improve the efficiency on the labor intensive phase of harvest for this kind of agriculture products. It is estimated that a laborer with brief training operating the machine would be equivalent to 40 people that not only would work during daytime, but also on the night shift as well. Also, using this new technology can allow a company to make additional crops that would increase their yields and annual revenues. This thesis was developed as a business plan to make this new product available for other agriculture companies that operates in the capsicums production sector in Peru; however, this new technology has the potential to be modified in order to be available to other kind of agriculture products, in Peru and other countries.

Otimização e análise mecânica de pastas geopoliméricas para uso em poços sujeitos à injeção cíclica de vapor

Oil wells subjected to cyclic steam injection present important challenges for the development of well cementing systems, mainly due to tensile stresses caused by thermal gradients during its useful life. Cement sheath failures in wells using conventional high compressive strength systems lead to the use of cement systems that are more flexible and/or ductile, with emphasis on Portland cement systems with latex addition. Recent research efforts have presented geopolymeric systems as alternatives. These cementing systems are based on alkaline activation of amorphous aluminosilicates such as metakaolin or fly ash and display advantageous properties such as high compressive strength, fast setting and thermal stability. Basic geopolymeric formulations can be found in the literature, which meet basic oil industry specifications such as rheology, compressive strength and thickening time. In this work, new geopolymeric formulations were developed, based on metakaolin, potassium silicate, potassium hydroxide, silica fume and mineral fiber, using the state of the art in chemical composition, mixture modeling and additivation to optimize the most relevant properties for oil well cementing. Starting from molar ratios considered ideal in the literature (SiO2/Al2O3 = 3.8 e K2O/Al2O3 = 1.0), a study of dry mixtures was performed,based on the compressive packing model, resulting in an optimal volume of 6% for the added solid material. This material (silica fume and mineral fiber) works both as an additional silica source (in the case of silica fume) and as mechanical reinforcement, especially in the case of mineral fiber, which incremented the tensile strength. The first triaxial mechanical study of this class of materials was performed. For comparison, a mechanical study of conventional latex-based cementing systems was also carried out. Regardless of differences in the failure mode (brittle for geopolymers, ductile for latex-based systems), the superior uniaxial compressive strength (37 MPa for the geopolymeric slurry P5 versus 18 MPa for the conventional slurry P2), similar triaxial behavior (friction angle 21° for P5 and P2) and lower stifness (in the elastic region 5.1 GPa for P5 versus 6.8 GPa for P2) of the geopolymeric systems allowed them to withstand a similar amount of mechanical energy (155 kJ/m3 for P5 versus 208 kJ/m3 for P2), noting that geopolymers work in the elastic regime, without the microcracking present in the case of latex-based systems. Therefore, the geopolymers studied on this work must be designed for application in the elastic region to avoid brittle failure. Finally, the tensile strength of geopolymers is originally poor (1.3 MPa for the geopolymeric slurry P3) due to its brittle structure. However, after additivation with mineral fiber, the tensile strength became equivalent to that of latex-based systems (2.3 MPa for P5 and 2.1 MPa for P2). The technical viability of conventional and proposed formulations was evaluated for the whole well life, including stresses due to cyclic steam injection. This analysis was performed using finite element-based simulation software. It was verified that conventional slurries are viable up to 204ºF (400ºC) and geopolymeric slurries are viable above 500ºF (260ºC)

Transporte de juvenis de curimbatá Prochilodus lineatus em diferentes densidades

Transportation of curimbata Prochilodus lineatus juveniles in different densities. Tins study evaluated the effects of curimbata Prochilodus lineatus transportation in three densities (100, 150 and 250 g L-1) on survival, metabolic, ionic and hematological (red series) variables Curimbata juveniles were transported in plastic bag during six hours, and sampled before packing, immediately after die arrival, 24 and 96 hours after transportation During recovery, higher mortality was seen in fish transported in die highest density Water variables, such as conductivity and total ammonia, presented increased values as density increased (p < 005). whereas the opposite occurred with dissolved oxygen Glucose level observed in the arrival was high, significantly reducing after 96 hours Among ionic variables, chloride decreased in higher fish densities and according to sampling times Red series hematological variables, such as hematocrit, red blood cell and hemoglobin, Increased in arrival, but diminished 96 hours after transportation There were no significant differences in the interaction between density and time of sampling for mentioned variables 250 g L-1 density induced the highest mortality rate and the worst variables values measured 96 hours of recovery after the stressing event was enough to return to initial values for hematological variables, but was not sufficient to return to initial values for metabolic and ionic variables.

Qualidade de abóbora minimamente processada armazenada em atmosfera modificada ativa

The active modified atmosphere effect was evaluated in the quality of squash fresh-cut (MP).. The squash pieces were conditioned in plastic packings and submitted the gases application in the following concentrations: 0.03% CO2 and 21% O-2 (controls T1); 5% CO2 and 4% O-2 (T2); 6% CO2 and 4% O-2 (T3); 7% CO2 and 4% O-2 (T4); 8% CO2 and 4% O-2 (T5). In T6 it was made vacuum application in the packing. The packings containing the squash were stored in to the temperature of 10 degrees C and relative humidity of 75% for 12 days. The evaluated analyses were weigth loss, total acidity (AT), pH, soluble solids (SS), ratio, firmness, color, antioxidant activity for DPPH and carotenoids content. The weigth loss was gradual and low until the ninth day of storage. The values of AT increased along the experimental period being superior for T1 and T2. The increase of SS during the storage of the fresh-cut squash went smaller for T3 and T4. The brightness stayed during the storage being superior for T5, already the color components red and yellow decreased along the experimental period.

Determinação de parâmetros de qualidade para formas farmacêuticas homeopáticas

All medicine, whether allopathic or homeopathic, must go through strict quality control, which must ratify their characteristics throughout the period of validity. During the time of preparation and storage, solutions of the drugs are in permanent contact with packaging materials that can release undesirable substances to the solution. Several factors may influence the release of packing materials, and factorial design (FD) is a useful tool for analyzing the phenomenon. The aim of this study was the determination of quality parameters for Homeopathic solid (globules) and liquid (drops) dosage forms. It was carried out analysis in homeopathic globules for weight variation, mechanical strength, and moisture content uniformity. For liquid preparations, standard solutions were prepared from natural rubber bulbs, which were subjected to exhaustive extraction with two ethanol solutions (30 and 70%) in the ultrasonic bath for 20 minutes at 25°C and 50°C in three successive cycles. Studies of transfer have been made within five days, by spectrophotometric analysis in the UV region at 312 nm with λmáx and 323 nm for samples in 70% ethanol and 30% respectively. PH values were analyzed. We also conducted two FD studies, where the first, the three-level variables were solvent (chloroform, ethanol and nhexane), sample mass (30, 60 and 90mg), particle size (large disk, small disk and powder sample). In the second study, the solvent level variables were different ethanolic degrees (EtOH 30%, 70% and pure). The percentage of lending in the solutions was 5.5%, 12.4%, 24.2% and 41% of the total estimated in the reference solution. The values of rate constants of transfer were determined in the order of 0.0134 days-1 and 0.0232 days-1 in absorbance values, the solutions in ethanol at 30% and 70% respectively. These results suggest that the speed of transfer of materials from rubber is affected both by the nature of the vehicle as by the temperature

Conservação de mamão 'Formosa' minimamente processado armazenado sob refrigeração

O objetivo deste trabalho foi avaliar a qualidade de produtos minimamente processados de mamão 'Formosa', fatias ou metades, armazenados sob diferentes temperaturas (3ºC, 6ºC e 9ºC). Utilizou-se de frutos que, depois de selecionados quanto ao grau de maturação e ausência de danos, foram lavados, desinfeccionados com cloro (200 mg.L-1) e armazenados a 12ºC, por 12 horas antes do processamento, que foi feito manualmente, a 12ºC. Os mamões, depois de descascados, foram cortados em fatias (5,0 x 2,5 cm) ou em metades longitudinais sem as pontas, que, depois de enxaguadas com água sanitizada (20 mg de cloro.L-1) e escorridas por 2-3 minutos, foram embaladas em bandejas de isopor recobertas com filme de PVC esticável (metades) ou em bandejas de tereftalato de polietileno - PET (fatias) e imediatamente armazenadas sob refrigeração. A avaliação destes produtos foi feita a cada 3 dias, quanto à resistência da polpa, coloração, pH e conteúdos de sólidos solúveis, acidez titulável, ácido ascórbico e de carboidratos, solúveis e de redutores. Durante o armazenamento, as fatias tenderam a se tornarem mais firmes, com a sua polpa apresentando pequeno escurecimento. Os conteúdos de carboidratos solúveis e de redutores e de sólidos solúveis não foram afetados pelo tipo de corte, temperatura de armazenamento ou embalagem. Durante o armazenamento, os teores de acidez titulável aumentaram nas fatias e diminuíram nas metades e observou-se influência da temperatura. Não se observaram reduções nos teores de ácido ascórbico durante o armazenamento, ou influência dos cortes ou das embalagens. Os produtos mantiveram-se adequados para comercialização até o 10º dia de armazenamento.

Estabilidade aeróbia de silagens do capim-marandu submetidas a diferentes intensidades de compactação na ensilagem

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

Avaliação de diferentes tipos de atmosferas modificadas na vida útil de carambolas minimamente processadas

Este trabalho teve por objetivo a avaliação da vida útil potencial de carambolas cv. Golden Star, minimamente processadas, armazenadas em diferentes tipos de embalagens plásticas, para a concepção da atmosfera modificada. Os frutos colhidos fisiologicamente maturos apresentaram coloração verde-amarelada, sólidos solúveis (SS) médios de 6,8 ºBrix e massa média de 185 g. Antes da aplicação dos tratamentos, os frutos foram selecionados, higienizados em solução de hipoclorito de sódio (NaOCl) a 100 mg. L-1, resfriados por 12 horas a 15 ± 0,5 °C, seccionados transversalmente, sendo então novamente higienizados em solução de NaOCl a 10 mg.L-1, por 3 minutos. em seguida, os pedaços em forma de estrelas foram acondicionados em bandejas rígidas de poliestireno, com capacidade para 250 g, e revestidas com os seguintes materiais: T1: filme plástico perfurado de polietileno de baixa densidade (PEBD), de 0,006 mm; T2: filme plástico poliolefínico com antiembassamento da Dupont® (AGF), de 0,015 mm; T3: filme plástico poliolefínico da Dupont® (HF), de 0,015 mm; T4: filme plástico de PEBD, de 60 µm; T5: filme plástico de PEBD, de 80 µm; T6: filme plástico de polipropileno (PP), de 22 µm, e T7: bandeja rígida de polietileno tereftalato (PET), com capacidade para 500 mL, com tampa do mesmo material. As embalagens foram então armazenadas em câmara frigorífica a 12 ± 0,5 °C e 90 ± 3% de U.R, por 18 dias. Observou-se que não houve diferença significativa quanto aos sólidos solúveis (SS) e acidez titulável (AT). O maior número de microrganismos e valor de pH foram observados nos frutos embalados nos filmes plásticos de PEBD de 0,006 mm, AGF e HF de 0,015 mm da Dupont®. Entretanto, os frutos acondicionados nas embalagens PET apresentaram o maior teor de ácido ascórbico. da mesma forma, somente nas embalagens PET é que se conseguiu modificação atmosférica eficiente do ponto de vista da manutenção dos atributos de qualidade durante o AR. Assim, esse tratamento proporcionou adequado controle microbiológico e manutenção das características de qualidade por 18 dias para as carambolas minimamente processadas.

Avaliação econômica das perdas de banana no mercado varejista: um estudo de caso

O objetivo do presente estudo foi a determinação das perdas físicas e econômicas de banana em diferentes equipamentos varejistas na Cidade de Botucatu - SP e suas possíveis causas. Os equipamentos foram sorteados aleatoriamente. As informações foram coletadas através da aplicação de questionário para a determinação das perdas de três variedades de banana. O resultado mostrou perda global de 39 toneladas, correspondente a 11,1% da quantidade comercializada, sendo 10,5% em supermercados, 15,0% em quitandas/sacolões e 10,6% em feiras livres. O valor total das perdas anuais atingiu R$ 35.038,00, em valores de maio de 2002. A manipulação excessiva do cliente, excedente de oferta, uso de embalagem inadequada e baixa qualidade da fruta foram as principais causas de perdas. Conclui-se pela necessidade de conscientização do cliente, do uso de embalagens plásticas e de cuidados no manuseio da fruta durante toda pós-colheita.

Qualidade pós-colheita de mangas, não-refrigeradas, e submetidas ao controle da ação do etileno

O presente trabalho objetivou-se na caracterização físico-química de mangas cv. Tommy Atkins e Haden, submetidas ao controle da ação do etileno, através da exposição dos frutos à ação de adsorvedores de etileno. Os frutos colhidos em estádio de fisiologicamente maturos foram embalados em filmes de polietileno de baixa densidade (PEBD) de 0,006 mm de espessura, com ou sem o sachê de adsorção de etileno, e acondicionados em embalagens de papelão (0,65 x 0,52 m), sem o controle da temperatura e da umidade relativa (30 ± 3 ºC e 70 ± 5 % de U.R.). Os tratamentos ficaram constituídos dessa maneira: T1 - mangas cv. Tommy Atkins, com o sachê de adsorção; T2 - mangas cv. Tommy Atkins, sem o sachê de adsorção; T3- mangas cv. Haden com o sachê de adsorção, e T4 - mangas cv Haden sem o sachê de adsorção. As análises de firmeza de polpa, sólidos solúveis (SS), acidez titulável (AT), pH, ácido ascórbico e concentração de etileno foram realizadas na instalação do experimento (dia 0), e aos 7; 14; 21; 28 e 35 dias; e aos 35 dias foi realizado um teste de preferência. Ao final do experimento, observou-se que, em ambas as cultivares, a menor concentração de etileno nas embalagens, a maior firmeza de polpa, a maior contenção no avanço e na diminuição do SS e AT, respectivamente, bem como a melhor manutenção do conteúdo de ácido ascórbico foram detectadas nos frutos acondicionados em embalagens contendo o sachê de adsorção de etileno. Não foram detectadas variações significativas nos valores de pH. No teste de preferência, houve variação significativa, onde os frutos acondicionados sob ação do adsorvedor de etileno foram preferidos por parte dos julgadores.

Synthesis and physical properties of lipid-based poly(ester-urethane)s, I: Effect of varying polyester segment length

Four aliphatic thermoplastic poly(ester-urethane)s (PEUs) with similar molecular weights but varying polyesters molecular weight (534-1488 g/mol) were prepared from polyester diols, obtained by melt condensation of Azelaic acid and 1,9-Nonanediol, and 1,7-heptamethylene di-isocyanate (HPMDI) all sourced from vegetable oil feedstock. The thermal, and mechanical properties, and crystal structure of PEUs were investigated using DSC, TGA, DMA, tensile analysis and WAXD. For sufficiently long polyester chain, WAXD data indicated no hydrogen bonds polyethylene (PE)-like crystalline packing and for short polyester chains, small crystal domains with significant H-bonded polyamide (PA)-like packing. Crystallinity decreased with decreasing polyester molecular weights. The polymorphism of PEUs and consequently their melting characteristics were found to be largely controlled by polyester segment length. TGA of the PEUs indicated improved thermal stability with decreasing polyester chain length, suggesting a stabilization effect by urethane groups. Mechanical properties investigated by DMA and tensile analysis were found to scale predictably with the overall crystallinity of PEUs. (C) 2012 Elsevier Ltd. All rights reserved.

Obtenção e caracterização de extrato microencapsulado de resíduo agroindustrial de acerola

Acerola (Malpighia emarginata D.C.) is a red fruit widely cultivated in Brazil, especially in the Northeastern region. Its increasing demand is attributed to its high ascorbic acid contents. Besides ascorbic acid, widely known by its health-benefit effects, acerola is rich in anthocyanins, which contribute for the antioxidant power of the fruit. Acerola processing produces a bright-red pomace, usually discarded. The further processing of this pomace, in order to explore its antioxidant compounds, could enhance acerola market value and rentability of its processing. Both ascorbic acid and anthocyanins are highly susceptible to degradation, that can be delayed by microencapsulation, which consists on packing particles (core) in an edible matrix (wall material). This work has been made with the purpose of producing a microencapsulated acerola pomace extract, which could be used by the food industry as a functional ingredient with antioxidant and coloring properties. Antioxidant compounds were recovered by pressing the pomace diluted in a solvent (a citric acid aqueous solution), by using a central composite design, with two variables: citric acid concentration in the solvent (0-2%), and solvent: pomace mass ratio (2:1-6:1). The acerola pomace extract was then microencapsulated by spray drying. A central composite design was adopted, with three variables: inlet temperature of the spray dryer (170o-200oC), wall material: acerola solids mass ratio (2:1-5:1), and degree of maltodextrin replacement by cashew tree gum as wall material (0-100%). The cashew tree gum was used because of its similarity to arabic gum, which is regarded as the wall material by excellence. The following conditions were considered as optimal for extraction of anthocyanins and ascorbic acid: solvent/pomace ratio, 5:1, and no citric acid in the solvent. 82.47% of the anthocyanins were recovered, as well as 83.22% of the ascorbic acid. Anthocyanin and ascorbic acid retentions were favored by lower inlet temperatures, higher wall material: acerola solids mass ratio and higher maltodextrin replacement by cashew tree gum, which was presented as a promising wall material. The more adequate microencapsulation conditions, based not only on retention of antioxidant compounds but also on physical properties of the final powder, were the following: inlet temperature, 185oC; wall material: acerola solids mass ratio, 5:1, and minimum degree of maltodextrin replacement by cashew tree gum, 50%

Molecular and morphological characterization of bis benzimidazo perylene films and surface-enhanced phenomena

Thin solid films of bis benzimidazo perylene (AzoPTCD) were fabricated using physical vapor deposition (PVD) technique. Thermal stability and integrity of the AzoPTCD PVD films during the fabrication (similar to 400 degrees C at 10(-6) Torr) were monitored by Raman scattering. Complementary thermogravimetric results showed that thermal degradation of AzoPTCD occurs at 675 degrees C. The growth of the PVD films was established through UV-vis absorption spectroscopy, and the surface morphology was surveyed by atomic force microscopy (AFM) as a function of the mass thickness. The AzoPTCD molecular organization in these PVD films was determined using the selection rules of infrared absorption spectroscopy (transmission and reflection-absorption modes). Despite the molecular packing, X-ray diffraction revealed that the PVD films are amorphous. Theoretical calculations (density functional theory, B3LYP) were used to assign the vibrational modes in the infrared and Raman spectra. Metallic nanostructures, able to sustain localized surface plasmons (LSP) were used to achieve surface-enhanced resonance Raman scattering (SERRS) and surface-enhanced fluorescence (SEF).