960 resultados para phase s(n)2 reactions


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In the present work multilayered micro/nanocrystalline (MCD/NCD) diamond coatings were developed by Hot Filament Chemical Vapour Deposition (HFCVD). The aim was to minimize the surface roughness with a top NCD layer, to maximize adhesion onto the Si3N4 ceramic substrates with a starting MCD coating and to improve the mechanical resistance by the presence of MCD/NCD interfaces in these composite coatings. This set of features assures high wear resistance and low friction coefficients which, combined to diamond biocompatibility, set this material as ideal for biotribological applications. The deposition parameters of MCD were optimized using the Taguchi method, and two varieties of NCD were used: NCD-1, grown in a methane rich gas phase, and NCD-2 where a third gas, Argon, was added to the gas mixture. The best combination of surface pre-treatments in the Si3N4 substrates is obtained by polishing the substrates with a 15 μm diamond slurry, further dry etching with CF4 plasma for 10 minutes and final ultrasonic seeding in a diamond powder suspension in ethanol for 1 hour. The interfaces of the multilayered CVD diamond films were characterized with high detail using HRTEM, STEM-EDX and EELS. The results show that at the transition from MCD to NCD a thin precursor graphitic film is formed. On the contrary, the transition of the NCD to MCD grade is free of carbon structures other than diamond, as a result of the richer atomic hydrogen content and of the higher substrate temperature for MCD deposition. At those transitions, WC nanoparticles were found due to contamination from the filament, being also present at the first interface of the MCD layer with the silicon nitride substrate. In order to study the adhesion and mechanical resistance of the diamond coatings, indentation and particle jet blasting tests were conducted, as well as tribological experiments with homologous pairs. Indentation tests proved the superior behaviour of the multilayered coatings that attained a load of 800 N without delamination, when compared to the mono and bilayered ones. The multilayered diamond coatings also reveal the best solid particle erosion resistance, due to the MCD/NCD interfaces that act as crack deflectors. These results were confirmed by an analytical model on the stress field distribution based on the von Mises criterion. Regarding the tribological testing under dry sliding, multilayered coatings also exhibit the highest critical load values (200N for Multilayers with NCD-2). Low friction coefficient values in the range μ=0.02- 0.09 and wear coefficient values in the order of ~10-7 mm3 N-1 m-1 were obtained for the ball and flat specimens indicating a mild wear regime. Under lubrication with physiological fluids (HBSS e FBS), lower wear coefficient values ~10-9-10-8 mm3 N-1 m-1) were achieved, governed by the initial surface roughness and the effective contact pressure.

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Cationic porphyrins have been widely used as photosensitizers (PSs) in the inactivation of microorganisms, both in biofilms and in planktonic forms. However, the application of curcumin, a natural PS, in the inactivation of biofilms, is poorly studied. The objectives of this study were (1) to evaluate and compare the efficiency of a cationic porphyrin tetra (Tetra-Py+-Me) and curcumin in the photodynamic inactivation of biofilms of Pseudomonas spp and the corresponding planktonic form; (2) to evaluate the effect of these PSs in cell adhesion and biofilm maturation. In eradication assays, biofilms of Pseudomonas spp adherent to silicone tubes were subjected to irradiation with white light (180 J cm-2) in presence of different concentrations (5 and 10 μM) of PS. In colonization experiments, solid supports were immersed in cell suspensions, PS was added and the mixture experimental setup was irradiated (864 J cm-2) during the adhesion phase. After transference solid supports to new PS-containing medium, irradiation (2592 J cm-2) was resumed during biofilm maturation. The assays of inactivation of planktonic cells were conducted in cell suspensions added of PS concentrations equivalent to those used in experiments with biofilms. The inactivation of planktonic cells and biofilms (eradication and colonization assays) was assessed by quantification of viable cells after plating in solid medium, at the beginning and at the end of the experiments. The results show that porphyrin Tetra-Py+-Me effectively inactivated planktonic cells (3.7 and 3.0 log) and biofilms of Pseudomonas spp (3.2 and 3.6 log). In colonization assays, the adhesion of cells was attenuated in 2.2 log, and during the maturation phase, a 5.2 log reduction in the concentration of viable cells was observed. Curcumin failed to cause significant inactivation in planktonic cells (0.7 and 0.9 log) and for that reason it was not tested in biofilm eradication assays. In colonization assays, curcumin did not affect the adhesion of cells to the solid support and caused a very modest reduction (1.0 log) in the concentration of viable cells during the maturation phase. The results confirm that the photodynamic inactivation is a promising strategy to control installed biofilms and in preventing colonization. Curcumin, however, does not represent an advantageous alternative to porphyrins in the case of biofilms of Pseudomonas spp.

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The 5a-reductase of Penicillium decumbens ATCC 10436 was used as a model for the mammalian enzyme to investigate the mechanism of reduction of testosterone to 5adihydrotestosterone . The purpose of this study was to search for specific 5a-reductase inhibitors which antagonize prostate cancer . In a whole-cell biotransformation mode, this organism reduced testosterone (1) to 5a-dihydrosteroids (8) and 5aandrostane- 3, 17-dione (9) in yields of 28% and 37% respectively. Control experiments have shown that 5aandrostane- 3, 17-dione (9) can be produced from the corresponding alcohol (8) in a subsequent reaction separate from that catalysed by the 5a-reductase enzyme . Androst-4- ene-3, 17-dione (2) is reduced to give only (9) with a recovery of 80% The stereochemistry of the reduction was determined by 500 MHz ^H NMR analysis of the products resulting from the deuterium labelled substrates. The results were obtained by an analysis of the NOE difference spectra, double-quantum filtered phase sensitive COSY 2-D spectra, and ^^c-Ir 2-D shift correlation spectra of deuterium labelled products. According to the unambiguous assignment of the signals due to H-4a and H-4Ii in 5a-dihydro steroids, the NMR data show clearly that addition of hydrogen to the 4{5)K bond has occurred in a trans manner at positions 413 and 5a. To Study the reduction mechanism of this enzyme, several substrates were prepared as following; 3-methyleneandrost-4-en- 17fi-ol(3), androst-4-en-17i5-ol(5) , androst-4-en-3ii, 17fi-diol (6) and 4, 5ii-epoxyandrostane-3, 17-dione (7) . Results suggest that this enzyme system requires an oxygen atom at the 3-position of the steroid in order to bind the substrate. Furthermore, the mechanism of this 5a-reductase may proceed via direct addition of hydrogen at the 4,5 position without involvement of a carbonyl group as an intermediate.

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Introduction & Objectifs : Pour assurer l’analgésie postopératoire, l’anesthésiste dispose, en plus des différentes classes de médicaments administrés par voie orale ou intraveineuse, de diverses techniques pour bloquer l’influx nerveux douloureux en administrant les anesthésiques locaux (AL) de manière centrale ou périphérique. La ropivacaïne (ROP), un AL à longue durée d’action, est un médicament de première intention partout dans le monde, en raison de sa grande efficacité et de son faible risque de toxicité. Contrairement à certains pays, la ROP n'est toujours pas indiquée au Canada pour la rachianesthésie (bloc central) en raison d'un manque de données probantes. Jusqu'à présent, les efforts de recherche ont essentiellement porté sur la sécurité ainsi que sur la durée d’action du médicament lorsqu’administré par voie spinale. De plus, les doses optimales de ROP pour l’anesthésie régionale périphérique ne sont pas encore précisément connues. La posologie devrait être adaptée au site d’administration ainsi qu’à l’intensité et la durée du stimulus produit par la chirurgie. Ultimement, cela permettrait aux cliniciens d’identifier le régime optimal en fonction des facteurs démographiques qui pourraient affecter la pharmacocinétique (PK) et la pharmacodynamie (PD) de l’AL (objectif global de ces travaux). Validation de la Méthode Analytique Manuscrit 1 : Une méthode analytique spécifique et sensible permettant de déterminer les concentrations plasmatiques de ROP a d’abord été optimisée et validée. Validation du Biomarqueur Manuscrit 2 : Nous avons ensuite mis au point et évalué la fiabilité d’une méthode quantitative basée sur la mesure du seuil de perception sensorielle (CPT) chez le volontaire sain. Ce test nécessite l’application d’un courant électrique transcutané qui augmente graduellement et qui, selon la fréquence choisie, est capable de stimuler spécifiquement les fibres nerveuses impliquées dans le cheminement de l’influx nerveux douloureux. Les résultats obtenus chez les volontaires sains indiquent que la mesure CPT est fiable, reproductible et permet de suivre l’évolution temporelle du bloc sensitif. Études cliniques Manuscrit 3 : Nous avons ensuite caractérisé, pendant plus de 72 h, l’absorption systémique de la ROP lorsqu’administrée pour un bloc du nerf fémoral chez 19 patients subissant une chirurgie du genou. Le modèle PK populationnel utilisé pour analyser nos résultats comporte une absorption biphasique durant laquelle une fraction de la dose administrée pénètre rapidement (temps d’absorption moyen : 27 min, IC % 19 – 38 min) dans le flux sanguin systémique pendant que l’autre partie, en provenance du site de dépôt, est redistribuée beaucoup plus lentement (demi-vie (T1/2) : 2.6 h, IC % 1.6 – 4.3 h) vers la circulation systémique. Une relation statistiquement significative entre l’âge de nos patients et la redistribution de l’AL suggère que la perméabilité tissulaire est augmentée avec l’âge. Manuscrit 4 : Une analyse PK-PD du comportement sensitif du bloc fémoral (CPT) a été effectuée. Le modèle développé a estimé à 20.2 ± 10.1 mg la quantité de ROP nécessaire au site d’action pour produire 90 % de l’effet maximal (AE90). À 2 X la AE90, le modèle prédit un début d’action de 23.4 ± 12.5 min et une durée de 22.9 ± 5.3 h. Il s’agit de la première étude ayant caractérisé le comportement sensitif d’un bloc nerveux périphérique. Manuscrit 5 : La troisième et dernière étude clinique a été conduite chez les patients qui devaient subir une chirurgie du genou sous rachianesthésie. Tout comme pour le bloc du nerf fémoral, le modèle PK le plus approprié pour nos données suggère que l’absorption systémique de la ROP à partir du liquide céphalo-rachidien est biphasique; c.à.d. une phase initiale (T1/2 : 49 min, IC %: 24 – 77 min) suivie (délai: 18 ± 2 min) d'une phase légèrement plus lente (T1/2 : 66 min, IC %: 36 – 97 min). L’effet maximal a été observé beaucoup plus rapidement, soit aux environs de 12.6 ± 4.9 min, avant de revenir aux valeurs de base 210 ± 55 min suivant l’administration de l’agent. Ces données ont permis d’estimer une AE50 de 7.3 ± 2.3 mg pour l'administration spinale. Conclusion : En somme, ces modèles peuvent être utilisés pour prédire l’évolution temporelle du bloc sensitif de l’anesthésie rachidienne et périphérique (fémorale), et par conséquent, optimiser l’utilisation clinique de la ROP en fonction des besoins des cliniciens, notamment en ce qui a trait à l’âge du patient.

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Résumé Introduction : L’entrainement avec le ballon d’exercice pendant la grossesse a des effets positifs sur le déroulement de l’accouchement. Le but de l’étude était d’identifier si une association existe entre le volume d’entrainement avec le ballon d’exercice durant la grossesse en milieu naturel sur l’issue du déroulement de l’accouchement, soit la durée des phases 1 (dilatation/phase active) et 2 (expulsion), ainsi que l’usage de la péridurale et de la césarienne. Méthode: Cette étude quasi-expérimentale a été menée auprès d'un échantillon de convenance composée de 32 femmes enceintes qui ont pris part entre un et 28 cours d'exercice supervisé durant la grossesse (programme Ballon Forme), avec la possibilité d'effectuer des exercices supplémentaires à la maison avec le ballon d’exercice. Un questionnaire et un journal de bord ont été remplis par les participantes, avec l'aide d'une infirmière de l’hôpital pour les données médicales. Résultats: Un volume d’entrainement élevé, incluant l’entraînement sous forme de cours et à domicile, a été significativement associé à une durée plus courte d’accouchement, que ce soit pour le temps total de l’accouchement (r = -0,408, p = 0,031) ou pour les deux phases spécifiques de l’accouchement [la phase 1: r = -0,372 ; p = 0,043 et la phase 2: r = -0,415, p = 0,028]. Un volume d’entrainement élevé a aussi été lié à une réduction de la deuxième phase chez les femmes qui donnaient naissance pour la première fois. La durée totale des exercices exécutés lors des cours a été significativement associée à cette réduction comparativement aux exercices à la maison. Aucun effet indésirable n'a été observé avec le volume d’entrainement élevé sur les paramètres de l’accouchement et la santé du bébé (Apgar et poids du bébé à la naissance). En fait, un nombre très faible de césarienne (6%), de recours à la péridurale (47%) et d'extraction instrumentale (forceps ou ventouse: 13%) a été observé dans notre échantillon de femmes. Conclusion: La pratique du ballon d’exercice est une avenue prometteuse pour les femmes enceintes et un niveau élevé d’entraînement est associé à un accouchement plus rapide et sans complications pour le bébé. L’implantation de ce programme pourrait éventuellement contribuer à réduire considérablement les coûts de santé au Québec en favorisant l’accouchement naturel. Des interventions et des recherches ultérieures devront considérer et examiner cette modalité spécifique d’entrainement pour les femmes enceintes.

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Understanding of the Atmospheric Boundary Layer (ABL) is imperative in the arena of the monsoon field. Here, the features of the ABL are studied employing Conserved Variable Analysis (CVA) using equivalent potential temperature and humidity. In addition, virtual potential temperature and wind are used during active and weak phases of monsoon. The analysis is carried out utilising the radiosonde observations during the monsoon months for two stations situated in the west coast of India. All these parameters show considerable variations during active and weak monsoon phases in both the stations. The core speed and core height vary with these epochs. The core speed is found to be more than 38 knots in the active monsoon phase around 1.2 km over Trivandrum and around 2 km over Mangalore. But during weak monsoon phase the core wind speed is decreased and core height is elevated over both stations. The wind direction shows an additional along shore component during weak monsoon period. The Convective Boundary Layer (CBL) height shows increase during weak monsoon phase over both stations due to less cloudiness and subsequent insolation. The CBL height during the southwest monsoon is more over Mangalore and is attributed by the orographic lifting in the windward side of the Western Ghats while the influence of the Ghats is less over Trivandrum.

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The chemical mechanism of the (1)PN formation was successfully studied by using the CCSD(T)/6-311++G(3df,3pd) level of theory. The (1)NH(3) + (3)PH and (4)P + NH(3) reaction paths are not energetically favorable to form the (1)PN molecule. However, the (3)NH + (3)PH, (4)N + (3)PH(3), (4)N + (3)PH, (4)P + (3)NH, and (4)P + (2)NH(2) reaction paths to form the (1)PN molecule are only energetically favorable by taking place through specific transition states to form the (1)PN molecule. The NH(3) + (3)PH, (4)N + (1)PH(3), NH(3) + (4)P, and (4)N + (2)PH(2) reactions are spin-forbidden and the probability of hopping for these reactions was estimated to be 0 by the Landau-Zener theory. This is the first detailed study on the chemical mechanism for the (1)PN formation. (C) 2009 Elsevier B.V. All rights reserved.

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A major concern in solvent extraction processes is the loss of extractant into the aqueous phase due to its slight solubility in the aqueous phase. Similarly, in membrane extraction processes, extractant loss through extractant leakage from the membrane into the aqueous phase is also a concern. Several published membrane extraction studies using Aliquat 336 as the extractant, have expressed this concern, but none has studied extractant leakage quantitatively. It is the authors’ opinion that the extractant leakage should be considered as a technical parameter of a membrane. In our laboratory active progress has been made in using Aliquat 336 ‘entangled’ into the polymer membranes to remove heavy metal ions from wastewater samples. In this work, we studied the loss of Aliquat 336 from the point of view of its solubility in aqueous solutions. The results showed that the solubilities of Aliquat 336 in an aqueous phase acidified with 2 M HCl is about 0.1 g/100 m/ of the solution. This figure provides a useful guideline for evaluating the leakage of the Aliquat 336 extractant from the membranes.

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The aims of this study are (1) to establish a reliable and valid quality-of-life (QOL) questionnaire for Chinese patients with head and neck (H&N) cancer who are treated with radiation therapy and (2) to evaluate the impact of the immediate side effects of treatment on the QOL of these patients. The 39-item "Quality of Life Radiation Therapy Instrument with Head and Neck Companion Module" (QOL-RTI/H&N) was translated into Chinese. In the reliability evaluation phase (study module 1), the questionnaire was administered twice to 56 H&N cancer patients, 7 days apart, during the second and third week of radiation therapy. In the validity evaluation phase (study module 2), 138 patients completed the QOL-RTI/H&N before starting and at the end of radiation therapy. Sixty-nine of these 138 patients also completed the QOL-RTI/H&N during the second week of their radiation therapy, at the same time as completing the Functional Assessment of Cancer Therapy-Head and Neck (FACT-H&N) questionnaire. Cronbach alpha coefficients were 0.88 for the general-tool QOL-RTI and 0.90 for the H&N subscale. Test-retest reliability was satisfactory with intraclass correlation coefficients of 0.89 for the general-tool QOL-RTI and 0.75 for the H&N subscale. The instrument can discriminate between patients with stage I or II disease and those with stage III or IV disease (P < .05). Concurrent validity was established by the good agreement with the FACT-H&N (r = 0.86, P < .001). A highly significant deterioration was in the QOL from the baseline to the end of treatment (mean difference for general tool = 1.95, P < .001; mean difference for H&N subscale = 4.85, P < .001). The Chinese QOL-RTI/H&N is a reliable and valid tool for determining the QOL in H&N cancer patients receiving radiation therapy. The immediate side effects of treatment had a significantly negative impact on the patients' QOL. The impact was relatively large for the functional and treatment-site aspects.

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Mechanochemical processing of anhydrous chloride precursors with Na2CO3 has been investigated as a means of manufacturing nanocrystalline SnO2 doped ZnO photocatalysts. High-energy milling and heat-treatment of a 0.1SnCl2+0.9ZnCl2+Na2CO3+4NaCl reactant mixture was found to result in the formation of a composite powder consisting of oxide grains embedded within a matrix of NaCl. Subsequent washing with deionized water resulted in removal of the NaCl matrix phase and partial hydration of the oxide reaction product with the consequent formation of ZnSn(OH)6. The extent of this hydration reaction was found to decrease in a linear fashion with the temperature of the post-milling heat-treatment over the range of 400–700 °C. For a heat-treatment temperature of 700 °C, the SnO2 doped ZnO powder was found to exhibit significantly higher photocatalytic activity than either single-phase SnO2 or ZnO powders that were synthesized using similar processing conditions. The heightened photocatalytic activity of the SnO2 doped ZnO was attributed to its higher specific surface area and the enhanced charge separation arising from the coupling of ZnO with SnO2.

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Secondary ion emission from water ice has been studied using Au+, Au3+, and C60+ primary ions. In contrast to the gas phase in which the spectra are dominated by the (H2O)nH+ series of ions, the spectra from ice using all three primary ions are principally composed of two series of cluster ions (H2O)nH+ and (H2O)n+. Dependent on the conditions, the unprotonated series can dominate the spectra. Since in the gas phase (H2O)n+ is unstable with respect to the formation of the protonated ion series, the presence of the solid must provide a means to stabilize their formation. The cluster ion yields under Au+ bombardment are very low and can be understood in terms of sputtering on the borderline between linear cascade and thermal spike behavior. There is a 104 increase in yield across the whole spectrum compared to Au+ when Au3+ and C60+ species are used as primary ions. The character of the spectra differed between these two primary ions, but insights into the mechanism of secondary ion emission for both is discussed within an energy deposition framework provided by the fluid flow-based mesoscale energy deposition footprint (MEDF) model that predicts a cone-shaped zone of activation and emission. C60+ differs from Au3+ in that it delivers its energy closer to the surface, and it is argued this has consequences for the cluster ion distribution and yield. Increasing the ion dose by sputtering suppresses the yield of (H2O)n+ and increases the yield of the protonated ions in the small cluster region, whereas the yield in the large cluster regime is suppressed significantly. The three primary ions show rather different behavior, and this is discussed in the light of the sputtering models. Finally, negative ion spectra including cluster ions have been observed for the first time. C60+ delivers the highest yields, but these are less than 10 times the positive ion yields, probably because the O and OH fragment ions on which the clusters are based are easily neutralized by protons.

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BACKGROUND: Needs assessment should be the starting point for curriculum development. In medical education, expert opinion and consensus methods are commonly employed. AIM: This paper showcases a more practice-grounded needs assessment approach. METHODS: A mixed-methods approach, incorporating a national survey, practice audit, and expert consensus, was developed and piloted in thrombosis medicine; Phase 1: National survey of practicing consultants, Phase 2: Practice audit of consult service at a large academic centre and Phase 3: Focus group and modified Delphi techniques vetting Phase 1 and 2 findings. RESULTS: Phase 1 provided information on active curricula, training and practice patterns of consultants, and volume and variety of thrombosis consults. Phase 2's practice audit provided empirical data on the characteristics of thrombosis consults and their associated learning issues. Phase 3 generated consensus on a final curricular topic list and explored issues regarding curriculum delivery and accreditation. CONCLUSIONS: This approach offered a means of validating expert and consensus derived curricular content by incorporating a novel practice audit. By using this approach we were able to identify gaps in training programs and barriers to curriculum development. This approach to curriculum development can be applied to other postgraduate programs.

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

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Avaliou-se o efeito da substituição parcial do farelo de soja (FS) por hidrolisado protéico do conteúdo celular de levedura (HPCCL), proteína isolada de soja (PIS) ou hidrolisado protéico de mucosa intestinal de suínos (HPMIS) em dietas com leite em pó integral (LPI) sobre o desempenho, os níveis séricos de uréia e a incidência de diarréia em leitões desmamados. Foram utilizados 40 leitões desmamados aos 21 dias de idade (20 machos castrados e 20 fêmeas), distribuídos em delineamento em blocos ao acaso, com cinco tratamentos (dietas) e oito repetições. As dietas foram fornecidas em três fases, de acordo com a idade dos animais: fase pré-inicial 1 (21 aos 35 dias de idade): dieta à base de milho e farelo de soja (FS); dieta com 15,0% LPI; dieta com 15,0% LPI + 3,5% HPMIS; dieta com 15,0% LPI + 5,0% de PIS; dieta com 15,0% LPI + 5,0% HPCCL. Na fase pré-inicial 2 (36 aos 49 dias de idade), foi mantida a dieta à base de milho e farelo de soja e o LPI foi reduzido para 7,5% em todas as dietas, o HPMIS para 1,5%, a PIS para 4% e o HPCCL foi mantido em 5%. Na fase inicial (50 aos 70 dias de idade), foi mantida a dieta à base de milho e farelo de soja, o LPI foi retirado de todas as dietas e os animais que nas fases pré-inicial 1 e 2 foram alimentados com as dietas contendo LPI e LPI + HPMIS passaram a ser alimentados com a dieta à base de milho e farelo de soja; a PIS foi reduzida para 3% e o HPCCL para 2,5%. No período de 21 a 35 dias, a dieta LPI + PIS proporcionou maior ganho diário de peso e melhor conversão alimentar. Nas fases seguintes, não houve diferença no desempenho entre as dietas. Até cinco dias após o desmame, os animais alimentados com as rações FS e LPI + PIS apresentaram menor índice de diarréia. Os níveis séricos de uréia não foram influenciados pelas dietas. A utilização de PIS, HPMIS e HPCCL em dietas complexas contendo leite em pó pode consistir em alternativa biologicamente viável em dietas para leitões.

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