886 resultados para 030106 Quality Assurance Chemometrics Traceability and Metrological Chemistry


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Studies within the QLIF project reviewed in this article suggest that organic or low-input management is more likely to result in milk with fatty acid profiles that are higher in α-linolenic acid and/or beneficial isomers of conjugated linoleic acid and antioxidants with up to a 2.5-fold increase in some cases, relative to milk from conventional production. These advantages are preserved during processing, resulting in elevated contents or concentrations of these constituents in processed dairy products of organic or low input origin. Much of the literature suggests that these benefits are very likely to be a result of a greater reliance on forages in the dairy diets (especially grazed grass). Since the adoption of alternative breeds or crosses is often an integral part sustaining these low-input systems, it is not possible to rule out an interaction with genotype in these monitored herds. The results suggest that milk fat composition with respect to human health can be optimized by exploiting grazing in the diet of dairy cows. However, in many European regions this may not be possible due to extremes in temperature, soil moisture levels or both. In such cases milk quality can be maintained by the inclusion of oil seeds in the dairy diets.

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Aim Most vascular plants on Earth form mycorrhizae, a symbiotic relationship between plants and fungi. Despite the broad recognition of the importance of mycorrhizae for global carbon and nutrient cycling, we do not know how soil and climate variables relate to the intensity of colonization of plant roots by mycorrhizal fungi. Here we quantify the global patterns of these relationships. Location Global. Methods Data on plant root colonization intensities by the two dominant types of mycorrhizal fungi world-wide, arbuscular (4887 plant species in 233 sites) and ectomycorrhizal fungi (125 plant species in 92 sites), were compiled from published studies. Data for climatic and soil factors were extracted from global datasets. For a given mycorrhizal type, we calculated at each site the mean root colonization intensity by mycorrhizal fungi across all potentially mycorrhizal plant species found at the site, and subjected these data to generalized additive model regression analysis with environmental factors as predictor variables. Results We show for the first time that at the global scale the intensity of plant root colonization by arbuscular mycorrhizal fungi strongly relates to warm-season temperature, frost periods and soil carbon-to-nitrogen ratio, and is highest at sites featuring continental climates with mild summers and a high availability of soil nitrogen. In contrast, the intensity of ectomycorrhizal infection in plant roots is related to soil acidity, soil carbon-to-nitrogen ratio and seasonality of precipitation, and is highest at sites with acidic soils and relatively constant precipitation levels. Main conclusions We provide the first quantitative global maps of intensity of mycorrhizal colonization based on environmental drivers, and suggest that environmental changes will affect distinct types of mycorrhizae differently. Future analyses of the potential effects of environmental change on global carbon and nutrient cycling via mycorrhizal pathways will need to take into account the relationships discovered in this study.

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The study of decaying organisms and death assemblages is referred to as forensic taphonomy, or more simply the study of graves. This field is dominated by the fields of entomology, anthropology and archaeology. Forensic taphonomy also includes the study of the ecology and chemistry of the burial environment. Studies in forensic taphonomy often require the use of analogues for human cadavers or their component parts. These might include animal cadavers or skeletal muscle tissue. However, sufficient supplies of cadavers or analogues may require periodic freezing of test material prior to experimental inhumation in the soil. This study was carried out to ascertain the effect of freezing on skeletal muscle tissue prior to inhumation and decomposition in a soil environment under controlled laboratory conditions. Changes in soil chemistry were also measured. In order to test the impact of freezing, skeletal muscle tissue (Sus scrofa) was frozen (−20 °C) or refrigerated (4 °C). Portions of skeletal muscle tissue (∼1.5 g) were interred in microcosms (72 mm diameter × 120 mm height) containing sieved (2 mm) soil (sand) adjusted to 50% water holding capacity. The experiment had three treatments: control with no skeletal muscle tissue, microcosms containing frozen skeletal muscle tissue and those containing refrigerated tissue. The microcosms were destructively harvested at sequential periods of 2, 4, 6, 8, 12, 16, 23, 30 and 37 days after interment of skeletal muscle tissue. These harvests were replicated 6 times for each treatment. Microbial activity (carbon dioxide respiration) was monitored throughout the experiment. At harvest the skeletal muscle tissue was removed and the detritosphere soil was sampled for chemical analysis. Freezing was found to have no significant impact on decomposition or soil chemistry compared to unfrozen samples in the current study using skeletal muscle tissue. However, the interment of skeletal muscle tissue had a significant impact on the microbial activity (carbon dioxide respiration) and chemistry of the surrounding soil including: pH, electroconductivity, ammonium, nitrate, phosphate and potassium. This is the first laboratory controlled study to measure changes in inorganic chemistry in soil associated with the decomposition of skeletal muscle tissue in combination with microbial activity.

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The photolytic phenanthrene-based precursors for both β-methoxycarbene and β-ethoxycarbene were synthesized with and without a deuterium label attached to the a carbon. The incorporation of this deuterium label allowed distinction between a 1, 2-H shift and a 1, 2-O shift pathway to the respective alkyl vinyl ether, without the influence of a primary kinetic isotope effect. Photolyses of these precursors gave rearrangement products of the expected β-alkoxycarbenes. In the case of β-methoxycarbene, no methyl vinyl ether was observed due to its volatility. However, the appearance of aldehyde peaks in the NMR spectra, from an apparent further rearrangement to acetaldehyde through an enol intermediate, indicated that a 1,2-H shift had occurred. Ethyl vinyl ether was isolated following the photolysis of the β-ethoxycarbene precursor. Quantification of the two pathways showed less than 2% undergoing an ethoxy shift to the ethyl vinyl ether. Yield experiments on this photolysis demonstrated a maximum yield of β-ethoxycarbene as 43%, though this decreased as the experiment continued. Computational work on the β-ethoxycarbene system indicates that the triplet scate is more stable than the singlet. In addition, the activation energy to the 1.2-H shift pathway is remarkably low and is clearly consistent with the observed overwhelming preference for this pathway in the experiment.

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The increasing availability of social statistics in Latin America opens new possibilities in terms of accountability and incentive mechanisms for policy makers. This paper addresses these issues within the institutional context of the Brazilian educational system. We build a theoretical model based on the theory of incentives to analyze the role of the recently launched Basic Education Development Index (Ideb) in the provision of incentives at the sub-national level. The first result is to demonstrate that an education target system has the potential to improve the allocation of resources to education through conditional transfers to municipalities and schools. Second, we analyze the local government’s decision about how to allocate its education budget when seeking to accomplish the different objectives contemplated by the index, which involves the interaction between its two components, average proficiency and the passing rate. We discuss as well policy issues concerning the implementation of the synthetic education index in the light of this model arguing that there is room for improving the Ideb’s methodology itself. In addition, we analyze the desirable properties of an ideal education index and we argue in favor of an ex-post relative learning evaluation system for different municipalities (schools) based on the value added across different grades

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Plant nutrition can positively influence quality of seeds by improving plant tolerance to adverse climate. In this context, silicon is currently considered a micronutrient and it is beneficial to plant growth, especially Poaceaes such as white oat and wheat, thereby improving physiological quality of seeds. This study had the objective of evaluating the effects of silicon leaf application on plant tillering, silicon levels and physiological quality of white oat and wheat seeds besides establishing correlations between them. Two experiments were carried out in winter with white oat and wheat. The experimental design was the completely randomized block with eight replications. Treatments consisted of foliar application of silicon (0.8% of soluble silicon, as stabilized orthosilicic acid) and a control (with no application). Silicon levels in leaves were determined at flowering whereas the number of plants and panicles/spikes per area was counted right before harvest. Seed quality was evaluated right after harvest through mass, germination and vigor tests. Data was submitted to variance analysis and means were compared by the Tukey test at a probability level of 5%. Person's linear correlation test was performed among silicon level in plants, tillering and seed quality data. Silicon leaf application increases root and total length of white oat seedlings as an effect of higher Si level in leaves. Silicon leaf application increases mass of wheat seeds without affecting germination or vigor.

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Cellulose is the major constituent of most plants of interest as renewable sources of energy and is the most extensively studied form of biomass or biomass constituent. Predicting the mass loss and product yields when cellulose is subjected to increased temperature represents a fundamental problem in the thermal release of biomass energy. Unfortunately, at this time, there is no internally consistent model of cellulose pyrolysis that can organize the varied experimental data now available or provide a guide for additional experiments. Here, we present a model of direct cellulose pyrolysis using a multistage decay scheme that we first presented in the IJQC in 1984. This decay scheme can, with the help of an inverse method of assigning reaction rates, provide a reasonable account of the direct fast pyrolysis yield measurements. The model is suggestive of dissociation states of d-glucose (C6H10O5,), the fundamental cellulose monomer. The model raises the question as to whether quantum chemistry could now provide the dissociation energies for the principal breakup modes of glucose into C-1, C-2, C-3, C-4, and C-5 compounds. These calculations would help in achieving a more fundamental description of volatile generation from cellulose pyrolysis and could serve as a guide for treating hemicellulose and lignin, the other major biomass constituents. Such advances could lead to the development of a predictive science of biomass pyrolysis that would facilitate the design of liquifiers and gasifiers based upon renewable feedstocks. (C) 1998 John Wiley & Sons, Inc.

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The effects of ambient temperature and humidity, month, age and genotype on sperm production and semen quality in AI bulls in Brazil were evaluated. Data from two consecutive years were analyzed separately. Seven Bos indicus and 11 Bos taurus bulls from one artificial insemination (AI) center were evaluated in Year 1 and 24 B. indicus and 16 B. taurus bulls from three AI centers were evaluated in Year 2. Ambient temperature and humidity did not significantly affect sperm production and semen quality, probably because there was little variation in these variables. Month accounted for less than 2% of the variation in sperm production and semen quality. Increased bull age was associated with decreased sperm motility (P < 0.10) and increased minor sperm defects (P < 0.001) in Year 1. B. indicus bulls had greater (P < 0.005) sperm concentration than B. taurus bulls in both years (1.7 x 10(9)/ml versus 1.2 x 10(9)/ml in Year 1 and 1.6 x 10(9)/ml versus 1.2 x 10(9)/ml in Year 2, respectively). Ejaculate volume was not significantly affected by genotype in Year 1 (6.6 ml versus 6.9 ml in B. indicus and B. taurus bulls, respectively), but B. indicus bulls had greater (P < 0.05) total (11.4 x 10(9) versus 8.2 x 10(9)) and viable (6.7 x 10(9) versus 4.9 x 10(9)) numbers of spermatozoa in the ejaculate than B. taurus bulls. In Year 2, B. taurus bulls had greater (P < 0.05) ejaculate volume than B. indicus bulls (8.2 ml versus 6.7 ml, respectively) and total and viable number of spermatozoa in the ejaculate were not significantly different between genotypes (10.3 x 10(9) versus 9.1 x 10(9) and 6.1 x 10(9) versus 5.4 x 10(9) in B. indicus and B. taurus bulls, respectively). Sperm motility was not significantly affected by genotype (mean, 59%). In Year 1, B. indicus bulls tended (P < 0.10) to have more major sperm defects and had more (P < 0.05) total sperm defects than B. taurus bulls (11.8% versus 8.7% and 13.6% versus 10.0%, respectively). In Year 2, B. indicus bulls tended (P < 0.10) to have more total sperm defects than B. taurus bulls (16.2% versus 13.3%, respectively). In conclusion, neither ambient temperature and humidity nor month (season) significantly affected sperm production and semen quality. B. indicus bulls had significantly greater sperm concentration and B. taurus bulls had significantly fewer morphologically defective spermatozoa. (C) 2002 Elsevier B.V. B.V. All rights reserved.

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The objective was to evaluate the effects of genetic group and age on growth, carcass, and meat traits of rabbits. A total of 144 straightbred Botucatu and White German Giant x Botucatu crossbred rabbits were involved. Rabbits were weaned at 35 d and sequentially, slaughtered, four per genetic group x sex combination, at: 42, 49, 56, 63, 70, 77, 84 and 91 d. A 2x2 factorial arrangement was employed in a completely randomized design with repeated measures for growth traits, and a split-plot for carcass and meat traits. Crossbred rabbits were heavier (2032 vs. 1962 g; P < 0.01), consumed more feed (143.5 vs. 131.0 g/d; P < 0.01), and presented higher slaughter weight (2169 vs. 2093 g, P=0.02) and dressing percentage (59.0 vs. 58.2%; P=0.07) than straightbreds throughout the experiment. No difference between genetic groups was detected for feed conversion and empty gastrointestinal weight corrected for slaughter weight (SW). Crossbreds showed higher skin weight (308.2 vs. 299.7 g, P = 0.06) and distal parts of leg weight (75.7 vs. 71.4 g; P < 0.01), both corrected for SW. No genetic group effect was detected on dissectible fat and hind part weights. Chilled commercial carcass (1284 vs. 1229 g: P=0.02), chilled reference carcass (1036 vs. 1000 g, P=0.06), fore part (297.9 vs. 283.3 g; P=0.01) and loin (308.7 vs. 295.5 g; P=0.05) were heavier in crossbreds than in straightbreds, but these differences were attributed to differences in SW. Uncorrected weights of head, kidneys, liver and thoracic viscera were higher in the crossbred group, but only head (116.6 vs. 113.6 g; P=0.06) and thoracic viscera (30.4 vs. 28.6 g; P=0.01) were, in fact, proportionately heavier in crossbreds than in straightbreds. No effect of genetic group was detected on meat to bone ratio, muscle ultimate pH and chemical composition of the Longissimus dorsi muscle. All traits, except for ash and fat contents of the Longissimus muscle, showed age effects (P < 0.01). Crossbreeding may be recommended for the production of whole commercial carcasses, but it is not clearly advantageous for the production of retail cuts. Slaughter should take place between 63 and 70 d of age for both genetic groups.

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The stable free radical 2,2,6,6-tetramethylpiperidine-N-oxyl-4-amino-4-carboxylic acid (TOAC) is the only spin labeled amino acid that has been used to date to successfully label peptide sequences for structural studies. However, severe difficulty in coupling the subsequent amino acid has been the most serious shortcoming of this paramagnetic marker. This problem stems from the low nucleophilicity of TOAC's amine group towards the acylation reaction during peptide chain elongation. The present report introduces the alternative beta -amino acid 2,2,5,5-tetramethylpyrrolidine-N-oxyl-3-amino-4-carboxylic acid (POAC), potentially useful in peptide and protein chemistry. Investigations aimed at addressing the stereochemistry of this cyclic molecule through X-ray diffraction measurements of crystalline and bulk samples revealed that it consists only of the trans conformer. The 9-fluorenylmethyloxyearbonyl group (Fmoc) was chosen for temporary protection of the POAC amine function, allowing insertion of the probe at any position in a peptide sequence. The vasoactive octapeptide angiotensin II (AII, DRVYIHPF) was synthesized by replacing Pro(7) with POAC. The reaction of Fmoc-POAC with the peptidyl-resin occurred smoothly, and the coupling of the subsequent amino acid showed a much faster reaction when compared with TOAC. POAC(7)-AII was obtained in good yield, demonstrating that, in addition to TOAC, POAC is a convenient amino acid for the synthesis of spin labeled peptide analogues. The present findings open the possibility of a wide range of chemical and biological applications for this novel beta -amino acid derivative, including structural investigations involving its differentiated bend-inducing characteristics.

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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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Purpose: This study evaluated the adhesive quality of simplified self-adhesive and conventional resin cements to Y-TZP in dry and aged conditions. Methods: Y-TZP ceramic blocks (N=192) (5 x 5 x 2 mm) were embedded in acrylic resin and randomly divided into two groups, based on surface conditioning: 96% isopropanol or chairside tribochemical silica coating and silanization. Conditioned ceramics were divided into four groups to receive the resin cements (Panavia F 2.0, Variolink II, RelyX U100 and Maxcem). After 24 hours, half of the specimens (n=12) from each group were submitted to shear bond strength testing (0.5 nun/minute). The remaining specimens were tested after 90 days of water storage at 37 degrees C and thermocycling (12,000x, 5 degrees C-55 degrees C). Failure types were then assessed. The data were analyzed using three-way ANOVA and the Tukey's test (alpha=0.05). Results: Significant effects of ceramic conditioning, cement type and storage conditions were observed (p<0.0001). The groups cleaned using alcohol only showed low bond strength values in dry conditions and the bond strength was reduced dramatically after aging. Groups conditioned using silica coating and silanization showed higher bond strengths both in dry and aged conditions. A high number of specimens failed prematurely prior to testing when they were cleaned using 96% isopropanol. Conclusion: Overall, silica coating and silanization showed higher, stable bond strengths with and without aging. The durability of resin-ceramic adhesion varied, depending on the adhesive cement type.