Sequential spectrofluorimetric determination of free and total glycerol in biodiesel in a multicommuted flow system

A new procedure for spectrofluorimetric determination of free and total glycerol in biodiesel samples is presented. It is based on the oxidation of glycerol by periodate, forming formaldehyde, which reacts with acetylacetone, producing the luminescent 3,5-diacetyl-1,4-dihydrolutidine. A flow system with solenoid micro-pumps is proposed for solution handling. Free glycerol was extracted off-line from biodiesel samples with water, and total glycerol was converted to free glycerol by saponification with sodium ethylate under sonication. For free glycerol, a linear response was observed from 5 to 70 mg L(-1) with a detection limit of 0.5 mg L(-1), which corresponds to 2 mg kg(-1) in biodiesel. The coefficient of variation was 0.9% (20 mg L(-1), n = 10). For total glycerol, samples were diluted on-line, and the linear response range was 25 to 300 mg L(-1). The detection limit was 1.4 mg L(-1) (2.8 mg kg(-1) in biodiesel) with a coefficient of variation of 1.4% (200 mg L(-1), n = 10). The sampling rate was ca. 35 samples h(-1) and the procedure was applied to determination of free and total glycerol in biodiesel samples from soybean, cottonseed, and castor beans.

Multi-commutation in spectrometry

We review recent developments in manifold components and the introduction of light-emitting-diode technology in spectroscopic detection in order to evaluate the tremendous possibilities offered by multi-commutation for infield and in-situ measurements, based on the use of multi-pumping and low-voltage, portable batteries, which make possible a dramatic reduction in size, weight and power requirements of spectrometric devices. (C) 2009 Elsevier Ltd. All rights reserved.

Natural and human forcing in recent geomorphic change; case studies in the Rio de la Plata basin

An analysis of geomorphic system`s response to change in human and natural drivers in some areas within the Rio de la Plata basin is presented The aim is to determine whether an acceleration of geomorphic processes has taken place in recent years and, if so, to what extent it is due to natural (climate) or human (land-use) drivers Study areas of different size, socio-economic and geomorphic conditions have been selected: the Rio de la Plata estuary and three sub-basins within its watershed Sediment cores were extracted and dated ((210)Pb) to determine sedimentation rates since the end of the 19th century. Rates were compared with time series on rainfall as well as human drivers such as population, GDP, livestock load, crop area, energy consumption or cement consumption, all of them related to human capacity to disturb land surface Data on river discharge were also gathered Results obtained indicate that sedimentation rates during the last century have remained essentially constant in a remote Andean basin, whereas they show important increases in the other two, particularly one located by the Sao Paulo metropolitan area Rates in the estuary are somewhere in between It appears that there is an intensification of denudation/sedimentation processes within the basin. Rainfall remained stable or varied very slightly during the period analysed and does not seem to explain increases of sedimentation rates observed. Human drivers, particularly those more directly related to capacity to disturb land surface (GDP, energy or cement consumption) show variations that suggest human forcing is a more likely explanation for the observed change in geomorphic processes It appears that a marked increase in denudation, of a ""technological"" nature, is taking place in this basin and leading to an acceleration of sediment supply This is coherent with similar increases observed in other regions (C) 2010 Elsevier B V All rights reserved

Composite materials of thermoplastic starch and fibers from the ethanol-water fractionation of bagasse

The aim of this study was to evaluate the potential of the fibrous material obtained from ethanol-water fractionation of bagasse as reinforcement of thermoplastic starches in order to improve their mechanical properties. The composites were elaborated using matrices of corn and cassava starches plasticized with 30 wt%glycerin. The mixtures (0,5,10 and 15 wt% bagasse fiber) were elaborated in a rheometer at 150 degrees C. The mixtures obtained were pressed on a hot plate press at 155 degrees C. The test specimens were obtained according to ASTM D638. Tensile tests, moisture absorption tests for 24 days (20-23 degrees C and 53% RH, ASTM E104), and dynamic-mechanical analyses (DMA) in tensile mode were carried out. Images by scanning electron microscopy (SEM) and X-ray diffraction were obtained. Fibers (10 wt% bagasse fiber) increased tensile strength by 44% and 47% compared to corn and cassava starches, respectively. The reinforcement (15 wt% bagasse fiber) increased more than fourfold the elastic modulus on starch matrices. The storage modulus at 30 C (E(30 degrees C)`) increased as the bagasse fiber content increased, following the trend of tensile elastic modulus. The results indicate that these fibers have potential applications in the development of biodegradable composite materials. (c) 2011 Elsevier B.V. All rights reserved.

Climate as the most important factor determining anti-fungal biocide performance in paint films

The effect of Pigment Volume Content (PVC) on fungal growth on acrylic paint formulations with and without biocide, exposed to weathering in three different climatic regions in Brazil for four years, was studied Latex paints. with PVC of 30%, 35% and 50%, were applied to autoclaved aerated concrete blocks pre-covered with acrylic sealer and acrylic plaster They were exposed to equatorial, tropical and temperate climates in north, south-east, and south Brazil Cladosporium was the most abundant fungal genus detected in the biofilm on the surfaces of all paint formulations at all sites after four years Heaviest fungal colonization occurred in the tropical south-east and lightest in the temperate south of the country, but more phototrophs, principally cyanobacteria, were detected in the equatorial region PVC and presence of biocides were shown to be of less importance than environmental conditions (irradiance, humidity and temperature) for biofilm formation and consequent discolouration These results have important implications for testing of paint formulations (C) 2010 Elsevier B V All rights reserved

Chemical interaction between EVA and Portland cement hydration at early-age

Ethylene/vinyl acetate (EVA) copolymer. as latex or redispersable powder, is added to mortars and concrete to improve the fracture toughness, impermeability and bond strength to various substrates. The physical and chemical interactions were already proved after one day of hydration but during the first hour just the physical interaction was identified and some evidences of a chemical interaction. The aim of this paper was to evaluate the chemical interaction between EVA and Portland cement during the first hours of hydration in the thermogravimetric analysis. The results confirmed that the EVA hydrolyses in pH alkaline and consumes calcium ions from the solution, forming an organic salt (calcium acetate). reducing the calcium hydroxide content. And, its interaction occurred in the first 15 min of hydration. (C) 2009 Elsevier Ltd. All rights reserved.

Inhibition of Auxin Transport from the Ovary or from the Apical Shoot Induces Parthenocarpic Fruit-Set in Tomato Mediated by Gibberellins

Fruit-set in tomato (Solanum lycopersicum) depends on gibberellins and auxins (GAs). Here, we show, using the cv MicroTom, that application of N-1-naphthylphthalamic acid (NPA; an inhibitor of auxin transport) to unpollinated ovaries induced parthenocarpic fruit-set, associated with an increase of indole-3-acetic acid (IAA) content, and that this effect was negated by paclobutrazol (an inhibitor of GA biosynthesis). NPA-induced ovaries contained higher content of GA(1) (an active GA) and transcripts of GA biosynthetic genes (SlCPS, SlGA20ox1, and -2). Interestingly, application of NPA to pollinated ovaries prevented their growth, potentially due to supraoptimal IAA accumulation. Plant decapitation and inhibition of auxin transport by NPA from the apical shoot also induced parthenocarpic fruit growth of unpollinated ovaries. Application of IAA to the severed stump negated the plant decapitation effect, indicating that the apical shoot prevents unpollinated ovary growth through IAA transport. Parthenocarpic fruit growth induced by plant decapitation was associated with high levels of GA(1) and was counteracted by paclobutrazol treatment. Plant decapitation also produced changes in transcript levels of genes encoding enzymes of GA biosynthesis (SlCPS and SlGA20ox1) in the ovary, quite similar to those found in NPA-induced fruits. All these results suggest that auxin can have opposing effects on fruit-set, either inducing (when accumulated in the ovary) or repressing (when transported from the apical shoot) that process, and that GAs act as mediators in both cases. The effect of NPA application and decapitation on fruit-set induction was also observed in MicroTom lines bearing introgressed DWARF and SELF-PRUNING wild-type alleles.

Adenanthera pavonina TRYPSIN INHIBITOR RETARD GROWTH OF Anagasta kuehniella (LEPIDOPTERA: PYRALIDAE)

Anagasta kuehniella is a polyphagous pest that feeds on a wide variety of stored products. The possible roles suggested for seed proteinase inhibitors include the function as a part of the plant defensive system against pest via inhibition of their proteolytic enzymes. In this study, a trypsin inhibitor (ApTI) was purified from Adenanthera pavonina seed and was tested for insect growth regulatory effect. The chronic ingestion of ApTI did result in a significant reduction in larval survival and weight. Larval and pupal developmental time of larvae fed on ApTI diet at 1% was significantly longer; the larval period was extended by 5 days and pupal period was 10 days longer, therefore delaying by up to 20 days and resulting in a prolonged period of development from larva to adult. As a result, the ApTI diet emergence rate was only 28% while the emergence rate of control larvae was 80%. The percentage of surviving adults (%S) decreased to 62%. The fourth instar larvae reared on a diet containing 1% ApTI showed a decrease in tryptic activity of gut and that no novel proteolytic form resistant to ApTI was induced. In addition, the tryptic activity in ApTI -fed larvae was sensitive to ApTI. These results suggest that ApTI have a potential antimetabolic effect when ingested by A. kuehniella. (C) 2010 Wiley Periodicals, Inc.

Regulatory effects of an inhibitor from Plathymenia foliolosa seeds on the larval development of Anagasta kuehniella (Lepidoptera)

The Mediterranean flour moth, Anagasta kuehniella, is one of the most important insect pests of grains, reported worldwide, feeding on stored grains and products of rice, rye, corn and wheat. Plants synthesize a variety of molecules, including trypsin inhibitors, to defend themselves against attack by insects. In this study, a trypsin inhibitor (PFTI) was purified from Plathymenia foliolosa (Benth.) seeds and was tested for insect growth regulatory effect. The survival and mass of A. kuehniella larvae feeding on control seeds were about 82.7% and 5 ring, respectively, whereas survival on seeds containing 0.7% PFTI was about 56%, while a 66.1% reduction in the average mass of the larvae was observed. The results from dietary utilization experiments with A. kuehniella larvae showed a reduction in efficiency of conversion of ingested food and digested food, and an increase in approximate digestibility and metabolic cost. The level of trypsin was significantly decreased in larval midgut and increased in the feces of larvae reared on a diet containing 0.7% PFTI. Results indicate that PFTI possesses a toxic effect against A. kuehniella larvae. (C) 2008 Elsevier Inc. All rights reserved.

Purification and Characterization of a Trypsin Inhibitor from Plathymenia foliolosa Seeds

A novel trypsin inhibitor (PFTI) was isolated from Plathymenia foliolosa (Benth.) seeds by gel filtration chromatography on a Sephadex G-100, DEAE-Sepharose, and trypsin-Sepharose columns. By SDS-PAGE, PFTI yielded a single band with a M(r) of 19 kDa. PFTI inhibited bovine trypsin and bovine chymotrypsin with equilibrium dissociation constants (K(i)) of 4 x 10(-8) and 1.4 x 10(-6) M, respectively. PFTI retained more than 50% of activity at up to 50 degrees C for 30 min, but there were 80 and 100% losses of activity at 60 and 70 degrees C, respectively. DTT affected the activity or stability of PFTI. The N-terminal amino acid sequence of PFTI showed a high degree of homology with various members of the Kunitz family of inhibitors. Anagasta kuehniella is found worldwide; this insect attacks stored grains and products of rice, oat, rye, corn, and wheat. The velvet bean caterpillar (Anticarsia gemmatalis) is considered the main defoliator pest of soybean in Brazil. Diatraea saccharalis, the sugar cane borer, is the major pest of sugar cane crops, and its caterpillar-feeding behavior, inside the stems, hampers control. PFTI showed significant inhibitory activity against trypsin-like proteases present in the larval midguts on A. kuehniella and D. saccharalis and could suppress the growth of larvae.

Viroid species associated with the bark-cracking phenotype of `Tahiti` acid lime in the State of Sao Paulo, Brazil

Viroids have been used as ""graft transmissible dwarfing agents"" (GTDA) in several countries, mainly to reduce growth of citrus trees, thus increasing their density in orchards. In the State of Sao Paulo, Brazil, plants of the acid lime `Tahiti` are usually grafted with a complex of GTDA, presumably viroids. The aim of the present work was the identification and molecular characterization of the viroids infecting trees of acid lime `Tahiti` displaying ""Quebra galho"" (bark-cracking). Viroids were identified and characterized by biological indexing in `Etrog` citron, Northern-blot hybridization, RT-PCR, cloning and complete sequencing of the RNA genomes. Citrus exocortis viroid (CEVd), Hop stunt viroid (HSVd) and Citrus dwarfing viroid (CDVd) were found in different combinations. Although we have not been able to infer a direct relationship between the agronomical performance and symptom severity with the presence of a specific viroid or viroid combination, the differences in the severity of ""Quebra-galho"" symptoms among different trees is probably associated with the presence (or absence) of CEVd, with its interaction with other viroids perhaps determining the different phenotypes observed in the field.

Pyrolysis-Gas Chromatography/Mass Spectrometry of Soil Organic Matter Extracted from a Brazilian Mangrove and Spanish Salt Marshes

The soil organic matter (SOM) extracted under different vegetation types from a Brazilian mangrove (Pai Matos Island, Sao Paulo State) and from three Spanish salt marshes (Betanzos Ria and Corrubedo Natural Parks, Galicia, and the Albufera Natural Park, Valencia) was investigated by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). The chemical variation was larger in SOM from the Spanish marshes than in the SOM of the Brazilian mangroves, possibly because the marshes included sites with both tidal and nontidal variation, whereas the mangrove forest underwent just tidal variation. Thus, plant-derived organic matter was better preserved under permanently anoxic environments. Moreover, given the low number of studied profiles and sedimentary-vegetation sequences in both areas, depth trends remain unclear. The chemical data also allow distinction between the contributions of woody and nonwoody vegetation inputs. Soil organic matter decomposition was found to cause: (i) a decrease in lignin contents and a relative increase in aliphatics; (ii) an increase in short-chain aliphatics at the expense of longer ones; (iii) a loss of odd-over-even dominance in alkanes and alkenes; and (iv) an increase in microbial products, including proteins, sterols, short-chain fatty acids, and alkanes. Pyrolysis-gas chromatography/mass spectrometry is a useful tool to study the behavior and composition of SOM in wetland environments such as mangroves and salt marshes. Additional profiles need to be studied for each vegetation type, however, to improve the interpretability of the chemical data.

Spatial patterns of soil attributes and components in a mangrove system in Southeast Brazil (Sao Paulo)

Purpose Among environmental factors governing innumerous processes that are active in estuarine environments, those of edaphic character have received special attention in recent studies. With the objectives of determining the spatial patterns of soil attributes and components across different mangrove forest landscapes and obtaining additional information on the cause-effect relationships between these variables and position within the estuary, we analyzed several soil attributes in 31 mangrove soil profiles from the state of So Paulo (Guaruja, Brazil). Materials and methods Soil samples were collected at low tide along two transects within the CrumahA(0) mangrove forest. Samples were analyzed to determine pH, Eh, salinity, and the percentages of sand, silt, clay, total organic carbon (TOC), and total S. Mineralogy of the clay fraction (< 2 mm) was also studied by X-ray diffraction analysis, and partitioning of solid-phase Fe was performed by sequential extraction. Results and discussion The results obtained indicate important differences in soil composition at different depths and landscape positions, causing variations in physicochemical parameters, clay mineralogy, TOC contents, and iron geochemistry. The results also indicate that physicochemical conditions may vary in terms of different local microtopographies. Soil salinity was determined by relative position in relation to flood tide and transition areas with highlands. The proportions of TOC and total S are conditioned by the sedimentation of organic matter derived from vegetation and by the prevailing redox conditions, which clearly favored intense sulfate reduction in the soils (similar to 80% of the total Fe is Fe-pyrite). Particle-size distribution is conditioned by erosive/deposition processes (present and past) and probably by the positioning of ancient and reworked sandy ridges. The existing physicochemical conditions appear to contribute to the synthesis (smectite) and transformation (kaolinite) of clay minerals. Conclusions The results demonstrate that the position of soils in the estuary greatly affects soil attributes. Differences occur even at small scales (meters), indicating that both edaphic (soil classification, soil mineralogy, and soil genesis) and environmental (contamination and carbon stock) studies should take such variability into account.

Bacterial communities and biogeochemical transformations of iron and sulfur in a high saltmarsh soil profile

Microbial community structure in saltmarsh soils is stratified by depth and availability of electron acceptors for respiration. However, the majority of the microbial species that are involved in the biogeochemical transformations of iron (Fe) and sulfur (S) in such environments are not known. Here we examined the structure of bacterial communities in a high saltmarsh soil profile and discuss their potential relationship with the geochemistry of Fe and S. Our data showed that the soil horizons Ag (oxic-suboxic), Bg (suboxic), Cri (anoxic with low concentration of pyrite Fe) and Cr-2 (anoxic with high concentrations of pyrite Fe) have distinct geochemical and microbiological characteristics. In general, total S concentration increased with depth and was correlated with the presence of pyrite Fe. Soluble + exchangable-Fe, pyrite Fe and acid volatile sulfide Fe concentrations also increased with depth, whereas ascorbate extractable-Fe concentrations decreased. The occurrence of reduced forms of Fe in the horizon Ag and oxidized Fe in horizon Cr-2 suggests that the typical redox zonation, common to several marine sediments, does not occur in the saltmarsh soil profile studied. Overall, the bacterial community structure in the horizon Ag and Cr-2 shared low levels of similarity, as compared to their adjacent horizons, Bg and Cr-1, respectively. The phylogenetic analyses of bacterial 16S rRNA gene sequences from clone libraries showed that the predominant phylotypes in horizon Ag were related to Alphaproteobacteria and Bacteroidetes. In contrast, the most abundant phylotypes in horizon Cr-2 were related to Deltaproteo-bacteria, Chloroflexi, Deferribacteres and Nitrospira. The high frequency of sequences with low levels of similarity to known bacterial species in horizons Ag and Cr-2 indicates that the bacterial communities in both horizons are dominated by novel bacterial species. (c) 2008 Elsevier Ltd. All rights reserved.

Influence of magnesium status and magnesium intake on the blood glucose control in patients with type 2 diabetes

Background & aims: This study was undertaken to assess magnesium intake and magnesium status in patients with type 2 diabetes, and to identify the parameters that best predict alterations in fasting glucose and plasma magnesium. Methods: A cross-sectional study was carried out in patients with type 2 diabetes (n = 51; 53.6 +/- 10.5 y) selected within the inclusion factors, at the University Hospital Onofre Lopes. Magnesium intake was assessed by three 24-h recalls. Urine, plasma and erythrocytes magnesium, fasting and 2-h postprandial glucose, HbA1, microalbuminuria, proteinuria, and serum and urine creatinine were measured. Results: Mean magnesium intake (9.37 +/- 1.76 mmol/d), urine magnesium (2.80 +/- 1.51 mmol/d), plasma magnesium (0.71 +/- 0.08 mmol/L) and erythrocyte magnesium (1.92 +/- 0.23 mmol/L) levels were low. Seventy-seven percent of participants presented one or more magnesium status parameters below the cut-off points of 3.00 mmol/L for urine, 0.75 mmol/L for plasma and 1.65 mmol/L for erythrocytes. Subjects presented poor blood glucose control with fasting glucose of 8.1 +/- 3.7 mmol/L, 2-h postprandial glucose of 11.1 +/- 5.1 mmol/L, and HbA1 of 11.4 +/- 3.0%. The parameters that influenced fasting glucose were urine, plasma and dietary magnesium, while plasma magnesium was influenced by creatinine clearance. Conclusions: Magnesium status was influenced by kidney depuration and was altered in patients with type 2 diabetes, and magnesium showed to play an important role in blood glucose control. (C) 2011 Elsevier Ltd and European Society for Clinical Nutrition and Metabolism. All rights reserved.