Thermoplasticization of High Amylose Starch by Chemical Modification Using Reactive Extrusion

Modified thermoplastic high amylose starch (MTPS) was synthesized by reactive extrusion in the presence of maleic anhydride (MA) as an esterification agent in a twin-screw extruder. The objective of this work was the preparation of reactive thermoplastic starch in the presence of glycerol and with different amounts of maleic anhydride (MA) and free-radical initiator, in order to improve processability and reactivity. The concentration of MA added varied from 2 to 6 wt% (of starch + glycerol), and the free-radical initiator, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, also called Luperox 101, varied from 0.1 to 0.5 wt% (of starch + glycerol). Characterization of maleated thermoplastic starch was performed using dynamic light scattering and thermal analysis. Further, proof of chemically modified extrudate was determined by Fourier transform infrared spectroscopy and by soxhlet extraction with acetone. The modified high amylose corn starch (20 or 30% glycerol) could be pelletized and gave pellets that were more transparent than thermoplastic starches not modified with maleic anhydride. There was negligible change in hydrodynamic radius as the percentage of maleic anhydride increased. However, as the percentage of Luperox 101 increased, the hydrodynamic radius decreased. It could be inferred that the molecular weight decreased as the percentage of free-radical initiator increased. Using the maximum temperature in the extrusion process of 165 °C instead of 135 °C caused a decrease in the hydrodynamic radius, due to the high influence of the temperature profile on the molecular weight of the thermoplastic starch. The MTPS samples presented higher melting temperatures compared to TPS samples. The soxhlet studies indicated that the plasticizer, glycerol, was chemically linked to the starch. Using the maximum temperature of 165 °C versus 135 °C in the extrusion temperature profile resulted in more interaction between glycerol and starch.     

Internal distribution of uranium and associated genotoxic damages in the chronically exposed bivalve Corbicula fluminea

Uranium (U) internal distribution and involved effects in the bivalve Corbicula fluminea have been studied after direct chronic exposure (90 d, 10 μg.L-1). U distribution was assessed at the subcellular level (Metal Rich Granules -MRG-, pellets and cytosol fractions) in two main organs of the bivalve (gills and visceral mass). Micro-localisation was investigated by TEM-EDX analysis in the gills epithelium. DNA damage in gill and hemolymph samples was measured by the Comet assay. The 90-d exposure period led to a significant increase of U concentration in gills over time (×5) and a large U quantity in subcellular granules in gills. Finally, a significant increase (×2) in DNA damage was noted in exposed gills and haemocytes. This study shows that the accumulation levels and consequently the potential toxicity cannot be successfully predicted only on the basis of concentration in water or in tissues and subcellular fractions after chronic exposure.     

Influence of hydroxypropyl-β-cyclodextrin on the biodegradation of C-phenanthrene and C-hexadecane in soil

Soil was spiked with [9-¹⁴C]phenanthrene and [1-¹⁴C]hexadecane at 50 mg kg⁻¹ and aged for 1, 25, 50, 100 and 250 d. At each time point, the microcosms were amended with aqueous solutions of cyclodextrin (HP-β-CD) at a range of concentrations (0-40 mM). Mineralisation assays and aqueous HP-β-CD extractions were performed to assess the effect of the amendments on microbial degradation. The results showed that amendments had no significant impact on the microbial degradation of either of the ¹⁴C-contaminants. Further, HP-β-CD extractions were correlated with the mineralisation of the target chemicals in each of the soil conditions. It was found that the HP-β-CD extraction was able to predict mineralisation in soils which had not been amended with cyclodextrin; however, in the soils containing the HP-β-CD, there was no predictive relationship. Under the conditions of this study, the introduction of HP-β-CD into soils did not enhance the biodegradation of the organic contaminants.     

Linking chemical extraction to microbial degradation of 14C-hexadecane in soil

Chemical extractions have been shown to measure the biodegradable fraction of aromatic contaminants in soil; however, there is little research on the chemical prediction of aliphatic hydrocarbon degradation. The aim of this study was to investigate the potential for cyclodextrin extractions to predict hexadecane biodegradation in soil. Soils were amended with 10 or 100 mg kg⁻¹ of a model alkane n-hexadecane and 100 Bq g⁻¹¹⁴C-n-hexadecane. Correlations between the extents of mineralisation and extractions of the ¹⁴C-contaminant were determined. Solvent shake extractions and aqueous CaCl₂ extractions were poor predictors of hexadecane bioaccessibility. However, the novel HP-α-CD shake extraction showed close correlation (r² = 0.90, n = 36, p < 0.05) to the mineralisation data. This novel extraction technique has the potential to be used to assess the biodegradable aliphatic hydrocarbon fraction in contaminated soils.     

Phytotoxicity and phytoremediation of 2,6-dinitrotoluene using a model plant, Arabidopsis thaliana

Biochemical and genetic studies of xenobiotic metabolism in the model plant Arabidopsis have significant potential in providing information for phytoremediation. This paper presents the toxicity of 2,6-dinitrotoluene (2,6-DNT) to Arabidopsis under axenic conditions, the fate and transformation of 2,6-DNT after uptake by the plant, and the effect of a putative glutathione S-transferase (GST), which is highly induced by 2,4,6-trinitrotoluene (TNT) in the previous study, on the detoxification of 2,6-DNT. 2,6-DNT had toxic effects on the growth of Arabidopsis based on whole seedling as well as root growth assays. Using [U- 14C]2,6-DNT, the recovery was over 87% and less than 2% accounted for the mineralization of 2,6-DNT in axenic liquid cultures during the 14d of exposure. About half (48.3%) of the intracellular radioactivity was located in the root tissues in non-sterile hydroponic cultures. 2-Amino-6-nitrotoluene (2A6NT) and two unknown metabolites were produced as transformation products of 2,6-DNT in the liquid media. The metabolites were further characterized by proton NMR spectra and the UV-chromatograms when the plant was fed with either 2,6-DNT or 2A6NT. In addition, polar unknown metabolites were detected at short retention times from radiochromatograms of plant tissue extracts. The GST gene of the wild-type of Arabidopsis in response to 2,6-DNT was induced by 4.7-fold. However, the uptake rates and the tolerance at different concentrations of 2,6-DNT and TNT were not significantly different between the wild-type and the gst mutant indicating that induction of the GST gene is not related to the detoxification of 2,6-DNT.     

Prenatal diagnosis and outcome of congenital splenic cyst: report of two cases

Congenital splenic cyst (CSC) is a rare condition, and only a few cases with prenatal diagnosis and no associated malformation have been reported. Spontaneous regression is possible in case of mild CSC (under 40 mm), but enlargement or secondary complications may lead to surgical treatment. We report, herein, two cases of isolated mild CSC with complete spontaneous postnatal regression. Copyright © 2006 John Wiley & Sons, Ltd.     

Inventories and Distribution of Radiocaesium in Arctic Marine Sediments: Influence of Biological and Physical Processes

Extensive surveys of sediment burdens of radiocaesium, specifically ¹³⁷Cs, and other radioactive contaminants in the Arctic during the 1990's, indicate that almost all anthropogenic radionuclides buried on continental shelves adjacent to Alaska are derived from global bomb fallout. the ¹³⁷Cs (half-life: 30.2y) activities observed in surface (0-4 cm) marine sediments however, vary widely, albeit much less than the expected current inventory resulting from bomb fallout at this latitude (∼100mBq cm^-2). This observed geographical variation provided the opportunity to evaluate physical and biological mechanisms that may affect caesium biogeochemistry on Arctic continental shelves. We investigated whether high biological productivity in portions of the Bering and Chukchi Seas is effective in removing dissolved radiocaesium from the water column, and whether biological production in overlying water affects total radiocaesium inventories in sediments. Based upon C/N ratios in the organic fraction of shallow sediments, we found no evidence that higher inventories or surface activities of radiocaesium are present in areas with higher deposition of particulate organic matter. Based upon stable carbon isotope ratios of organic matter in sediments, we found no evidence that terrestrial runoff contributes proportionally to higher surface activities, although terrestrial runoff may affect total inventories of the radionuclide. Radiocaesium content of surface sediments was significantly correlated with total organic carbon content of sediments and the proportion of sediments in the finest sediment fractions. Because high current flow can also be expected to influence distributions of those sedimentary parameters, we conclude that re-distribution of