High Aluminum Resistance in Buckwheat1 : II. Oxalic Acid Detoxifies Aluminum Internally

Buckwheat (Fagopyrum esculentum Moench. cv Jianxi), which shows high Al resistance, accumulates Al in the leaves. The internal detoxification mechanism was studied by purifying and identifying Al complexes in the leaves and roots. About 90% of Al accumulated in the leaves was found in the cell sap, in which the dominant organic acid was oxalic acid. Purification of the Al complex in the cell sap of leaves by molecular-sieve chromatography resulted in a complex with a ratio of Al to oxalic acid of 1:3. A 13C-nuclear magnetic resonance study of the purified cell sap revealed only one signal at a chemical shift 164.4 ppm, which was assigned to the Al-chelated carboxylic group of oxalic acid. A 27Al-nuclear magnetic resonance analysis revealed one major signal at the chemical shift of 16.0 to 17.0 ppm, with a minor signal at the chemical shift of 11.0 to 12 ppm in both the intact roots and their cell sap, which is consistent with the Al-oxalate complexes at 1:3 and 1:2 ratios, respectively. The purified cell sap was not phytotoxic to root elongation in corn (Zea mays). All of these results indicate that Al tolerance in the roots and leaves of buckwheat is achieved by the formation of a nonphytotoxic Al-oxalate (1:3) complex.

Redistribution of Soil Organic Matter by Permafrost Disturbance in the Canadian High Arctic

With increased warming in the Arctic, permafrost thaw may induce localized physical disturbance of slopes. These disturbances, referred to as active layer detachments (ALDs), redistribute soil across the landscape, potentially releasing previously unavailable carbon (C). In 2007–2008, widespread ALD activity was reported at the Cape Bounty Arctic Watershed Observatory in Nunavut, Canada. Our study investigated organic matter (OM) composition in soil profiles from ALD-impacted and undisturbed areas. Solid-state 13C nuclear magnetic resonance (NMR) and solvent-extractable biomarkers were used to characterize soil OM. Throughout the disturbed upslope profile, where surface soils and vegetation had been removed, NMR revealed low O-alkyl C content and biomarker analysis revealed low concentrations of solvent-extractable compounds suggesting enhanced erosion of labile-rich OM by the ALD. In the disturbed downslope region, vegetation remained intact but displaced material from upslope produced lateral compression ridges at the surface. High O-alkyl content in the surface horizon was consistent with enrichment of carbohydrates and peptides, but low concentrations of labile biomarkers (i.e., sugars) suggested the presence of relatively unaltered labile-rich OM. Decreased O-alkyl content and biomarker concentrations below the surface contrasted with the undisturbed profile and may indicate the loss of well-established pre-ALD surface drainage with compression ridge formation. However, pre-ALD profile composition remains unknown and the observed decreases may result from nominal pre-ALD OM inputs. These results are the first to establish OM composition in ALD-impacted soil profiles, suggesting reallocation of permafrost-derived soil C to areas where degradation or erosion may contribute to increased C losses from disturbed Arctic soils.

Potential Shifts in Canadian High Arctic Sedimentary Organic Matter Composition With Permafrost Active Layer Detachments

Increased temperature and precipitation in Arctic regions have led to deeper thawing and structural instability in permafrost soil. The resulting localized disturbances, referred to as active layer detachments (ALDs), may transport organic matter (OM) to more biogeochemically active zones. To examine this further, solid state cross polarization magic angle spinning 13C nuclear magnetic resonance (CPMAS NMR) and biomarker analysis were used to evaluate potential shifts in riverine sediment OM composition due to nearby ALDs within the Cape Bounty Arctic Watershed Observatory, Nunavut, Canada. In sedimentary OM near ALDs, NMR analysis revealed signals indicative of unaltered plant-derived material, likely derived from permafrost. Long chain acyclic aliphatic lipids, steroids, cutin, suberin and lignin occurred in the sediments, consistent with a dominance of plant-derived compounds, some of which may have originated from permafrost-derived OM released by ALDs. OM degradation proxies for sediments near ALDs revealed less alteration in acyclic aliphatic lipids, while constituents such as steroids, cutin, suberin and lignin were found at a relatively advanced stage of degradation. Phospholipid fatty acid analysis indicated that microbial activity was higher near ALDs than downstream but microbial substrate limitation was prevalent within disturbed regions. Our study suggests that, as these systems recover from disturbance, ALDs likely provide permafrost-derived OM to sedimentary environments. This source of OM, which is enriched in labile OM, may alter biogeochemical patterns and enhance microbial respiration within these ecosystems.

Redistribution of Soil Organic Matter by Permafrost Disturbance in the Canadian High Arctic

With increased warming in the Arctic, permafrost thaw may induce localized physical disturbance of slopes. These disturbances, referred to as active layer detachments (ALDs), redistribute soil across the landscape, potentially releasing previously unavailable carbon (C). In 2007–2008, widespread ALD activity was reported at the Cape Bounty Arctic Watershed Observatory in Nunavut, Canada. Our study investigated organic matter (OM) composition in soil profiles from ALD-impacted and undisturbed areas. Solid-state 13C nuclear magnetic resonance (NMR) and solvent-extractable biomarkers were used to characterize soil OM. Throughout the disturbed upslope profile, where surface soils and vegetation had been removed, NMR revealed low O-alkyl C content and biomarker analysis revealed low concentrations of solvent-extractable compounds suggesting enhanced erosion of labile-rich OM by the ALD. In the disturbed downslope region, vegetation remained intact but displaced material from upslope produced lateral compression ridges at the surface. High O-alkyl content in the surface horizon was consistent with enrichment of carbohydrates and peptides, but low concentrations of labile biomarkers (i.e., sugars) suggested the presence of relatively unaltered labile-rich OM. Decreased O-alkyl content and biomarker concentrations below the surface contrasted with the undisturbed profile and may indicate the loss of well-established pre-ALD surface drainage with compression ridge formation. However, pre-ALD profile composition remains unknown and the observed decreases may result from nominal pre-ALD OM inputs. These results are the first to establish OM composition in ALD-impacted soil profiles, suggesting reallocation of permafrost-derived soil C to areas where degradation or erosion may contribute to increased C losses from disturbed Arctic soils.

Potential Shifts in Canadian High Arctic Sedimentary Organic Matter Composition With Permafrost Active Layer Detachments

Increased temperature and precipitation in Arctic regions have led to deeper thawing and structural instability in permafrost soil. The resulting localized disturbances, referred to as active layer detachments (ALDs), may transport organic matter (OM) to more biogeochemically active zones. To examine this further, solid state cross polarization magic angle spinning 13C nuclear magnetic resonance (CPMAS NMR) and biomarker analysis were used to evaluate potential shifts in riverine sediment OM composition due to nearby ALDs within the Cape Bounty Arctic Watershed Observatory, Nunavut, Canada. In sedimentary OM near ALDs, NMR analysis revealed signals indicative of unaltered plant-derived material, likely derived from permafrost. Long chain acyclic aliphatic lipids, steroids, cutin, suberin and lignin occurred in the sediments, consistent with a dominance of plant-derived compounds, some of which may have originated from permafrost-derived OM released by ALDs. OM degradation proxies for sediments near ALDs revealed less alteration in acyclic aliphatic lipids, while constituents such as steroids, cutin, suberin and lignin were found at a relatively advanced stage of degradation. Phospholipid fatty acid analysis indicated that microbial activity was higher near ALDs than downstream but microbial substrate limitation was prevalent within disturbed regions. Our study suggests that, as these systems recover from disturbance, ALDs likely provide permafrost-derived OM to sedimentary environments. This source of OM, which is enriched in labile OM, may alter biogeochemical patterns and enhance microbial respiration within these ecosystems.

Sodium distribution in mixed alkali K-Na metaphosphate glasses

The local order and distribution of Na in the mixed alkali metaphosphate glasses K(x)Na(1-x)PO(3) were analyzed, with the aim to identify segregation or a random mixture of both cation species. X-Ray photoelectron spectroscopy and several nuclear magnetic resonance (NMR) techniques were applied, including (31)P and (23)Na high-resolution spectroscopy, (23)Na triple quantum-MAS NMR, rotational echo double resonance between (31)P and (23)Na, and (23)Na NMR spin echo decay. The structural picture emerging from these results reveals the similarity in the local Na environments in the glasses but also subtle structural adjustments with increasing degree of K replacement. While both cations are intimately mixed at the atomic scale, the (23)Na spin echo decay data suggest a detectable like-cation preference in the spatial distribution of the ions. These structural properties are consistent with those determined in Li-Rb metaphosphates, indicating that the origin of the mixed alkali effect observed in the conductivity of Na-K metaphosphate glasses may also be explained by structurally blocked ion diffusion.

New constituents from Mikania laevigata Shultz Bip. ex Baker

A new phenylpropanoid and two new diterpenes were isolated from the leaves of the plant Mikania laevigata Shultz Bip. ex Baker. The structures of these compounds were established by 1D- and 2D-nuclear magnetic resonance spectroscopic techniques and mass spectrometry data. Taraxerol, lupeol, coumarin, syringaldehyde, trans-melilotoside, cis-melilotoside, adenosine, patuletin 3-O-beta-D-glucopyranoside, kaempferol 3-O-beta-D-glucopyranoside, quercetin 3-O-beta-D-glucopyranoside, methyl 3,5-di-O-caffeoyl quinate, and 3,3`,5-trihydroxy-4`,6,7-trimethoxyflavone were isolated too. In addition, the compounds dihydrocoumarin, spathulenol, caryophyllene oxide, kaurenoic acid, beyerenoic acid, and lupeol acetate were identified by GC-MS. (C) 2010 Elsevier Ltd. All rights reserved.

A novel labdane diterpene from Acritopappus longifolius

A novel labdane diterpene was isolated from the plant Acritopappus longifolius. The structure of this compound was established by 1D- and 2D-nuclear magnetic resonance spectroscopic techniques and mass spectrometry data. N-Methyl-4-hydroxy-trans-proline, stigmasterol-3-O-beta-D-glycoside. and the flavonoids quercetin, luteolin, kaempferol, and rutin were also isolated. (C) 2010 Elsevier Ltd. All rights reserved.

Preparació de materials híbrids orgànico-inorgànics a partir de sals d'imidazoli

Estudi elaborat a partir d’una estada a l’ Ecole Nationale Supérieure de Chimie de Montpellier, França, durant 2006. S’han sintetitzat materials híbrids orgànico-inorgànics mitjançant el procés sol-gel i altres estratègies sintètiques. En alguns casos, s’ha intentat estructurar aquests materials, ja sigui per autoestructuració o per mitjà de tensioactius. Com a catalitzadors de les reaccions d'hidròlisi i policondensació s’han utilitzat àcids, bases i fluorurs. Els materials obtinguts s’han caracteritzat mitjançant diferents tècniques: BET (Brunauer-Emmett-Teller), TEM (microscopia electrònica de transmissió), SEM (microscòpia electrònica de rastreig), raigs X en pols , IR i RMN (ressonància magnètica nuclear) en estat sòlid. Amb aquests materials es pretén preparar catalitzadors heterogenis de Pd per reaccions d’acoblament creuat, i de Ru per reaccions de metàtesi. També s’han sintetitzat sals d'imidazoli amb cadenes hidrocarbonades llargues amb l'objectiu de preparar gels de sílice amb aquestes molècules atrapades dins la matriu inorgànica. Aquests materials s’utilitzaran com a organocatalitzadors i també es prepararan els corresponents catalitzadors de Pd per reaccions de Heck, Suzuki i Sonogashira. Les sals d’imidazoli s’han utilitzat com a tensioactius en la preparació de gels de sílice estructurats. Aquestes molècules han resultat ser cristalls líquids i s’han caracteritzar mitjançant DSC (differential scanning calorimetry), microscopia òptica i raigs X.

Alternative technique for biodiesel quality control using an optical fiber long-period grating sensor

We report the use of an optical fiber sensor to measure the soybean oil concentration in samples obtained from the mixture of pure biodiesel and commercial soybean oil. The operation of the device is based on the long-period grating sensitivity to the surrounding medium refractive index, which leads to measurable modifications in the grating transmission spectrum. The proposed analysis method results in errors in the oil concentration of 0.4% and 2.6% for pure biodiesel and commercial soybean oil, respectively. Techniques of total glycerol, dynamic viscosity, density, and hydrogen nuclear magnetic resonance spectroscopy were also employed to validate the proposed method.

Improvement of genistein content in solid genistein/-cyclodextrin complexes β

Genistein:β-cyclodextrin complexes with high drug loading (19.22%) were prepared by freeze-drying and characterized by differential scanning calorimetry and hydrogen nuclear magnetic resonance spectroscopy. The spatial configuration of the complex was proposed by means of 2D-NOESY experiment combined with molecular modeling. According to the results obtained, the interaction of genistein with β -cyclodextrin in a 1:1 complex is supposed to occur mainly through the insertion of the guest A-ring in cyclodextrin cavity, without rule out the possibility of inclusion through the B-ring, as previously reported in the literature.

Materiais híbridos orgânico-inorgânicos (ormosil) obtidos por sol-gel com potencial uso como filtro solar

This work aimed at the synthesis and characterization of particles of modified silica containing the organic filter dibenzoylmethane (DBM) by the hydrolytic sol-gel method, with modifications to the Stöber route. The structures of the resulting Xerogels were characterized by diffuse reflectance UV-VIS spectroscopy in the solid state, infrared absorption spectroscopy, Scanning Electron Microscopy (SEM) and 29Si Nuclear Magnetic Resonance (29Si NRM). The results showed favorable formation of hybrid organic-inorganic nanoparticles with efficient absorption/reflectance of radiation in the UV / VIS range, which enables their potential use as sunscreen.

Ionizing radiation induced degradation of poly (2-methoxy-5-(2 '-ethyl-hexyloxy)-1,4-phenylene vinylene) in solution

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Photopatternable di-ureasil-zirconium oxocluster organic-inorganic hybrids as cost effective integrated optical substrates

Organic-inorganic hybrids containing methacrylic acid (McOH, CH(2)= C(CH(3))COOH)) modified zirconium tetrapropoxide, Zr(OPr(n))(4), classed as di-ureasil-zirconium oxo-cluster hybrids, have been prepared and structurally characterized by X-ray diffraction (XRD), small-angle X-ray scattering (SAXS), Fourier transform infrared (FT-IR) and Raman (FT-Raman) spectroscopies, Si and C nuclear magnetic resonance (NMR), and atomic force microscopy (AFM). XRD and SAXS results have pointed out the presence of Si- and Zr-based nanobuilding blocks (NBBs) dispersed into the organic phase. Inter-NBBs correlation distances have been estimated for the pure di-ureasil and a model compound obtained. by hydrolysis/condensation of Zr(OPr(n))(4):McOH (molar ratio 1: 1): d(Si) approximate to 26 +/- 1 angstrom and d(Zr) approximate to 16 +/- 1 angstrom, respectively. In the case of the di-ureasil-zirconium oxo-cluster hybrids, these distances depend on the Zr relative molar percentage (rel. mol. Zr %) (d(Si) ranges from 18 to 25 angstrom and d(Zr) from 14 to 23 angstrom, as the rel. mol. Zr % increases from 5 to 75), suggesting that the Si- and Zr-based clusters are interconstrained. Complementary data from FT-IR, FT-Raman, (29)Si and (13)C NMR, and AFM support to a structural model where McOH-modified Zr-based NBBs (Zr-OMc) are present over the whole range of composition. At low Zr-OMc contents (rel. mol. Zr % <30) the clusters are well-dispersed within the di-ureasil host, whereas segregation occurs at the 0.1 mu m scale at high Zr-OMc concentration (rel. mol. Zr % = 50). No Zr-O-Si heterocondensation has been discerned. Monomode waveguides, diffractions gratings, and Fabry-Perot cavities have been written through the exposure of the hybrid monoliths to UV light. FT-Raman has shown that the chemical process that takes place under illumination is the polymerization of the methacrylate groups of the Zr-OMc NBBs. The guidance region in patterned channels is a Gaussian section located below the exposed surface with typical dimensions of 320 mu m wide and 88 mu m deep. The effective refractive index is 1.5162 (maximum index contrast on the order of 1 x 10(-4)) and the reflection coeficient of the Fabry-Perot cavity (formed by a grating patterned into a 0.278 cm channel) is 0.042 with a free spectral range value of 35.6 GHz.

Nanopartículas de sílica e ácido p-amino benzóico: um estudo de associação para protetores solares

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