Strain induced anomalous red shift in mesoscopic iron oxide prepared by a novel technique

Nano magnetic oxides are promising candidates for high density magnetic storage and other applications. Nonspherical mesoscopic iron oxide particles are also candidate materials for studying the shape, size and strain induced modifications of various physical properties viz. optical, magnetic and structural. Spherical and nonspherical iron oxides having an aspect ratio, ~2, are synthesized by employing starch and ethylene glycol and starch and water, respectively by a novel technique. Their optical, structural, thermal and magnetic properties are evaluated. A red shift of 0���24 eV is observed in the case of nonspherical particles when compared to spherical ones. The red shift is attributed to strain induced changes in internal pressure inside the elongated iron oxide particles. Pressure induced effects are due to the increased overlap of wave functions. Magnetic measurements reveal that particles are superparamagnetic. The marked increase in coercivity in the case of elongated particles is a clear evidence for shape induced anisotropy. The decreased specific saturation magnetization of the samples is explained on the basis of weight percentage of starch, a nonmagnetic component and is verified by TGA and FTIR studies. This technique can be modified for tailoring the aspect ratio and these particles are promising candidates for drug delivery and contrast enhancement agents in magnetic resonance imaging

Isolation, Stabilization and Characterization of Xanthophyll from Marigold Flower- Tagetes Erecta-L

The present paper deals with the chemistry, isolation, separation, characterisation and stabilisation of the Marigold oleoresin and its application as a natural food colorant. Marigold (Tagetes Erecta L), an ornamental plant belonging to the composite family, has a rich source of natural antioxidant-Lutein. A natural pigment, xanthophylls offer an alternative to synthetic dyes as a food colorant, due to its non-toxicity. Chromatographic separations of saponified and unsaponified oleoresin were performed and Trans-Lutein identified as the major constituent. Well-preserved flowers exhibit a high yield of Xanthophyll content (105.19 g/Kg) in contrast to the unpreserved flower sample (54.87 g/Kg), emphasizing the significance of flower preservation in the extraction of xanthophyll. The stability and amount of xanthophyll also increased from 105.19 g/Kg to 226.88 g/Kg on saponification and subsequent purification with Ethylene Dichloride

Block Copolymers of Unsaturated Polyesters and Functional Elastomers

Block copolymers of unsaturated polyester were prepared by condensation polymerization of hydroxyl or carboxyl terminated liquid rubbers with maleic anhydride, phthalic anhydride, and propylene glycol. The condensate obtained was mixed with styrene monomer to get an unsaturated polyester resin formulation. In this study, copolymers of unsaturated polyesters with hydroxy terminated polybutadiene, carboxy terminated nitrile rubber, and hydroxy terminated natural rubber were prepared. Mechanical properties such as tensile strength, tensile modulus, elongation at break, toughness, impact strength, surface hardness, abrasion resistance, and water absorption were evaluated after the resin was cured in appropriate molds for comparison with the control resin. The fracture toughness and impact resistance of CTBN-modified unsaturated polyester show substantial improvement by this copolymerization without seriously affecting any other property

Association Behavior of Biotinylated and Non-Biotinylated PolyEthylene Oxide-b-Poly(2-(Diethylamino)Ethyl Methacrylate)

Biotinylated and non-biotinylated copolymers of ethylene oxide (EO) and 2-(diethylamino)ethyl methacrylate (DEAEMA) were synthesized by the atom transfer radical polymerization technique (ATRP). The chemical compositions of the copolymers as determined by NMR are represented by PEO���������PDEAEMA������ and biotin-PEO���������PDEAEMA������ respectively. The aggregation behavior of these polymers in aqueous solutions at different pHs and ionic strengths was studied using a combination of potentiometric titration, dynamic light scattering (DLS), static light scattering (SLS), and transmission electron microscopy (TEM). Both PEO-b-PDEAEMA and biotin-PEO-b-PDEAEMA diblock copolymers form micelles at high pH with hydrodynamic radii (Rh) of about 19 and 23 nm, respectively. At low pH, the copolymers are dispersed as unimers in solution with Rh of about 6-7 nm. However, at a physiological salt concentration (cs) of about 0.16M NaCl and a pH of 7-8, the copolymers form large loosely packed Guassian chains, which were not present at the low cs of 0.001M NaCl. The critical micelle concentrations (CMC) and the cytotoxicity of the copolymers were investigated to determine a suitable polymer concentration range for future biological applications. Both PEO-b-PDEAEMA and biotin-PEO-b-PDEAEMA diblock copolymers possess identical CMC values of about 0.0023 mg/g, while the cytotoxicity test indicated that the copolymers are not toxic up to 0.05mg/g (> 83% cell survival at this concentration).

A New Class of Nonionic Photosensitive Surfactants: Some Insights Concerning Conformations

We report on a new class of nonionic, photosensitive surfactants consisting of a polar di(ethylene oxide) head group attached to an alkyl spacer of between two and eight methylene groups, coupled through an ether linkage to an azobenzene moiety. Structural changes associated with the interconversion of the azobenzene group between its cis and trans forms as mediated by the wavelength of an irradiating light source cause changes in the surface tension and self-assembly properties. Differences in saturated surface tensions (surface tension at concentrations above the CMC) were as high as 14.4 mN/m under radiation of different wavelengths. The qualitative behavior of the surfactants changed as the spacer length changed, attributed to the different orientations adopted by the different surfactants depending on their isomerization states, as revealed by neutron reflection studies. The self-assembly of these photosensitive surfactants has been investigated by light scattering, small angle neutron scattering, and cryo-TEM under different illuminations. The significant change in the self-assembly in response to different illumination conditions was attributed to the sign change in Gaussian rigidity, which originated from the azobenzene photoisomerization.

Exposici��n a plaguicidas en los habitantes de la ribera del r��o Bogot�� (Suesca) y en el pez Capit��n

Objetivo: considerando el elevado uso de plaguicidas en Colombia y los efectos nocivos que produce la exposici��n a estas sustancias para la salud humana y el ambiente, se realiz�� un estudio para la determinaci��n de biomarcadores de exposici��n y efecto de plaguicidas en la poblaci��n de Suesca que habita en la ribera del r��o Bogot��, de los niveles de plaguicidas en muestras de agua del r��o tomadas en el mismo municipio y en muestras de pez ���Capit��n de la sabana��� (Eremophylus mutisii) capturado en dicha zona. Materiales y m��todos: se realizaron determinaciones para organofosforados, carbamatos, ditiocarbamatos y organoclorados Tambi��n se explor��, mediante una encuesta, la exposici��n ocupacional a plaguicidas y el conocimiento y utilizaci��n de medidas de protecci��n personal en su actividad laboral. Adicionalmente, se examin�� el h��bito de la pesca de pez Capit��n y su consumo en la dieta de los habitantes de esta zona del r��o. Resultados: los resultados muestran la presencia de plaguicidas organoclorados y organofosforados en el r��o y en el tejido de los peces y organoclorados y etilentiourea en las muestras biol��gicas humanas. En el estudio participaron trabajadores directamente expuestos a plaguicidas, quienes manipulan productos de alta toxicidad; en su mayor��a conocen y emplean las medidas de protecci��n personal e higiene industrial. Conclusiones: existe contaminaci��n por plaguicidas en la cuenca alta del r��o Bogot�� que afecta a la fauna y a las poblaciones ribere��as. Es necesario promover mejores medidas para el cuidado del ambiente, para la protecci��n y para el autocuidado de las personas que manipulan plaguicidas en la zona.

Theoretical study of reactivity and dynamics of hybride-bridged diruthenium complexes and silylium

Esta tesis presenta un estudio computacional de los sistemas con hidruros puente. En la primera parte se estudia la qu��mica de complejos de dirutenio con cuatro hidruros puente. Esto incluye las siguientes reacciones: el intercambio del hidruro con hidr��geno molecular; la activaci��n del enlace C-H del etileno para formar el complejo de bis(vinilo)-etileno; el acoplamiento C-C entre el etileno coordinado y dos ligandos vinilo para producir el complejo rutenaciclopentadieno. Al final de esta parte, se discuten a detalle los mecanismos de estas reacciones. Adem��s, se demostr�� la importancia de la flexibilidad de los ligandos hidruro y la cooperaci��n entre los dos centros met��licos. En la segunda parte, se estudi�� el comportamiento fluxional de dos complejos μ-silileno y de un cati��n sililio. Con esto, se estableci�� la ruta m��s favorable en donde se realiza el intercambio de los ligandos hidruro y de los grupos metilo en los complejos μ-silileno. Finalmente, se encontr�� que hay dos posibles rutas relativas al cambio en la posici��n del puente Si-H-Si en el cation sililio poliag��stico, asociadas con la rotaci��n interna de los grupos sililo.

Enhanced phytoextraction: II. Effect of EDTA and citric acid on heavy metal uptake by Helianthus annuus from a calcareous soil

High biomass producing plant species, such as Helianthus annuus, have potential for removing large amounts of trace metals by harvesting the aboveground biomass if sufficient metal concentrations in their biomass can be achieved. However, the low bioavailability of heavy metals in soils and the limited translocation of heavy metals to the shoots by mosthigh biomass producing plant species limit the efficiency of the phytoextraction process. Amendment of a contaminated soil with ethylene diamine letraacetic acid (EDTA) or citric acid increases soluble heavy metal concentrations, potentially rendering them more available for plant uptake. This article discusses the effects of EDTA and citric acid on the uptake of heavy metals and translocation to aboveground harvestable plant parts in Helianthus annuus. EDTA was included in the research for comparison purposes in our quest for less persistent alternatives, suitable for enhanced phytoextraction. Plants were grown in a calcareous soil moderately contaminated with Cu, Pb, Zn, and Cd and treated with increasing concentrations of EDTA (0. 1, 1, 3, 5, 7, and 10 mmol kg(-1) soil) or citric acid (0. 01, 0. 05, 0.25, 0.442, and 0.5 mol kg(-1) soil). Heavy metal concentrations in harvested shoots increased with EDTA concentration but the actual amount of phytoextracted heavy metals decreased at high EDTA concentrations, due to severe growth depression. Helianthus annuus suffered heavy metal stress due to the significantly increased bioavailable metal fraction in the soil. The rapid mineralization of citric acid and the high buffering capacity of the soil made citric acid inefficient in increasing the phytoextracted amounts of heavy metals. Treatments that did not exceed the buffering capacity of the soil (< 0.442 mol kg(-1) soil) did not result in any significant increase in shoot heavy metal concentrations. Treatments with high concentrations resulted in a dissolution of the carbonates and compaction of the soil. These physicochemical changes caused growth depression of Helianthus annuus. EDTA and citric acid added before sowing of Helianthus annuus did not appear to be efficient amendments when phytoextraction of heavy metals from calcareous soils is considered.

Enhanced phytoextraction: I. Effect of EDTA and citric acid on heavy metal mobility in a calcareous soil

Phytoextraction, the use of plants to extract heavy metals from contaminated soils, could be an interesting alternative to conventional remediation technologies. However, calcareous soils with relatively high total metal contents are difficult to phytoremediate due to low soluble metal concentrations. Soil amendments such as ethylene diaminetetraacetate (EDTA) have been suggested to increase heavy metal bioavailability and uptake in aboveground plant parts. Strong persistence of EDTA and risks of leaching of potentially toxic metals and essential nutrients have led to research on easily biodegradable soilamendments such as citric acid. In our research, EDTA is regarded as a scientific benchmark with which degradable alternatives are compared for enhanced phytoextraction purposes. The effects of increasing doses of EDTA (0.1, 1, 10 mmol kg(-1) dry soil) and citric acid (0.01, 0.05,0.25,0.442, 0.5 mol kg(-1) dry soil) on bioavailable fractions of Cu, Zn, Cd, and Pb were assessed in one part of our study and results are presented in this article. The evolution of labile soil fractions of heavy metals over time was evaluated using water paste saturation extraction (similar to soluble fraction), extraction with 1 M NH4OAc at pH 7 (similar to exchangeable fraction), and extraction with 0.5 M NH4OAc + 0.5 M HOAc + 0.02 M EDTA atpH 4.65 (similar to potentially bioavailable fraction). Both citric acid and EDTA produced a rapid initial increase in labile heavy metal fractions. Metal mobilization remained constant in time for soils treated with EDTA, but metal fractions was noted for soils treated with citric acid. The half life of heavy metal mobilization by citric acid varied between 1.5 and 5.7 d. In the following article, the effect of heavy metal mobilization on uptake by Helianthus annutis will be presented.

Comparison of EDTA and EDDS as potential soil amendments for enhanced phytoextraction of heavy metals

Phytoextraction has been proposed as an alternative remediation technology for soils polluted with heavy metals or radionuclides, but is generally conceived as too slow working. Enhancing the accumulation of trace pollutants in harvestable plant tissues is a prerequisite for the technology to be practically applicable. The chelating aminopolycarboxylic acid, ethylene diamine tetraacetate (EDTA), has been found to enhance shoot accumulation of heavy metals. However, the use of EDTA in phytoextraction may not be suitable due to its high environmental persistence, which may lead to groundwater contamination. This paper aims to assess whether ethylene diamine disuccinate (EDDS), a biodegradable chelator, can be used for enhanced phytoextraction purposes. A laboratory experiment was conducted to examine mobilisation of Cd, Cu, Cr, Ni, Pb and Zn into the soil solution upon application of EDTA or EDDS. The longevity of the induced mobilisation was monitored for a period of 40 days after application. Estimated effect half lives ranged between 3.8 and 7.5 days for EDDS, depending on the applied dose. The minimum observed effect half life of EDTA was 36 days, while for the highest applied dose no decrease was observed throughout the 40 day period of the mobilisation experiment. Performance of EDTA and EDDS for phytoextraction was evaluated by application to Helianthus annuus. Two other potential chelators, known for their biodegradability in comparison to EDTA, were tested in the plant experiment: nitrilo acetic acid (NTA) and citric acid. Uptake of heavy metals was higher in EDDS-treated pots than in EDTA-treated pots. The effects were still considered insufficiently high to consider efficient remediation. This may be partly due to the choice of timing for application of the soil amendment. Fixing the time of application at an earlier point before harvest may yield better results. NTA and citric acid induced no significant effects on heavy metal uptake. (C) 2004 Elsevier Ltd. All rights reserved.

The structure of crystallisable copolymers of L-lactide, epsilon-caprolactone and glycolide

We apply a new X-ray scattering approach to the study of melt-spun filaments of tri-block and random terpolymers prepared from lactide, caprolactone and glycolide. Both terpolymers contain random sequences, in both cases the overall fraction of lactide units is similar to 0.7 and C-13 and H-1 NMR shows the lactide sequence length to be similar to 9-10. A novel representation of the X-ray fibre pattern as series of spherical harmonic functions considerably facilitates the comparison of the scattering from the minority crystalline phase with hot drawn fibres prepared from the poly(L-lactide) homopolymer. Although the fibres exhibit rather disordered structures we show that the crystal structure is equivalent to that displayed by poly(L-lactide) for both the block and random terpolymers. There are variations in the development of a two-phase structure which reflect the differences in the chain architectures. There is evidence that the random terpolymer includes non-lactide units in to the crystal interfaces to achieve a well defined two-phase structure. (c) 2005 Published by Elsevier Ltd.

Thermo-responsive microphase separated supramolecular polyurethanes

The ability to generate very stable assemblies via non-covalent interactions has enabled materials to be constructed that were not feasible via traditional covalent bond formation processes. A series of low molecular mass bisurethane and bisurea polymers have been developed that form stable self-assembled networks through hydrogen bonding interactions. Thermo-responsive polymers were generated by end-capping poly(ethylene-co-butylene) or polybutadiene chains with the bisurethane or bisurea motif. Microphase separation is observed via TEM and small-angle X-ray scattering (SAXS) for the modified pseudo polymers and significant differences in the temperature dependence of microphase separation are analysed via SAXS. The importance of the polarity of the end groups is manifested in distinct temperature-dependent microphase separation behaviour. Information on the local hydrogen bonding structure is provided by wide-angle X-ray scattering and variable temperature FTI

Headspace volatile markers for sensitivity of cocoa (Theobroma cacao L.) somatic embryos to cryopreservation

The mechanisms that reduce the viability of plant somatic embryos following cryopreservation are not known. The objective of the present study was to evaluate the sensitivity of cocoa (Theobroma cacao L.) somatic embryos at different stages of an encapsulation-dehydration protocol using stress-related volatile hydrocarbons as markers of injury and recovery. The plant stress hormone ethylene and volatile hydrocarbons derived from hydroxyl radicals (methane) and lipid peroxidation (ethane) were determined using gas chromatography headspace analysis. Ethylene and methane were the only volatiles detected, with both being produced after each step of the cryogenic protocol. Ethylene production was significantly reduced following exposure to liquid nitrogen, but then increased in parallel with embryo recovery. In contrast, the production of methane was cyclic during recovery, with the first cycle occurring earlier for embryos recovered from liquid nitrogen and desiccation than those recovered from earlier steps in the protocol. These results suggest that loss of somatic embryo viability during cryopreservation may be related to the oxidative status of the tissue, and its capacity to produce ethylene. This study has demonstrated that headspace volatile analysis provides a robust non-destructive analytical approach for assessing the survival and recovery of plant somatic embryos following cryopreservation.

The regulation of sweet cherry fruit abscission by polar auxin transport

Inconsistency of cropping is an important problem for UK sweet cherry production. Premature fruit abscission in Prunus can reduce yields severely, however, the environmental cues and hormonal signals that trigger abscission have not been identified. Auxin (IAA) is known to delay abscission by reducing the sensitivity of cells in the abscission zone to ethylene, a promoter of abscission. Therefore, the capacity for polar auxin transport (PAT) through sweet cherry pedicels was examined in relation to fruit abscission. Cherry ���spurs��� (short shoots) with similar leaf areas and different fruit numbers were phloem-girdled to restrict assimilate movement. Abscission from spurs with many fruit (eight or more) occurred within 14 days of girdling, whereas abscission from spurs with few (two) fruit was minimal. The pedicels��� capacity for PAT in spurs with different fruit numbers was determined 1, 3 and 9 days after girdling (DAG). Fruit were analysed for endogenous IAA concentration 3, 5, 7 and 9 DAG. PAT inhibitors 2,3,5-triiodobenzoic acid or 1-N-naphthylphtalamic acid were applied to pedicels of fruit not expected to abscise, i.e. on spurs with few fruit. The effect of these inhibitors on fruit abscission was determined 14 DAG. The proportion of the transported [3H]-IAA was lower from the outset in pedicels from spurs with many fruit. By 9 DAG, symptoms of fruit abscission were apparent and 40% less [3H] -IAA was transported through pedicels on spurs with many fruit. Fruit endogenous IAA concentrations were similar in the two groups of spurs. Application of PAT inhibitors shortly after girdling increased fruit abscission by 30%. The results suggest that although a decline in PAT is not the only cause of fruit abscission, the maintenance of PAT contributes to fruit retention.

Structural and equilibrium studies on mixed ligand complexes of Co(II), Ni(II), Cu(II) and Zn(II) with N-(2-benzimidazolyl)methyliminodiacetic acid and typical N,N donor ligands

Mixed ligand complexes: [Co(L)(bipy)] (.) 3H(2)O (1), [Ni(L)(phen)] (.) H2O (2), [Cu(L)(phen)] (.) 3H(2)O (3) and [Zn(L)(bipy)] (.) 3H(2)O (4), where L2- = two -COOH deprotonated dianion of N-(2-benzimidazolyl)methyliminodiacetic acid (H(2)bzimida, hereafter, H,L), bipy = 2,2' bipyridine and phen = 1,10-phenanthroline have been isolated and characterized by elemental analysis, spectral and magnetic measurements and thermal studies. Single crystal X-ray diffraction studies show octahedral geometry for 1, 2 and 4 and square pyramidal geometry for 3. Equilibrium studies in aqueous solution (ionic strength I = 10(-1) mol dm(-3) (NaNO3), at 25 +/- 1 degrees C) using different molar proportions of M(II):H2L:B, where M = Co, Ni, Cu and Zn and B = phen, bipy and en (ethylene diamine), however, provides evidence of formation of mononuclear and binuclear binary and mixed ligand complexes: M(L), M(H-1L)(-), M(B)(2+), M(L)(B), M(H-1L)(B)(-), M-2(H-1L)(OH), (B)M(H-1L)M(B)(+), where H-1L3- represents two -COOH and the benzimidazole NI-H deprotonated quadridentate (O-, N, O-, N), or, quinquedentate (O-, N, O-, N, N-) function of the coordinated ligand H,L. Binuclear mixed ligand complex formation equilibria: M(L)(B) + M(B)(2+) = (B)M(H-1L)M(B)(+) + H+ is favoured with higher pi-acidity of the B ligands. For Co(II), Ni(II) and Cu(II), these equilibria are accompanied by blue shift of the electronic absorption maxima of M(II) ions, as a negatively charged bridging benzimidazolate moiety provides stronger ligand field than a neutral one. Solution stability of the mixed ligand complexes are in the expected order: Co(II) < Ni(II) < Cu(II) > Zn(II). The Delta logK(M) values are less negetive than their statistical values, indicating favoured formation of the mixed ligand complexes over the binary ones. (c) 2005 Elsevier B.V. All rights reserved.