The work shown in this article demonstrate a novel example of converting olive industry solid waste (OISW) into a magnetic cellulose nanocrystalline (MNCs) to serve as selective magnetic sorbents for methylene blue. Olive industry solid waste contains about 40% cellulose. The cellulose was extracted in a powder form from olive industry solid waste by subjecting it to a multistep pulping and bleaching process. The extracted powder cellulose was then converted to nanocrystalline cellulose (NCs) by acid hydrolysis. The NCs were then treated with a solution of FeCl.6HO, FeSO, and HO by a colloidal suspension method which produced free-flowing porous MNCs. The produced MNCs are characterized by several spectroscopic and analytical techniques such as SEM, TEM, XRD, FTIR VSM, and TGA. The efficiency of the three polymers cellulose powder, NCs, and MNCs toward extracting methylene blue (MB) from water was evaluated. Cellulose powder and NCs showed acceptable tendency for methylene blue. However, MNCs showed excellent extraction efficiency toward MB. The thermodynamic studies revealed a spontaneous adsorption of MB by MNCs at various temperatures. The spontaneous adsorption could be attributed to the electrostatic interaction and H-bonding between MNCs and MB. However, the interaction between cellulose, NCs, and MB is limited to the H-bonding.
Hormones have not been found in concentrations of orders of magnitude higher than ng/ml. Here we report urine concentrations of a catecholamine (norepinephrine) ranging from 0.05 to 0.5 g/l, and concentrations of its metabolite DL-3,4-dihydroxyphenyl glycol (DOPEG) ranging from 1.0 to 44.5 g/l, in wild male red deer Cervus elaphus hispanicus after LC-MS analyses. The dark ventral patch of male red deer, a recently described sexually selected signal, contains high amounts of DOPEG (0.9-266.9 mg/l) stuck in the hairs, while DOPEG is not present in non-darkened hair. The formation of this dark patch is explained by the chemical structure of DOPEG, which is a catecholamine-derived odiphenol susceptible to be oxidized by air and form allomelanins, nitrogen-free pigments similar to cutaneous melanins; by its high concentration in urine; and by the urine spraying behavior of red deer by which urine is spread through the ventral body area. Accordingly, the size of the dark ventral patch was positively correlated with the concentration of DOPEG in urine, which was in turn correlated with DOPEG absorbed in ventral hair. These findings represent catecholamine concentrations about one million higher than those previously reported for any hormone in an organism. This may have favored the evolution of the dark ventral patch of red deer by transferring information on fighting capacity to 3 rivals and mates. Physiological limits for hormone production in animals are thus considerably higher than previously thought. These results also unveil a novel mechanism of pigmentation based on the self-application of urine over the fur.
Poly(styrene-co-divinylbenzene)-coated magnetic multiwalled carbon nanotube composite synthesized by in-situ high temperature combination and precipitation polymerization of styrene-co-divinylbenzene has been employed as a magnetic sorbent for the solid phase extraction of antidepressants in human urine samples. Fluoxetine, venlafaxine, citalopram and sertraline were, afterwards, separated and determined by capillary electrophoresis with diode array detection. The presence of magnetic multiwalled carbon nanotubes in native poly(styrene-co-divinylbenzene) not only simplified sample treatment but also enhanced the adsorption efficiencies, obtaining extraction recoveries higher than 89.5% for all analytes. Moreover, this composite can be re-used at least ten times without loss of efficiency and limits of detection ranging from 0.014 to 0.041 μg/mL were calculated. Additionally, precision values ranging from 0.08 to 7.50% and from 0.21 to 3.05% were obtained for the responses and for the migration times of the analytes, respectively.
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