Low-cost sugarcane bagasse and peanut shell magnetic-composites applied in the removal of carbofuran and iprodione pesticides.

In the present study, two agro-industrial wastes, sugarcane bagasse, and peanut shell were employed as support of magnetite nanoparticles for the synthesis of magnetic bio-composites: magnetic sugarcane bagasse (MBO) and magnetic peanut shell (MPSo). The presence of magnetite was verified by Raman spectroscopy. Magnetic nanoparticles shape and size distribution were studied by TEM, while composites morphologies were observed by SEM. Structural characteristics of the pesticides and their possible chemical adsorption on composites were analyzed by FTIR. The removal was carried out by a batch adsorption process, and UV-VIS technique was used for pesticide concentration estimation. Elovich model described better all systems pointing out to a chemical adsorption process occurring. Experimental data isotherms of carbofuran and iprodione can be best explained by more than one mathematical model, but Sip was the ordinary equation in all systems. Maximum adsorption capacities of 175 and 89.3 mg/g for carbofuran, and 119 and 2.76 mg/g for iprodione, were obtained for MBo and MPSo, respectively.

The influence of effective microorganisms (EM) and yeast on the degradation of strobilurins and carboxamides in leafy vegetables monitored by LC-MS/MS and health risk assessment.

The aim of this study was to determine the behaviour of strobilurin and carbocyamides commonly used in chemical protection of lettuce depending on carefully selected effective microorganisms (EM) and yeast (Y). Additionally, the assessment of the chronic health risk during a 2-week experiment was performed. The statistical method for correlation of physico-chemical parameters and time of degradation for pesticides was applied. In this study, the concentration of azoxystrobin, boscalid, pyraclostrobin and iprodione using liquid chromatography-mass spectrometry (LC-MS/MS) in the matrix of lettuce plants was performed, and there was no case of concentration above maximum residues levels. Before harvest, four fungicides and their mixture with EM (1 % and 10 %) and/or yeast 5 % were applied. In our work, the mixtures of 1%EM + Y and 10%EM + Y both stimulated and inhibited the degradation of the tested active substances. Adding 10%EM to the test substances strongly inhibited the degradation of iprodione, and its concentration decreased by 30 %, and in the case of other test substances, the degradation was approximately 60 %. Moreover, the addition of yeast stimulated the distribution of pyraclostrobin and boscalid in lettuce leaves. The risk assessment for the pesticides ranged from 0.4 to 64.8 % on day 1, but after 14 days, it ranged from 0.0 to 20.9 % for children and adults, respectively. It indicated no risk of adverse effects following exposure to individual pesticides and their mixtures with EM and yeast.

Comparing hypothetical structures generated in the third Cambridge blind test of crystal structure prediction.

In the third Cambridge blind test of crystal structure prediction, participants submitted extended lists of up to 100 hypothetical structures. In this paper these lists are analyzed for the two small semi-rigid molecules, hydantoin and azetidine, by performing a new energy minimization using an accurate force field, and grouping these newly minimized structures into clusters of equivalent structures. Many participants found the same low-energy structures, but no list appeared to be complete even for the structures with one independent molecule in the asymmetric unit. This may well be due to the fact that a cutoff at even 100 structures cannot ensure the presence of a structure that has a relatively high ranking in another force field. Moreover, some structures should have possibly been discarded because they correspond to transition states rather than true energy minima. The r.m.s. deviation between energies in corresponding clusters was calculated to compare the reported relative crystal energies for each pair of participants. Some groups of force fields show a reasonably good correspondence, yet the order of magnitude of their discrepancies is comparable to the energy differences between, say, the first ten structures of lowest energy. Therefore, even if we assume that energy is a sufficient criterion, it is not surprising that crystal structure predictions are still inconsistent and unreliable.

Determination of iodine values using 1,3-dibromo-5,5-dimethylhydantoin (DBH) and ethyl acetate as solvent. Analytical methods with DBH in respect to environmental and economical concern, part 18.

Iodine values (iodine numbers) of several fixed oils and lard can be determined in ethyl acetate, an easily biodegredable solvent, instead of chloroform according to PH. EUR. 2002. Iodine monobromide has been replaced by 1,3-dibromo-5,5-dimethylhydantoin (DBH) and potassium iodide (KI) and the reaction time was reduced to 5 min only. However, cod-liver oil and linseed oil require a reaction time of 30 min and a smaller weight of sample. Longer reaction times are also necessary for soya oil and wheat germ oil. Iodine values of linseed oil determined according to method A of PH. EUR. 2002, are dependent on the amount of sample, even in the range prescribed by the pharmacopoeia.

Cetylpyridinium tetrachlorozincate as standard for tenside titration. Analytical methods with 1,3-dibromo-5,5-dimethylhydantoin (DBH) in respect to environmental and economical concern, part 19.

The determination of the cationic active disinfectants benzalkonium chloride, benzethonium chloride, cetrimide, and cetylpyridinium chloride according to PH. EUR. 2002 resp. supplement 4.3/2003 can be improved using the DBH-method. By application of column extraction the iodide determination can be performed in the organic layer by visual indication. However, titration in aqueous solution with sodium dodecyl sulphate as titrant and methyl orange resp. bromophenol blue as indicator can be performed more simple. Cetylpyridinium tetrachlorozincate is recommended as a standard for tenside titration.

Determination of iodine values using 1,3-dibromo-5,5-dimethylhydantoin (DBH) without the employment of chlorinated hydrocarbons. Analytical methods of pharmacopoeias with DBH in respect to environmental and economical concern. Part 17.

Low and medium iodine values of fixed oils and fats can be determined in glacial acetic acid within reduced waiting times of only 5 min. Highly unsaturated compounds such as those of linseed oil, cod-liver oil, sunflower oil, soybean oil, wheat germ oil and the emulsifier sorbitan trioleate result too low values in comparison to PH. EUR. 2002 [2] and USP 2000 [3]. Cocoa butter with a low iodine number is insoluble in glacial acetic acid. The iodine values of nonionogenic emulsifiers such as ceteareth-30 (Macrogol cetostearyl ether PH. EUR. 2002), oleth-10 resp. 20 (Macrogol oleyl ether PH. EUR. 2002) and polysorbate-80 PH. EUR. 2002 are obtained in aqueous solutions. Oleth-2 (Macrogol oleyl ether PH. EUR. 2002), polyoxyl-40 castor oil (Macrolglycerol ricinoleate PH. EUR. 2002), polysorbate-60 PH. EUR. 2002 and sorbitan trioleate PH. EUR. 2002 need the addition of ethyl acetate. Fixed oils even with high iodine values can be determined in an o/w emulsion with a reaction time of 5 min in most cases, when nonionogenic emulsifiers such as ceteareth-30, polyoxyl-30 glycerol monolaurate or polyoxyl-60 hydrogenated castor oil (Macrolglycerol hydroxystearate PH. EUR. 2002) are used.

Determination of organically bound iodine by reductive mineralization with aluminium powder. Analytical methods of pharmacopoeias with DBH in respect to environmental and economical concern. Part 16.

PH. EUR. 2002, JAP 1996 and USP 2000 mineralize organically bound iodine in x-ray contrast media by boiling under reflux with zinc powder in alkaline solution. The reductive mineralization can be performed at room temperature without filtration, when aluminium powder is used. Resulting iodide is titrated by argentometry and potentiometric indication according to the pharmacopoeia or after oxidation with 1,3-dibromo-5,5-dimethylhydantoin by iodometry.

1,3-Dibromo-5,5-dimethylhydantoin (DBH) as oxidant and precipitant for drug identification according to PH. EUR Analytical methods of pharmacopoeias with DBH in respect of environmental and economical concern, Part 15(1).

Elemental bromine serves as oxidant for the identification of propylthiouracil, 2-thiouracil and sulphur according to PH. EUR. 2002. Phenol is identified according to PH. EUR. 2002 with bromine water as the sparingly water-soluble 2,4,4,6-tetrabromo-2,5-cyclohexadiene-1-one. These tests can be performed better using 1,3-dibromo-5,5-dimethylhydantoin (DBH).

Application of 1,3-dibromo-5,5-dimethylhydantoin (DBH) instead of bromine gas or bromine water decolorization for drug identification according to PH. EUR. Analytical methods of pharmacopoeias with DBH in respect to environmental and economical concern, Part 14.

PH. EUR. 2002 identifies biotin, flucytosine, polysorbate 80 and sorbic acid using the decolorization of bromine water. These tests can be better performed with 1,3-dibromo-5,5-dimethylhydantoin (DBH) in combination of the reaction with fluorescein sodium resp. sodium bromide. Also fluorescein sodium PH. EUR. Suppl 2002 can be identified with DBH.

Replacement of cyanogen bromide solution PH. EUR. with 1,3-dibromo-5,5-dimethylhydantoin (DBH). Analytical methods of pharmacopoeias with DBH in respect to environmental and economical concern, Part 13.

PH. EUR. 2002 identifies nicotinamid, nicotinic acid, and nikethamide according the reaction of König using cyanogen bromide solution prepared with bromine water and ammonium thiocyanate immediately before use. This colour reaction can be better performed with 1,3-dibromo-5,5-dimethylhydantoin (DBH) and sulphanilic acid as condensation component. The prescriptions of PH. EUR. have been improved in respect to environmental and economical concern.

Colour reactions of PH. EUR. for identification of drugs using 1,3-dibromo-5,5-dimethylhydantoin (DBH) instead of elemental bromine. Analytical methods of pharmacopoeias with DBH in respect to environmental and economical concern, Part 10.

PH. EUR. 2002 and supplements identify aloes (Rosenthaler reaction), amiloride hydrochloride, chlorhexidine, dienestrol, quinidine sulphate, quinine hydrochloride and quinine sulphate (Thalleioquine reaction) and trifluoperazine hydrochloride using elemental bromine. This colour reaction can be performed better with 1,3-dibromo-5,5-dimethylhydantoin (DBH). Some prescriptions of PH. EUR. have been improved in respect to environmental and economical concern. The identification of amiloride hydrochloride with bromine water according to PH. EUR. 2002 or with DBH shows no UV fluorescence as reported in the pharmacopoeia.

Determination of iron limiting values according to PH. EUR. using 1,3-dibromo-5,5-dimethylhydantoin (DBH) instead of elemental bromine. Analytical methods of pharmacopoeias with DBH in respect to environmental and economical concern. Part 8.

PH. EUR. 2002 uses elemental bromine performing iron limit tests for maleic acid (iron 5 ppm) and titanium dioxide (iron 200 ppm). 1,3-Dibromo-5,5-dimethylhydantoin (DBH) can replace bromine water. For the iron limit test of maleic acid bivalent iron is oxidized to trivalent iron by bromine resp. DBH, because the unsaturated, in high concentration existing acid reacts substantially slower. On the other hand maleic acid removes the excess of bromine. The bromine oxidation for the iron limiting values of titanium dioxide according to the pharmacopoeia is not required. Metallic iron as well as ferrous salts are converted to trivalent iron, when the titanium test solution is prepared by boiling with concentrated sulphuric acid in the presence of anhydrous sodium sulphate.

Determination of phenol and resorcinol using 1,3-dibromo-5,5-dimethylhydantoin (DBH) analogous to the Koppeschaar reaction. Analytical methods of pharmacopoeias with DBH in respect to environmental and economical concern, Part 6.

PH. EUR. 1997 determines phenol and resorcinol according to the Koppeschaar reaction using hepatotoxic and environmentally hazardous chloroform. Chlorinated hydrocarbons are not required when applying 1,3-dibromo-5,5-dimethylhydantoin (DBH). The reaction time for phenol can be reduced from 45 to 5 min. Blind values according to PH. EUR. 1997 result a systematic error of about -1.8%.