Determination of three anabolic compounds in calf urine by liquid chromatography with photodiode-array detection

A method for the determination of three anabolic hormones (diethylstilbestrol, dienestrol and trenbolone) in calf urine is described. After enzymatic hydrolysis, the samples were cleaned up by C18 solid-phase extraction. Drugs were extracted with hexane and analyzed by isocratic elution on a Discovery RP-Amide C16 5 microns column with photodiode-array detection at 240 and 347 nm. Both retention time and UV spectra were used for identification. Detection limits for the HPLC system were calculated to be 0.3 ng injected for all analytes in the standard mixture. However, for urine samples these limits increased because of the presence of unidentified matrix components. After extraction from urine, the limits of detection for the whole analytical procedure were 5 and 10 ng injected for trenbolone and stilbenes, respectively. The average recoveries of the hormones from spiked samples were in the range 53.1-56.7% with RSD between 11.3 and 14.5% for the whole procedure in the concentration range 25-2.5 ng ml-1.     

Selection of a Representative Matrix for Calibration in Multianalyte Determination of Pesticides in Vegetables by Liquid Chromatography-Electrospray Tandem Mass Spectrometry

An analytical method for determining residues of twenty pesticides by liquid chromatography (LC) coupled to electrospray ionisation (ESI) tandem mass spectrometry (MS-MS) in eight commodities, cucumber, tomato, pepper, green bean, eggplant, zucchini, melon and watermelon, has been developed and validated. On one hand, calibration curves prepared in solvent were compared with calibration curves prepared in a blank matrix extract of each target matrix. On the other hand, calibration curves and recoveries for each commodity were compared. Cucumber was selected as potential reference matrix for the target vegetables.     

Derivatives of 2-thiohydantoin as spectrophotometric analytical reagents. III

Summary The synthesis, characteristics, properties and reactions with metallic ions of the furfural-, thiophenal-, pyrrolal-, cinnamal-, acetal-, and propional-derivatives of 2-thiohydantoin have been studied. The reagents exhibit twopK values in aqueous solution, and sensitive colour reactions with Pd(II), Cu(I) and (II), Ag(I) and Hg(II). A comparison has been made of the reactivity of all the 2-thiohydantoin derivatives we have studied to date and conclusions have been drawn regarding the influence of the aromatic ring connected to 2-thiohydantoin.

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Derivative des 2-Thiohydantoins als spektrophotometrische Reagenzien. III

Zusammenfassung Die Synthese, die Kennzahlen, die Eigenschaften der Furfural-, Thiophenal-, Pyrrolal-, Acetal-, Propional- sowie des Zimtsäurealdehyd-Derivates des 2-Thiohydantoins und deren Reaktionen mit Metallionen wurden untersucht. In wäßriger Lösung kommen diesen Reagenzien zwei pK-Werte zu. Sie geben empfindliche Farbreaktionen mit Pd(II), Cu(I) und (II), Ag(I) und Hg(II). Die Reaktivität der genannten Derivative wurde untersucht und der Einfluß des mit 2-Thiohydantoin verbundenen aromatischen Ringes daraus ermittelt.

     

Backbone rearrangements of methyl (-)-kaur-9(11)-en-19-oate and its epoxide: structures of two diterpenes of a new skeletal type

cleavage of the epoxide ($\text{2}$) of methyl (-)-kaur-9(11)-en-19-oate ($\text{1b}$) with boron trifluoride-ether in benzene and in acetic anhydride yielded ($\text{3a}$) and ($\text{3b}$), respectively. On epoxidation with $\text{m}$-chloroperbenzoic acid in the presence of $\text{N}$-nitrosomethyl urea, ($\text{1b}$) suffered a backbone rearrangement to form ($\text{6}$).     

First seco-C oleananes from nature

[structure: see text] The triterpenes 8,14-seco-oleana-8(26),13-dien-3beta-ol (1) and its acetyl derivative 2 were isolated from Stevia viscida and Stevia eupatoria, respectively. Their structures were elucidated by 2D NMR, including carbon-carbon connectivity experiments, and confirmed by X-ray diffraction analysis of ketone 3. The absolute configuration was determined by NMR analysis of the Mosher esters of 1. The biogenetic implications of the new substances are discussed.     

Ammonolysis of mono(pentamethylcyclopentadienyl) titanium(IV) derivatives

Ammonolyses of mono(pentamethylcyclopentadienyl) titanium(IV) derivatives [Ti(eta5-C5Me5)X3] (X = NMe2, Me, Cl) have been carried out in solution to give polynuclear nitrido complexes. Reaction of the tris(dimethylamido) derivative [Ti(eta5-C5Me5)(NMe2)3] with excess of ammonia at 80-100 degrees C gives the cubane complex [[Ti(eta5-C5Me5)]4(mu3-N)4] (1). Treatment of the trimethyl derivative [Ti(eta5-C5Me5)Me3] with NH3 at room temperature leads to the trinuclear imido-nitrido complex [[Ti(eta/5-CsMes)(mu-NH)]3(mu3-N)] (2) via the intermediate [[Ti(eta5-C5Me5)Me]2(mu-NH)2] (3). The analogous reaction of [Ti(eta5-C5Me5)Me3] with 2,4,6-trimethylaniline (ArNH2) gives the dinuclear imido complex [[Ti(eta5-C5Me5)Me])2(mu-NAr)2] (4) which reacts with ammonia to afford [[Ti(eta5-C5Me5)(NH2)]2(mu-NAr)2] (5). Complex 2 has been used, by treatments with the tris(dimethylamido) derivatives [Ti(eta5-C5H5-nRn)(NMe2)3], as precursor of the cubane nitrido systems [[Ti4(eta5-C5Me5)3(eta5-C5H5-nRn)](mu3-N)4] [R = Me n = 5 (1), R = H n = 0 (6), R = SiMe3 n = 1 (7), R = Me n = 1 (8)] via dimethylamine elimination. Reaction of [Ti(eta5-C5Me5)Cl3] or [Ti(eta5-C5Me5)(NMe2)Cl2] with excess of ammonia at room temperature gives the dinuclear complex [[Ti2(eta5-C5Me5)2Cl3(NH3)](mu-N)] (9) where an intramolecular hydrogen bonding and a nonlineal nitrido ligand bridge the "Ti(eta5-C5Me5)Cl(NH3)" and "Ti(eta5-C5Me5)Cl2" moieties. The molecular structures of [[Ti(eta5-C5Me5)Me]2 (mu-NAr)2] (4) and [[Ti2(eta5-C5Me5)2Cl3(NH3)](mu-N)] (9) have been determined by X-ray crystallographic studies. Density functional theory calculations also have been conducted on complex 9 to confirm the existence of an intramolecular N-H...Cl hydrogen bond and to evaluate different aspects of its molecular disposition.     

Evaluation of surface- and ground-water pollution due to herbicides in agricultural areas of Zamora and Salamanca (Spain)

The pollution of agricultural land due to herbicides was assessed in the Guare?a and Almar river basins, situated in the provinces of Zamora and Salamanca (Spain). A set of fifteen herbicides, including triazines, ureas, amides and others, was selected owing to their frequency of use, the amounts used, their toxicity and their persistence in the environment. Solid-phase extraction with polymeric cartridges, followed by HPLC with diode-array detection, were used to monitor the herbicides. This technique was chosen owing to the wide range of functionality and polarity of the analytes under study. The detection limits obtained were in the 0.004-0.025 microg/l range (lambda=220 nm). Surface and ground waters, taken from different locations in the basins, were analyzed over a 6-month period. The presence of six out of the fifteen herbicides monitored--chlortoluron, atrazine, terbutryn, alachlor, diflufenican and fluazifop-butyl--was detected in several samples at levels ranging from the detection limit to 1.2 microg/l. The relationship of these herbicides to the agricultural activities of the zone is discussed.     

Transfer hydrogenation processes to mu(3)-alkylidyne groups on the organotitanium oxide [Ti(3)Cp*O(3)

The photochemical treatment of mu(3)-alkylidyne complexes [[TiCp*(mu-O)](3)(mu(3)-CR)] (R=H (1), Me (2), Cp*=eta(5)-C(5)Me(5)) with the amines (2,6-Me(2)C(6)H(3))NH(2), Et(2)NH, and Ph(2)NH and the imine Ph(2)C=NH leads to the partial hydrogenation of the alkylidyne moiety that is supported on the organometallic oxide, [Ti(3)Cp*O(3)], and the formation of new oxoderivatives [[TiCp*(3)(mu-CHR)(R'NR")] (R"=2,6-Me(2)C(6)H(3), R'=H, R=H (3), Me (4); R'=R"=Et, R=H (5), Me (6); R'=R"=Ph, R=H (7), Me (8)) and [[TiCp*(mu-O)](3)(mu-CHR)(N=CPh(2))] (R=H (9), R=Me (10)), respectively. A sequential transfer hydrogenation process occurs when complex 1 is treated with tBuNH(2), which initially gives the mu-methylene [[TiCp*(mu-O)](3)(mu-CH(2))(HNtBu)] (11) complex and finally, the alkyl derivative [[TiCp*(mu-O)](3)(mu-NtBu)Me] (12). Furthermore, irradiation of solutions of the mu(3)-alkylidyne complexes 1 or 2 in the presence of diamines o-C(6)H(4)(NH(2))(2) and H(2)NCH(2)CH(2)NH(2) (en) affords [[TiCp*(mu-O)](3)(mu(3)-eta(2)-NC(6)H(4)NH)] (13) and [[TiCp*(mu-O)](3)(mu(3)-eta(2)-NC(2)H(4)NH)] (14) by either methane or ethane elimination, respectively. In the reaction of 1 with en, an intermediate complex [[TiCp*(mu-O)](3)(mu-CH(2))(NHCH(2)CH(2)NH(2))] (15) is detected by (1)H NMR spectroscopy. Thermal treatment of the complexes 4-10 quantitatively regenerates the starting mu(3)-alkylidyne compounds and the amine R'(2)NH or the imine Ph(2)C=NH; however, heating of solutions of 3 or 4 in [D(6)]benzene or a equimolecular mixture of both at 170 degrees C produces methane, ethane, or both, and the complex [[TiCp*(mu-O)](3)[mu(3)-eta(2)-NC(6)H(3)(Me)CH(2)]] (16). The molecular structure of 8 has been established by single-crystal X-ray analysis.     

Investigation of surface structure and composition of in situ annealed Fe–Mn binary alloy samples using RHEED and electron spectroscopy

The formation of oxides at the surface of Fe–1.5%Mn and Fe–0.6%Mn binary alloys was investigated as a function of the conditions of the heat treatments. Both the influence of temperature and the atmosphere under which the experiments were performed were studied. The range of annealing temperatures was adjusted to 800°C. The atmosphere consisted of a mixture of N₂–5%H₂ and traces of water vapour, with different fixed dew points ranging from −10°C to −30°C. The state of the annealed surfaces was determined using in situ analytical devices attached to the annealing reactor in order to avoid surface contamination or the formation of native oxides after the experiments due to contact with air. The structure and composition of the surfaces were determined by reflection high-energy electron diffraction (RHEED) and electron spectroscopy (XPS, AES). Copyright © 2002 John Wiley & Sons, Ltd.     

Synthesis,characterization and a thermogravimetric study of copper,cobalt and tin mono- and bis-adducts with ethyleneurea,ethylenethiourea and propyleneurea

This paper describes the synthesis, characterization and a thermogravimetric (t.g.) study of 11 adducts of general formula MCl₂·nL (M = Cu, Co and Sn; n = 1 and 2 for Sn, and 2 for Cu and Co; L = ethyleneurea eu, ethylenethiourea etu, and propyleneurea pu). The i.r. results shows that the eu and pu adducts are coordinated through oxygen, whereas for etu nitrogen is the coordination site. The (C=O) or (C=S) trend is: Cu > Co > Sn. The t.g. curves show that the adducts release ligand molecules in a single mass loss step. As regards considering adducts with the same stoichiometry, the observed thermal stability trend is: etu > pu > eu.