Comparative study of three immunoassays based on monoclonal antibodies for detection of the pesticide parathion-methyl in real samples

Three immunoassay systems: indirect, direct competitive enzyme-linked immunosorbent assay (IC-ELISA and DC-ELISA), fluorescence polarization immunoassay (FPIA) based on monoclonal antibodies for the detection of parathion-methyl (PM) were developed and optimized. Several PM derivatives (haptens) were conjugated to proteins and fluoresceinthiocarbamyl ethylenediamine (EDF) to obtain immunogens and competitors. The influence of immunogen and competitor structures on the assay performance was investigated. IC-ELISA was the most sensitive of all techniques developed, with a detection limit of 0.08 ng ml⁻¹, but assay time was the longest (3.5 h per 96-well microtitre plate). DC-ELISA was easier to perform and quicker (1.5 h per 96-well microtitre plate) but less sensitive than IC-ELISA (detection limit was 0.5 ng ml⁻¹). FPIA was the fastest and simplest (7 min per 10 samples) but the least sensitive (detection limit was 15 ng ml⁻¹) technique. The methods were characterized by high specificity and reproducibility. The cross-reactivity for parathion-ethyl was around 30-40% for IC-ELISA and FPIA, but significantly higher (125%) for DC-ELISA. The immunoassays were applied to the analysis of PM residues in different food and environmental matrices. Methanol extracts of vegetable, fruit and soil samples were used for the analysis. Recoveries for most spiked samples averaged between 85 and 110%. The methods developed can be used for screening of food and environmental samples for PM residues without complicated clean-up.     

Neue Kupferkomplexe mit Phosphaalkenliganden. Molekülstruktur von [Cu{P(Mes*)C(NMe2)2}2]BF4 (Mes* = 2,4,6‐tBu3C6H2)

New Copper Complexes Containing Phosphaalkene Ligands. Molecular Structure of [Cu{P(Mes*)C(NMe₂)₂}₂]BF₄ (Mes* = 2,4,6‐tBu₃C₆H₂) Reaction of equimolar amounts of the inversely polarized phosphaalkene tBuP=C(NMe₂)₂ ( 1a ) and copper(I) bromide or copper(I) iodide, respectively, affords complexes [Cu₃X₃{μ‐P(tBu)C(NMe₂)₂}₃] ( 2 ) (X =Br) and ( 3 ) (X = I) as the formal result of the cyclotrimerization of a 1:1‐adduct. Treatment of 1a with [Cu(L)Cl] (L = PiPr₃; SbiPr₃) leads to the formation of compounds [CuCl(L){P(tBu)C(NMe₂)₂}] ( 4a ) (L = PiPr₃) and ( 4b ) (L = SbiPr₃), respectively. Reaction of [(MeCN)₄Cu]BF₄ with two equivalents of PhP=C(NMe₂)₂ ( 1b ) yields complex [Cu{P(Ph)C(NMe₂)₂}₂]BF₄ ( 5b ). Similarly, compounds [Cu{P(Aryl)C(NMe₂)₂}₂]BF₄ ( 5c (Aryl = Mes and 5d (Aryl = Mes*)) are obtained from ArylP=C(NMe₂)₂ ( 1c : Aryl = Mes; 1d : Mes*) and [(MeCN)₄Cu]BF₄ in the presence of SbiPr₃. Complexes 2 , 3 , 4a , 4b , and 5b‐5d are characterized by means of elemental analyses and spectroscopy (¹H‐, ¹³C{¹H}‐, ³¹P{¹H}‐NMR). The molecular structure of 5d is determined by X‐ray diffraction analysis.     

Effect of the Electrode Potential on the Oxygen Reaction Rate in the Electrode System O2, Au/La0.88Sr0.12Ga0.82Mg0.18O2.85

The polarization dependences of a porous gold electrode in contact with a solid electrolyte of the composition La_0.88Sr_0.12Ga_0.82Mg_0.18O_2.85 are studied at 600–800°C and oxygen pressures of 2 × 10⁻²-1 atm. It is shown that the rate of cathodic reduction of oxygen out of the gas phase depends on the preliminary treatment of the sample. The activation energy is equal to 110–135 kJ mol⁻¹ at a low polarization. After increasing the polarization, the activation energy for the cathodic reduction of oxygen equals 75–85 kJ mol⁻¹ and depends on the oxygen pressure as a power function with a power index of 1/4. The rate of the anodic evolution of oxygen is dependent neither on the preliminary treatment of the sample nor on the oxygen pressure in the gas phase and the polarization curve has a characteristic segment, which corresponds to a limiting overvoltage.__________Translated from Elektrokhimiya, Vol. 41, No. 8, 2005, pp. 954–962.Original Russian Text Copyright © 2005 by Shkerin, Sokolova, Beresnev.     

Synthesis and absolute configuration of (1S,8S)-as-hydrindacene-1,8-diol as determined by the circular dichroism exciton chirality method

2,3,6,7-Tetrahydro-as-indacene-1,8-dione 4 was prepared in 4 steps starting from 2-methyl-furan by modification of a literature procedure. Appliance of Noyori’s asymmetric transfer hydrogenation, resulted in (1S,8S)-1,2,3,6,7,8-hexahydro-as-indacene-1,8-diol 5 in high yield (81%) and excellent enantioselectivity (>99% ee) or (8S)-8-hydroxy-3,6,7,8-tetrahydro-2H-as-indacen-1-one 6 in moderate yield (58%) and equally high enantioselectivity (98.5% ee), depending on the conditions. The asymmetric reduction was expected to yield the (S)-alcohols using the (S,S)-Ts-DPEN ligand, which was confirmed by the appliance of the exciton chirality method on the corresponding bis(p-dimethylamino)benzoate 7.     

Oxidation-Induced Structural Alterations and Its Effect on Chaperone Function of Rat Lens α-Crystallin

An ascorbate-FeCl₃-EDTA-H₂O₂ system was used to oxidize rat lens α-crystallins. Under this oxidative insult, the chaperone activity of α-crystallin toward γ-crystallin was shown to decrease significantly, which is quite different from the result reported by Wang and Spector. (Invest. Ophthalmol. Vis. Sci. 1995 , 36, 311-321.) Fluorescence spectroscopy and circular dichroism were employed to characterize the structural changes of oxidized α-crystallin. It was found that fluorescence intensity of l-anilinonaphthalene-8-sul-phonate (ANS) bound to oxidized α-crystallin increased comparing to that bound to normal α-crystallin, suggesting oxidation causes the exposure of more hydrophobic regions. Further, α-crystallin's fluorescence intensity in response to tryptophan residues showed a pseudo first order decline. Amino acid analysis of normal versus oxidized α-crystallin confirmed actual decline in tryptophan levels, showing about 80% of tryptophan being modified after 10-hour oxidation. Circular dichroism showed both changes in the secondary and tertiary structures of oxidized α-crystallin, characterized by a large loss of aromatic-type amino acid interactions and a large loss of β-sheet structure. In conclusion, modified tryptophan, secondary and tertiary structural changes of α-crystallin correlate best with the reduction of chaperone function, the curves all showing a linear slope for 10 hours, then plateauing. These results indicate that the decrease of α-crystallin chaperone activity is attributed to the structural changes.     

Stereochemistry of planarchiral compounds,part X

2,7-Dibromo-1,6-methano[10]anulene (3) and 2,9-Dibromo-syn-1,6:8,13-diimino[14]anulene (9) were quantitatively separated into their enantiomers by chromatography on triacetylcellulose (TAC) in ethanol. X-ray structure analysis (Bijvoet technique) established the chiralities (+)(R)-3 and (+)(S)-9 for the dextrorotatory enantiomers.Comparison of the CD spectra allowed the configurational assignment to further optically active [10] and [14] anulenes which were also accessible by chromatography onTAC. Conversion of (+)(R)-2-bromo-1,6-methano[10]anulene (2) into the corresponding methylester (–)-4 confirmed its previously proposed chirality (–)(R).2,7-Dibromo-1,6-oxido[10]anulene (7) and 2,9-dibromo-syn-diimino[14]anulene (9) are in contrast to the 2,9-dibromo-syn-dioxido[14]anulene (10) optically stable until 250°C. Consequently their inversion barriers are higher than 42 kcal (176 kJ) mol^–1.The CD spectra of mono and disubstituted anulenes (with C₁ and C₂ symmetry, resp.) are compared: For the [10]anulenes theCotton effect around 330 nm seems to be specific for their configuration with a positive effect indicating (S)-chirality and vice versa. Some regularities concerning the chromatographic resolutions are discussed.

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Stereochemie planar chialer Verbindungen, 10. Mitt.: Röntgenkristallstruktur und absolute Chiralität überbrückter [10]- und [14] Anulene

Zusammenfassung 2,7-Dibrom-1,6-methano[10]anulen (3) und 2,9-Dibrom-syn-1,6:8,13-diimino[14]anulen (9) wurden durch Chromatographie an Triacetylcellulose (TAC) in Ethanol quantitativ in ihre Enantiomeren getrennt. Röntgenstruktur-analyse (Bijvoet-Technik) bewies für die rechtsdrehenden Enantiomeren die Chiralität (+)(R)-3 bzw. (+)(S)-9.Ein Vergleich der CD-Spektren ermöglichte die Konfigurationszuordnung weiterer optisch aktiver [10]- und [14]Anulene, die gleichfalls durch Chromato-graphie anTAC erhalten worden waren. Umwandlung von (+)(R)-2-Brom-1,6-methano[10]anulen (2) in den entsprechenden Methylester (–)-4 bestätigte dessen schon früher vorgeschlagene Chiralität (–)(R).Dibrom-1,6-oxido[10]anulen (7) und Dibrom-diimino[14]anulen (9) sind im Gegensatz zum Dioxido[14]anulen (10) bis 250°C optisch stabil. Ihre Inver-sionsbarrieren liegen somit über 42 kcal (176kJ) mol^–1.Die CD-Spektren von mono- und disubstituierten Anulenen (mit C₁ bzw. C₂-Symmetrie) werden verglichen: Für die [10]Anulene scheint derCottoneffekt um 330 nm konfigurationsspezifisch zu sein, wobei ein positiver Effekt (S)-Chiralität anzeigt — und vice versa. Einige Regelmäßigkeiten bezüglich der chromatographischen Enantiomerentrennung werden diskutiert.

     

Chirality due to deuterium substitution: synthesis and circular dichroism of (+)(R) p -2,7-dideuterio-1,6-methano[10]annulene

Summary The title compound was prepared from (–)(S) _p -2,7-dibromo-1,6-methano[10]annulene by treatment withn-Bu-Li and subsequent quenching with D₂O. The optical rotations at four wavelengths and the circular dichroism spectrum are reported.

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Chiralität durch Deuterium-Substitution: Synthese und Circulardichroismus von (+)(R) _p -2,7-Dideuterio-1,6-methano[10]annulen (Kurze Mitt.)

Zusammenfassung Die Titelverbindung wurde aus (–)(S) _p -2,7-Dibrom-1,6-methano[10]annulen durch Umsetzung mitn-Bu-Li und nachfolgende Reaktion mit D₂O dargestellt. Optische Rotationen bei vier Wellenlängen und das Circulardichroismus-Spektrum wurden bestimmt.

     

Investigation on corrosion inhibition and adsorption mechanism of azomethine derivatives at mild steel/0.5 ​M ​H2SO4 solution interface: Gravimetric,electrochemical, SEM and EDX studies

The inhibition performance of five azomethine derivatives such as: 1-(4-Methyloxy phenylimino)-1-(phenylhydrazono)-propan-2-one (SB₁), 1-(4-Methylphenylimino)-1-(phenylhydrazono) propan-2-one (SB₂), 1-(phenylimino)-1(phenylhydrazono)-propan-2-one (SB₃), 1-(4-Bromo phenylimino)-1(phenylhydrazono)-propan-2-one (SB₄) and 1-(4-Chlorophenylimino)-1(phenylhydrazono) -propan-2-on (SB₅) as corrosion inhibitors for mild steel in sulfuric acid 0.5 ?M were investigated using different methods. All experimental results demonstrate that these compounds are eficients inhibitors. The inhibition efficiencies ($IE$) increase with inhibitors concentration. At 7.5 $\times$ 10^?5 ?M, the $IE$ was 97.27%, 96.31%, 94.23%, 93.19 and 91.64% for SB₁, SB₂, SB₃, SB₄ and SB₅, respectively. The potentiodynamic polarization results indicated that all the studied inhibitors act as mixed type. The adsorption process on mild steel surface obeyed Langmuir isotherm. The associated activation parameters and thermodynamic have been calculated and discussed. The adsorbed film formed on the metal surface was characterized by SEM and EDX.     

A Procedure for Transforming Impedance Spectra for the Determination of Mechanism of Electrochemical Reactions

Transformation of impedance spectra into relaxation time spectra (RTS) is used for determining contributions of individual processes of the oxygen electroreduction reaction (OER) to the polarization resistance of the electrochemical cell. The transformation technique involves the solution of the convolution equation found with the aid of a modified Van Cittert iteration algorithm checked on model impedance spectra. The technique, when used to analyze impedance spectra of electrochemical cells air|Pt|YSZ|YSZ + Pt|air, shows that the conversion of a globular structure of the YSZ + Pt cermet layer to a columnar one is accompanied by a change of peak amplitudes in RTS. The revealed RTS dynamics when heated to 750°C is compared with peculiarities of individual processes in OER.     

On the synthesis and chiroptical properties of the tri- and tetragalloylquinic acids

Summary A synthesis of the potential pharmaceutical agents 3,4,5-trigalloylquinic acid and 1,3,4,5-tetragalloylquinic acid is described. It involves three steps starting from commercially available quinic acid and provides overall yields of about 15%. The acylation of benzyl or 4-nitrobenzyl quinate with tribenzylgalloyl chloride is the key step. It leads selectively to the triacyl product in the case of benzyl quinate and can be either stopped at the triacyl stage or driven to the tetraacyl derivative in the case of the 4-nitrobenzyl quinate. From the chiroptical properties of the two compounds their stereochemistry was derived by means of the benzoate rule.

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Zu Synthese und chiroptischen Eigenschaften der Tri- und Tetragalloylchinasäuren

Zusammenfassung Eine Synthese von 3,4,5-Trigalloylchinasäure und 1,3,4,5-Tetragalloylchinasäure. die potentielle Pharmaka darstellen, wird beschrieben. Sie umfaßt drei Stufen, welche ausgehend von kommerziell erhältlicher Chinasäure Gesamtausbeuten um 15% ergeben. Die entscheidende Stufe dabei ist die Acylierung von Benzyl- oder 4-Nitrobenzylchinat mit Tribenzylgalloylchlorid. Sie führt im Falle des Benzylchinats selektiv zum Triacylprodukt und kann im Fall des 4-Nitrobenzylchinats entweder auf der Stufe des Triacylderivates abgebrochen oder bis zum Tetraacylprodukt durchgezogen werden. Aus den chiroptischen Eigenschaften der beiden Verbindungen wurde ihre Stereochemie abgeleitet.