Development of a class selective immunoassay for the type II pyrethroid insecticides

A general and broad class selective enzyme-linked immunosorbent assay was developed for the type II pyrethroid insecticides, such as cypermethrin, deltamethrin, cyhalothrin, cyfluthrin, fenvalerate, esfenvalerate and fluvalinate. Polyclonal antibodies were generated by immunizing with a type II pyrethroid immunogen ((RS)-α-cyano-3-phenoxybenzyl (RS)-cis,trans-2,2-dimethyl-3-carboxyl-cyclopropanecarboxylate) conjugated with thyroglobulin. Antisera were screened against nine different coating antigens. The antibody-antigen combination with the most selectivity for type II pyrethroids such as cypermethrin was further optimized and tested for tolerance to co-solvent, pH and ionic strength changes. The IC₅₀s of the optimized immunoassay were 78 μg l⁻¹ for cypermethrin, 205 μg l⁻¹ for cyfluthrin, 120 μg l⁻¹ for cyhalothrin, 13 μg l⁻¹ for deltamethrin, 6 μg l⁻¹ for esfenvalerate, 8 μg l⁻¹ for fenvalerate and 123 μg l⁻¹ for fluvalinate. No cross-reactivity was measured for the type I pyrethroids such as permethrin, bifenthrin, phenothrin, resmethrin and bioresmethrin. This assay can be used in monitoring studies to distinguish between type I and II pyrethroids.     

Synthetic and biological studies of pyrazolines and related heterocyclic compounds

This review provides a comprehensive survey relating to the synthesis and biological applications of pyrazolines and related heterocycles in the last five years (2007–2011). These compounds are usually prepared from the cyclization of chalcones with hydrazine and its derivatives under the alcoholic conditions. The major incentive behind the synthesis of these compounds was the immense biological activities associated to these heterocyclic derivatives. The aim of this review is to find out different methods for the synthesis of pyrazoline derivatives.     

First example of continuous-flow reaction conditions for biomimetic reductive amination of fluorine-containing carbonyl compounds

This study presents the first example of continuous-flow reaction conditions for biomimetic reductive amination of fluorinated carbonyl compounds using silica-adsorbed DBU as catalyst for on-column process. This new on-column process features operationally convenient conditions, higher chemical yields and purity of products as compared with traditional in-flask reactions. Furthermore the removal of base-catalyst is not an issue in this process at all, as the catalyst (DBU) remains on the column in the “reaction zone”, the feature which makes the overall process substantially more efficient and inexpensive, in particular, for large-scale synthesis of the target α-perfluoroalkyl amines.     

An entirely new methodology for synthesizing perfluorinated compounds: synthesis of perfluoroalkanesulfonyl fluorides from non-fluorinated compounds

A new synthetic procedure for the preparation of perfluoroalkanesulfonyl fluorides utilizing liquid-phase direct fluorination with elemental fluorine has been developed. Direct fluorination of a partially fluorinated ester, which has alkanesulfonyl fluoride in the end, was synthesized from non-fluorinated counterparts and perfluorinated acid fluoride according to the PERFECT process, gave the desired perfluorinated product in moderate yield as well as by-products arising from CS bond cleavage. The results of the direct fluorination of some model substrates suggest that the CS bond cleavage occurred due to radical formation at the α-position rather than the β-position.     

Synthetic, spectroscopic and structural studies of two novel phosphanyl(organyl)borane compounds

The titanium (II) complex, Cp₂Ti(HBcat)₂, catalyzes the hydroboration of diphenylvinylphosphine by catecholborane and pinacolborane to afford exclusive anti-Markovnikov phosphanyl(organyl)boranes cleanly, rapidly and in good yields. Spectroscopic and X-ray studies of the phosphanyl(organyl)borane products show no evidence of boron-phosphorus interaction, indicating that the compounds preclude formation of Lewis pairs.     

A new strategy for the synthesis of highly functionalised fluorinated compounds by reaction of lithium dianions of carboxylic acids with perfluoroketene dithioacetals

The reaction of perfluoroketene dithioacetal with lithium dienediolates of carboxylic acids proceeds at the ω position probably through an addition to the π system followed by elimination of the vinylic fluoride. The preparative value of this reaction depends strongly on the reaction and work-up conditions. The overall process lead to highly functionalised synthons containing a trifluoromethyl group.     

Aerosol-OT-gamma-alumina admicelles for the concentration of hydrophobic organic compounds in water

A novel admicelle composing of a dialkylated anionic surfactant, di-2-ethylhexyl sodium sulfosuccinate (Aerosol-OT, AOT) and gamma-alumina was prepared by mixing them in acidic aqueous solution. The amount of the maximum sorption of AOT on 1 g of alumina at pH 2 was ca. 130 mg. By comparing the fluorescence spectra of N-phenyl-1-naphthylamine in different solvents, the solvent property of AOT-gamma-alumina admicelles was corresponding to that of toluene or diethyl ether. Thus, the AOT-gamma-alumina admicelles had greater hydrophobicity than SDS-gamma-alumina admicelles having similar hydrophobicity to 1-octanol or ethyl acetate. Hydrophobic organic compounds, chlorophenols having more than three chloro substituents, octylphenol, nonylphenol, dibutyl phthalate was almost quantitatively (98% or more) collected onto AOT admicelles composing of 1.5 g gamma-alumina and 150 mg AOT. The greater collection yields rather than those in SDS-admicellar system were ascribable to greater hydrophobicity and stability of AOT admicelles. After the 500-fold concentration, traces (nM) of organic contaminants in water samples were successfully detected with an HPLC having a photometric detector.     

Structure-activity relationships of pyrethroid insecticides. Part 2. The use of molecular dynamics for conformation searching and average parameter calculation

Summary Molecular dynamics simulations have been performed on a number of conformationally flexible pyrethroid insecticides. The results indicate that molecular dynamics is a suitable tool for conformational searching of small molecules given suitable simulation parameters. The structures derived from the simulations are compared with the static conformation used in a previous study. Various physicochemical parameters have been calculated for a set of conformations selected from the simulations using multivariate analysis. The averaged values of the parameters over the selected set (and the factors derived from them) are compared with the single conformation values used in the previous study.     

Synthetic and structural studies on new diiron azadithiolate (ADT)-type model compounds for active site of [FeFe]hydrogenases

A series of new diiron azadithiolate (ADT) complexes (1-8), which could be regarded as the active site models of [FeFe]hydrogenases, have been synthesized starting from parent complex [(μ-SCH(2))(2)NCH(2)CH(2)OH]Fe(2)(CO)(6) (A). Treatment of A with ethyl malonyl chloride or malonyl dichloride in the presence of pyridine afforded the malonyl-containing complexes [(μ-SCH(2))(2)NCH(2)CH(2)O(2)CCH(2)CO(2)Et]Fe(2)(CO)(6) (1) and [Fe(2)(CO)(6)(μ-SCH(2))(2)NCH(2)CH(2)O(2)C](2)CH(2) (2). Further treatment of 1 and 2 with PPh(3) under different conditions produced the PPh(3)-substituted complexes [(μ-SCH(2))(2)NCH(2)CH(2)O(2)CCH(2)CO(2)Et]Fe(2)(CO)(5)(PPh(3)) (3), [(μ-SCH(2))(2)NCH(2)CH(2)O(2)CCH(2)CO(2)Et]Fe(2)(CO)(4)(PPh(3))(2) (4), and [Fe(2)(CO)(5)(PPh(3))(μ-SCH(2))(2)NCH(2)CH(2)O(2)C](2)CH(2) (5). More interestingly, complexes 1-3 could react with C(60) in the presence of CBr(4) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) via Bingel-Hirsch reaction to give the C(60)-containing complexes [(μ-SCH(2))(2)NCH(2)CH(2)O(2)CC(C(60))CO(2)Et]Fe(2)(CO)(6) (6), [Fe(2)(CO)(6)(μ-SCH(2))(2)NCH(2)CH(2)O(2)C](2)C(C(60)) (7), and [(μ-SCH(2))(2)NCH(2)CH(2)O(2)CC(C(60))CO(2)Et]Fe(2)(CO)(5)(PPh(3)) (8). The new ADT-type models 1-8 were characterized by elemental analysis and spectroscopy, whereas 2-4 were further studied by X-ray crystallography and 6-8 investigated in detail by DFT methods.     

Kinetics and mechanism of triethylamine-catalyzed 1,3-proton shift: Optimized and substantially improved reaction conditions for biomimetic reductive amination of fluorine-containing carbonyl compounds

Kinetic study of the triethylamine (TEA)-catalyzed isomerization of imine, derived from benzylamine and trifluoroacetophenone to the corresponding N-benzylidene-2,2,2-trifluoro-1-(phenyl)ethylamine has revealed concerted nature of the mechanism of this reaction via a virtually unionized transition state. As a synthetic bonus of this kinetic study, we found that application of a polar solvent (acetonitrile) and four equivalents of TEA provide for optimal reaction conditions at high concentrations. We demonstrate that application of these reaction conditions allows to substantially increase the reaction rates, chemical yields and results in cleaner formation of the target products.     

Comparison of different stationary phases for bioanalytical studies of biologically active compounds

In this study, the chromatographic behaviour of four mixtures of compounds was tested on columns possessing various surface properties. Cocaine, dimefluron, nabumetone, and tramadol were chosen as the test compounds. Cocaine is a tropane alkaloid, which is relatively often abused as a drug. This is why many papers have already been written about its determination in human biological samples. Dimefluron, a derivative of benzo[c]fluorene, is a new perspective drug being investigated for its potential antineoplastic effects. Nabumetone is a non-steroidal anti-inflammatory prodrug used for treatment of inflammatory and degenerative rheumatic diseases. Tramadol, derived from an opioid structure is used as an anodyne for treatment of severe pain. As a medicament it is usually determined either in biological samples or in pharmaceuticals. The above-mentioned model drugs were separated using chromatographic columns with C18, C8, palmitamidopropyl, and pentafluorophenylpropyl chains. The best conditions for separation of the individual compounds and their metabolites were chosen on the basis of resolution, retention times, and peak symmetry.     

Synthetic studies on indoles and related compounds. XXXI. Chemical confirmation of the synthetic route for the benz[f]indole skeleton and its application

To confirm the structure of ethyl 9-methoxybenz[f]indole ( 8a ) prepared from ethyl pyrrole-2-carboxylate ( 4 ) via a new synthetic route, the following chemical correlation work was performed. Ethyl 9-methoxybenz[f]in-dole ( 8a ) was converted to 1-benzyl-3-methyl-5,6,7,8-tetrahydrobenz[f]indole ( 25 ), which was alternatively and authentically synthesized from ethyl 3-methylpyrrole-2-carboxylate ( 11 ). On the basis of the established route to the benz[f]indole nucleus, two representative benz[f]indoles, benz[f]indole ( 1 ) and 4,9-dioxobenz[f]indole ( 26 ) were synthesized.     

Evaluation of matrix solid‐phase dispersion extraction for the determination of polycyclic aromatic hydrocarbons in household dust with the aid of experimental design and response surface methodology

A simple, fast, and inexpensive procedure for sample preparation based on matrix solid‐phase dispersion was developed for the determination of Environmental Protection Agency 16 priority polycyclic aromatic hydrocarbons in indoor dust samples. Parameters that affect the extraction efficiency such as type of dispersant, elution solvent, and solvent volume were evaluated and optimized with the aid of experimental design and response surface methodology. Analysis was performed by HPLC coupled with UV‐Vis diode array detector (UV‐DAD). For verification, a GC coupled with a mass spectrometer in SIM mode was also applied. Recoveries obtained were from 53 to 120% for all target analytes with detection limits ranging from 0.2 to 10 ng/g and 0.2 to 2 ng/g for LC‐UV‐DAD and GC‐MS, respectively. The optimized method was used for the analysis of 11 household dust samples collected from private houses.     

Methods of studies on quantitative structure–activity relationships for chiral compounds

Chiral compounds are very important in drug development, organic synthesis, materials science, toxicology, or environmental chemistry. Therefore, for creating new drugs, several methods have been suggested in recent years. In several laboratories in the world, some new methods for the derivations of the parameters were constructed and used for studies on quantitative structure–activity/property relationships of chiral molecules. The algorithms reviewed in this paper involve Zargeb group chiral indices, chiral molecular connectivity index, chiral topological charge index, chiral A_m index, chiral indices based on the matrixes, chiral indices based on chiral product, conformation‐independent chirality code, conformation‐dependent chirality code, quantitative two‐dimensional chirality degrees of benzenoids, and so on. Copyright © 2012 John Wiley & Sons, Ltd.     

Synthetic studies toward macrocidins: an RCM approach for the construction of the central cyclic core

The central macrocyclic core of the macrocidins was constructed using RCM as the key reaction. A preliminary investigation dealing with the key reactions, that is, the Dieckmann cyclization and the RCM, revealed that RCM of the β-ketoamide is better than RCM of the corresponding acyltetramic acid.     

Phosphorylated amino acids: model compounds for solid-state 31P NMR spectroscopic studies of proteins

Solid-state 31P NMR spectroscopy was applied to measure the isotropic chemical shifts, chemical shift anisotropies and asymmetry parameters of three phosphorylated amino acids, O-phospho-L-serine, O-phospho-L-threonine and O-phospho-L-tyrosine. The cross-polarization buildup rates and longitudinal relaxation times of 31P and 1H were-determined and compared with the values measured for a triphosphate (GppCH2p) bound to a crystalline protein (Ras). It is shown that the phosphorylated amino acids are well-suited model compounds, e.g. for the optimization of experiments on crystalline proteins. Two-dimensional exchange experiments on O-phospho-L-tyrosine indicate the existence of an exchange between the two different conformations of the molecule.     

Theoretical studies of bond dissociation energies for removal of the nitrile group in some nitrile compounds

The CCN bond distances and bond dissociation energies (BDEs) are estimated by utilizing quantum chemical calculations for 16 nitrile compounds. Since DFT methods have been researched to have low basis sets sensitivity for small and medium molecules in our earlier work [Jun Zhao, Xinlu Cheng, Xiangdong. Yang, J. Mol. Struct. (Theochem) 766 (2006) 87] 16 nitrile compounds are studied by employing the hybrid density functional theory (B3LYP, B3PW91, B3P86) and the complete basis set (CBS-Q) method in conjunction with the 6-311G^** basis set. The obtained results are compared with the available experimental data. It is demonstrated that CBS-Q method, which can produce reasonable BDEs for some systems, seems unable to predict accurate BDEs here. While, the B3P86 calculated results agree very well with the experimental values. So B3P86 method is suitable for computing the reliable BDEs of CCN bond for nitrile compounds.     

Lead structures for applications in photodynamic therapy. Part 2: Synthetic studies for photo-triggered release systems of bioconjugate porphyrin photosensitizers

Photodynamic therapy (PDT) selectivity and specificity can be improved by binding the photosensitizers to target receptors. One approach is to cross-link porphyrins to a biological target receptor via the photocleavable o-nitrobenzyl linker, where a controlled released of the porphyrin can be monitored upon irradiation. The synthetic pathways involved esterification of a porphyrin-carboxylic acid and a unit containing the o-nitrobenzyl alcohol moiety and the bioconjugate. Reactions of a model porphyrin and o-nitrobenzyl alcohol using the carbonyl activating carbodiimide reagent DCC gave a stable N-acyl urea porphyrin, whereas use of EDAC (1-ethyl-3-(3-dimethyl aminopropyl)carbodiimide hydrochloride) gave the desired compounds. Further studies were carried out on the attachment of carbohydrates (i.e., potentially receptor binding ligands) through such a linker to porphyrins. Preliminary irradiation experiments of such a compound show that upon UV irradiation (350 nm) for 80 min, approximately 50% of the porphyrin was cleaved to release the carboxylic acid porphyrin photosensitizer indicating the utility of such systems as photosensitizers delivery systems.     

A clever strategy for permeability studies of methyl bromide and some organic compounds through high-barrier plastic films

An analytical strategy has been proposed and optimized to study the permeability of several flexible plastic materials, some of them with high-barrier properties, versus naphthalene, methyl bromide, toluene, ethylbenzene, and ortho- and para-xylenes. The strategy involves using a system of concentric plastic bags made from the materials to be tested polyethylene (PE) and used as permeable plastics to facilitate the homogeneous distribution of a solid compound, such as naphthalene, in vapour phase. After the permeation test, the vapour phase containing the pollutants that cross the plastic barrier is trapped in a 12% ethanol–water solution and further analysed by SPME in headspace mode. Several experimental conditions as well as different samples were tested. The results obtained are shown and discussed.     

Comparative studies of immobilized chiral stationary phases based on polysaccharide derivatives for enantiomeric separation of 15 azole compounds

Immobilized polysaccharide‐based columns showed excellent enantioselectivity in normal phase separation mode. In this work, enantioseparation abilities of four immobilized polysaccharide‐derived chiral stationary phases (Chiralpak IA, Chiralpak IB, Chiralpak IC, and Chiralpak ID) toward 15 azole compounds were evaluated. Separation was carried out using n‐hexane as mobile phase with ethanol, 1‐propanol, 1‐butanol, and 2‐propanol as modifiers. And twelve compounds have achieved baseline separation with the resolutions ranging between 2.05 and 21.73. The enantioseparation on the four polysaccharide‐based chiral columns using different alcohol modifiers was compared. In general, the best separation performance was identified as Chiralpak IC, which was able to resolve 11 compounds to baseline and two partially under the screening conditions. Separation on Chiralpak IB was not satisfactory, because only four compounds were baseline separated.