Novel aromatic carboxamides from dehydroabietylamine as potential fungicides: Design,synthesis and antifungal evaluation

The present study was carried out to design and synthesize a number of novel aromatic carboxamide derivatives of dehydroabietylamine. The preliminary antifungal assay indicated that most of title compounds displayed moderate to good antifungal activity toward the six fungal strains in vitro. Compounds 3i, 3q, 4b and 4d showed significant antifungal activity against Sclerotinia sclerotiorum, with EC₅₀ values ranging from 0.067 ～ 0.393 mg/L. Compounds 3i, 4b and 4d also showed pronounced mycelial growth inhibition activities against B. cinerea and A. solani. Furthermore, in the in vivo assay, compound 4b exhibited brilliant protective activity against S. sclerotiorum-infected rape leaves. Meanwhile, the in vivo bioassay on tomato plants infected by B. cinerea showed that compound 3i and 4d displayed excellent protective activity at 200 mg/L, which were near to boscalid. Primary mechanistic study revealed that 4b could inhibit sclerotia formation as well as reduce the exopolysaccharide level. SEM and TEM analysis indicated that 4b possessed a strong ability to destroy the surface morphology of mycelia, cell structure and seriously interfere with the growth of the fungal pathogen. In addition, 4b exhibited good inhibitory activity (IC₅₀ = 23.3 ± 1.6 μM) toward succinate dehydrogenase (SDH). Molecular modeling study confirmed the binding modes between compound 4b and SDH. The above antifungal results and fungicidal mechanism study revealed that this class of dehydroabietylamine derivatives could be potential SDH inhibitors and lead compounds for novel fungicides development.     

Off-Line and On-Line Preconcentration Techniques for the Determination of Phenylureas in Freshwaters

Abstract

Phenylurea herbicides are analysed by reversed-phase liquid chromatography using UV detection at 244 nm after a concentration step in order to determine ppb or sub-ppb levels in drinking and river waters. With an average UV detection limit of 5 ng, a 500 ml sample volume is necessary to reach the 10 ppt level for spiked LC grade water samples and enables easy determination of concentrations below the ppb level for river water samples. Off-line and on-line methods are compared for the concentration step. Off-line concentration consists in a liquid sorption on n-octadecyl silica (C18) and elution by a suitable organic solvent. Polar phenylureas have low retention volumes on C18 silica and consequently the length of the concentration column has to be 10 cm to concentrate them at the ppb level from 100 ml of water and longer for lower levels of detection. Nevertheless, we show that increasing the size of the concentration column does not improve the limits of detection because of the numerous interferences also concentrated when percolating high volumes of water. On-line technology can be used only with short precolumns and requires a sorbent with a great retention for phenylureas. The copolymer-based PRP-1 is found to be an excellent sorbent and it is then possible to apply on-line precolumn technology with preconcentration through two precolumns (10 × 21 mm ID) in series, the first one being packed with C18 silica and the other with the PRP-1 polymer. Interfering compounds are then trapped onto the first precolumn acting as a filter and common phenylurea-breakthrough volumes on the PRP-1 precolumn are higher than 500 ml. Knowing the amounts preconcentrated on both precolumns and using UV and electrochemical detection help the identification of phenylureas in river water.     

Synthesis, Structure and H+/K+-ATPase Inhibitory Activity of Novel Triazolyl Substituted Tetrahydrobenzofuran Derivatives via One-pot Three-component Click Reaction

Eleven triazolyl substituted tetrahydrobenzofuran derivatives were synthesized in high yields as novel H⁺/K⁺‐ATPase inhibitor via one‐pot CuI‐catalyzed three‐component click reaction of azide, secondary amine and 3‐bromopropyne under mild conditions in water. Their structures were characterized by NMR, IR, ESI‐MS, elemental analysis and single‐crystal X‐ray diffraction analysis. Most of the target compounds exhibited better H⁺/K⁺‐ATPase inhibitory activity than commercial omeprazole with IC₅₀ values less than 15 µmol·L^?1. The initial structure‐activity analysis suggested that the triazole substituted by cycloalkyl, aromatic ring or O‐containing side‐chain seemed to be beneficial for enhancing the activity.     

Electrochemical Behaviour and Square Wave Voltammetry of the Rice Herbicides Molinate,Bensulfuron-Methyl,Mefenacet and Thiobencarb

Abstract

Cyclic, differential pulse and square wave voltammetry were applied to develop an electroanalytical procedure for the determination of a group of herbicides used to treat rice crops: molinate, bensul-ruron-methyl, mefenacet and thiobencarb. The oxidation mechanism causes adsorption problems and consequent poisoning of the electrode surface by the products of the electrochemical reaction. Parameters such as pH, frequency and electrochemical electrode surface treatment were optimized. The analytical methodology developed using square wave voltammetry was applied to the determination of molinate and bensulfuron-methyl in simple or mixed commercial products.     

On The Fluorometric Method for the Measurement of β-Cyanoalanine Synthase Activity

Abstract

A modification of a fluorescence assay method for β-cyanoalanine synthase has been described which involves the direct coupling of the product of cyanide and cysteine to resazurin, to produce the fluorescent resosurfin, The fluorescence produced was found to be directly proportional to the rate of the reaction.     

A QM/MM study on the reaction pathway leading to 2‐Aceto‐2‐hydroxybutyrate in the catalytic cycle of AHAS

The reaction between the intermediate 2‐hydroxyethyl‐thiamin diphosphate (HEThDP^?) and 2‐ketobutyrate, in the third step of the catalytic cycle of acetodydroxy acid synthase, is addressed from a theoretical point of view by means of hybrid quantum/molecular mechanical calculations. The QM region includes one molecule of 2‐ketobutyrate, the HEThDP^? intermediate, and the residues Arg 380 y Glu 139; whereas the MM region includes the rest of the protein. The study includes potential energy surface scans to identify and characterize critical points on it, transition state search and activation barrier calculations. The results show that the reaction occurs via a two‐step mechanism corresponding to the carboligation and proton transfer in the first stage; and the product release in the second step. © 2014 Wiley Periodicals, Inc.     

High‐Level Incorporation of Silver in Gold Nanoclusters: Fluorescence Redshift upon Interaction with Hydrogen Peroxide and Fluorescence Enhancement with Herbicide

High‐level incorporation of Ag in Au nanoclusters (NCs) is conveniently achieved by controlling the concentration of Ag⁺ in the synthesis of bovine serum albumin (BSA)‐protected Au NCs, and the resulting structure is determined to be bimetallic Ag₂₈Au₁₀‐BSA NCs through a series of characterizations including energy‐dispersive X‐ray spectroscopy, mass spectroscopy, and X‐ray photoelectron spectroscopy, together with density functional theory simulations. Interestingly, the Ag₂₈Au₁₀ NCs exhibit a significant fluorescence redshift rather than quenching upon interaction with hydrogen peroxide, providing a new approach to the detection of hydrogen peroxide through direct comparison of their fluorescence peaks. Furthermore, the Ag₂₈Au₁₀ NCs are also used for the sensitive and selective detection of herbicide through fluorescence enhancement. The detection limit for herbicide (0.1 nm ) is far below the health value established by the U.S. Environmental Protection Agency; such sensitive detection was not achieved by using AuAg NCs with low‐level incorporation of Ag or by using the individual metal NCs.