GC-MS法检测牛肉中拟除虫菊酯的残留量

建立了柱层析法/气相色谱(GC)-负化学离子源(NCI)质谱检测牛肉中7种常用拟除虫菊酯杀虫剂残留的方法.样品经乙腈提取,通过中性氧化铝层析柱净化后,再由气相色谱-负化学离子源质谱选择离子监测技术(SIM)进行测定.7种菊酯类农药标准溶液在10～1 000 μg/L范围内线性关系良好,r2均大于0.997,在10、20...     

Steric and Electronic Effects on the Configurational Stability of Residual Chiral Phosphorus‐Centered Three‐Bladed Propellers: Tris‐aryl Phosphanes

A series of tris‐aryl phosphanes, structurally designed to exist as residual enantiomers or diastereoisomers, bearing substituents differing in size and electronic properties on the aryl rings, were synthesized and characterized. Their electronic properties were evaluated on the basis of their electrochemical oxidation potential determined by voltammetry. The configurational stability of residual phosphanes, evaluated by dynamic HPLC on a chiral stationary phase or/and by dynamic ¹H and ³¹P NMR spectroscopy, was found to be rather modest (barriers of about 18–20 kcal mol^?1), much lower than that shown by the corresponding phosphane oxides (barriers of about 25–29 kcal mol^?1). For the first time, the residual antipodes of a tris‐aryl phosphane were isolated in enantiopure state and the absolute configuration assigned to them by single‐crystal anomalous X‐ray diffraction analysis. In this case, the racemization barrier could be calculated also by CD signal decay kinetics. A detailed computational investigation was carried out to clarify the helix reversal mechanism. Calculations indicated that the low configurational stability of tris‐aryl phosphanes can be attributed to an unexpectedly easy phosphorus pyramidal inversion which, depending upon the substituents present on the blades, can occur even on the most stable of the four conformers constituting a single residual stereoisomer.     

A Cheminformatics Study Regarding the Human Health Risks Assessment of the Stereoisomers of Difenoconazole

Difenoconazole is a chemical entity containing two chiral centers and having four stereoisomers: (2R,4R)-, (2R,4S)-, (2S,4R)- and (2S,4S)-difenoconazole, the marketed product containing a mixture of these isomers. Residues of difenoconazole have been identified in many agricultural products and drinking water. A computational approach has been used to evaluate the toxicological effects of the difenoconazole stereoisomers on humans. It integrates predictions of absorption, distribution, metabolism, excretion and toxicity (ADMET) profiles, prediction of metabolism sites, and assessment of the interactions of the difenoconazole stereoisomers with human cytochromes, nuclear receptors and plasma proteins by molecular docking. Several toxicological effects have been identified for all the difenoconazole stereoisomers: high plasma protein binding, inhibition of cytochromes, possible hepatotoxicity, neurotoxicity, mutagenicity, skin sensitization potential, moderate potential to produce endocrine disrupting effects. There were small differences in the predicted probabilities of producing various biological effects between the distinct stereoisomers of difenoconazole. Furthermore, there were significant differences between the interacting energies of the difenoconazole stereoisomers with plasma proteins and human cytochromes, the spectra of the hydrogen bonds and aromatic donor–acceptor interactions being quite distinct. Some distinguishing results have been obtained for the (2S,4S)-difenoconazole: it registered the highest value for clearance, exposed reasonable probabilities to produce cardiotoxicity and carcinogenicity and negatively affected numerous nuclear receptors.     

Stereoselective Synthesis and Biological Profile of All Stereoisomers of Lactam Analogues of Strigolactones GR24 and GR18

Strigolactones (SLs) are signaling molecules involved in plant development and governing interactions with soil microorganisms in the rhizosphere as well as the germination of parasitic weeds. Developing their use in Crop Protection is a promising approach to a sustainable agriculture by mitigating biotic and abiotic stresses. Recently, a new class of lactam analogues of SL has emerged, namely strigolactams, displaying outstanding potency to induce the germination of parasitic weed O. cumana as well as enhanced chemical and soil stability. Herein, we describe the stereoselective synthesis of GR24 and GR18 lactams harnessing the chemistry of chiral keteniminium (KI) salts, in particular the unprecedented reactivity of chloro-substituted KI, supported by DFT calculations. We disclose subsequently the biological activity on corn of the 32 stereopure strigolactams prepared, highlighting the crucial influence of stereochemistry and lactam substitution, rationalized by docking analyses. Finally, we performed stability studies in soil, which reveal that stereoisomers display very different half-lives, reflecting the significant impact of stereochemistry on degradation kinetics.