Synthesis of a Photolabeling Probe for the Study of Antiviral Mechanism of Ribavirin

Ribavirin has been used in urgency to treat SARS patients recently. In order to study its antiviral mechanism by photolabeling approach, we have synthesized and characterized 5-azido-1-β-D-ribofuranosyl-1,2,4-triazole-3-carboxiamide 1 as a photolabeling probe of ribavirin. The azidotriazole nucleoside showed rapid and clean photochemical reaction, suggesting that 1 is a promising probe to study the antiviral mechanism ofribarivin by photolabeling.     

内吸性杀菌剂三唑醇(酮)立体异构体的研究Ⅱ

三唑醇(Triadimenol,又称Baytan)是一种优良的内吸性广谱杀菌剂。谷类作物的种子经处理后,防治病虫害的效果极为突出,可增产粮食20%。此化合物化学名称为1-(对-氯苯氧基)-1-(1′,2′,4′-三氮唑-1′基)-3,3二甲基丁醇-2,结构式(Ⅰ)见后。由于分子中含有两个手性碳原子,故应有四种光学异构体。我们实验室曾分离出毫克量的三唑醇两个非对映异构体(A体和B体),生物测定表明两者的药效有明显差別,并确定有效者为A体。根据~1H-NMR中偶合常数,     

N-Arylation of azoles with low basicity by 1,4-dimethoxybenzene during undivided electrolysis

The reactions of 1,4-dimethoxybenzene with 4-nitropyrazole, 3,4-dinitro-5-methylpyrazole, 1,2,4-triazole, 3-nitro-1,2,4-triazole, and tetrazole were studied during undivided amperostatic electrolysis on a Pt electrode in MeCN, CH₂Cl₂, and MeOH. The main reaction products were 2-azolyl-1,4-dimethoxybenzenes and (or) 1,4-diazolyl-1,4-dimethoxycyclohexa-2,5-dienes. In all cases except 1,2,4-triazole, N-arylation occurs only in the presence of the Alk₄N⁺ salts of azoles or 2,4,6-trimethylpyridine as a base. The mechanism of the reactions is discussed.     

Solid-phase extraction of triazole fungicides from water samples using disks impregnated with carbon nanotubes followed by GC-MS analysis

Triazole fungicides are pesticides widely employed in the cultivation of fruits, vegetables and grains. However, their ability to change the steroid hormone biosynthesis may result in endocrine complications for mammals, as well as changes in cholesterol and triglyceride levels and hepatotoxicity. The analysis of the triazole fungicides in superficial waters is important in order to monitor the risk for the biota. However, the use of efficient extraction procedures has been necessary in order to concentrate these pesticides before the analysis. In-disk solid-phase extraction (SPE) can be highlighted as a potential pre-concentration technique, mainly because the possibility to extract the analytes from a large sample volume, increasing the method detectability. Carbon nanotubes (CNTs) have been often used as solid extraction phase due to their high sorption capacity, surface area and internal volume, as well as mechanical, chemical and thermal stability. In this paper, we proposed the preparation of a new SPE disk impregnated with CNTs for the extraction of triazole fungicides from environmental water samples. The disks were obtained by acid corrosion of a cellulose membrane followed by its impregnation with CNTs. The developed method was validated for the analysis of triadimenol, tebuconazole and epoxiconazole, according to international validation protocols. The limits of quantification obtained for triadimenol, tebuconazole and epoxiconazole were 0.1, 0.1 and 0.05 µg L^?1, respectively. The linearity ranged from 0.05 to 10.00 µg L^?1 for epoxiconazole and from 0.1 to 10.00 µg L^?1 for triadimenol and tebuconazole, with correlation coefficients higher than 0.999 for all of them. The precisions, expressed as relative standard deviation, were lower than 12%. The accuracies were within ?12.07% to 17.7% (expressed as relative error).     

ORGANOPHOSPHORUS COMPOUNDS AS POTENTIAL FUNGICIDES. PART I. N-(ω-GUANI-DINOALKYL)AMINOALKANEPHOSPHONIC ACIDS AND THEIR AMINOPHOSPHONIC PRECURSORS: PREPARATION,NMR SPECTROSCOPY,AND FAST ATOM BOMBARDMENT MASS SPECTROMETRY

Abstract

N-(ω-Aminoalkyl)- and N-(ω-guanidinoalkyl)-aminoalkanephosphonic acids have been prepared from α, ω-diaminoalkanes by reaction with chloromethanephosphonic acid (or an ester of a halogeno-alkanephosphonic acid), followed by treatment with S-methylisothiouronium chloride. Ethylene diamine yielded 1-phosphonomethyl-2-iminoimidazolidine. A number of 1:1 salts of the α, ω-diamines and chloromethanephosphonic acid are also reported. Doubly charged zwitterionic structures are assigned to both ω-amino and ω-guanidino compounds on the basis of ³¹P and ¹³C nmr data. Thus the addition of an excess of acid (D₂SO₄) causes the ³¹P chemical shift to move to higher field, from ca. 8 to 14 ppm, whilst ¹ Jpc increases from ca. 130 to 150 Hz. The ¹H and ¹³C chemical shifts of the terminal methylene groups in the polymethylene chain are unaffected by acidification.

Fast atom bombardment mass spectrometry gives rise to characteristic [M + H]⁺ ions, frequently as the base peak, and to fragmentations involving the loss of phosphorous acid, or the formation of ions resulting from carbon-nitrogen or carbon-carbon cleavage. The compounds show activity against a number of fungal pathogens and other microbial organisms.     

Alternative solvent‐based methyl benzoate vortex‐assisted dispersive liquid–liquid microextraction for the high‐performance liquid chromatographic determination of benzimidazole fungicides in environmental water samples

Vortex‐assisted dispersive liquid–liquid microextraction using methyl benzoate as an alternative extraction solvent for extracting and preconcentrating three benzimidazole fungicides (i.e., carbendazim, thiabendazole, and fluberidazole) in environmental water samples before high‐performance liquid chromatographic analysis has been developed. The selected microextraction conditions were 250 μL of methyl benzoate containing 300 μL of ethanol, 1.0% w/v sodium acetate, and vortex agitation speed of 2100 rpm for 30 s. Under optimum conditions, preconcentration factors were 14.5–39.0 for the target fungicides. Limits of detection were obtained in the range of 0.01–0.05 μg/L. The proposed method was then applied to surface water samples and the recovery evaluations at three spiked concentration levels of 5, 30, and 50 μg/L were obtained in the range of 77.4–110.9% with the relative standard deviation <7.4%. The present method was simple, rapid, low cost, sensitive, environmentally friendly, and suitable for the trace analysis of the studied fungicides in environmental water samples.     

Facile synthesis of a novel magnetic covalent organic frameworks for extraction and determination of five fungicides in Chinese herbal medicines

A novel magnetic covalent organic framework was synthesized via a one-step coating approach with solvothermal reaction employing 2,4,6-tris(4-aminophen-yl)-1,3,5-triazine and 2,4,6-triformylphloroglucinol as two building blocks by covalent bonding. The prepared magnetic covalent organic frameworks were properly characterized by different techniques and employed as adsorbents of magnetic solid-phase extraction. An analytical method was developed for the simultaneous determination of five fungicides in two Chinese herbal medicine samples via magnetic solid-phase extraction coupled to ultra high performance liquid chromatography with tandem mass spectrometry analysis. Under optimized magnetic solid-phase extraction conditions, the method exhibited satisfactory recoveries (74.0−109.6%) with relative standard deviations of 0.4−4.6%, low limits of detection (0.003−0.015 μg/kg), and good linearity (R² > 0.9960). Compared with the traditional extraction method, the proposed method required a lower amount of adsorbent (3 mg) and extraction time (5 min). The adsorbent also had favorable reusability (not less than eight times). Therefore, the magnetic covalent organic frameworks could be a promising adsorbent for the extraction and quantitation of fungicides in Chinese herbal medicines.     

含有脲桥结构的苯氧乙酰胺衍生物的合成与表征

为了开发新型高效低毒杀菌剂,设计合成了5个未见文献报道的含有脲桥结构的苯氧乙酰胺类化合物,其结构经元素分析,1H NMR和IR确证.     

Insights on the Synthesis of N-Heterocycles Containing Macrocycles and Their Complexion and Biological Properties

Macrocyclic chemistry has been extensively developed over the past several decades. In fact, the architecture of new macrocyclic models has undergone exponential growth to offer molecules with specific properties. In this context, an attempt is made in this study to provide an overview of some synthetic methods allowing the elaboration of N-heterocycles containing macrocycles (imidazole, triazole, tetrazole, and pyrazole), as well as their applications in the complexation of metal cations or as pharmacological agents.     

气相色谱-正化学源-质谱联用技术测定葡萄和葡萄酒中多种唑类杀菌剂的残留量

建立了可用于葡萄和葡萄酒中20种唑类杀菌剂残留量的分散型固相萃取-气相色谱-正化学离子源质谱分析方法.葡萄和葡萄酒样品分别用乙腈(含1%冰醋酸)和乙酸乙酯提取,分散型固相萃取法净化,由气相色谱-正化学离子源质谱分时段选择离子监测技术进行测定与确证,外标法定量.20种农药在50～1000 μg/L范围内线性均良好; 所有农药的方法定量限(LOQ)均低于10 μg/kg;在3个添加水平(10, 20和40 μg/kg)下,所有农药的回收率均处于71.2%～102.2%之间, RSD≤10.6%.