N-对三氟甲基苯基-α-氨基烷基膦酸酯的合成、晶体结构及生物活性

采用活性基团拼接法将氟原子引入α-氨基烷基膦酸酯中,合成了一系列含氟芳基α-氨基烷基膦酸酯类新化合物,结构经元素分析,IR,1H NMR及MS确认.对所合成的化合物进行了抑制烟草花叶病毒(TMV)田间生物测试,结果表明,该类化合物具有良好的抑制TMV活性,其中4d化合物在0.0005%浓度下对烟草花叶病毒(TMV)防效达到了67.03%.就此对4d化合物作了单晶培养,并就晶体结构进行了X衍射分析.结构表明4d化合物分子属单斜晶系,空间群P21/c.晶胞参数a=1.1957(5)nm,b=1.0664(5)nm,c=1.5943(7)nm,α=90°,β=97.623(8)°,γ=90°,V=2.0150(15)nm3,Z=4.Dc=1.336 Mg/m3,μ=0.189nm-1,F(000)=840.     

Detection of TMV with ODA-H(2)O(2)-HRP voltammetric enzyme-linked immunoassay system

o-Dianisidine (ODA)-H₂O₂-horseradish peroxidase (HRP) voltammetric enzyme-linked immunoassay system has firstly been used for the detection of tobacco mosaic virus (TMV). HRP catalyzes strongly the oxidation reaction of ODA by H₂O₂, the product of which produces a sensitive second order derivative linear sweep voltammetric peak at potential of −0.56 V (versus SCE) in Britton–Robinson (BR) buffer. HRP activity has been measured with this voltammetric peak and TMV detected through immunoreaction. The detection limit for HRP is 9.25×10^-7 mU l⁻¹ and the linear range is 2.5×10⁻⁶–5.0×10⁻⁴ mU l⁻¹. The detection limit for the clarified TMV is 0.25 ng ml⁻¹ and the highest dilution ratio detected for the infected leaf sap is 1:8×10⁵. The sensitivity for TMV detection with this method is higher than that with the enzyme-linked immunosorbent spectrophotometric assay (ELISA) using ODA-H₂O₂-HRP system. The processes of the enzyme-catalyzed reaction and the electro-reduction of the product of the enzyme-catalyzed reaction have been described.     

Design,synthesis, biological activity evaluation and mechanism of action of myricetin derivatives containing thioether quinazolinone

Plant bacteria and viruses have a huge negative impact on food crops in the world. Therefore, it is important to create new and efficient green pesticides. In this paper, a series of myricetin derivatives containing quinazolinone sulfide were introduced. Good antibacterial and antiviral activities of the drug molecules 2-((3-((5,7-dimethoxy-4-oxo-2-(3,4,5-trimethoxyphenyl)-4H-chromen-3-yl)oxy)propyl)thio)-6-fluoro-3-phenylquinazolin-4(3H)-one (T5) and 2-((4-((5,7-dimethoxy-4-oxo-2-(3,4,5-trimethoxyphenyl)-4H-chromen-3-yl)oxy)butyl)thio)-6-methyl-3-phenylquinazolin-4(3H)-one (T15) respectively were found by biological activity screening. The value of dissociation constant (K_d) of compound T15 to TMV CP was 0.024 ± 0.006 μM, determined by Microscale thermophoresis (MST), which was far less than the value of 8.491 ± 2.027 μM of commercial drug ningnanmycin (NNM). The interaction between compound T15 and TMV CP was further verified by molecular docking. Compound T15 formed strong hydrogen bonds with residues SER:49 and SER:15 (1.92 Å, 2.20 Å, respectively), which were superior to the traditional hydrogen bonds formed by NNM with residue SER:215 (3.64 Å). In addition, the effects of compound T15 on the contents of chlorophyll and peroxidase (POD) in tobacco were studied, and the results indicated that compound T15 could enhance the disease resistance of tobacco plants to a certain extent.     

Two new compounds from the fruit of Ailanthus altissima

A new phenolic derivative, 4-hydroxyphenol-1-O-[6-O-(E)-feruloyl-β-d-glucopyranosyl]-(1→6)-β-d-glucopyranoside (1), and a new terpenylated coumarin, named altissimacoumarin H (2) were identified from the fruit of Ailanthus altissima (Mill.) Swingle (Simaroubaceae), together with ten known compounds (3–12), including two coumarins and eight phenylpropanoids. Their structures were determined on the basis of chemical method and spectroscopic data. Antiviral effect against Tobacco mosaic virus (TMV) of all the compounds obtained were evaluated using leaf-disc method.     

14-羟基菲并[9,10,3’,4’]吲哚里西啶的合成及生物活性研究

以吡咯为起始原料, 以三氟氧钒(VOF3)氧化偶联重排反应为关键步骤, 经过7步反应, 合成了结构骨架全新的14-羟基菲并[9,10,3’,4’]吲哚里西啶化合物8, 总收率为55%. 采用1H NMR, 13C NMR, IR, MS和HRMS对中间体和目标产物进行了表征. 初步的抗烟草花叶病毒生物活性测试结果表明, 目标化合物8对烟草花叶病毒无明显抑制作用, 但具有较好的抗肿瘤活性, 中间体9-氧代-14-羟基-14a-甲氧基菲并[9,10,3’,4’]吲哚里西啶化合物7却表现出了很好的抗烟草花叶病毒活性.     

EDXRF spectrometry determination of tungsten in tobacco plants after antiviral treatment with 12-tungstophosphoric acid and its compounds

In this study, we have developed a sensitive, rapid and simple procedure for the energy dispersive X-ray fluorescence (EDXRF) spectrometry measurement of tungsten in tobacco plant parts. Only 0.1 g of dried plant material is needed instead of the usual 1 g. EDXRF spectrometry is used for quantitative measurement, after the foliar application of solutions of tungstophosphoric acid (WPA), its magnesium salt and compounds with glycine (Gly) and alanine (Ala), in exact quantities. After that, the leaves, trunks and summits were collected and prepared separately. Tungsten is determined directly in raw dried material, and the overlap of the tungsten peak with zinc's that is present is avoided by the spectral deconvolution to obtain quantitative results. The prepared dry tablets weighed 100 mg, and measurement time was 2000 s. The radioisotope excitation source used was ¹⁰⁹Cd and tungsten was identified and quantified at the L_α1 and L_α2 lines at the energies of 8397.6 eV and 8335.2 eV, respectively. EDXRF spectrometry was applied in a wide range of concentrations (up to 2000 mg/kg), with an estimated detection concentration limit of 15 mg/kg, calculated on dried material. Quantitative analysis of different parts of the treated plant plus the washings gave 94.47% recovery of the applied tungsten in different compound forms. After the foliar application of investigated WPA compounds, there were noticed both vertical and horizontal distributions of tungsten through out the tobacco plants, according to the EDXRF spectrometry results. This conclusion is also in agreement with the positive effects of WPA on Tobacco mosaic tobamovirus (TMV) infection of Nicotiana tabacum (Solanaceae).     

烟草花叶病毒在受限空间下的自组装行为

以烟草花叶病毒(TMV)为基本构建单元,研究了其在毛细管、载玻片-载玻片和柱透镜-硅片3种不同受限空间下的自组装行为。 结果表明,由于接触线有规律、重复性的粘滑运动,在3种受限体系下TMV均可组装得到高度规整的条带结构。 在毛细管内组装可得到垂直于管的长轴方向的有序条带。 随接触线深入管中心,条带跨距(l)与带宽(w)均逐渐增大。 在2个平行载玻片所构成的可控空间内所得到的条带以2条互相垂直的中心线为轴对称排列,并沿从载玻片边缘至轴向中心方向条带跨距和带宽梯度增大。 同样,利用柱透镜 硅片所组成的体系可得到类似平行线状条带,其跨距、带宽及条带高度沿从外部边缘至柱透镜/硅片接触中心方向逐渐减小。 在3种体系下,棒状TMV粒子均平行于接触线的方向取向。 TMV浓度对组装结构具有显著影响,随着浓度的增加,条带跨距和带宽均增加,直至条带结构消失形成连续膜。     

Synthesis and Biological Activity of Novel Diphenyl N- Substituted Carbamimidoylphosphoramidate Derivatives

Abstract

An efficient synthesis of a series of novel diphenyl N-substituted carbamimidoyl phosphoramidate derivatives was accomplished in two steps. Diphenyl phosphorochloridate (1) was reacted with cyanamide (2) in the presence of 1,4–dimethylpiperazine as a base in THF at 50–55 °C to form an intermediate, diphenyl cyanophosphoramidate (3). Subsequently 3 was reacted with various aromatic/heterocyclic amines (4) in the presence of 1,4–dimethyl piperazine as a base at 55–60 °C to form the corresponding title compounds 5(a-k). The title compounds were tested for antiviral activity against Tobacco mosaic virus (TMV) in vitro, antibacterial and antifungal activities at two different concentrations of 50 and 100 μg/mL. The title compounds exhibited good antiviral and antimicrobial activities when compared to the standards.     

A simple and efficient method for synthesis of fluorine-containing saccharide esters and antiviral activity

Sixteen new fluorine-containing saccharide esters from fluorine-containing benzoic acids and α-O-acetylglycosyl bromide were synthesized in the presence of 4-dimethylaminopyridine (DMAP) and triethylamine (Et₃N) under mild conditions in good yields and their structures were clearly verified by IR, ¹H NMR, MS and elemental analysis. This method has high stereospecificity, the configuration is unitary, the new synthesized compounds are all of β-configuration. The results of bioassay showed that these title compounds possess potential antiviral activities against tobacco mosaic virus (TMV).     

Synthesis and Biological Activities of Novel 1,2,4-Triazole Derivatives Containing 1,2,3-Thiadiazole Ring

A series of novel 1,2,4-triazole derivatives containing 1,2,3-thiadiazole ring was designed and synthesized. Their structures were confirmed by IR, 1^H NMR, high resolution mass spectrometer（HRMS） and electrospray ionization-mass spectromcter（ESI-MS） combined with melting points and elemental analysis. Preliminary bioassays indi- cate that these compounds exhibit good insecticidal activity against Aphis laburni at 100 μg/mL, especially compound 6b shows mortality of no less than 95%. Most of the compounds show good activities against tobacco mosaic virus（TMV） with different modes in vivo at 100 μg/mL. Compound 6d standed out, showing a good insecticidal activity and very high induction effects against TMV in vivo. Collectively, our data demonstrate a new strategy for insect and virus control.