Synthesis, insecticidal activity, and QSAR of novel nitromethylene neonicotinoids with tetrahydropyridine fixed cis configuration and exo-ring ether modification

To keep the nitro group in the cis position, a series of nitromethylene neonicotinoids containing a tetrahydropyridine ring with exo-ring ether modifications were designed and synthesized. All of the compounds were characterized and confirmed by 1H NMR, high-resolution mass spectroscopy, elemental analysis, and IR. The bioassay tests showed that some of them exhibited good insecticidal activities against pea aphids. On the basis of 10 nitromethylene derivatives, the quantitative structure-bioactivity relationship (QSAR) was analyzed and established. The results suggested that AlogP98 and Dipole_Mopac might be the important parameters related with biological activities.     

Design, synthesis, and biological activities of milbemycin analogues

Milbemycins have received considerable interest in agricultural chemistry due to a special action mode, extremely high activity against arachnoide pests, low toxicity to mammals, and environmentally benign characteristics. Two series of novel milbemycin analogues (4Ia-6IIc) containing alkyl and aryl groups at the 4'- and 13-positions were designed and synthesized by five schemes. These analogues were identified by (1)H NMR, (13)C NMR, and elemental analysis (or HRMS). Their insecticidal activities against carmine spider mite, oriental armyworm, and black bean aphid were evaluated. The results showed that all of the title compounds had low acaricidal activity against carmine spider mite. However, most of them exhibited good insecticidal activities against oriental armyworm and black bean aphid at a concentration of 200 mg L(-1). The most potent substituents of 2,2-dimethylbutanoyl (4Ib), phenylacetyl (4IIm), and (Z)-1-(methoxyimino)-1-phenylacetyl (4IIn) exhibited the highest larvicidal activities, and its insecticidal LC(50) values against oriental armyworm were 0.250, 0.204, and 0.350 mg L(-1), while its insecticidal LC(50) values against black bean aphid were 0.150, 0.070, and 0.120 mg L(-1), respectively. These substituents provided some hints for further investigation on structure modification.     

Design, synthesis, and biological evaluation of phosphoramide derivatives as urease inhibitors

The design, synthesis, and biological evaluation of phosphoramide derivatives as urease inhibitors to reduce the loss of ammonia has been carried out. Forty phosphorus derivatives were synthesized and their inhibitory activities evaluated against that of jack bean urease. In addition, in vivo assays have been carried out. All of the compounds were characterized by IR, (1)H NMR, MS, and elemental microanalysis. In some cases, detailed molecular modeling studies were carried out, and these highlighted the interaction between the enzyme active center and the compounds and also the characteristics related to their activity as urease inhibitors. According to the IC(50) values for in vitro inhibitory activity, 12 compounds showed values below 1 microM and 8 of them represent improvements of activity in comparison to the commercial urease inhibitor N-n-butylthiophosphorictriamide (NBPT) (100 nM) (AGROTAIN). On the basis of the activity results and the conclusions of the molecular modeling study, a structural model for new potential inhibitors has been defined.     

Design, synthesis, and biological activities of arylmethylamine substituted chlorotriazine and methylthiotriazine compounds

Heterocyclic rings were introduced into the core structure of s-triazine to design and synthesize a series of novel triazines containing arylmethylamino moieties. These compounds were characterized by using spectroscopic methods and elemental analysis. Their herbicidal, insecticidal, fungicidal, and antitumor activities were evaluated. Most of these compounds exhibited good herbicidal activity, especially against the dicotyledonous weeds, and compound F8 was almost at the same level as the control compound atrazine. Their structure-activity relationships were discussed. At the same time, some triazines had interesting fungicidal and insecticidal activities, of which F4 exhibited 100% efficacy against Puccinia triticina even at 20 ppm, and F5 showed Lepidopteran-specific activity in both leaf-piece and artificial diet assays. Moreover, these compounds showed antitumor activities against leukemia HL-60 cell line and lung adenocarcinoma A-549 cell line.     

Design, synthesis, and fungicidal activity of macrolactones and macrolactams with a sulfonamide side chain

Four series of novel macrolactones and macrolactams12-alkylsulfonamido-1,15-pentadecanlactones ( 5), 12-alkylsulfonamido-15-methyl-1,15-pentadecanlactones ( 6), 12-alkylsulfonamido-1,15-pentadecanlactams ( 7), and N-(alkylsulfonamidoethyl)-1,12-dodecanlactams ( 8)were designed and synthesized from readily available 2-nitrocyclododecanone or cyclododecanone. Their structures were confirmed by (1)H NMR, IR, and elemental analysis. The bioassay showed that these compounds displayed fair to excellent fungicidal activity against Rhizoctonia solani Kuhn and have a gradual increase of fungicidal activity in the order of 6, 7, 8, and 5. Among them, compounds 5a, 5b, and 5c displayed excellent fungicidal activity against R. solani comparable with the commercial fungicide carbendazim. Above results illustrated that the rule on the relationship between the activity and hydrogen-bonding, namely the macrocyclic compounds with a hydrogen-bonding acceptor and a hydrogen-bonding donor on the ring and having a three methylenes distance between two polarizable groups have the best fungicidal activity against R. solani, has a general suitability to the macrocyclic compounds, and pesticide molecules may combine with a target enzyme by hydrogen-bonding. The facts, which compound 6 has a much lower fungicidal activity against R. solani than compound 5 but their difference in chemical structure is only that there is a methyl group on the C15 for compound 6 and none but hydrogen atom on the C15 for compound 5, indicated that a methyl group plays an inhibitory role to the fungicidal activity. It suggests that the existence of a methyl group with a great volume between two polarizable groups would interfere in the interaction of pesticide molecules and the target enzyme.     

农业景观害虫控制生境管理及植物配置方法

集约化农业生产过程中,化学农药所带来的大量环境问题日益引起关注。为减少农药的投入及其所产生的环境负效应,生物防治害虫的方法在国内外得到了更多的关注与发展。生境管理是一种有利于天敌群落发展,而不利于害虫种群增长的保护性生物防治方法,其实质是通过为自然天敌提供诸如花蜜、替代猎物或寄主、躲避不利干扰的庇护所等资源,将农业景观中天敌的害虫控制服务和功能最大化,或者通过构建不适宜害虫取食和繁殖的环境条件起到抑制或阻碍害虫发展的作用。本文在参阅国内外文献的基础上,阐述了生境管理控制害虫的机理,并总结国外生物防治的实践经验以及近些年国内外的相关研究,概括提出田间尺度上害虫生物防治的非作物生境及作物生境的建设和植物配置方法,为通过生境管理提升农业景观中害虫生物防治生态系统服务提供参考。     

Design, synthesis, and fungicidal activities of new strobilurin derivatives

Strobilurins are one of the most important classes of agricultural fungicides. To discover new strobilurin analogues with high activity against resistant pathogens, a series of new strobilurin derivatives bearing structurally diverse heterocycle side chains 3a-m and 4a-g were designed and synthesized via a microwave-assisted procedure. The advantages, such as good to excellent yields, shorter reaction times, mild reaction conditions, and simple purification procedures, distinguish the present synthetic protocol as a highly efficient method for the preparation of strobilurin thioether derivatives. Bioassays indicated that most of the compounds showed broad-spectrum fungicidal activity in vitro. Interestingly, as compared to the control of a commercial strobilurin fungicide, Kresoxim-methyl, compounds 3b, 3g, 4c, and 4d possessed remarkably higher in vitro fungicidal activity against six kinds of tested fungi. Exhilaratingly, compound 3g exhibited higher in vivo activity against Sphaerotheca fuliginea and Pseudoperoniospora cubensis than Kresoxim-methyl, and the in vivo fungicidal activities of compound 4d and Kresoxim-methyl against S. fuliginea and P. cubensis are at the same level. The present work demonstrated that strobilurin analogues containing benzothiazole side chains could be used as a lead structure for further developing novel fungicides.     

Design, synthesis, and insecticidal activities of novel monohalovinylated pyrethroids

A series of novel monohalovinylated pyrethroids are designed and synthesized to replace one halo atom with a hydrogen atom on the double bond of dihalopyrethroids. Bioassays indicate that some of the synthesized compounds, such as 3j and 1j, exhibit high insecticidal activities against mosquitoes ( Culex pipiens pallens ), oriental armyworms ( Mythimna separata ), alfalfa aphids ( Aphis medicagini ), and carmine spider mites ( Tetranychus cinnabarinus ). Photolytic results of E-cis-1j suggest that monohalovinylated pyrethroids are photodegraded more easily than compound 12.     

Design, synthesis, crystal structure analysis, and insecticidal evaluation of phenylazoneonicotinoids

On the basis of research of the proposed modes of action between neonicotinoids and insect nicotinic acetylcholine receptor (nAChR), a series of phenylazoneonicotinoids were designed and synthesized to further promote the π-π interaction between molecule and amino acid residues. The target compounds have been identified on the basis of satisfactory analytical and spectral ((1)H NMR, (13)C NMR, HRMS, and X-ray) data. The preliminary results revealed that tiny differences in substitutes resulted in different configurations and great bioactivity variations. Some compounds with electron-donating groups on positions 2 and 6 of the phenyl ring presented higher insecticidal activity than imidacloprid against cowpea aphids ( Aphis craccivora ). The impressive crystal structure of the excellent insecticidal activity compound 9q clearly proved that the functional electronegative pharmacophore was approximately vertical to the methyleneimidazolidine plane. The differences in the mode of interaction on nAChR of typical compounds 9h and 9q remain unclear.     

Design, synthesis, and antiviral activity evaluation of phenanthrene-based antofine derivatives

On the basis of our previous structure-activity relationship (SAR) and antiviral mechanism studies, a series of phenanthrene-based antofine derivatives (1-12 and 18-50) were designed targeting tobacco mosaic virus (TMV) RNA and synthesized and systematically evaluated for their antiviral activity against TMV. The bioassay results showed that most of these compounds exhibited good to excellent in vivo anti-TMV activity, of which compounds 19 and 27 displayed higher activity than commercial Ribavirin, thus emerging as potential inhibitors of plant virus. The novel concise structure provides another new template for antiviral studies.     

Bioactive compounds and 1,3-Di[(cis)-9-octadecenoyl]-2-[(cis,cis)-9, 12-octadecadienoyl]glycerol from Apium graveolens L. seeds

Bioassay-directed isolation and purification of the hexane extract of Apium graveolens L. seeds led to the characterization of three compounds: beta-selinene (1), 3-n-butyl-4,5-dihydrophthalide (2) and 5-allyl-2-methoxyphenol (3). The structures of these compounds were established by using (1)H and (13)C NMR spectral methods. Compounds, 1-3 demonstrated 100% mortality on fourth-instar Aedes aegyptii larvae at 50, 25, and 200 microg mL(-)(1), respectively, in 24 h. Also, 2 inhibited the growth of Candida albicans and Candida kruseii at 100 microg mL(-)(1). It inhibited both topoisomerase-I and -II enzyme activities at 100 microg mL(-)(1). Compound 2 displayed 100% mortality at 12.5 and 50 microg mL(-)(1), respectively, when tested on nematodes, Panagrellus redivivus and Caenorhabditis elegans. The triglyceride, 1,3-di[(cis)-9-octadecenoyl]-2-[(cis,cis)-9, 12-octadecadienoyl]glycerol (4) and 3 were isolated for the first time from A. graveolens seeds, although 4 was not biologically active.     

Design, synthesis, and insecticidal evaluation of new benzoylureas containing isoxazoline and isoxazole group

Twenty-two new benzoylphenylureas containing isoxazoline and the isoxazole group were designed and synthesized, and their structures were characterized by (1)H NMR and elemental analysis (or HRMS). The larvicidal activities against Oriental armyworm, mosquito, and diamondback moth of the new compounds were evaluated. Compounds I-1 and III-1 showed nearly the same level of insecticidal activity against Oriental armyworm as commercial insecticide Flucycloxuron and surprisingly exhibited much higher larvicidal activities against diamondback moth than Flucycloxuron.     

2-fluoroabscisic acid analogues: their synthesis and biological activities

Fluorine was introduced into the 2-position of the side chain of abscisic acid (ABA) analogues by Wittig reaction of alpha-ionone derivatives with ethyl triethylphosphono-2-fluoroacetate. The effects of the fluorinated analogues were evaluated on inhibition of cress seed germination and inhibition of gibberellin-inducible alpha-amylase induction in embryoless barley half-seeds. (2E, 4E)-2-Fluoro-5-(1'-hydroxy-2',6', 6'-trimethyl-2'-cyclohexen-1'-yl)-3-methyl-2,4-pentadienoic acid (5b) showed potent inhibitory activity at the same level as ABA in the cress seed germination test, and 5b also inhibited gibberellin-inducible alpha-amylase induction at 4 x 10(-)(6), 3 times the concentration of ABA (1 x 10(-)(6)) for 50% inhibition of alpha-amylase production. 5b also showed dehydrin induction activity. These results indicate that fluorinated ABA analogues mimic ABA action and can be a lead for a plant growth regulator which regulates plant growth or protects plants from environmental stresses.     

不同氮效率木薯品种根系形态、构型及氮吸收动力学特征

【目的】比较分析低氮 (N) 条件下不同氮效率木薯品种的根系形态、构型及吸收动力学变化,以阐明木薯氮高效吸收机制,为指导木薯生产和木薯品种选育提供理论基础。【方法】于2015年在广西大学国家重点实验室温室大棚内进行了试验。盆栽试验采用双因素 (品种 × 氮水平) 区组设计。供试木薯品种包括氮高效品种华南10号 (SC10) 与氮低效品种华南205(SC205)。氮水平包括不施氮 (N0) 和施N 55.2 mg/kg土 (N1)。每盆装10 kg土,种植1株幼苗。木薯出苗60天后,取出并洗净根系,利用根系扫描仪EPSON2000进行根系图像采集,利用WinRHIZO PRO根系分析软件分析图片,获得根系形态指标。将整株植株分成根、茎、叶三个部分,测量干重和氮含量。根系分层试验在大型根系观测系统中进行。吸收动力学试验采用改进常规耗竭法,并比较分析了木薯根系形态、根系构型特征及硝态氮吸收动力学参数差异。【结果】N1和N0条件下,氮高效品种SC10生物量和氮素积累量均显著高于氮低效品种SC205(P < 0.05)。N0条件下,SC10的整株生物量降幅为37.4%,SC205的降幅为69.4%,品种SC10的降幅显著低于SC205 (P < 0.05);SC10的根、茎、叶和全株氮积累量均显著高于SC205,全株氮积累量为SC205的152%。与N1相比,N0处理的木薯品种SC10总根长、根系表面积和细根根长的降幅分别为11.0%、10.0%和20.4%,SC205的降幅分别高达35.9%、27.7%和50.2%,两个品种下降幅度差异显著 (P < 0.05)。低氮诱导木薯根系分布下移,SC10根系呈上宽下窄三角形,最深可达180 cm土层;SC205根系呈椭圆形,最深达130cm土层。氮素吸收动力学试验结果发现SC10、SC205的Km分别为3.27和7.87 mmol/L,表明SC10根系对NO₃–的亲和性更高。【结论】氮高效品种SC10的根系对硝态氮的亲和力 (Km) 几乎是氮低效品种SC205的两倍。在氮素胁迫条件下,氮高效品种可形成优于氮低效品种的根系构型,特别是根系的总根长、根系表面积和细根根长的下降幅度显著小于氮低效品种,是有效缓解氮胁迫的重要原因。     

兰州百合真空干燥图形组态系统研制

为了实现各类生产数据的良性管理和干燥全过程的高效监控等质量保证措施,引入图形组态理念,从对干燥现场的分类抽象和对各类过程数据的动态重构入手,研制了基于Visual Graph图形开发工具和SQL 2005数据库的面向兰州百合真空干燥的图形组态系统,并应用于工程实践。同时探讨了图形组态系统网络化编辑和控制的实现策略。实际应用表明：兰州百合真空干燥图形组态系统能够增强多源异构数据的协调管理,实现干燥过程的高效监控,满足用户对操作界面直观简便的需求。     

Allium chemistry: synthesis, natural occurrence, biological activity, and chemistry of Se-alk(en)ylselenocysteines and their gamma-glutamyl derivatives and oxidation products

Syntheses are reported for gamma-glutamyl Se-methylselenocysteine (Sa), selenolanthionine (16), Se-1-propenylselenocysteine (Gd), Se-2-methyl-2-propenyl-L-selenocysteine (6e), and Se-2-propynyl-L-selenocysteine (6f). Oxidation of 8a and Se-methylselenocysteine (Ga) gives methaneseleninic acid (24), characterized by X-ray crystallography, and dimethyl diselenide (25). Oxidation of Se-2-propenyl-L-selenocysteine (6c) gives allyl alcohol and 3-seleninoalanine (22). Compound 22 is also formed on oxidation of 16 and selenocystine (4). Oxidation of 6d gives 2-[(E,Z)-1-propenylseleno]propanal (36). These oxidations occur by way of selenoxides, detected by chromatographic and spectroscopic methods. The natural occurrence of many of the Se-alk(en)ylselenocysteines and their gamma-glutamyl derivatives and oxidation products is discussed. Three homologues of the potent cancer chemoprevention agents 6a and 6c, namely 6d-f, were evaluated for effects on cell growth, induction of apoptosis, and DNA-damaging activity using two murine mammary epithelial cell lines. Although each compound displays a unique profile of activity, none of these compounds (Gd-f) is likely to exceed the chemopreventive efficacy of selenocysteine Se-conjugates Ga and 6c.     

NMR-based metabolomics reveals that conjugated double bond content and lipid storage efficiency in HepG2 cells are affected by fatty acid cis/trans configuration and chain length

In the present study the metabolic response to various fatty acids was investigated in HepG2 cells by using a (1)H NMR-based approach. To elucidate the effect of cis/trans configuration, the cells were exposed to either oleic acid (C18:1 cis-9), elaidic acid (C18:1 trans-9), vaccenic acid (C18:1 trans-11), linoleic acid (C18:2), or palmitic acid (C16:0), and multivariate data analysis revealed a strong effect of fatty acid on the lipophilic metabolite fraction. Inspection of the spectra revealed that the difference between the observed responses could be ascribed to the appearance of resonances from conjugated double bonds (5.65, 5.94, and 6.28 ppm) in cells exposed to vaccenic acid, revealing that vaccenic acid upon uptake by the HepG2 cells is converted into a conjugated fatty acid. Upon exposure of the HepG2 cells to either butyric acid (C4:0), caproic acid (C6:0), lauric acid (C12:0), myristic acid (C14:0), or palmitic acid (C16:0), an effect of fatty acid length was also evident, and data indicated that short-chain fatty acids (C4-C6) are immediately converted, whereas medium-long-chain fatty acids (C12-16) are incorporated into triglycerides and deposited in the cells. In conclusion, the present study demonstrates that (1)H NMR spectroscopy is a useful method for studying the uptake of fatty acids in in vitro cells.     

Urbanization-induced glomalin changes and their associations with land-use configuration,forest characteristics,and soil properties in Changchun,Northeast China

Journal of Soils and Sediments - Glomalin-related soil protein (GRSP), produced by arbuscular mycorrhizal fungi, plays crucial roles in the global carbon cycle and improves soil quality. However,...     

Chalk and chalk debris as a medium for plant growth, with particular reference to Channel Tunnel spoil

Abstract. Four lithological types of chalk are recognized. Normal white chalk has 34–50% porosity, nearly all of which holds water conventionally'available'to plants. Hard chalk and grey chalk have less porosity and available water; chalk marl has very little available water. Significant capillary rise from below the root zone can be expected in normal white chalk only, and is not halted by fragmentation. Chalk has little N and usually little P. Only grey chalk and chalk marl have much ettractable K and Mg. These also slake, impeding roots. Thus, fertilized plants tolerant of high pH can grow well on normal white chalk debris, but on raw chalk marl, e.g. Channel Tunnel spoil, they need irrigation. Interesting plants volunteer on chalk debris, even on slaked chalk marl by the sea.