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Spatiotemporal visualization of the synthesis and accumulation of rotenone in Derris elliptica roots using mass spectrometry imaging 利用质谱成像技术研究黑参根鱼藤酮合成和积累的时空可视化
Pub Date : 2023-12-01 DOI: 10.1016/j.aac.2023.07.002
Ping Li , Yingying Chen , Qingrong Xie , Yizhu Xu , Zhen Li , Yuan Li , Zhibin Yin , Xinhai Zhu , Hanhong Xu , Xinzhou Wu

The discovery of novel botanical pesticides as a preferred alternative to synthetic pesticides is regarded as an environmentally friendly strategy, yet it remains a great challenge due to limited insights into the synthesis and accumulation of active ingredient intermediates. Herein, we demonstrate the use of gold nanoparticle (AuNP)-assisted laser desorption/ionization mass spectrometry imaging (LDI-MSI) for the tissue-specific distribution and spatiotemporal accumulation effect of rotenone and active ingredient intermediates in its biosynthetic pathway within the roots of Derris elliptica. The MSI results revealed that rotenone was mainly concentrated in the epidermis, cortex, and xylem in the first two years and began to accumulate in the phloem since the 3rd year. Meanwhile, the rotenone contents increased in the epidermis, cortex, and xylem in the 4th year and finally decreased in the 5th year. The ultra-performance liquid chromatography (UPLC) results revealed that there was a significant difference in rotenone content between the root and non-root bark (p < 0.05) except for the 1st year. It reached its maximum value at 9.71% in the root bark in the 4th year and 7.98% in the non-root bark in the 1st year, which was in accordance with the MSI results. Additionally, the active ingredient intermediates in the Hydroxylation/Methylation and Rotenoid Phases of the biosynthetic pathway of rotenone were concentrated in the root region. Taken together, the collective results provide the scientific guidance for the scientific cultivation of D. elliptica and the efficient extraction of botanical pesticides.

发现新的植物性农药作为合成农药的首选替代品被认为是一种环保策略,但由于对活性成分中间体的合成和积累的了解有限,这仍然是一个巨大的挑战。在此,我们展示了使用金纳米颗粒(AuNP)辅助激光解吸/电离质谱成像(LDI-MSI)来研究鱼藤酮及其活性成分中间体在黄参根内生物合成途径中的组织特异性分布和时空积累效应。MSI结果表明,鱼藤酮在前2年主要集中在表皮、皮质和木质部,从第3年开始在韧皮部积累。同时,鱼藤酮在表皮、皮质和木质部的含量在第4年呈上升趋势,在第5年呈下降趋势。超高效液相色谱(UPLC)结果显示,鱼藤酮的含量在根和非根树皮之间存在显著差异(p <0.05),但第一年除外。在第4年,根皮和非根皮在第1年分别达到最大值,分别为9.71%和7.98%,与MSI结果一致。此外,鱼藤酮生物合成途径中羟基化/甲基化阶段和类鱼藤酮阶段的活性成分中间体集中在根区。综上所述,本研究结果为科学栽培和高效提取植物性农药提供了科学指导。
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引用次数: 0
Silver nanoparticles: From in vitro green synthesis to in vivo biological effects in plants 银纳米粒子:从体外绿色合成到植物体内的生物效应
Pub Date : 2023-12-01 DOI: 10.1016/j.aac.2023.08.004
Na Zhang , Juzhi Sun , Liyan Yin , Junli Liu , Chunli Chen

Silver nanoparticles (AgNPs) are extensively utilized in industrial, biotechnological and medical fields because of their specific physical and chemical properties, which shown small size effects, surface and interface effects, quantum scale effects. Inevitably, wastewater containing AgNPs is leached into the soil. AgNPs in soil may be absorbed by plant roots and they affect plant growth. Understanding the complex interactions between AgNPs and plants is of crucial significance since plants are essential to the ecological environment as key players in ecosystems. Most previous reports have focused on AgNP phytotoxicity rather than positive effects in the plant field. This article reviews recent studies on the important aspects about nanoparticles including the green synthesis, absorption, migration, accumulation, biotransformation, biological effects, and the underlying molecular mechanisms of AgNPs affecting plants. We provide insights into the interactions between AgNPs and plants, helping to further understand AgNP-related effects and biosafety in agricultural production, as well as the practical application of various nanomaterials in agriculture.

银纳米粒子(AgNPs)因其特殊的物理和化学性质,包括小尺寸效应、表面和界面效应、量子尺度效应,被广泛应用于工业、生物技术和医疗领域。含有 AgNPs 的废水不可避免地会渗入土壤。土壤中的 AgNPs 可能会被植物根系吸收,从而影响植物生长。了解 AgNPs 与植物之间复杂的相互作用具有重要意义,因为植物作为生态系统中的关键角色,对生态环境至关重要。以前的大多数报告都侧重于 AgNP 的植物毒性,而不是其在植物领域的积极作用。本文综述了有关纳米粒子重要方面的最新研究,包括绿色合成、吸收、迁移、积累、生物转化、生物效应以及 AgNPs 影响植物的潜在分子机制。我们深入探讨了 AgNPs 与植物之间的相互作用,有助于进一步了解 AgNP 的相关效应和农业生产中的生物安全性,以及各种纳米材料在农业中的实际应用。
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引用次数: 1
A fluorescent probe based on BODIPY for hydrogen sulfide imaging in living cells and zebrafish 基于BODIPY的荧光探针用于活细胞和斑马鱼的硫化氢成像
Pub Date : 2023-12-01 DOI: 10.1016/j.aac.2023.08.002
Xiaolong Ding , Qi Wang , Degen Chen , Yiliang Chen , Wenwen Pan , Qi Sun , Qian Chen , Xinya Han

A novel fluorescent probe based on 4,4-Difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) structure as fluorophore with 7-nitro-1,2,3-benzoxadiazole (NBD) served as detection unit was designed for specific and sensitive detection of H2S in living cells and zebrafish. In this work, we prepared a novel fluorescent probe for detection of hydrogen sulfide with strong fluorescent enhancement, good biocompatible and excellent specifically detection. The probe 1 displayed emission at 580 nm with excited wavelength at 530 nm in aqueous solution which organic proportion was only 10%. This probe exhibits highly selectively and specifically to detect H2S compared with other related interferences including sulphur-amino acids, sulfite ion and cations. In the addition of H2S into the detection system, the fluorescent intensity was sharply increased about 170-fold with the limitation detection as low as 16.8 nM. The sensing mechanism was through the cleave reaction between analyte and NBD unit which was characterized by high resolution mass spectrum (HRMS). This platform also permits low biotoxicity which can successfully be utilized to evaluate the concentration level of H2S and imaging in living cells and zebrafish.

设计了一种以4,4-二氟-4-硼-3a,4 -二氮-s-茚二烯(BODIPY)结构为荧光团,以7-硝基-1,2,3-苯并恶二唑(NBD)为检测单元的新型荧光探针,用于活细胞和斑马鱼体内H2S的特异、灵敏检测。本研究制备了一种荧光增强强、生物相容性好、特异性强的新型硫化氢荧光探针。探针1在有机含量为10%的水溶液中发射波长为580nm,激发波长为530nm。与含硫氨基酸、亚硫酸盐离子和阳离子等干扰物相比,该探针具有高度的选择性和特异性。在检测系统中加入H2S后,荧光强度急剧提高约170倍,检测限低至16.8 nM。其传感机理是通过分析物与NBD单元之间的裂解反应,并用高分辨率质谱(HRMS)对其进行表征。该平台具有低生物毒性,可成功用于评估活细胞和斑马鱼的H2S浓度水平和成像。
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引用次数: 0
Agarose hydrogel doped with soluble Se-chitosan for Se-enriched cultivation of sprouts 可溶性硒壳聚糖掺杂琼脂糖水凝胶用于豆芽富硒培养
Pub Date : 2023-12-01 DOI: 10.1016/j.aac.2023.09.001
Yun Wang , Wei Yang , Jian Zhu , Qifei Chen , Na Li

Se-chitosan with a high Se content of 139 mg/g was successfully synthesized using the glacial acetic acid-sodium selenite (HAc-Na2SeO3) method. The chemical structure of Se-chitosan was characterized by FTIR, XRD, TGA, UV–vis and 13C NMR, confirming that selenite acid was introduced into chitosan via the esterification reaction of the hydroxyl group at C6 and the electrostatic interaction of the amino group at C2 of chitosan. Agarose hydrogels were designed as an efficient carrier of Se-chitosan for Se-enriched cultivation of sprouts. The hydrogels exhibited a porous structure, which is beneficial for Se diffusion in hydrogels. The growth indexes of sprouts grown in Agar/Se-chitosan composite hydrogels with different Se concentrations, including plant weight, plant height and Se content, were investigated. The results showed that in the Se-enriched cultivation of sprouts, Se-chitosan possessed an excellent Se enrichment effect. As the Se concentration in Agar/Se-chitosan composite hydrogels increases from 0 to 1600 μg/L, the Se content of the sprouts will also increase from 0.92 mg/kg to 6.79 mg/kg accordingly. Moreover, it is necessary to control the amount of Se-chitosan added to the hydrogels; otherwise, the growth of sprouts will be inhibited. This research provided a simple and effective method for the fabrication of Se-containing hydrogels for Se-enriched cultivation of sprouts.

采用冰醋酸-亚硒酸钠(HAc-Na2SeO3)法制备了硒含量为139 mg/g的硒壳聚糖。采用FTIR、XRD、TGA、UV-vis和13C NMR等手段对壳聚糖的化学结构进行了表征,证实了亚硒酸是通过壳聚糖C6位羟基的酯化反应和C2位氨基的静电相互作用引入壳聚糖的。设计了琼脂糖水凝胶作为硒壳聚糖的高效载体,用于豆芽的富硒培养。水凝胶呈多孔结构,有利于硒在水凝胶中的扩散。研究了不同硒浓度的琼脂/硒-壳聚糖复合水凝胶中豆芽的生长指标,包括株重、株高和硒含量。结果表明,在豆芽富硒培养中,硒壳聚糖具有良好的富硒效果。当琼脂/硒-壳聚糖复合水凝胶中的硒浓度从0 μg/L增加到1600 μg/L时,豆芽中的硒含量也相应从0.92 mg/kg增加到6.79 mg/kg。此外,还需要控制硒壳聚糖在水凝胶中的添加量;否则,芽苗菜的生长将受到抑制。本研究为豆芽富硒培养用含硒水凝胶的制备提供了一种简单有效的方法。
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引用次数: 0
Exploiting natural products to discover multitarget inhibitors of insect chitinolytic enzymes 利用天然产物发现昆虫几丁质分解酶的多靶点抑制剂
Pub Date : 2023-12-01 DOI: 10.1016/j.aac.2023.07.007
Yi Ding , Qiong Lu , Tian Liu , Qing Yang

Multitarget insecticides are more likely to achieve comprehensive regulation of insects with a low risk of resistance. Insect chitinolytic enzymes, including GH18 chitinases and GH20 β-N-acetyl-d-hexosaminidase, are attractive targets for multitarget insecticide design by virtue of their similar substrate binding mode and catalytic mechanism. On the other hand, natural products with diverse skeletal structures are potential repositories of chitinolytic enzyme inhibitors. This minireview first presents the theoretical basis of developing multitargeted inhibitors against insect chitinolytic enzymes and then focuses on the progress in developing multitarget inhibitors derived from natural products. These may provide ideas for the exploitation of novel pesticide leads from natural products by targeting multiple targets.

多靶点杀虫剂更容易实现对抗性风险低的昆虫的综合调控。昆虫几丁质降解酶,包括GH18几丁质酶和GH20 β- n -乙酰-d-己糖氨酸酶,由于其相似的底物结合模式和催化机制,是多靶点杀虫剂设计的重要靶点。另一方面,具有不同骨架结构的天然产物是几丁质水解酶抑制剂的潜在储存库。本文首先介绍了开发昆虫几丁质水解酶多靶点抑制剂的理论基础,然后重点介绍了天然产物多靶点抑制剂的研究进展。这可能为通过靶向多种靶点从天然产物中开发新型农药线索提供思路。
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引用次数: 3
Recent advances in the natural products-based lead discovery for new agrochemicals 基于天然产品的新型农用化学品先导发现的最新进展
Pub Date : 2023-12-01 DOI: 10.1016/j.aac.2023.09.004
Pei Zhang , Chun-Bao Duan , Bing Jin , Abdallah S. Ali , Xinya Han , Haifeng Zhang , Ming-Zhi Zhang , Wei-Hua Zhang , Yu-Cheng Gu

Crops will be harmed by fungi, pests and weeds during their growth. In the past half century, scientists have conducted in-depth research on natural products extracted from microorganisms, plants or animals, and used natural products and their derivatives as the lead for pesticides discovery. Natural product pesticides have the advantages of easy degradation in the environment, selective control and safety to non-target organisms. This review summarizes the studies on natural products pesticides in recent years, including natural products of chemical modification and biosynthesis, mainly fungicides, herbicides, insecticides and acaricides. We classify natural products according to their active fragments, and discuss their effects on the control of agricultural fungi, pests and weeds. Ultimately, we found that lead discovery based on natural products has great advantages in pesticide development.

农作物在生长过程中会受到真菌、害虫和杂草的危害。近半个世纪以来,科学家们对从微生物、植物或动物中提取的天然产物进行了深入研究,并以天然产物及其衍生物作为农药研发的先导。天然产物农药具有在环境中易降解、选择性防治、对非靶标生物安全等优点。本综述总结了近年来对天然产物农药的研究,包括化学修饰和生物合成的天然产物,主要有杀菌剂、除草剂、杀虫剂和杀螨剂。我们根据活性片段对天然产物进行了分类,并讨论了它们对农业真菌、害虫和杂草的防治效果。最终,我们发现基于天然产物的先导发现在农药开发中具有巨大优势。
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引用次数: 2
In memoriam: James Nicholas Seiber (1940–2023) 悼念詹姆斯-尼古拉斯-塞伯(1940-2023)
Pub Date : 2023-12-01 DOI: 10.1016/j.aac.2023.08.005
Yang Guang-Fu
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引用次数: 0
Novel quinoxalinone-1,2,3-triazole derivatives as potential antifungal agents for plant anthrax disease: Design, synthesis, antifungal activity and SAR study 新型喹喔啉酮-1,2,3-三唑衍生物作为植物炭疽病的潜在抗真菌剂:设计、合成、抗真菌活性和 SAR 研究
Pub Date : 2023-11-25 DOI: 10.1016/j.aac.2023.11.003

A series of quinoxalinone-1,2,3-triazole derivatives have been synthesized and tested for antifungal activity against phytopathogenic fungus through mycelial growth inhibition in vitro, spore germination inhibition in vitro and control effect in vivo. The results showed that the pharmacophore quinoxalinone and 1,2,3-triazole displayed promising antifungal activity. The EC50 value against C. gloeosporioides of 6a-1 was 1.17 μg/mL and the compound 6c-1 showed the good bioactivity against C. fragariae Brooks and P. oryzae Cav., displaying EC50 values of 5.56, 4.62 μg/mL, respectively. The inhibitory of spore germination by 6a-1 was performed with EC50 value of 1.91 μg/mL. In addition, the in vivo bioassay indicated that 6a-1 possessed effective control against Pepper Anthrax Disease in protective treatment. For given activity data of target compounds, structure-activity relationship (SAR) study was operated, hoping for optimizing the target structure to find lead compound with higher activity.

本研究合成了一系列喹喔啉酮-1,2,3-三唑衍生物,并通过体外菌丝生长抑制、体外孢子萌发抑制和体内对照效应测试了这些衍生物对植物病原真菌的抗真菌活性。结果表明,药源喹喔啉酮和 1,2,3- 三唑具有良好的抗真菌活性。化合物 6c-1 对 C. fragariae Brooks 和 P. oryzae Cav.具有良好的生物活性,其 EC50 值分别为 5.56 和 4.62 μg/mL。6a-1 对孢子萌发的抑制作用的 EC50 值为 1.91 μg/mL。此外,体内生物测定表明,6a-1 在保护性治疗中可有效控制辣椒炭疽病。针对目标化合物的活性数据,研究人员进行了结构-活性关系(SAR)研究,希望通过优化目标化合物的结构,找到活性更高的先导化合物。
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引用次数: 0
A new binding mode for ecdysteroid analog tebufenozide as a multitargeted IGR with chitinase 蜕皮激素类似物特丁苯并噻与甲壳素酶多靶点 IGR 的新结合模式
Pub Date : 2023-11-22 DOI: 10.1016/j.aac.2023.11.006

Tebufenozide, an efficient insect growth regulator (IGR) against lepidopteran pests, presents a novel mode of action with minimal non-target impact. By competing with ecdysteroids for ecdysone receptor (EcR) binding, it regulates insect growth precisely. This study explores tebufenozide's potential as a multitarget IGR, targeting both EcR and Ostrinia furnacalis chitinase I (OfChtI). The inhibitory activity against OfChtI is comparable to that of substrates (GlcNAc)5, with an IC50 of 45.77 ​μM. Our computational findings indicate that tebufenozide binds at the subsite −1 to +1 of OfChtI through various interactions. Notably, tebufenozide establishes a pi-pi interaction with the flipped sidechain of Trp107, enabling tebufenozide to deeply penetrate into the S1 pocket, thereby obstructing substrate binding to OfChtI. These insights highlight the potency of multitarget strategies, laying the groundwork for innovative IGR designs that offer comprehensive pest management solutions.

特丁苯酰菌胺是一种高效的昆虫生长调节剂(IGR),可防治鳞翅目害虫,其作用模式新颖,对非目标影响最小。通过与蜕皮激素竞争蜕皮激素受体(EcR)的结合,它可以精确地调节昆虫的生长。本研究探讨了特丁苯并噻唑作为多靶点 IGR 的潜力,它同时针对 EcR 和 Ostrinia furnacalis 几丁质酶 I(OfChtI)。它对 OfChtI 的抑制活性与底物(GlcNAc)5 相当,IC50 为 45.77 μM。我们的计算结果表明,特丁福诺嗪通过各种相互作用与 OfChtI 的位点 -1 至 +1 结合。值得注意的是,特丁福诺嗪与Trp107的翻转侧链建立了pi-pi相互作用,使特丁福诺嗪能够深入S1口袋,从而阻碍底物与OfChtI结合。这些见解凸显了多靶标策略的功效,为提供全面虫害管理解决方案的创新 IGR 设计奠定了基础。
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引用次数: 0
A timing self-cleaning nanoherbicide: Design of triple-structure nanovectors for weed control and pesticide residues treatment 定时自清洁纳米除草剂:设计用于除草和处理农药残留的三重结构纳米载体
Pub Date : 2023-10-26 DOI: 10.1016/j.aac.2023.10.002
Jiao Cheng , Mei Li , Ri-xin Zhu , Jing-yi Li , Jun Yin , Wang Xiao
Pesticide residues treatment is a crucial issue for both agricultural production and environmental protection. In recent years, designing self-cleaning nanoformulations has emerged as a promising strategy for reducing pesticide residues in a convenient and cost-effective manner. However, traditional physical blending methods of photodegradation reagents with nanocarriers have limitations in terms of pesticide residue degradation efficiency and active ingredient efficacy. Here, a new type of timing self-cleaning nanoherbicide dicamba@mSiO2/ATA/TiO2 with a triple structure was fabricated. Dicamba, a widely used herbicide that was attracting increasing concern over its high efficiency and broad spectrum, was selected as the model herbicide and loaded on the mSiO2 shell. In the stage of pesticide release, the TiO2 and dicamba were separated by the timing-barrier. Therefore, the efficacy of dicamba was not affected by the photocatalyst. During the release process, the ATA layer continuously absorbed the reactive oxygen species (ROS) produced by TiO2 and was gradually degraded. Finally, the barrier was destroyed, and the residual dicamba in the carrier was degraded by TiO2. Compared with the traditional physical blending method, this triple structure avoided the degradation of active ingredients by photocatalysts during the pesticide release period. The experimental results suggested that this nanoformulation improved the efficacy of the herbicide, and reduced the pesticide residues, providing a new approach for self-cleaning nanopesticides research.
农药残留处理是农业生产和环境保护的关键问题。近年来,设计自清洁纳米制剂已成为一种以便捷、经济的方式减少农药残留的可行策略。然而,光降解试剂与纳米载体的传统物理混合方法在农药残留降解效率和有效成分功效方面存在局限性。本文制备了一种具有三重结构的新型定时自清洁纳米除草剂麦草畏@mSiO2/ATA/TiO2。麦草畏是一种广泛使用的除草剂,因其高效、广谱而日益受到关注。在农药释放阶段,TiO2 和麦草畏被定时屏障隔开。因此,麦草畏的药效不受光催化剂的影响。在释放过程中,ATA 层不断吸收 TiO2 产生的活性氧(ROS),并逐渐降解。最后,阻隔层被破坏,载体中残留的麦草畏被 TiO2 降解。与传统的物理混合法相比,这种三重结构避免了农药释放期光催化剂对有效成分的降解。实验结果表明,该纳米制剂提高了除草剂的药效,减少了农药残留,为自清洁纳米农药的研究提供了新的思路。
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引用次数: 0
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Advanced Agrochem
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