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Peptides from Spider Venoms: A Natural Source of Bioinsecticides 蜘蛛毒液中的多肽:生物杀虫剂的天然来源
Pub Date : 2019-07-26 DOI: 10.2533/CHIMIA.2019.505
F. Benfatti
With the increasing global population and decreasing available arable land, there is a burden heavier than ever before on our ability to provide safe, nutritious and sustainable food. Therefore the control of insects, weeds and pathogens that harm agricultural production remains essential.[1,2]Arthropods and insects in particular damage $470 billion-worth of global crop production per year.[3]Annual crop yield lost to insects, currently 18–26% worldwide, is expected to increase in a warming climate.[4]Not only do arthropods threaten food production, they can also act as vectors transmitting deadly diseases.[5] The control of arthropod pests in both the agricultural and public health sector relies primarily on the application of chemical insecticides. Repeated use of commercial products has led to the development and global expansion of pest resistance.[6]Furthermore, there is growing public concern about the potential environmental and long-term human health impacts of certain agrochemicals. Hence, the discovery of selective, effective and environmentally safe agrochemical alternatives to address the pest control challenge remains a necessity.While the crop protection market is dominated by small molecules, new modalities, such as silencing RNA,[7]microbial toxins,[8]and peptidic neurotoxins have received increased attention. Peptides in particular (defined as proteins less than 10 kDa) represent an appealing option as bioinsecticides, due to their potential to be highly potent, while showing exquisite species selectivity. Furthermore, being fully biodegradable into amino acids, peptides guarantee favorable environmental impact. A great natural source of insecticidal peptides are the venoms of insect predators, e.g. spiders, scorpions, centipedes, wasps, predacious mites. Venoms used by insectivores to subjugate their prey are cocktails containing inorganic salts, small molecules such as biogenic amines, peptides and high molecular mass proteins, such as proteases.[9] Of particular interest for crop protection are the venom components that target receptors and ion channels in the insect nervous system.[10,11] An incredibly rich source of such insecticidal neuropeptides are spider venoms. ArachnoServer 3.0, a manually curated database of spider-venom peptides and proteins, contains to date >1500 peptide toxins from 100 spiders.[12] However, only a few are sufficiently potent to warrant consideration as bioinsecticides (i.e. LD50 < 1500 pmol g by injection).[13] In addition to high intrinsic potency, there are several other requirements for a spider-venom peptide to be considered as a bioinsecticide lead, as summarized in Table 1.[14] Selectivity is crucial: ideally, a toxin should target only a narrow range of pest species while not harming vertebrates and other arthropods (e.g. pollinators and natural predators of the target pest species). This is the case of ω-Hexatoxin-Hv1a (ω-HXTXHv1a), a component of the Australian funnel web spider venom and
随着全球人口的增加和可用耕地的减少,我们提供安全、营养和可持续粮食的能力比以往任何时候都更加沉重。因此,控制危害农业生产的昆虫、杂草和病原体仍然至关重要。[1,2]节肢动物和昆虫尤其严重,每年给全球农作物生产造成价值4700亿美元的损失。目前,全球每年因昆虫而损失的作物产量为18-26%,预计在气候变暖的情况下还会增加。节肢动物不仅威胁粮食生产,它们还能成为传播致命疾病的媒介在农业和公共卫生部门,节肢动物害虫的控制主要依靠化学杀虫剂的应用。商业产品的重复使用导致了害虫抗性的发展和全球扩张。此外,公众越来越关注某些农用化学品对环境和人类健康的潜在长期影响。因此,发现有选择性、有效和环境安全的农用化学品替代品来解决虫害防治挑战仍然是必要的。虽然作物保护市场以小分子为主,但新的模式,如沉默RNA,[8]微生物毒素,[8]和肽性神经毒素已受到越来越多的关注。特别是多肽(定义为小于10 kDa的蛋白质),由于其潜在的高效力,同时显示出精致的物种选择性,代表了一个有吸引力的生物杀虫剂选择。此外,多肽是完全可生物降解的氨基酸,保证了良好的环境影响。杀虫肽的一个重要的天然来源是昆虫捕食者的毒液,如蜘蛛、蝎子、蜈蚣、黄蜂、食肉螨。食虫动物用来征服猎物的毒液是含有无机盐、小分子(如生物胺)、多肽和高分子质量蛋白质(如蛋白酶)的混合物对作物保护特别感兴趣的是针对昆虫神经系统中受体和离子通道的毒液成分。[10,11]蜘蛛毒液是这种杀虫神经肽的一个极其丰富的来源。ArachnoServer 3.0是一个人工整理的蜘蛛毒液肽和蛋白质数据库,迄今为止包含了来自100只蜘蛛的1500种肽毒素然而,只有少数是足够有效的,值得考虑作为生物杀虫剂(即LD50 < 1500 pmol g注射)除了高内在效价外,蜘蛛毒液肽被认为是生物杀虫剂铅还有其他几个要求,如表1所示选择性是至关重要的:理想情况下,毒素应该只针对一小部分害虫物种,而不伤害脊椎动物和其他节肢动物(例如,传粉者和目标害虫物种的天敌)。ω-Hexatoxin-Hv1a (ω-HXTXHv1a)就是一个例子。ω-HXTXHv1a是澳大利亚漏斗网蜘蛛毒液的一种成分,也是已知最有效的杀虫肽之一,即使在非常高浓度的情况下也对脊椎动物无害重要的是,ω-HXTX-Hv1a也被证明对蜜蜂无毒,这是现代杀虫剂的严格要求毒素的大小/复杂性对生物杀虫剂的开发也至关重要:复杂性越高,就越难以经济地生产大量用于农业应用的肽。威士达公司(美国)最近推出的Spear T提供了概念证明,蜘蛛毒液肽可以一路进入市场并大规模生产。Spear T的有效成分是GS-ω/κ-HXTXHv1a,这是一种蜘蛛毒液衍生的肽,已被商业化用于温室生物杀虫剂,针对多种昆虫然而,除了少数例外,从蜘蛛毒液中分离出来的肽类神经毒素通常对昆虫没有口服活性。与大多数其他肽和蛋白质相比,这些肽的稳定性不是一个问题,因为它们的特殊折叠,称为抑制剂胱氨酸结,为它们提供了显着的化学和热稳定性以及对蛋白酶的抗性蛇毒肽缺乏口服杀虫活性的原因是其通过肠道上皮到达目标部位的能力有限,即位于昆虫血腔(体腔)的神经。蜘蛛没有在进化压力下产生口服活性肽毒素,因为它们将毒液直接注射到猎物的血液中。已经确定了一系列策略来显着增强毒液肽的口服活性,以尝试允许其现场应用(图1)。一种选择是化学修饰肽。ω-Hexatoxin-Hv1a的头尾环化已被进行,目的是增加其口服效力,不幸的是没有成功。
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引用次数: 4
Progress in Synthetic 2D Polymers Obtained at the Air/Water Interface 空气/水界面合成二维聚合物的研究进展
Pub Date : 2019-07-26 DOI: 10.2533/CHIMIA.2019.487
A. Schlüter
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引用次数: 3
Synthesis of Molecular 2D Materials via Low-energy Electron Induced Chemical Reactions 利用低能电子诱导化学反应合成二维分子材料
Pub Date : 2019-07-26 DOI: 10.2533/CHIMIA.2019.473
A. Turchanin
After the demonstration of a variety of inorganic two-dimensional (2D) materials (graphene, hBN, MoS2, etc.), molecular 2D materials have attracted a significant research interest as well. However, the direct synthesis of these materials is an exceptionally challenging task for chemists. In this review article, a simple and robust physical method for the synthesis of molecular 2D materials is presented based on low-energy electron induced chemical reactions in aromatic molecular layers. In this way, ultrathin (~1 nm) molecular nanosheets with adjustable chemical and physical properties called Carbon Nanomembranes (CNM) can be prepared. Moreover, the method enables the synthesis of various other 2D organic-inorganic hybrids (e.g. MoS2-CNM, graphene-CNM lateral heterostructures, etc.) or ~20 nm thick nanosheets of organic semiconductors. Mechanisms of the reaction and functional properties of these molecular 2D materials including their chemical functionalization and engineering of hybrid hierarchical structures for application in nanoscience and nanotechnology are discussed
在各种无机二维(2D)材料(石墨烯,hBN, MoS2等)的演示之后,分子二维材料也引起了重大的研究兴趣。然而,对化学家来说,直接合成这些材料是一项极具挑战性的任务。本文介绍了一种基于芳香族分子层中低能电子诱导化学反应合成二维分子材料的简便、可靠的物理方法。通过这种方法,可以制备出具有可调节化学和物理性质的超薄(~ 1nm)分子纳米片,称为碳纳米膜(CNM)。此外,该方法还可以合成各种其他二维有机-无机杂化物(例如MoS2-CNM,石墨烯- cnm横向异质结构等)或~ 20nm厚的有机半导体纳米片。讨论了这些分子二维材料的反应机理和功能特性,包括它们的化学功能化和杂化层次结构工程在纳米科学和纳米技术中的应用
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引用次数: 7
Translation of Academic Health Innovations Goes National Foundation of the Platform for Swiss Translational and Clinical Bio-Manufacturing (TCBM) TCBM Steering Committee 瑞士转化和临床生物制造(TCBM) TCBM指导委员会平台国家基金会翻译学术健康创新
Pub Date : 2019-07-26 DOI: 10.2533/CHIMIA.2019.509
R. Aeberhard
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引用次数: 0
2019 Chemistry Travel Award by SCNAT and SCS 由中国科学院和国家科学院颁发的2019年化学旅游奖
Pub Date : 2019-07-26 DOI: 10.2533/CHIMIA.2019.514
L. Merz
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引用次数: 0
Two-dimensional Polymers in Microscopy and Spatially Resolved Vibrational Analysis – A Review 二维聚合物在显微镜和空间分辨振动分析中的应用综述
Pub Date : 2019-07-26 DOI: 10.3929/ETHZ-B-000353673
T. Niepel, Yashashwa Pandey, R. Zenobi
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引用次数: 0
The 54th Conference on Stereochemistry: Bürgenstock Conference 2019, Brunnen, May 5–9, 2019 第54届立体化学会议:2019年<s:1> rgenstock会议,布伦嫩,2019年5月5-9日
Pub Date : 2019-07-26 DOI: 10.2533/CHIMIA.2019.511
E. Pazos, Fabien B. L. Cougnon
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引用次数: 0
Ditopic and Tetratopic 4,2':6',4''-Terpyridines as Structural Motifs in 2D- and 3D-Coordination Assemblies 二异位和四异位4,2':6',4' -三联吡啶作为二维和三维配位体的结构基序
Pub Date : 2019-07-26 DOI: 10.2533/CHIMIA.2019.462
C. Housecroft, E. Constable
We overview the coordination chemistry of ditopic and tetratopic ligands with 4,2':6',4''-terpyridine metal-binding domains and illustrate the adaptability of these divergent ligands as building blocks in 2Dand 3D-coordination networks. The ditopic ligands we discuss are limited to roles as linkers in coordination assemblies, while the tetratopic ligands have the potential to be 4-connecting nodes. Both diand tetratopic ligands are equipped with functionalities, typically alkyloxy chains, the nature of which has a profound effect upon the coordination assembly. Combinations of 4-connecting ligand nodes with metal-linkers lead to both 2Dand 3D-networks, while combinations of 4-connecting metal and ligand nodes give 3D-architectures. We also demonstrate constraint of the coordination assembly to 2-dimensions by depositing ditopic 4,2':6',4''-terpyridine ligands onto Au(111) or Cu(111) platforms with Cu adatoms in the former case; highly ordered ladder assemblies result which are independent of solvent molecules or anions.
我们概述了具有4,2':6',4 " -三吡啶金属结合域的二异位和四异位配体的配位化学,并说明了这些分散配体作为二维和三维配位网络的构建块的适应性。我们讨论的二异位配体仅限于在配位组装中作为连接体的作用,而四异位配体具有成为4连接节点的潜力。双异位配体和四异位配体都具有官能团,通常是烷基氧基链,其性质对配位组装有深远的影响。4连接配体节点与金属连接体的组合可以形成2d和3d网络,而4连接金属和配体节点的组合可以形成3d架构。我们还通过在Au(111)或Cu(111)平台上沉积双位4,2':6',4 " -三吡啶配体来证明配位组装对二维的约束;高度有序的阶梯组装结果独立于溶剂分子或阴离子。
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引用次数: 11
Nano-thin 2D Soft Materials – Design Principles and Prospects 纳米薄二维软材料-设计原则和前景
Pub Date : 2019-07-26 DOI: 10.2533/CHIMIA.2019.468
Mykhailo Vybornyi, Hao Yu, R. Häner
Established less than a decade ago, the fascinating field of two-dimensional (2D) soft materials is advancing continuously towards widespread recognition. After demonstrating the feasibility of obtaining nano-thin supramolecular sheets and morphologically related tubular objects, considerable efforts are undertaken to explore the functional potential of soft nanosheets. Self-assembly is a major tool for the controlled formation of nanometer sized 2D objects. In this account, we share our current understanding of the structural requirements to direct the self-assembly of water-soluble, negatively charged oligomers in 2D. The discussion covers some promising areas of utilization such as the reporting of weak mechanical perturbations, the assembly of light-harvesting antennae, the transfer of excitation energy and the polymerization of pre-organized assemblies. The systems presented in this work illustrate the potential of 2D supramolecular materials as complementary systems to their covalent counterparts.
二维(2D)软材料这一迷人的领域成立不到十年,目前正不断向广泛认可的方向发展。在证明了获得纳米薄超分子片和形态相关的管状物体的可行性之后,人们开始努力探索软纳米片的功能潜力。自组装是控制形成纳米尺寸二维物体的主要工具。在这篇文章中,我们分享了我们目前对结构要求的理解,以指导水溶性、带负电荷的低聚物在二维中的自组装。讨论涵盖了一些有希望的应用领域,如弱机械扰动的报告,光收集天线的组装,激发能的转移和预先组织的组装的聚合。在这项工作中提出的系统说明了二维超分子材料作为其共价对应物的互补系统的潜力。
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引用次数: 0
Ten Years of Liquid-phase Exfoliation of Layered Crystals – A Bright Future ahead? 层状晶体液相剥离的十年——光明的未来?
Pub Date : 2019-07-26 DOI: 10.2533/CHIMIA.2019.498
C. Backes
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引用次数: 1
期刊
CHIMIA International Journal for Chemistry
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