The unique role of halogen substituents in the design of modern agrochemicals

The past 30 years have witnessed a period of significant expansion in the use of halogenated compounds in the field of agrochemical research and development. The introduction of halogens into active ingredients has become an important concept in the quest for a modern agrochemical with optimal efficacy, environmental safety, user friendliness and economic viability. Outstanding progress has been made, especially in synthetic methods for particular halogen‐substituted key intermediates that were previously prohibitively expensive. Interestingly, there has been a rise in the number of commercial products containing ‘mixed’ halogens, e.g. one or more fluorine, chlorine, bromine or iodine atoms in addition to one or more further halogen atoms. Extrapolation of the current trend indicates that a definite growth is to be expected in fluorine‐substituted agrochemicals throughout the twenty‐first century. A number of these recently developed agrochemical candidates containing halogen substituents represent novel classes of chemical compounds with new modes of action. However, the complex structure–activity relationships associated with biologically active molecules mean that the introduction of halogens can lead to either an increase or a decrease in the efficacy of a compound, depending on its changed mode of action, physicochemical properties, target interaction or metabolic susceptibility and transformation. In spite of modern design concepts, it is still difficult to predict the sites in a molecule at which halogen substitution will result in optimal desired effects. This review describes comprehensively the successful utilisation of halogens and their unique role in the design of modern agrochemicals, exemplified by various commercial products from Bayer CropScience coming from different agrochemical areas. Copyright © 2009 Society of Chemical Industry     

Natural products as a source of agrochemicals and leads for chemical synthesis

The use of natural products as a source of new agrochemicals and the procedures that can be undertaken to discover such compounds are reviewed using examples from both the literature and our own experiences. The commercial successes obtained to date show that natural products are a powerful source of new agrochemicals. The results from a survey of the views of the agrochemical industry of natural product work indicated a high level of interest, with 16 of the 19 companies that replied being involved in natural product work either through in-house or external programmes of work. Possible approaches to the key challenges of atural product work, for example choice of sources and screens, avoiding known metabolites and obtaining sufficient compound for biological evaluation, are discussed.     

Work of the EPPO/IOBC Panel on biological control agents

EPPO started work on biological control agents (BCAs) in 1996, and the joint EPPO/IOBC Panel was established in 1997. The history of the Panel is provided and EPPO Standards developed by the Panel are described. These Standards are: PM 6/1 ‘First import of exotic biological control agents for research under contained conditions’, PM 6/2 ‘Import and release of non‐indigenous biological control agents’ and PM 6/3 ‘List of biological control agents widely used in the EPPO region’. The last of these has been annually updated as a ‘Positive List’ of BCAs for which EPPO recommends its member countries to use a simplified procedure for import and releases. EPPO activities in biological control have been focused on the safety aspects of the introduction of invertebrate BCAs. However, the scope of EPPO's work in this area is now under review, and a number of issues are being considered by the Working Party on Phytosanitary Regulations. These include the remit of the Panel and Standards in relation to micro‐organisms, the evaluation of potential environmental benefits as well as potential risks from releases and the potential for use of BCAs against regulated pests and those recommended for regulation.     

The insect vector Cacopsylla picta vertically transmits the bacterium ‘Candidatus Phytoplasma mali’ to its progeny

The phloem‐sucking psyllid Cacopsylla picta plays an important role in transmitting the bacterium ‘Candidatus Phytoplasma mali’, the agent associated with apple proliferation disease. The psyllid can ingest ‘Ca. Phytoplasma mali’ from infected apple trees and spread the bacterium by subsequently feeding on uninfected trees. Until now, this has been the most important method of ‘Ca. Phytoplasma mali’ transmission. The aim of this study was to investigate whether infected C. picta are able to transmit ‘Ca. Phytoplasma mali’ directly to their progeny. This method of transmission would allow the bacteria to bypass a time‐consuming reproductive cycle in the host plant. Furthermore, this would cause a high number of infected F₁ individuals in the vector population. To address this question, eggs, nymphs and adults derived from infected overwintering adults of C. picta were reared on non‐infected apple saplings and subsequently tested for the presence of ‘Ca. Phytoplasma mali’. In this study it was shown for the first time that infected C. picta individuals transmit ‘Ca. Phytoplasma mali’ to their eggs, nymphs and F₁ adults, thus providing the basis for a more detailed understanding of ‘Ca. Phytoplasma mali’ transmission by C. picta.     

Challenges for herbicide resistance evolution and management: 50 years after Harper

Evolved resistance to herbicides is a classic example of ‘evolution in action’. This paper calls for a greater integration of ‘evolutionary‐thinking’ into herbicide resistance research. This integration, it is argued, should lead weed scientists to become less focused on simply describing resistance and more driven towards a deeper understanding of the evolutionary forces that underpin resistance evolution. I have attempted in this short paper to initiate a debate into how this might be done. In the first instance, I have highlighted the widespread misunderstanding and mis‐measurement by weed scientists of fitness and fitness costs. I have also speculated on the potential for herbicide rotations to exacerbate resistance problems by selecting for generalist (metabolic) resistance. Finally, I have discussed in greater detail the contribution of herbicide rates to resistance evolution and have reported work conducted in Australia which has shown the potential for low herbicide doses to rapidly select for very high levels of resistance in Lolium rigidum. The controversial hypotheses and suggestions put forward need to be tested by field experimentation. They may prove to be unfounded or incorrect, but if they cause us to question and expand the current resistance paradigm they will have been useful.     

Latest generation of halogen‐containing pesticides

Agriculture is confronted with enormous challenges, from production of enough high‐quality food to water use, environmental impacts and issues combined with a continually growing world population. Modern agricultural chemistry has to support farmers by providing innovative agrichemicals, used in applied agriculture. In this context, the introduction of halogen atoms into an active ingredient is still an important tool to modulate the properties of new crop protection compounds. Since 2010, around 96% of the launched products (herbicides, fungicides, insecticides/acaricides and nematicides) contain halogen atoms. The launched nematicides contain the largest number of halogen atoms, followed by insecticides/acaricides, herbicides and fungicides. In this context, fungicides and herbicides contain in most cases fluorine atoms, whereas nematicides and insecticides contain in most cases ‘mixed’ halogen atoms, for example chlorine and fluorine. This review gives an overview of the latest generation of halogen‐containing pesticides launched over the past 6 years and describes current halogen‐containing development candidates. © 2017 Society of Chemical Industry     

Vectorizing agrochemicals: enhancing bioavailability via carrier‐mediated transport

Systemicity of agrochemicals is an advantageous property for controlling phloem sucking insects, as well as pathogens and pests not accessible to contact products. After the penetration of the cuticle, the plasma membrane constitutes the main barrier to the entry of an agrochemical into the sap flow. The current strategy for developing systemic agrochemicals is to optimize the physicochemical properties of the molecules so that they can cross the plasma membrane by simple diffusion or ion trapping mechanisms. The main problem with current systemic compounds is that they move everywhere within the plant, and this non‐controlled mobility results in the contamination of the plant parts consumed by vertebrates and pollinators. To achieve the site‐targeted distribution of agrochemicals, a carrier‐mediated propesticide strategy is proposed in this review. After conjugating a non‐systemic agrochemical with a nutrient (α‐amino acids or sugars), the resulting conjugate may be actively transported across the plasma membrane by nutrient‐specific carriers. By applying this strategy, non‐systemic active ingredients are expected to be delivered into the target organs of young plants, thus avoiding or minimizing subsequent undesirable redistribution. The development of this innovative strategy presents many challenges, but opens up a wide range of exciting possibilities. © 2018 Society of Chemical Industry     

Multivariate quantitative structure-activity relationship (QSAR) methods which may be applied to pesticide research

Regression analysis is the most commonly used technique in QSAR studies. Whilst regression has its advantages, it also suffers from a number of disadvantages. A variety of mathematical and statistical techniques exist which complement or replace regression. These may he classified as ‘supervised’ and ‘unsupervised’ learning methods where supervision refers to the use made of biological data in the analysis. These terms are discussed and examples of three unsupervised and two supervised learning methods are presented. The techniques described are Non-Linear Mapping, Principal Components Analysis, Cluster Analysis, Canonical Correlation Analysis and Factor Analysis. Although the examples presented are mostly pharmaceutical applications, it is proposed that the extra complexity of pesticide research data, compared with pharmaceutical, makes it very well suited to analysis by these methods.     

Progress of modern agricultural chemistry and future prospects

Agriculture is facing an enormous challenge: it must ensure that enough high‐quality food is available to meet the needs of a continually growing population. Current and future agronomic production of food, feed, fuel and fibre requires innovative solutions for existing and future challenges, such as climate change, resistance to pests, increased regulatory demands, renewable raw materials or requirements resulting from food chain partnerships. Modern agricultural chemistry has to support farmers to manage these tasks. Today, the so‐called ‘side effects’ of agrochemicals regarding yield and quality are gaining more importance. Agrochemical companies with a strong research and development focus will have the opportunity to shape the future of agriculture by delivering innovative integrated solutions. This review gives a comprehensive overview of the innovative products launched over the past 10 years and describes the progress of modern agricultural chemistry and its future prospects. © 2015 Society of Chemical Industry     

Characteristics of deep drainage and soil water in the mobile sandy lands of Inner Mongolia,northern China

 Quantification of deep drainage and the response of soil water content to rainfall patterns are critical for an effective management strategy of soil water conservation and groundwater utilization. However, information on how rainfall characteristics influence soil water dynamics and deep drainage in mobile sandy lands are lacking. We used an underground chamber to examine the response of deep drainage and soil water content in mobile sandy lands to rainfall characteristics during the growing season of 2010, 2011 and 2012. Results showed that rainfall in this area was dominated by small events (≤5 mm), which increased soil water content in the surface soil layers (0–40 cm), but did not increase soil water content at the deeper soil layers (greater than 40 cm). Soil water content at the 0–100 cm depth increased significantly when the total amount of rain was >20 mm. Rainfall amount, intensity and the duration of dry intervals were significantly related to the soil water content at different soil layers. Deep drainage was significantly correlated with rainfall amount and intensity, but not with the duration of the dry interval. The coefficients of deep drainage in mobile sandy lands ranged from 61.30% to 67.94% during the growing seasons. Our results suggested that rainfall infiltration in these widespread mobile sandy lands had considerable potential to increase soil water storage while recharging the groundwater in this region.     

Potential roles for microbial endophytes in herbicide tolerance in plants

Herbicide tolerance in crops and weeds is considered to be monotrophic, i.e. determined by the relative susceptibility of the physiological process targeted and the plant's ability to metabolise and detoxify the agrochemical. A growing body of evidence now suggests that endophytes, microbes that inhabit plant tissues and provide a range of growth, health and defence enhancements, can contribute to other types of abiotic and biotic stress tolerance. The current evidence for herbicide tolerance being bitrophic, with both free‐living and plant‐associated endophytes contributing to tolerance in the host plant, has been reviewed. We propose that endophytes can directly contribute to herbicide detoxification through their ability to metabolise xenobiotics. In addition, we explore the paradigm that microbes can ‘prime’ resistance mechanisms in plants such that they enhance herbicide tolerance by inducing the host's stress responses to withstand the downstream toxicity caused by herbicides. This latter mechanism has the potential to contribute to the growth of non‐target‐site‐based herbicide resistance in weeds. Microbial endophytes already contribute to herbicide detoxification in planta, and there is now significant scope to extend these interactions using synthetic biology approaches to engineer new chemical tolerance traits into crops via microbial engineering. © 2015 The Authors. Pest Management Science published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.     

Liberibacters associated with orange jasmine in Brazil: incidence in urban areas and relatedness to citrus liberibacters

Two surveys (2005/2006 and 2009) were conducted in the state of São Paulo, Brazil, to investigate the incidence of ‘Candidatus Liberibacter asiaticus’ and ‘Ca. L. americanus’, two liberibacters associated with citrus huanglongbing (HLB) disease and both transmitted by Diaphorina citri, in orange jasmine (Murraya exotica), a widespread ornamental tree in cities and villages. The graft‐transmissibility of the two species, and their DNA relatedness to citrus‐associated liberibacters, were also investigated. Quantitative PCR was applied to PCR‐positive orange jasmine and HLB‐positive citrus growing in backyards and orchards to assess their inoculum source potentials. Liberibacters were detected in 91 of 786 sampled orange jasmine plants in 10 of 76 sampled locations. PCR‐positive trees exhibited yellow shoots and/or dieback symptoms indistinguishable from those on PCR‐negative trees. ‘Candidatus Liberibacter americanus’ was more common in 2005/2006 (96·6%) and ‘Ca. L. asiaticus’ in 2009 (84·8%). rplJ nucleotide sequences were identical within all populations of either species. Graft transmission succeeded only in homologous host combinations, including ‘Ca. L. americanus’ (2/10) from/to orange jasmine and ‘Ca. L. americanus’ (5/18) and ‘Ca. L. asiaticus’ (5/9) from/to citrus. Symptoms were mild and developed less rapidly in orange jasmine than in citrus, probably as a result of lower liberibacter multiplication rates. Respective titres of ‘Ca. L. americanus’ and ‘Ca. L. asiaticus’ in orange jasmine averaged 4·3 and 3·0 log cells g^?1 tissue, compared with 5·5 and 7·3 in citrus. The results indicate that orange jasmine does not favour liberibacter multiplication as much as citrus. However, its importance in HLB epidemics should not be underestimated as it is a preferred host of D. citri and is not under any strict tree‐eradication programme or measures for insect control.     

Consistency in pest risk analysis – how can it be achieved and what are the benefits?*

This paper describes the efforts in the PRATIQUE EU project to increase consistency that were integrated into the revised EPPO Decision‐support scheme (DSS) for Pest Risk Analysis (PRA). The establishment section is used here to illustrate the changes and improvements of the DSS, as it has undergone the most comprehensive changes with reformulation and restructuring of many questions and detailed rating guidance. When revising the establishment section of the EPPO DSS for PRA, there were three principal objectives that influenced the revision: (i) to focus the assessment on the most relevant factors influencing establishment; (ii) to identify the area where establishment is possible before assessing the suitability of that area, and (iii) to enhance the consistency of the establishment section by providing rating guidance with sub‐questions and examples. To simplify the process, some questions were rephrased as closed questions (answer is either yes or no). Clearer notes were provided to explain what information is needed to answer the questions. Furthermore, consistency has been enhanced by developing tools to help assessors when deciding on an appropriate overall risk rating and uncertainty score by providing a visual summary of the risk ratings and uncertainty scores (‘Visualizer’) and a method for integrating all the responses to the questions to provide a summary score for each major section and an overall assessment of risk (‘Rule based matrix model’).     

A chemical switch for detecting insect infestation

BACKGROUND: Plants emit phytochemicals as a defensive mechanism against herbivores. A small sensor switch that responds to these chemicals could be used to stop insect infestation at early stages. RESULTS: Polyethylene‐co‐vinyl acetate was chosen as the best polymer for this particular application, based on its swelling response to plant volatiles. When the carbon concentration of the active layer was low enough to be near the percolation threshold, the sensor could be used as a ‘chemical switch’. The resistance of the sensor increased significantly, mimicking a ‘switch‐off’ response when exposed to the analyte vapor. When the analyte vapor was no longer present, the sensor returned back to its original condition, showing a ‘switch‐on’ response. The percolation point was obtained when the carbon concentration of the polymer/carbon composite was kept at 2.5 wt%. CONCLUSION: A low‐mass‐fraction carbon composite sensor has been designed and fabricated to detect γ‐terpinene, α‐pinene, p‐cymene, farnesene, limonene and cis‐hexenyl acetate. The sensor is inexpensive, easy to fabricate and highly stable in air. Copyright © 2011 Society of Chemical Industry     

Association of ‘Candidatus Liberibacter asiaticus’ root infection,but not phloem plugging with root loss on huanglongbing‐affected trees prior to appearance of foliar symptoms

Huanglongbing (HLB) is a systemic disease of citrus caused by phloem‐limited bacteria ‘Candidatus Liberibacter’ spp. with ‘Ca. Liberibacter asiaticus’ (Las) the most widespread. Phloem‐limited bacteria such as liberibacters and phytoplasmas are emerging as major pathogens of woody and herbaceous plants. Little is known about their systemic movement within a plant and the disease process in these tissues. Las movement after initial infection was monitored in leaves and roots of greenhouse trees. Root density, storage starch content, and vascular system anatomy in relation to Las presence in field and greenhouse trees, both with and without symptoms, showed the importance of root infection in disease development. Las preferentially colonized roots before leaves, where it multiplied and quickly invaded leaves when new foliar flush became a sink tissue for phloem flow. This led to the discovery that roots were damaged by root infection prior to development of visible foliar symptoms and was not associated with carbohydrate starvation caused by phloem‐plugging as previously hypothesized. The role of root infection in systemic insect‐vectored bacterial pathogens has been underestimated. These findings demonstrate the significance of early root infection to tree health and suggest a model for phloem‐limited bacterial movement from the initial insect feeding site to the roots where it replicates, damages the host root system, and then spreads to the rest of the canopy during subsequent leaf flushes. This model provides a framework for testing movement of phloem‐limited bacteria to gain greater understanding of how these pathogens cause disease and spread.     

There has never been a better time or a greater need for resistance management

Integrated pest management (IPM) and sustainable agriculture benefit from selective and environmentally benign crop-protection products. The performance of these products, however, is threatened by resistance. If it is to be prevented from standing in the path of progress, resistance must be managed. As agricultural practices move towards IPM and sustainable crop protection, selection pressure will be concentrated on products which are compatible with these systems. Producers, researchers, government and extension workers cannot solve these complex problems alone. The key to success is collaboration. The Insecticide Resistance Action Committee (IRAC) was set up by the crop-protection industry in 1984 to promote and co-ordinate its contribution to resistance management. Today, it is collaborating with research institutes, government organisations and extension services to combat resistance. IRAC focuses on research and communication projects which reduce selection pressure, organising workshops in ‘resistance hot spots’ and providing input to draft legislation. Selected examples of IRAC's collaborative work are described. ©1997 SCI     

基于深度学习的实蝇图像智能识别方法的建立

实蝇科昆虫很多种类是世界性的重要检疫性有害生物。实蝇的快速准确识别对于保护国门生物安全、促进我国农产品出口具有重要意义。本研究建立了一种基于深度学习的实蝇图像智能识别方法,针对实蝇科昆虫的翅图像特征,以桔小实蝇、南瓜实蝇、瓜实蝇、具条实蝇4种实蝇（每种250头共1 000头）为例,通过标本制作与图像采集、图像预处理、创建数据集训练物体检测模型等模块不断调整优化实现对实蝇图像的自动识别。结果表明在图像色阶参数90/1/220,通过百度Easy DL平台Paddle Paddle深度学习框架结合Auto Model Search训练图像分类模型,选择超高精度算法、高级训练配置epoch并使用数据增强策略进行模型训练时识别准确率达95%以上。本方法具有操作简单、准确率高、可扩展性强等特性,通过智能手机拍摄待测样本输入系统即可进行准确识别,可应用于果蔬园实蝇监测、出入境口岸实蝇检疫以及昆虫科普教育等场景,并可为其他昆虫自动识别研究提供有益借鉴。     

Transmission of ‘Candidatus Liberibacter solanacearum’ in carrot seeds

A protocol for the specific detection and quantification of ‘Candidatus Liberibacter solanacearum’ in carrot seeds using real‐time PCR was developed. The bacterium was detected in 23 out of 54 carrot seed lots from 2010 to 2014, including seeds collected from diseased mother plants. The average total number of ‘Ca. L. solanacearum’ cells in individual seeds ranged from 4·8 ± 3·3 to 210 ± 6·7 cells per seed from three seed lots, but using propidium monoazide to target live cells, 95% of the cells in one seed lot were found to be dead. Liberibacter‐like cells were observed in the phloem sieve tubes of the seed coat and in the phloem of carrot leaf midrib from seedlings. The bacterium was detected as early as 30 days post‐germination, but more consistently after 90 days, in seedlings grown from PCR positive seed lots in an insect‐proof P2 level containment greenhouse. Between 12% and 42% of the seedlings from positive seed lots tested positive for ‘Ca. L. solanacearum’. After 150 days, symptoms of proliferation were observed in 12% of seedlings of cv. Maestro. ‘Candidatus Liberibacter solanacearum’ haplotype E was identified in the seeds and seedlings of cv. Maestro. No phytoplasmas were detected in seedlings with symptoms using a real‐time assay for universal detection of phytoplasmas. The results show that to prevent the entry and establishment of the bacterium in new areas and its potential spread to other crops, control of ‘Ca. L. solanacearum’ in seed lots is required.     

Resistance and systemic dispersal of Xanthomonas fragariae in strawberry germplasm (Fragaria L.)

The angular leaf spot disease caused by Xanthomonas fragariae is an important plant disease with major impact for the strawberry nursery industry. Currently there is no plant protection product available for controlling the disease effectively. Planting of resistant cultivars seems to be promising, but all commercially used cultivars are susceptible and no donor with a high level of resistance has yet been found. Therefore, a total of 145 genotypes from the Fruit Genebank Dresden (Germany) were evaluated for resistance to X. fragariae by artificial inoculation. Six genotypes were classified as partly resistant, out of which only two (US4808 and US4809) are octoploid. Fragaria vesca f. alba, Fragaria nilgerrensis ‘Yunnan’, F. vesca ‘Illa Martin’ and F. moschata ‘Bauwens’ were also classified as partially resistant, but they are only of limited use for breeding because of their variable ploidy level. Fully resistant genotypes could not be detected. The systemic dispersal of the bacteria in strawberry plants was investigated after inoculation of leaves with X. fragariae strain XF3.9.C and the GFP‐tagged strain XF3.9.C_(pKAN). The systemic spread was evaluated after 3, 7, 14 and 28 days post‐inoculation (dpi) by nested PCR and fluorescence microscopy. After 3 dpi, X. fragariae could be found in all tissues tested including the inoculated leaf, its petiole, the rhizome, the heart bud up to the youngest fully expanded leaf and its petiole. The systemic spread was also detectable in partially resistant genotypes.     

High diversity,expanding populations and purifying selection in phytoplasmas causing coconut lethal yellowing in Mozambique

In this study, the putative phytoplasma species causing coconut lethal yellowing disease in Mozambique and Tanzania were characterized. The 16S rRNA and secA genes were sequenced. Phylogenetic analysis revealed that Mozambican coconut phytoplasmas belong to three different types: ‘Candidatus Phytoplasma palmicola’ 16SrXXII‐A, a second strain that was previously isolated in Tanzania and Kenya (16SrIV‐C), and a third strain that was different from all known lethal yellowing phytoplasma species. The third strain potentially represents a novel species and is closely related to pine phytoplasma. Co‐infection with ‘Ca. Phytoplasma pini’‐related and ‘Ca. Phytoplasma palmicola’ 16SrXXII‐A strains was observed. Furthermore, sequence variation in ‘Ca. Phytoplasma palmicola’ at the population level was consistent with purifying selection and population expansion.