Cuticular lipids of insects as potential biofungicides: methods of lipid composition analysis

The main function of cuticular lipids in insects is the restriction of water transpiration through the surface. Lipids are involved in various types of chemical communication between species and reduce the penetration of insecticides, chemicals, and toxins and they also provide protection from attack by microorganisms, parasitic insects, and predators. Hydrocarbons, which include straight-chain saturated, unsaturated, and methyl-branched hydrocarbons, predominate in the cuticular lipids of most insect species; fatty acids, alcohols, esters, ketones, aldehydes, as well as trace amounts of epoxides, ethers, oxoaldehydes, diols, and triacylglycerols have also been identified. Analyses of cuticular lipids are chemically relatively straightforward, and methods for their extraction should be simple. Classically, extraction has relied mainly on application of apolar solvents to the entire insect body. Recently, several alternative methods have been employed to overcome some of the shortcomings of solvent extraction. These include the use of solid-phase microextraction (SPME) fibers to extract hydrocarbons from the headspace of heated samples, SPME to sample live individuals, and a less expensive method (utilized for social wasps), which consists of the collection of cuticular lipids by means of small pieces of cotton rubbed on the body of the insect. Both classical and recently developed extraction methods are reviewed in this work. The separation and analysis of the insect cuticular lipids were performed by column chromatography, thin-layer chromatography (TLC), high performance liquid chromatography with a laser light scattering detector (HPLC-LLSD), gas chromatography (GC), and GC–mass spectrometry (MS). The strategy of lipid analysis with the use of chromatographic techniques was as follows: extraction of analytes from biological material, lipid class separation by TLC, column chromatography, HPLC-LLSD, derivatization, and final determination by GC, GC-MS, matrix-assisted laser desorption/ionization (MALDI) time-of-flight (TOF) MS, and liquid chromatography–mass spectrometry (LC-MS).     

Analysis of chemical profiles of insect adhesion secretions by gas chromatography–mass spectrometry

This article reports on the chemical analysis of molecular profiles of tarsal secretions of the desert locust Schistocerca gregaria (Forsskål, 1775) by gas chromatography hyphenated with quadrupol mass spectrometry (GC–MS) as well as ¹H-nuclear magnetic resonance (¹H NMR) spectroscopy. Special focus of this study was to elaborate on sampling methods which enable selective microscale extraction of insect secretions in a spatially controlled manner, in particular tarsal adhesive secretions and secretions located on cuticle surfaces at the tibia. Various solvent sampling procedures and contact solid-phase microextraction (SPME) methods were compared in terms of comprehensiveness and extraction efficiencies as measured by signal intensities in GC–MS. Solvent sampling with water as extraction solvent gave access to the elucidation of chemical profiles of polar compound classes such as amino acids and carbohydrates, but is extremely tedious. Contact SPME on the other hand can be regarded as a simplified and more elegant alternative, in particular for the lipophilic compound fraction. Many proteinogenic amino acids and ornithine as well as carbohydrate monomers arabinose, xylose, glucose, and galactose were detected in tarsal secretions after acid hydrolysis of aqueous extracts. Qualitatively similar but quantitatively significantly different molecular profiles were found for the lipid fraction which contained mainly n-alkanes and internally branched monomethyl-, dimethyl-, and trimethyl-alkanes in the C23–C49 range as well as long chain fatty acids and aldehydes. Especially, hydrocarbons with >C40 carbon numbers have previously been rarely reported for insect secretions. The results suggest that the investigated insect secretions are complex emulsions which allow the attachment of tarsi on various otherwise incompatible materials of smooth and rough surfaces. The solid consistence of the established alkanes at ambient temperatures might contribute to a semi-solid consistence of the adhesive, amalgamating partly opposing functions such as slip resistance, tarsal release, desiccation resistance, and mechanical compliance. The methods developed can be extended to other similar applications of studying compositions of insect secretions of other species.     

Microanalytical methodology relating to the identification of insect sex pheromones and related behavior-control chemicals.

Methods currently in use in the extraction, isolation, and identification of insect sex attractants, which are needed for use in pest control, are described briefly. Because amounts of these materials in insects are generally minute, specialized microanalytical methods and techniques have been developed to aid in the determination of their chemical structures.     

Raman microspectroscopic studies of amber resins with insect inclusions

Raman microscope spectra of specimens of Baltic and Mexican amber resins containing insect inclusions have been analysed using near-infrared excitation to assess the potential for discrimination between the keratotic remains of the insects and the terpenoid matrix. For the Mexican amber specimen the insect spectra exhibit evidence of significant protein degradation compared with the insect remains in the Baltic amber specimen. In both cases the Raman spectra of the insect remains are still distinguishable from the amber resins. Despite its better preservation, however, no spectra could be obtained from the inside of the larger insect preserved in the Baltic amber in agreement with the observation that most insect inclusions in amber are hollow. It is noted that the Mexican amber insect is located adjacent to a large gas bubble in the amber matrix, to which the observed degradation of the insect and its poor state of preservation are attributed. It is concluded that Raman spectra of insect inclusions can provide useful information about the chemical composition of the remains and that confocal microscopy is particularly advantageous in this respect.     

RNAi for Insect Control: Current Perspective and Future Challenges

The research on the RNA interference (RNAi) for the control of insect pests has made significant growth in recent years. The availability of the genomic sequences of insects has further widened the horizons for the testing of this technology to various insect groups. Different modes of application of double-stranded RNA (dsRNA) have been tested; however, the practicability of delivery of dsRNA in insects still remains the biggest challenge. Till date, the oral delivery of dsRNA in insects is one of the efficient approaches for the practical application of this technique. The uptake of dsRNA from the insect gut is mediated either by SID-1/SID-2 transmembrane proteins or by endocytosis; however, the systemic RNAi machinery still remains to be revealed in insect species. The RNAi-mediated gene knockdown has shown striking results in different insect groups, pointing it to be the upcoming technique for insect control. However, before the successful application of this technique for insect control, some potential issues need to be resolved. This review presents the account of prospects and challenges for the use of this technology for insect control.     

信号处理技术在重叠化学信号解析中的应用*

重叠峰解析是目前分析化学中亟须解决的一个重要问题,化学计量学用于重叠峰解析就是借助某些数学或统计学方法,把通过化学方法和仪器未能完全分离的复合量测信号分解成几个单儿组分的信号,从而从重叠谱中获取每个组分的相关信息。本文综述了几种常见信号处理技术在重叠化学信号分辨中的应用,引用文献146篇。     

Chemical Vapor Detection Using a Reconstituted Insect Olfactory Receptor Complex

The sensing of vapor odorants is highly demanded in the field of life and medical sciences. Although olfactory receptors (ORs) have potentials to recognize volatile organic compounds, the interaction of ORs, chemical vapors, and peptide components in olfactory mucus has yet to be analyzed to develop OR‐based sensors. A bioinspired electrophysiology technique is shown to record the response of reconstituted insect ORs to chemical vapors. To mimic the interface between ORs and olfactory mucus, OR expressing spheroids were loaded into a hydrogel microchamber array. A negative extracellular field potential shift of spheroids was successfully observed by the stimulation of their vapor cognate ligand. Importantly, the ligand repertoire of the OR of malaria vector mosquito examined by this method differed from that of in vivo studies. Our method is useful to develop protein‐based gas sensing techniques and to examine the binding of ORs and chemical vapors.     

Recent advances in application of liquid-based micro-extraction: A review

Liquid-based micro-extraction is a novel “green” sample preparation technique using micro-litre levels of organic solvent to extract target analytes from various sample matrices for subsequent instrumental analysis. This technique developed rapidly from its introduction in the mid-1990s. Micro-extraction methods can be conveniently combined with a wide selection of instruments commonly used in a chemical laboratory; they significantly reduce analysis time and costs of solvents’ use and waste disposal. This review focuses on recent advances in several liquid-based micro-extraction methods, including single-drop micro-extraction, hollow fibre-liquid phase micro-extraction, and dispersive liquid-liquid micro-extraction. Examples of application of these methods to environmental, food, and biomedical analysis are listed.     

工科化学课程的教学思考与实践

针对我校非化工专业的学生,运用多元化教学手段、启发式引导,以及培养学生用化学思维认知社会生活,完成化学理论知识传授的同时,也实现了"以学生为本"的教学理念,给学生以高素质的化学通才教育。     

Sonochemistry II.—Effects of ultrasounds on homogeneous chemical reactions and in environmental detoxification

Sonication of aqueous solutions causes cavitation in the liquid which results in the formation of H· and ·OH radical species that can be used to reduce or oxidize certain chemical compounds. This article focuses on the effect of ultrasounds in homogeneous reactions to examine the type of chemistry that ensues. It also deals with a rather novel method of using ultrasounds in combination with photochemical methods of inducing chemical reactions; this sonophotochemical technique remains to be explored and exploited. Finally, we examine and explore the potential utilization of ultrasounds to convert environmental hazardous substances into more benign substrates, or better still to mineralize organics into carbon dioxide.     

Structures of cordypyridones A-D, antimalarial N-hydroxy- and N-methoxy-2-pyridones from the insect pathogenic fungus Cordyceps nipponica.

Bioassay-guided fractionation of the extracts from the insect pathogenic fungus Cordyceps nipponica BCC 1389 led to the isolation of N-hydroxy- and N-methoxy-2-pyridones, cordypyridones A-D (1-4). Structures of these compounds, including absolute configuration, were determined by spectroscopic methods, chemical conversions and single-crystal X-ray diffraction analyses. Codypyridones A and B, atropisomers of each other, exhibited potent in vitro antimalarial activity with IC(50) values of 0.066 and 0.037 microg/mL, respectively, while their cytotoxicity was much weaker.     

Integration of chemical stiff ODEs using exponential propagation method

In this paper, we study the numerical long time integration of large stiff systems of differential equations arising from chemical reactions by exponential propagation methods. These methods, which typically converge faster, use matrix-vector products with the exponential or other related function of the Jacobian that can be effectively approximated by Krylov sabspace methods. We equip these methods to an automatic stepsize control technique and apply the method of order 4 for numerical integration of some famous stiff chemical problems such as Belousov-Zhabotinskii reaction, the Chapman atmosphere, Hydrogen chemistry, chemical Akzo-Nobel problem and air pollution problem.     

中草药化学成分提取新技术

介绍五种提取新技术棗微波萃取技术、超临界二氧化碳萃取技术、超声波提取技术、半仿生提取技术和酶法的原理和特点,以及这些新技术近年来在中草药化学成分提取工艺中的研究应用现状,并展望了它们的应用前景。     

Capillary electrophoretic determination of main components of natural dyes with MS detection

CE with UV-Vis and MS detections was investigated as a technique for detection of main components of selected natural dyes of plant and insect origin. The BGE giving the best separation of the investigated flavonoids and anthraquinoids, suitable for MS detection consisted of 40 mM ammonium acetate solution of pH 9.5 with 40% ACN. LODs obtained with MS detection were even one order of magnitude lower than the ones obtained with UV-Vis detection. Application of MS detection enabled determination of eleven dye compounds from three different chemical groups in 15 min. and proved to be more satisfactory than diode-array detection in the electrophoretic analysis of main classes of natural dyes both in terms of selectivity and sensitivity of analysis.     

Probing molecular structure by the chemical resolution of hydrogen migrations

Methyl chloride chemical ionization mass spectrometry has been used to probe molecular stereochemistry in simple model systems such as cyclic diols and cyclic dicarboxylic acids. The methylation technique, which is based on the chemical resolution of hydrogen migrations, often yields ionic fragments that enable the differentiation of cis and trans isomers. This technique, like protonation methods, fails to differentiate the isomers of 1,2-cyclohexanediol. However, it does allow differentiation of the isomers of 1,2-cyclohexanedicarboxylic acid, species that cannot be distinguished via protonation techniques. The utility of methylation in conjunction with MS/MS is also discussed.     

A new non-destructive method for chemical analysis of particulate matter filters: the case of manganese air pollution in Vallecamonica (Italy)

Total Reflection X-ray Fluorescence (TXRF) is a well-established technique for chemical analysis, but it is mainly employed for quality control in the electronics semiconductor industry. The capability to analyze liquid and uniformly thin solid samples makes this technique suitable for other applications, and especially in the very critical field of environmental analysis. Comparison with standard methods like inductively coupled plasma (ICP) and atomic absorption spectroscopy (AAS) shows that TXRF is a practical, accurate, and reliable technique in occupational settings. Due to the greater sensitivity necessary in trace heavy metal detection, TXRF is also suitable for environmental chemical analysis. In this paper we show that based on appropriate standards, TXRF can be considered for non-destructive routine quantitative analysis of environmental matrices such as air filters. This work has been developed in the frame of the EU-FP6 PHIME (Public Health Impact of long-term, low-level Mixed element Exposure in susceptible population strata) Integrated Project (www.phime.org). The aim of this work was to investigate Mn air pollution in the area of Vallecamonica (Italy).     

Elemental concentrations of aquatic insect larvae and attached algae on stone surfaces in an uncontaminated stream

Elemental concentrations of aquatic insect larvae and attached algae in an uncontaminated river were analyzed by instrumental neutron activation analysis (INAA) via the k₀-standardization method. The aquatic insect larvae found were all intolerant species. No significant difference was observed in the elemental concentrations of aquatic insect larvae and attached algae along the river. Similar elemental concentrations were observed in the aquatic insect larvae collected at a fixed sampling point for two years. An analysis by the ratio-matching technique indicated a higher generic relationship between aquatic insect larvae and attached algae than river water.     

薄膜荧光传感器研究进展

按薄膜荧光传感器的制备方法, 从物理薄膜、化学薄膜和自组装单层膜等三个方面综述了近年来薄膜荧光传感器的研究进展. 在此基础上, 展望了薄膜荧光传感器的研究前景.     

化学与刑侦

化学原理在侦破工作中应用的重要性日益突出,以化学为基础的侦破技术在近年来得到了迅速发展,成为打击犯罪、维护治安的重要手段。本文介绍了几种重要的分析方法在刑侦工作中的重要应用。     

Electrophoretically mediated microanalysis of beta-galactosidase on microchips.

Electrophoretically mediated microanalysis (EMMA) is a method of accomplishing chemical analyses, typically in an open-tubular capillary, due to the difference in the electrophoretic mobility between the particular reagents. This work reports on combining this technique onto microfabricated systems. Two methods of this technique were applied, constant potential and zero potential EMMA onto chips. A dosage response curve was run using this constant potential mode that resulted in a linear response over three orders of substrate concentration magnitude. The chemical system used here is beta-galactosidase (beta-Gal) as the enzyme and fluorescein mono-beta-D-galactopyranoside (FMG) as the substrate. The zero potential mode was used to amplify product turnover using various incubation times. Using this technique and a 10 min incubation, approximately 40000 enzyme molecules could be detected. The zero potential mode is also used in conjunction with an internal standard to show how one can quantitate using this method. The power and ease of utility of this technique is described.