Sequestration of distasteful compounds by some pharmacophagous insects

Several pharmacophagous insects have been shown to sequester specific kairomonal substances or their derivatives in their body tissues. Turnip sawflies,Athalia rosae, visit a plant,Clerodendron trichototmum (Verbenaceae), and feed voraciously on the leaf surface. Clerodendrins were characterized as the potent phagostimulants forA. rosae adults. The insect sequesters some of the analogs and becomes extremely bitter on its body surface. Some chrysomelid leaf beetles associated with cucurbitacins were found to store high concentrations of these bitter principles in their body. South American polyphagous beetles,Diabrotica speciosa andCerotoma arcuata, are strongly arrested by root components from the cucurbit plant,Ceratosanthes hilariana, and selectively accumulate 23,24-dihydrocucurbitacin D, effectively gaining bitterness. Similarly, four species of Asian pumpkin leaf beetles belonging to the genusAulacophora were shown to sequester the same compound in body tissue as the major bitter principle. Three phenylpropanoids closely related to methyl eugenol were found to accumulate in the rectal glands of the male Oriental fruit fly,Dacus dorsalis. One of the rectal gland components, 2-allyl-4,5-dimethoxyphenol was shown to be released in the air during courtship. In all of these cases, selectively sequestered compounds strongly deterred feeding by some predators, thus serving as allomones in this context. Kairomonal and pheromonal functions linked with allomonal sequestration by pharmacophagous feeding has also been suggested.     

Swelling behavior of pH‐ and temperature‐sensitive copolymers containing 2‐hydroxy‐ethyl methacrylate and N‐vinyl‐2‐pyrrolidone crosslinked with new crosslinkers

Copolymers of 2‐hydroxyethyl methacrylate (HEMA) and N‐vinyl‐2‐pyrrolidone (VP) and homopolymers of HEMA and VP were crosslinked in the presence of different mol% of melamine trimethacrylamide (MMAm) and melamine triacrylamide (MAAm) as crosslinkers by bulk radical polymerization. The resultant xerogels were characterized by extracting the soluble fractions and measuring the equilibrium water content. Lower critical solution transition temperatures (LCST) were measured by DSC. The properties of crosslinked HEMA and VP copolymers, VP and HEMA series were evaluated in terms of compositional drift of polymerization, heterogeneous crosslinking, and chemical structure of the relevant components. Soluble fractions of the crosslinked networks were reduced by varying the MAAm and MMAm concentrations. The influence of environmental conditions such as temperature and pH on the swelling behavior of these polymeric gels was investigated. The swelling behaviors of the resulting gels show pH sensitivity. This behavior is explained on the basis that amide groups of VP or crosslinkers could be hydrolyzed to form negatively charged carboxylate ion groups in the produced networks in response to an external pH variation. Copyright © 2004 Society of Chemical Industry     

Effect of primary polymer chain rigidity on intramolecular cyclization and intramolecular crosslinking in free‐radical crosslinking monomethacrylate/dimethacrylate copolymerizations

d‐Bornyl methacrylate (BoMA) was chosen as a typical example of bulky monomethacrylate monomers, the polymerization of which led to the formation of a rigid polymer chain. To discuss the effect of primary polymer chain rigidity on intramolecular cyclization, we compared the solution copolymerization results of BoMA with 1 mol % ethylene dimethacrylate (EDMA; n = 1) and poly(ethylene glycol dimethacrylate) [CH₂?C(CH₃)CO(OCH₂CH₂)_nOCOC(CH₃)?CH₂, n = 9 (PEGDMA‐9)] with those of methyl methacrylate (MMA) with 1 mol % EDMA and PEGDMA‐9; the dependence of the weight‐average degree of polymerization on conversion for the former BoMA copolymerization systems was completely opposed to that for the latter MMA systems, and this was a reflection of a reduced occurrence of intramolecular cyclization caused by the rigidity of the primary polymer chain. The effect of primary polymer chain rigidity on intramolecular crosslinking was discussed through a comparison of both BoMA/EDMA and MMA/EDMA copolymerizations. The correlations of the intrinsic viscosity, root‐mean‐square (rms) radius of gyration, and second virial coefficient with the molecular weight were examined for both BoMA/EDMA (90/10) and MMA/EDMA (90/10) copolymerizations in a dilute solution because microgelation was observed in solution MMA/EDMA (90/10) copolymerization as a reflection of a locally extensive occurrence of intramolecular crosslinking. The logarithmic plots of both the intrinsic viscosity and rms radius of gyration versus the molecular weight for MMA/EDMA copolymerization were compared with those for the corresponding BoMA/EDMA copolymerizations. The second virial coefficients were greater than 10^?5 mol cm³ g^?2 for BoMA/EDMA copolymers, even when the conversion was very close to the gel point, whereas they were quite low, that is, less than 10^?5 mol cm³ g^?2, for an MMA/EDMA copolymer obtained at more than 15% conversion. These were ascribed to a suppressed occurrence of intramolecular crosslinking, a reflection of the lessened flexibility of the polymer main chain and a steric effect due to the bulky d‐bornyl groups. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1086–1093, 2004     

1,3-cycloaddition of nitrile oxide to olefinic fatty acid esters: synthesis of isoxazolines

Fatty acid isoxazolines were prepared as 1,3-cyclo adducts by the reaction of dipolar nitrile oxides and dipolarophilic olefinic fatty esters. The structures of the isoxazolines were established with the help of elemental analysis, infrared, nuclear magnetic resonance and mass spectrometry spectral data.     

氧化甲基橙褪色分光光度法测定微量铬

Ｃｒ（Ⅵ）对甲基进具有褪色作用，借此可以进行分光光度法测定铬。实验表明，在１．４４～２．８８ｍｏｌ·Ｊ－１Ｈ２ＳＯ４介质中，有色溶液的最大吸收波长为５１０ｎｍ，铬量在０～１００μｇ／２５ｍｌ范围内与有色溶液的吸光度减少值成线性关系。方法简单、快速、准确、选择性好。在用于测定淤泥中的微量铬时，结果满意。     

金属氧化物催化热降解废聚甲基丙烯酸甲酯的动力学研究

利用热重分析的方法研究了MgO,CaO,Fe2O3,Al2O3,CuO5种金属氧化物对废聚甲基丙烯酸甲酯(PMMA)热降解过程的影响,并考察了该5种金属氧化物的催化活性,其由高到低的顺序为MgO>CaO>Fe2O3>Al2O3>CuO。提出了金属氧化物催化热降解PMMA时,金属离子与碳自由基侧链的羰基氧结合形成中间态,减弱酯基对自由基的共轭效应,从而增加自由基的活性,促使热降解反应进行的反应机理。同时还求得了在各种氧化物存在下热降解过程的表观活化能Ea。在MgO存在下,废有机玻璃热降解的Ea为153.08kJ/mol,指前因子A为4.27×1012min-1,初始热降解温度下的速率常数k为1.56×10-3min-1。     

主要腐殖型凝析气藏的成熟度特征

凝析气约占中国已发现天然气资源的1/3,腐殖型凝析气是其重要组成部分。前人基于模拟实验,对腐殖型凝析气的成熟度分布范围进行过研究,但其结果差异较大,需用实际资料进行验证。经统计分析国内外主要腐殖型凝析气藏的156个凝析气甲烷碳同位素、72个凝析油甲基菲比值和甲基菲指数数据,结合腐殖型有机质生烃演化模式,发现腐殖型凝析气成熟度主要为R_o=0.57%~1.36%,在R_o=0.49%~0.57%和R_o=1.36%~2.28%时也具有一定的生气潜力。处于这3个阶段的腐殖型烃源岩均可排出凝析气,经运移聚集,可形成常规凝析气藏,留在烃源岩内部的可形成页岩凝析气藏。其中,R_o=0.57%~1.36%的腐殖型凝析气藏是重要的勘探目标区。     

MTBE装置设备腐蚀的探讨

甲基叔丁基醚(MTBE)装置生产过程中普遍存在设备酸腐蚀的问题,通过对MTBE生产装置各工艺系统中可能产生的酸进行理论分析,认定甲酸的存在是设备腐蚀的主要原因。甲酸的来源为甲醇原料带入(甲酸质量分数在0.001 5%以下)、甲酸盐与催化剂磺酸离子交换产生、甲醇原料带入的甲酸甲酯(质量分数0.01%以上)在生产过程中水解产生。根据理论分析结合实际生产数据推断,甲酸甲酯水解是甲酸的主要来源,因此提出在甲醇原料的采购指标中增加甲酸甲酯含量分析的监控指标,要求甲酸甲酯的质量分数控制在0.005%以下,能有效减少甲酸的生成,达到控制设备腐蚀的目的。     

Fabrication of Copper Nanowire Films and their Incorporation into Polymer Matrices for Antibacterial and Marine Antifouling Applications

With the ban of tributyltin, copper‐based biocides are now widely used in antifouling coatings as the major active ingredients. Given the past experience of heavy‐metal accumulation in harbors with limited water exchange, there is a significant interest in developing copper materials that greatly reduce the amount of copper ions released into marine surroundings. In this paper, copper nanowires (NWs) encapsulated in polymer matrices are investigated as the means to control the release of copper ions and to achieve a long‐lasting antifouling effect. Very long CuNWs with high aspect ratio in organic solution are drop‐coated onto substrates to fabricate uniform thin films. They are then incorporated into an elastomeric polydimethylsiloxane (PDMS) matrix. A small amount of CuNWs in PDMS can inhibit barnacle cyprid settlement, while it exhibits low mortality to cyprids and nauplii present in the surrounding seawater environment. The low levels of copper released after 50 days suggest that the intersecting and interconnected CuNWs embedded in PDMS could potentially release copper ions continuously over a few years in seawater. This approach provides a novel platform to use hybrid materials as effective marine antifouling coatings, and may be applied to fouling release materials to enhance their antifouling properties.