1,4—二氧六环产品的气相色谱与气相色谱／质谱的分析

用气相色谱与气相色谱／质谱来定性和定量分析由二甘醇制备的１，４－二氧六环和副产物。确定了１，４－二氧六环中所含的杂质，对共沸精馏法分离及提纯１，４－二氧六环有重要指导价值。     

硫酸铜催化制备1，4 二氧六环

以无水硫酸铜为催化剂使一缩二乙二醇（二甘醇）环化脱水，制备１，４ 二氧六环，产率＞９２％。并对其结构进行了分析确认     

硫酸铜催化制备1，4二氧六环

以无水硫酸铜为催化剂使一缩二乙二醇（二甘醇）环化脱水，制备１，４二氧六环，产率＞９２％。并对其结构进行了分析确认     

反—1,2—双[2—（5—取代苯基恶唑基）]乙烯的结构与光性能及光二…

测试了反－１，２－双「（２－（５－苯基恶唑基）」乙烯类化合物在１，４－二氧六环中的荧光寿命及其在不同溶剂中的光二聚量子产率，计算了其荧光辐射速率常数和非辐射速率常数，研究了取代基效应及溶剂性质对该类化合物光二聚反应的影响。     

二甘醇脱水制备1,4-二氧六环新工艺

以HZSM-5与硫酸铜为原料制备催化剂Cu-ZSM-5。探讨了以Cu-ZSM-5为催化剂,二甘醇脱水制备1,4-二氧六环的工艺。催化剂的性能主要通过二甘醇的转化率和1,4-二氧六环的选择性来评价。分别研究了催化剂用量、反应温度和反应时间对二甘醇转化率及1,4-二氧六环选择性的影响。较优的反应条件为:催化剂用量为总反原料质量的4.7%,控制反应温度180℃左右,反应300min,二甘醇的转化率为95.1%,1,4-二氧六环的选择为性86.1%,且催化剂可以多次循环使用。     

杂多酸催化二甘醇制取二氧六环

用杂多酸为催伦剂，以二甘醇为原料合成二氧六环。结果表明，用磷钨酸做催化剂，反应转化率为９９％，二氧六环的选择性为９６％。其适宜的工艺条件为：反应温度１７０～１８０℃，反应时间３ｈ，催化剂用量１．０％～１．５％（ｍ）。所得产品纯度≥９９％，水分≤０．２％。     

近临界水体系中添加物促进的二甘醇脱水环化研究

考察了一缩二乙二醇(又名二甘醇DEG)在近临界水体系中两种不同添加物存在下的反应活性,并测定了在不同时间、温度、物料/水比、压力以及添加物浓度下二甘醇脱水环化产物-1,4-二氧六环(Dioxane)的产率.实验结果表明,在无任何添加物存在的近临界水体系中,二甘醇可以进行环化脱水生成1,4-二氧六环,但产率相对较低.当温度为340℃,反应时间为240 min,1,4-二氧六环的产率仅为9.84 %(wt).向反应体系引入ZnCl2,所得1,4-二氧六环产率较纯水条件下有很大提高.在浓度为0.5 %(wt) 的ZnCl2 溶液中,当温度为340℃,反应时间为120 min,1,4-二氧六环的产率最高可达50.89 % (wt);在浓度为1.0 %(wt) ZnCl2 溶液中,相同反应温度和时间下,1,4-二氧六环的产率最高可达36.18 %(wt).在相同反应条件下,向反应体系中引入Na2CO3,二甘醇几乎没有转化,检测不到1,4-二氧六环.根据产物产率变化规律和传统条件下二甘醇脱水机理,提出了近临界水中引入少量添加物情况下DEG脱水反应可能的反应历程.     

二甘醇用杂多酸盐催化合成二氧六环

研究了用杂多酸盐作催化剂，以二甘醇为原料制取二氧六环。试验发现，磷钨酸银、磷钨酸铜、硅钨酸银、硅钨酮铜具有较高的活性和选择性，在反应温度为２２０￣２４０℃，催化剂浓度为０．５％￣１．０％，反应１．５￣２．０ｈ时，转化率达９８％以上。二氧六环选择怀为：磷钨酸银９３％，硅钨酸银９５％，磷钨酸铜８７％，硅钨酸铜９０％，催化剂可重复使用５次以上。     

18—冠—6的合成

用钾离子为模板，采用稀释法，以三甘醇和３，６－二氧－１，８－二氯辛烷为原料，经Ｗｉｌｌｉａｍｓｏｎ反应合成了１８－冠－６，并用硝基甲烷进行提纯。考察了反应时间，反应物配比，氢氧化钾加入方式对产率的影响。实验结果表明；反应时间为２０ｈ，三甘醇和三甘醇的二氯化物的物质的量比为１．１：１，氢氧化钾粉状加入时，１８－冠－６的产率可达５１．５８％。产物的结构红外光谱及熔点确认。     

二甘醇二丁醚的制备

采用改进的Ｗｉｌｌａｍｓｏｎ合成反应方法，以二甘醇、溴丁烷及固体氢氧化钠，一步法合成二甘醇二丁醚。就影响醚化反应收率各因素：原料配比、反应温度、反应时间以及催化剂用量进行了探讨，得到最佳的操作条件为：二甘醇：溴丁烷：固碱物质的量比＝１．０：２．２：２．４，反应温度７５℃，反应时间６￣７ｈ，在经条件下收率可达８５％。     

Olfactory-based behavioral interactions among five species in the southern pine bark beetle group

Olfactory-mediated behavioral interactions were investigated among the five scolytid species comprising the southern pine bark beetle group. Behavioral response, as determined from field trap catch data, showed that each species was attracted in greatest numbers to the pheromonal blend produced by conspecifies. Interspecifically,D. frontalis displayed no cross-attractancy toIps pheromonal blends, but was weakly attracted to the pheromonal blend of femaleD. terebrans. ThreeIps species displayed varying degrees of cross-attraction as well as to theDendroctonus pheromonal blends. More specifically,I. calligraphus was attracted toI. avulsus and, to a very limited extent, also to the maleD. terebrans pheromonal blend.I. avulsus was somewhat more cross-attractive thanI. calligraphus and showed attraction to the pheromonal blends of femaleD. frontalis, male and femaleD. terebrans, maleI. calligraphus, and maleI. grandicollis. I. grandicollis showed the greatest degree of cross-attraction, particularly in response to theDendroctonus pheromonal blends.Research support in part by CSRS grant 86-CRCR-1-2270, NATO grant CRG.0710/86 and Texas Agricultural Experiment Station project MS1525 (while M.T.S. and T.L.P. were with Texas A&M University). The findings, opinions, and recommendations expressed herein are those of the authors and not necessarily those of the U.S. Department of Agriculture.     

Density-Dependent Reduction and Induction of Milkweed Cardenolides by a Sucking Insect Herbivore

The effect of aphid population size on host-plant chemical defense expression and the effect of plant defense on aphid population dynamics were investigated in a milkweed-specialist herbivore system. Density effects of the aposematic oleander aphid, Aphis nerii, on cardenolide expression were measured in two milkweed species, Asclepias curassavica and A. incarnata. These plants vary in constitutive chemical investment with high mean cardenolide concentration in A. curassavica and low to zero in A. incarnata. The second objective was to determine whether cardenolide expression in these two host plants impacts mean A. nerii colony biomass (mg) and density. Cardenolide concentration (microgram/g) of A. curassavica in both aphid-treated leaves and opposite, herbivore-free leaves decreased initially in comparison with aphid-free controls, and then increased significantly with A. nerii density. Thus, A. curassavica responds to aphid herbivory initially with density-dependent phytochemical reduction, followed by induction of cardenolides to concentrations above aphid-free controls. In addition, mean cardenolide concentration of aphid-treated leaves was significantly higher than that of opposite, herbivore-free leaves. Therefore, A. curassavica induction is strongest in herbivore-damage tissue. Conversely, A. incarnata exhibited no such chemical response to aphid herbivory. Furthermore, neither host plant responded chemically to herbivore feeding duration time (days) or to the interaction between herbivore initial density and feeding duration time. There were also no significant differences in mean colony biomass or population density of A. nerii reared on high cardenolide (A. curassavica) and low cardenolide (A. incarnata) hosts.     

Ancestral semiochemical attraction persists for adjoining populations of siblingIps bark beetles (Coleoptera: Scolytidae)

Three species ofIps pine bark beetles in Hopping's group IX (S.L. Wood'sgrandicollis group),Ips confusus, I. lecontei, andI. paraconfusus, are parapatrically distributed in the American Southwest. They share post-Pleistocene altitudinal ecotones with their host pines. Adjacent to these areas of host overlap, we tested the hypothesis that aggregation pheromones produced by male beetles and/or host volatiles are sufficient to elicit the speciesspecific colonization behaviors typical of these threeIps species in nature. A more distantly related species,I. pini (Hopping's group IV, S.L. Wood'spini group) was used for outgroup comparison. Under the influence of pheromone, males ofI. confusus andI. paraconfusus do not discern among unin-fested log bolts of host and nonhost pine prior to bark contact. Males responding to pheromones emanating from infested bolts are similarly undiscriminating. Females ofI. confusus andI. lecontei olfactorily discern the combination of conspecific males in host pine from other possible beetlepine combinations; females ofI. paraconfusus do not. FemaleI. pini discerned conspecific pheromone from that ofI. lecontei. The bark beetle predator,Enoclerus lecontei, is attracted by, but does not discriminate among, the male-produced volatiles of these Group IXIps species. These results support a hypothesis that divergence in pheromonal responses by these group IXIps species has evolved following their speciation, having been manifested first in the female sex. Evolutionarily, the derived pheromonal messages have preceded their behavioral discrimination by these beetles. Additional speciesspecific cues may operate between the sexes in the field that may preclude heterospecific pairings.     

Interspecific response to sex pheromones,and calling behavior of severalAttagenus species (Coleoptera: Dermestidae)

Females of severalAttagenus species demonstrated calling behaviors similar to those previously reported forA. elongatulus. Attagenus rufipennis females did not call until they were 12–14 days old. OtherAttagenus species called at approx. 4 days of age. All species exhibited diurnal periods of calling activity. Interspecific pheromone responses were tested, withA. megatoma megatoma, A. megatoma canadensis, A. megatoma japonicus, andA. schaefferi spurcus showing equal cross-responses. Male response to females was demonstrated inA. rufipennis andA. bicolor. Attagenus rufipennis, bicolor, andelongatulus males responded only to female extracts of their own species.Mention of a proprietary product does not constitute an endorsement by the USDA.     

Allelopathic interactions among algae

Five species of green algae isolated from the Cleveland County, Oklahoma, area and a commercially obtained yellow-green alga were tested for allelopathic interactions. Axenic cultures ofPandorina morum Bory were stimulated in three sterile filtrates from nonaxenic cultures ofScenedesmus incrassatulus var.mononae G.M. Smith, with the oldest filtrate showing the least stimulation. By measuring the growth of axenic cultures inoculated into sterile filtrates of old cultures, instances of inhibition and stimulation were recorded in three screening experiments.Cosmarium vexatum West filtrate was inhibitory to the five other species, a characteristic probably important in its role of producing waterblooms in ponds and swamps. The allelopathic effects of filtrates of the five other species onBolrydium becherianum Vischer could be a key to its restriction to terrestrial sites. Instances of heat lability of the active substances were noted. These interactions, both allelopathic and stimulatory, probably play a significant role in the succession of algal blooms in nature.     

国外生物降解聚合物的种类及主要组分

据１９９６～１９９８年国外有关文献的汇集,由美,日,德等国主要研制,生产的生物降解聚合物种类为：１,单一型生物降解聚合物;（１）合成酯（酸）类;（２）淀粉基材料;（３）天然高分子材料;２、复合型生物降解聚合物;（１）不同种类的烃基互聚物;（２）烃酯（酸）／聚酯（３）脂肪族聚酯／芳香族聚酯共聚物;（３）淀粉基复合型,（５）光／生物降解聚合物;３、可生物降解水溶性聚合物。     

Plant-determined variation in the cardenolide content,thin-layer chromatography profiles,and emetic potency of monarch butterflies,Danaus plexippus L. Reared on milkweed plants in California: 2.Asclepias speciosa

The pattern of variation in gross cardenolide concentration of 111Asclepias speciosa plants collected in six different areas of California is a positively skewed distribution which ranges from 19 to 344 g of cardenolide per 0.1 g dry weight with a mean of 90 g per 0.1 g. Butterflies reared individually on these plants in their native habitats ranged from 41 to 547 g of cardenolide per 0.1 g dry weight with a mean of 179 g. Total cardenolide per butterfly ranged from 54 to 1279 g with a mean of 319 g. Differences in concentrations and total cardenolide contents in the butterflies from the six geographic areas appeared minor, and there were no differences between the males and the females, although the males did weigh significantly more than females. The uptake of cardenolide by the butterflies was found to be a logarithmic function of the plant concentration. This results in regulation: larvae which feed on low-concentration plants produce butterflies with increased cardenolide concentrations relative to those of the plants, and those which feed on high-concentration plants produce butterflies with decreased concentrations. No evidence was adduced that high concentrations of cardenolides in the plants affected the fitness of the butterflies. The mean emetic potencies of the powdered plant and butterfly material were 5.62 and 5.25 blue jay emetic dose fifty units per milligram of cardenolide and the number of ED₅₀ units per butterfly ranged from 0.28 to 6.7 with a mean of 1.67. Monarchs reared onA. speciosa, on average, are only about one tenth as emetic as those reared onA. eriocarpa. UnlikeA. eriocarpa which is limited to California,A. speciosa ranges from California to the Great Plains and is replaced eastwards byA. syriaca L. These two latter milkweed species appear to have a similar array of chemically identical cardenolides, and therefore both must produce butterflies of relatively low emetic potency to birds, with important ecological implications. About 80% of the lower emetic potency of monarchs reared on A. speciosa compared to those reared onA. eriocarpa appears attributable to the higher polarity of the cardenolides inA. speciosa. Thin-layer Chromatographie separation of the cardenolides in two different solvent systems showed that there are 23 cardenolides in theA. speciosa plants of which 20 are stored by the butterflies. There were no differences in the cardenolide spot patterns due either to geographic origin or the sex of the butterflies. As when reared onA. eriocarpa, the butterflies did not store the plant cardenolides withR _f values greater than digitoxigenin. However, metabolic transformation of the cardenolides by the larvae appeared minor in comparison to when they were reared onA. eriocarpa. AlthoughA. eriocarpa andA. speciosa contain similar numbers of cardenolides and both contain desglucosyrioside, the cardenolides ofA. speciosa overall are more polar. ThusA. speciosa has no or only small amounts of the nonpolar labriformin and labriformidin, whereas both occur in high concentrations inA. eriocarpa. A. speciosa plants and butterflies also contain uzarigen, syriogenin, and possibly other polar cardenolides withR _f values lower than digitoxin. The cardenolide concentration in the leaves is not only considerably less than inA. eriocarpa, but the latex has little to immeasurable cardenolide, whereas that ofA. eriocarpa has very high concentrations of several cardenolides. Quantitative analysis ofR _f values of the cardenolide spots, their intensities, and their probabilities of occurrence in the chloroform-methanol-formamide TLC system produced a cardenolide fingerprint pattern very different from that previously established for monarchs reared onA. eriocarpa. This dispels recently published skepticism about the predictibility of chemical fingerprints based upon ingested secondary plant chemicals.Lepidoptera: Danaidae.Apocynales: Asclepiadaceae.This study was supported by U.S. National Science Foundation grants DEB 75-14265 and 78-10658 to Amherst College and BSR-8119382 to the University of Florida with L.P. Brower as Principal Investigator and DEB75-14266, DEB78-15419, and DEB-81-19391 to the University of California at Davis with J.N. Seiber as Principal Investigator.     

Influence of life history differences of two tachinid parasitoids ofHelicoverpa zea (Boddie) (Lepidoptera: Noctuidae) on their interactions with glandular trichome/methyl ketone-based insect resistance in tomato

The effects of glandular trichome/methyl ketone (2-tridecanone and 2-undecanone) -based insect resistance in the wild tomato,Lycopersicon hirsutum f.glabratum C.H. Mull, accession PI 134417, onArchytas marmoratus (Townsend) andEucelatoria bryani (Sabrosky) (Diptera: Tachinidae), both parasitoids ofHelicoverpa (=Heliothis)zea (Boddie) (Lepidoptera: Noctuidae), were investigated in the laboratory.A. marmoratus deposits larvae (planidia) on the foliage of its host's food plant; planidia attach to passing hosts, penetrate the cuticle, and develop in the host pupae.E. bryani larviposits directly into its host; its larvae develop in the host larva.A. marmoratus planidia are killed by glandular trichomes of PI 134417 and also by trichomes of hybrid lines with no methyl ketones. The methyl ketones are toxic to planidia, but at least part of the effect is due to other factors, possibly physical entanglement. Both species can be affected indirectly by methyl ketones in the diet of the host. 2-Undecanone reduces the percentage ofA. marmoratus larvae that reach pupation. This effect is evidently due to premature death and desiccation of the host pupa caused by 2-undecanone. 2-Tridecanone in host diets had no effect onA. marmoratus. InE. bryani, 2-tridecanone in the diet of the host reduced the number of parasitoids yielded by each parasitized host, although not the overall percentage of hosts parasitized. 2-Undecanone in the diet of the host had no effect onE. bryani.We thank M. Woodall for typing; V.B. Covington, D. Bumgarner, and B. O'Brien for technical assistance; L.A. Jones for assistance with gas chromatography; P.H. Adler for supplyingE. bryani puparia to initiate colony; and Drs. F. Gould, G.C. Rock, and M. Barbercheck for comments.     

Modified dynamic matrix control

DMC (Dynamic Matrix Control) has been used successfully in industry for the last decade. It can deal with constraints and unusual dynamic behavior directly. It also shows a good control performance for the servo problem. Relatively, it can’t reject disturbances systematically. We propose a modified DMC method to control the regulatory process more efficiently. The proposed DMC method makes the control output by subtracting the estimated disturbance from the control output of the original DMC. Here, the disturbance is estimated by a new disturbance estimator. It shows better control performances than the original DMC.     

Soil nutrient depletion by agricultural production in Southern Mali

The degree of soil mining by agricultural production in Southern Mali is assessed by calculating nutrient balances: differences between the amount of plant nutrients exported from the cultivated fields, and those added to the fields. Export processes include extraction by crops, losses due to leaching, to erosion, and to volatilization and denitrification. Inputs include applications of fertilizer and manure, restitution of crop residues, nitrogen fixation, atmospheric deposition of nutrients in rain and dust, and enrichment by weathering of soil minerals. Nutrient balances are calculated for N, P, K, Ca, and Mg. Both pessimistic and optimistic estimates are given.The resulting figures indicate, even when the most optimistic estimates are used, large deficits for nitrogen, potassium and magnesium. For the region as a whole, the calculated deficits are -25 kg N/ha,-20 kg K/ha, and -5 kg Mg/ha. Further, acidification is to be expected, in particular in areas where cotton is grown. The deficits are caused by traditional cereal crops, but also by cotton and especially by groundnut. The latter two crops are fertilized, but insufficiently. It is important to note, that the negative figures are not automatic recommendations for application of a specific amount of additional fertilizer. For phosphorus and calcium the balance of the region as a whole appears to be about in equilibrium, but locally large variations may occur.Erosion and denitrification are important causes of nutrient loss, accounting respectively for 17 and 22% of total nitrogen exports. Atmospheric deposition and weathering of minerals in the soil are still important nutrient inputs that contribute as much as nutrients as organic and mineral fertilizer combined. Nutrient depletion is very large in comparison to the amount of fertilizer applied. Drastic options, such as doubling the application of fertilizer or manure, or halving erosion losses, even if feasible, would still not be enough to make up for the calculated deficits.The annual value of withdrawn nutrients, if related to prices of fertilizers, varies between 10,000 and 15,000 FCFA/ha (40-60 US $/ha). Since the estimated average gross margin from farming in this area is 34,000 FCFA/ha (123 US $/ha), soil mining appears to provide an amount equal to 40% of farmers' total income from agricultural activities.