有机硅行业2009年回顾及2010年预测

有机硅行业2009年有机硅单体的产能已经达到109万吨,产量为50多万吨。硅橡胶的产量为45—48万吨,硅油的产能为10万吨,产量为6万吨。硅树脂的产能为2万吨,产量为1万吨,需求量2万吨,进口量为1万吨。硅烷偶联剂供不应求,估计产量为10万吨。气相白炭黑产量为1．8万吨。     

杀虫剂、杀菌剂、除草剂的定量色谱分析

以氰戊菊酯、三唑酮和莠去津分别作为杀虫剂、杀菌剂、除草剂的代表,对三类农药的色谱定量分析进行了探讨。选择3%SE-30色谱柱,以邻苯二甲酸二壬酯为氰戊菊酯的内标,以邻苯二甲酸二丙酯为三唑酮的内标,以三唑酮为莠去津的内标,在不同温度下完成上述农药有效成分的定量分析。结果表明,氰戊菊酯的标准偏差为0.11,变异系数为0.57%,回收率为99.62%;三唑酮的标准偏差为0.15,变异系数为0.73%,回收率为99.35%;莠去津的标准偏差为0.12,变异系数为0.31%,回收率为99.8%。     

龙眼茶茶粕中茶皂素提取工艺的研究

以永泰龙眼茶茶粕为原料,考察乙醇浓度、浸提时间、料液比、浸提温度等因素对茶皂素提取的影响,并进一步考察了超声波辅助提取茶皂素的工艺条件。结果表明,茶皂素的最佳提取工艺条件为:浸提时间为2 h,乙醇浓度为75%,料液比为1∶4,提取溶液温度为80℃。超声波辅助提取茶皂素的最佳工艺条件为:超声频率为40 k Hz,超声功率为500 W,浸提时间为50 min,乙醇浓度为75%,料液比为1∶4,提取溶液温度为80℃。利用超声波辅助乙醇法提取茶皂素的得率为12.9%,茶皂素纯度为65.6%。     

氧化-酯化-MMA接枝复合变性木薯淀粉的合成与表征

以木薯淀粉为主要原料,经双氧水氧化、邻苯二甲酸酐酯化,再与甲基丙烯酸甲酯进行接枝合成出复合变性淀粉。实验得到较佳的反应条件为:氧化反应时间为2h,温度为40℃,氧化剂用量为5mL,酯化反应时间为4.5h,温度为45℃,催化剂用量为4%;接枝反应的接枝时间为4.0h,温度为40℃,投料比(MMA∶酯化淀粉)为1.75∶1,引发剂浓度为0.05mol/L。用红外光谱(FTIR)、扫描电镜(SEM)对原料和复合变性薯淀粉的结构进行了表征。     

生产玉米红曲色素

延边大学药学院研究出玉米中红曲色素的生产工艺。研究人员以红曲霉为菌种,种子液体培养发酵、红曲固体发酵来生产红曲色素。结果发现红曲固体发酵的最佳条件是：接种量为6％,玉米初始水分为35％,发酵温度为28℃～32℃。最佳浸取工艺为：溶剂为70％乙醇水溶液,提取温度为60℃,提取时间为2h。     

化学试剂络合对改性活性炭吸附痕量铂、钯的影响

为了更准确地测定土壤中的铂、钯,在体积分数为5%的盐酸介质中,选用不同试剂为络合剂,改性活性炭为吸附剂,电感耦合等离子体质谱法测定土壤中的铂、钯。实验研究表明:经盐酸羟胺改性的活性炭富集,铂、钯的回收率为92.3%~102.4%;8-羟基喹啉为络合剂时,铂的回收率为86.4%~104.9%,钯的回收率为91.7%~100.0%;抗坏血酸为络合剂时,铂的回收率为82.6%~100.9%,钯的回收率为86.2%~98.3%;硫脲为络合剂时,铂的回收率为78.2%~105.1%,钯的回收率为81.9%~95.3%。方法检出限:铂为0.017 ng/mL,钯为0.021 ng/mL。该方法操作简便,分析速度快,灵敏度高,具有良好的测定精密度和准确度,适用于超痕量铂、钯的分析。     

石蜡制备高碳醇工艺条件研究

以石蜡为原料,硼酸酐为催化剂,经催化氧化、水洗、水解、萃取制备高碳醇。研究发现在催化剂用量为6%(基于石蜡质量,下同),氧化时间为4 h,氧化温度为190℃,NaOH质量分数为4%,水解温度为85℃,水解时间为3 h为最佳的工艺条件,产率最高。利用FTIR分析产物的结构,结果表明,制备产物的官能团与目标产物一致。对该工艺条件下合成的产物进行测定,酸值为0.34,产率为20.12%,高于其他工艺条件。     

用褐煤活化一步法制备活性炭的研究

介绍了以褐煤为原料,磷酸为活化剂,硫酸为添加剂,采用炭活化一步法制备活性炭的实验,讨论了浸渍温度、炭活化温度、炭活化时间、磷酸的浓度、磷酸溶液与褐煤的液固比、硫酸的用量等主要因素对活性炭性能的影响。结果表明,适宜的工艺条件为:浸渍温度为80℃,炭活化温度为400℃,炭活化时间为60min,磷酸质量分数为40%,磷酸溶液与褐煤的液固比为5:1,硫酸的用量为褐煤质量6%。在该适宜的工艺条件下制备的活性炭,强度为88.2%,比表面积为1 158.6 m2/g,吸碘值为946.5 mg/g,吸亚甲基蓝值为203.4mg/g。     

米糠油脱磷脂与脱色工艺的研究

研究了米糠油脱磷脂及脱色方法,以提高脱磷脂、脱色的效果。采用正交试验法分别考察了多种因素对脱磷脂及脱色操作的影响,找到了最佳脱磷及脱色的工艺操作指标。实验结果表明,最佳脱胶工艺条件为:毛油温度为90℃,磷酸用量为油重的0.3%,水的用量为油重的6.0%,快速搅拌时间为40min,食盐用量为油重的1.5%。最佳脱色工艺条件:活性白土的量为油重的3%,油温为110℃,反应时间为30min,废白土的用量为油重的2%。     

脱硫用催化剂制备及评价

以硅酸乙酯为原料,乙醇为溶剂,磷钨酸为负载物,通过溶胶凝胶法制备负载磷钨酸的二氧化硅固体催化剂。正交实验优选出脱硫最佳条件为:氧化剂过氧化氢用量为4 mL,催化剂用量为3 g,反应温度为50℃,反应时间为90min。催化剂回收再利用率高。     

Host selection behavior of bark beetles (Coleoptera: Scolytidae) attackingPinus ponderosa,with special emphasis on the western pine beetle,Dendroctonus brevicomis

Detection of weakened hosts from a distance by bark beetles through olfaction was investigated in field experiments. No significant numbers of Scolytidae were attracted to anaerobically treated pine bolts, stem disks, or sugar and ponderosa pine bark including phloem. Treatment of living trees with cacodylic acid induced attacks byDendroctonus brevicomis, D. ponderosae, Ips latidens, Gnathotrichus retusus, andPityophthorus scalptor, beginning two weeks after treatment. There was no significant difference between landing rates ofD. brevicomis andD. ponderosae on screened treated trees and screened controls. There was a significant increase in landing rates ofG. retusus andI. latidens, because both species had penetrated the screen and produced pheromones. Tree frilling alone did not increase the landing rate of bark beetles. Freezing of the lower trunk with dry ice did not increase significantly the landing rate ofD. brevicomis, D. ponderosae, G. retusus, orI. latidens on screened trees, whereas unscreened frozen trees were attacked by all four species. There was no significantly higher landing rate byD. brevicomis, D. ponderosae, I. paraconfusus, I. latidens, G. retusus, orHylurgops subcostulatus on screened trees evidencing symptoms of severe infection by the root pathogenVerticicladiella wagenerii, than on symptornless trees. These experiments show thatD. brevicomis, D. ponderosae, I. paraconfusus, I. latidens, andG. retusus land, apparently indiscriminately, on healthy and stressed hosts. Thus, in these species host discrimination must occur after landing and prior to sustained feeding.These studies were supported in part by the U.S.D.A. Forest Service, Cooperative State Research Services (2598-RRF.W-1 10) and the National Science Foundation and Environmental Protection Agency through a grant (NSF GB-34719/BM575-04223) to the University of California; and by the Canada Department of the Environment. The findings, opinions and recommendations are not necessarily those of the University of California or the funding agencies.From a thesis submitted by H.A. Moeck to the University of California, Berkeley, in partial fulfillment of the requirements for the degree Doctor of Philosophy in Entomology.     

Defensive strategy of twoHypselodoris nudibranchs from Italian and Spanish coasts

Hypselodoris nudibranchs from different geographic areas (Spain and Italy) have been studied in order to investigate their general defensive strategy. Longifolin (1) and nakafuran-9 (2) are the main ichthyodeterrent allomones used by the mollusks to avoid predation. Evidence of their dietary origin is presented and the very effective strategy against predators, which includes secretion of allomones into the mucus and their storage into specific mantle dermal formations (MDFs), is also discussed.F.P.I.-M.E.C. Spanish fellowship (University of Barcelona) at the I.C.M.I.B.     

Cuticular Hydrocarbons as Chemotaxonomic Characters of Pine Engraver Beetles (Ips spp.) in the grandicollis Subgeneric Group

Cuticular hydrocarbons were extracted, identified, and evaluated as chemotaxonomic characters from all species of adult Ips pine engraver beetles in the grandicollis subgeneric group. The grandicollis group consists of Ips grandicollis (Eichhoff), I. cribricollis (Eichhoff), I. lecontei Swaine, I. montanus (Eichhoff), I. paraconfusus Lanier, I. confusus (LeConte), and I. hoppingi Lanier. In order to provide outgroups for a phylogenetic analysis, cuticular hydrocarbons were also analyzed from Orthotomicus caelatus (Eichhoff), I. latidens (LeConte) (latidens subgeneric group), and I. pini (Say) (pini subgeneric group). Two hundred forty-eight hydrocarbon components were identified by gas chromatography–mass spectrometry. The members of the grandicollis group provided 206 of these compounds. The components represented eight classes: n-alkanes, alkenes, alkadienes, terminally branched methylalkanes, internally branched methylalkanes, dimethylalkanes, trimethylalkanes, and tetramethylalkanes. Different populations of O. caelatus, I. grandicollis, I. lecontei, I. montanus, I. paraconfusus, I. confusus, and I. hoppingi provided no evidence for interpopulational variation in cuticular hydrocarbons. Single populations only were analyzed for I. latidens, I. pini, and I. cribricollis. Sexual dimorphism in cuticular hydrocarbons occurred only in I. lecontei where females produced eight unique components with a pentatriacontane parent chain. Several phylogenetic analyses based on hydrocarbon phenotypes agreed in general with the established morphologically based system of relatedness and with published phylogenies reconstructed from protein and nucleic acid characters. Nearly all hydrocarbon analyses suggested a close relationship between I. grandicollis and I. cribricollis; between I. lecontei and I. montanus; and among the sibling species I. paraconfusus, I. confusus, and I. hoppingi. The presence or absence of specific n-alkanes (n-docosane, n-triacontane); certain dimethylalkanes (terminally branched with octacosane and triacontane parent chains and internally branched with heptacosane, hentriacontane, and docotriacontane parent chains); and 3,7,11-; 3,7,15-trimethylheptacosane permit facile discrimination of I. paraconfusus, I. confusus, and I. hoppingi. These three sibling species are difficult to resolve by external morphology. These data support the species status of I. hoppingi rather than it being considered a host race of the I. confusus complex. They also support the species status of I. cribricollis rather than it being considered part of I. grandicollis. In contrast to other published phylogenies reconstructed from molecular data, phylogenies reconstructed from cuticular hydrocarbons repeatedly place I. lecontei as an integral part of the grandicollis subgeneric group. Thus, cuticular hydrocarbon and pheromone alcohol composition of I. lecontei support its inclusion in the grandicollis subgeneric group.     

Extracts of Flourensia cernua (L): Volatile Constituents and Antifungal, Antialgal, and Antitermite Bioactivities

The chemical components of tarbush (Flourensia cernua) leaves were fractionated by extracting successively with hexanes, diethyl ether, and ethanol. Volatile profiles of each fraction were identified by using GC-MS. The hexanes fraction contained mostly monoterpenoids, while the ethanol fraction volatiles were primarily sesquiterpenoids. Crude fractions were tested for activity against fungi, algae, and termites. Application of as little as 1 g of the essential oil from the hexanes fraction was sufficient to provide visible antifungal activity in bioautography assays. The diethyl ether fraction showed selective activity against the cyanobacterium responsible for the 2-methylisoborneol-induced off-flavor sometimes associated with catfish farming operations. All three fractions exhibited a high degree of antitermite activity.     

A Simulation Model for Heat Pump Dryer Plants for Fruits and Roots.

Dryer design requires food properties, drying rate and mass-heat transfer coefficients. These values change continuously during drying due to changes in food fractions, particularly the water fraction. The high energy demand and costs allied to inefficient devices, creates a great need for new processing equipment. Along these guide-lines, several heat pump drying research projects were established at the Norwegian University of Science and Technology. The heat pump dryer provides high quality final product as its drying conditions can be controlled. Its efficiency and non-polluting operation come from closed air-refrigerant circuits and from its ability to fully recover the latent heat of moist air as it exits the drying chamber. Most of the above features are quite the opposite of the conventional dryer characteristics. Several experiments were made on heat pump drying of fruits and roots at temperatures from -22.5 to 40°C to obtain data and correlations on thermophysical properties, specific enthalpy and rehydration. Also, tests were done on drying rate, moisture content, drying constant, effective mass diffusivity and heat and mass transfer equations. The next important phase is the development of a simulation model to predict the performance and characteristics of the heat pump dryer plant. The objectives of the present work are to develop and lo test a heat pump dryer simulation model. The simulation provides results on the characteristics of both plant and components which are integrated by heat and mass transfer equations. The program has menus with click-on icons, input and output pop-up dialogue boxes. The usual commands such as, file-open, file-save, edit-delete are available in this program simply called Hpdryer. The model contains moist air psychrometric. natural and conventional refrigerant property libraries. Ammonia is a time-tested, self-alarming and natural refrigerant. It has been used extensively in the past, and it has better thermodynamic and transport properties than halocarbons. Safety is easily attained by design and its restrictive standards have helped increase its use in several countries. There are 36 ammonia installations in Norway and in the United Kingdom, including a drying plant. Ammonia has zero Odp, zero Gwp and the recent R&D has led to viable small-sale heat pump plants. Ammonia and dichlarodifluoromethane refrigerants were used in the test cases simulated by Hpdryer madel.     

Recognition of aphid parasitoids by honeydew-collecting ants: The role of cuticular lipids in a chemical mimicry system

The aphidiid waspLysiphlebus cardui parasitizes in ant-attendedAphis fabae cirsiiacanthoidis colonies without causing aggressive behavior in the antLasius niger. By contrast,Trioxys angelicae, another aphidiid parasitoid of aphids, is rapidly recognized and vigorously attacked by the ants.L. niger workers also responded differently to dead individuals ofL. cardui andT. angelicae. DeadL. cardui parasitoids were often ignored when encountered byL. niger, whereas deadT. angelicae individuals were immediately grasped by ants that discovered them. However, hexane-washed parasitoids caused a similar reaction pattern in the ants, in that both aphidiid species were tolerated in the aphid colony. Lure experiments demonstrated that chemical stimuli on the cuticle are major cues for the ants to distinguish between the parasitoids. The hexane extract ofL. cardui transferred to washed individuals ofT. angelicae resulted in ant responses characteristic towardsL. cardui, andL. niger workers displayed the typical removal pattern they normally showed towardsT. angelicae whenT. angelicae extract was applied toL. cardui individuals. Both parasitoid species treated with the hexane extract ofA. fabae cirsiiacanthoidis were similarily treated by the ants as were aphid control individuals. The suggestion that the aphidiid waspL. cardui uses chemical mimicry is discussed.     

ON ESTIMATING THRESHOLDS IN AUTOREGRESSIVE MODELS

Abstract. The problem of estimating the threshold parameter, i.e., the change point, of a threshold autoregressive model is studied. By introducing smoothness into the model, sampling properties of the conditional least-squares estimate may be obtained. Artificial and real data are used for illustrations.     

Identification and Distribution of Oviposition Stimulants for Monarch Butterflies in Hosts and Nonhosts

Flavonol glycosides that act as oviposition stimulants for monarch butterflies were surveyed from a range of asclepiad hosts and some nonhosts. Major stimulants also were identified as quercetin-3-O-(2-O--xylosyl)--D-galactoside and quercetin-3-O--D-galactoside from Asclepias syriaca and A. incarnata, respectively. The flavonol glycosides in A. curassavica, A. tuberosa, A. incarnata, A. syriaca, A. humistrata, A. albicans, A. eriocarpa, Calotropis procera, Cynanchum acutum, Vincetoxicum (Cynanchum) nigrum and in nonhosts Hoya australis and Nerium oleander were compared and characterized by HPLC and spectral studies. There was great variation in quercetin glycoside content. On the basis of the sugar moieties attached to quercetin, the asclepiad glycosides were classified broadly as those containing: (1) galactose, glucose, and rhamnose; (2) galactose, glucose, and xylose; and (3) galactose, glucose, xylose, and rhamnose. In most cases, galactose was attached to the 3-O-position (1) of quercetin and other sugars were attached either to the 2 or 6 position of galactose. The sugars of triglycosides were attached at both 2 and 6 positions. A geographical pattern of flavonol distribution that may have affected the evolution of host recognition by the butterflies is suggested.     

Attraction of Dibrachys cavus (Hymenoptera: Pteromalidae) to its Host Frass Volatiles

The European grapevine moth, Lobesia botrana (Lepidoptera: Tortricidae), is a polyphagous insect able to develop on grapes and wild plants. We tested the hypothesis that the parasitoid Dibrachys cavus (Hymenoptera: Pteromalidae) uses the larval frass in its host search. A two-armed olfactometer was used to measure the attractiveness of L. botrana larvae, their silk, or their frass after larvae were fed on different host plants. Frass of three Lepidoptera (L. botrana, Eupoecillia ambiguella, Sphinx ligustri) and one Orthoptera (Chorthippus brunneus) was assayed, but only L. botrana was used to test an effect of the larval host plant (two grape cultivars and three other plant species) to D. cavus females. Larvae without frass did not attract D. cavus whatever their origin, but their frass was attractive at a dose of 2–3 days equivalent of larval frass production. The silk produced by a single larva (L. botrana) was not attractive to D. cavus. The parasitoid was most attracted to the odor of S. ligustri; the frass of L. botrana was more attractive than that of E. ambiguella, irrespective of the species on which D. cavus had been reared. There was no difference in attractiveness of frass collected from L. botrana raised on food containing different plants. Chemical extracts using five different polarity solvents (acetone, dichloromethane, hexane, methanol, and water) differed in attractiveness to D. cavus. Water and dichloromethane were the most attractive. This suggests that a complex volatile signal made from intermediate to polar volatiles may be involved in attraction. D. cavus used frass to discriminate between different potential host species. Our results revealed that the larval food of L. botrana did not modify frass attractiveness, but that the moth species did.     

Interspecific activity of semiochemicals among sibling species ofPissodes (Coleoptera: Curculionidae)

Pissodes strobi, P. approximatus, andP. nemorensis are sibling species of pine weevils that can hybridize in the laboratory but are presumed to be reproductively isolated in nature. Males of all three species produce the terpenoids grandisol and grandisal; these compounds serve as an aggregation pheromone forP. approximatus andP. nemorensis when deployed with odors from pine bolts. A series of field experiments examined the possibility of cross-attraction among the three species. Tests in New York and Florida found that parapatrically distributedP. approximatus andP. nemorensis were cross-attractive, but different photoperiodic conditioning was required for pheromone production in males of the two species. Long-day pheromone production (P. approximatus-type.) was inherited in interspecific hybrids. Other tests showed thatP. strobi males, or hybrid males from crosses ofP. strobi withP. approximatus, were not attractive to sympatricP. approximatus. When the response ofP. strobi was assessed to males of eitherP. strobi orP. approximatus confined on white pine leaders (the breeding site ofP. strobi), no evidence of cross-attraction or pheromone activity was found;P. strobi were caught in equal numbers onP. strobi-baited leaders,P. approximatus-baited leaders, and unbaited leaders. Tests of interspecific interactions found that maleP. strobi produce an allelochemical signal that interrupts the response ofP. approximatus to its natural or synthetic aggregation pheromone. This interspecific response is apparently adaptive for members of both species (classified as an allomone-kairomone or synomone) because it may ultimately serve to prevent interspecific matings that would lower the fitness of the parents.