[2, 7, 12, 18-四甲基-3, 8-二(-1-羟基乙基)-13, 17-二羧基乙基]-卟啉的改进合成

在酸性条件下,氯化血红素(Ⅰ)与还原性铁粉作用生成原卟啉(Ⅱ),通过HBr-冰醋酸加成不经提纯直接加入NaOH溶液,OH-取代仲位Br制得[2,7,12,18-四甲基-3,8-二(1-羟基乙基)-13,17-二羧基乙基]-卟啉(血卟啉,Ⅲ),反应总产率达到90.6%。探讨了脱铁过程中反应温度、时间、还原剂用量等因素对原卟啉(Ⅱ)合成的影响,反应时间和pH对血卟啉(Ⅲ)合成的影响。结果表明,当氯化血红素和铁粉的摩尔比为1∶1、反应温度为110℃时,原卟啉的产率最高达98.3%;当pH=10,反应时间为6 h时,血卟啉的产率最高达92.1%。通过IR、MS和1HNMR对产物结构进行了表征。     

次氯化血红素的合成

以氯化血红素为原料,用间苯二酚还原合成了次氯化血红素。讨论了反应温度、反应时间、间苯二酚用量对次氯化血红素产率的影响,并进行了正交优化实验。在反应时间45min、反应温度165℃、m(氯化血红素)∶m(间苯二酚)=1∶5的最佳反应条件下,次氯化血红素产率可达97.8%,与最近的报道相比产率提高了约55%。传统方法需在高温下加入乙醚,既不方便,又很危险,该文以研磨水洗法取代乙醚溶解法实现了这一反应,安全、经济、简便。产物进行了精制和表征。     

超声波激励法改进合成[2,7,12,18-四甲基-3,8-二(-1-羟基乙基)-13,17-二甲氧基羰基乙基]-卟啉

以氯化血红素(1)为原料,经过加成和取代反应制得血卟啉(2)。然后在超声波激励下,以血卟啉(2)作为原料,浓硫酸作为催化剂,甲醇既作溶剂又作反应剂,合成了[2,7,12,18-四甲基-3,8-(-1-羟基乙基)-13,17-二甲氧基羰基乙基]-卟啉(血卟啉二甲酯,3),两步反应总产率达到74.8%。探讨了反应时间、催化剂用量以及超声功率对血卟啉二甲酯(3)合成的影响,并且将超声波激励法与加热搅拌法进行了比较。实验结果表明,同加热搅拌法相比,超声激励法反应时间更短,产率更高,副产物更少。产物结构通过1 H NMR、MS和IR测试技术进行了表征。     

低共熔法萃取分离油酚混合物过程中油的夹带

采用季铵盐与酚形成低共熔溶剂(DES)从含酚的混合物中萃取分离酚是一种有效的油酚分离方法, 然而分离过程中, 中性油的夹带会影响分离效率。以含苯酚200 g·L^-1的甲苯溶液作为模拟油酚混合物, 氯化胆碱(ChCl)作为分离剂, 研究了氯化胆碱的加入量、萃取温度(25～55℃)及模拟油中直链烷烃的浓度等因素对酚的萃取分离及中性油夹带的影响。结果表明, 随着ChCl加入量增大, 酚萃取率升高, 中性油的夹带量减少;ChCl过量时, 酚的萃取量恒定且达到极大值, 中性油夹带量恒定且夹带量最小;萃取温度对酚的萃取率影响不大, 对中性油的夹带量在ChCl加入量不足时随温度升高而增多, 当ChCl加入量足量时与温度变化关系不大;模拟油中直链烷烃的浓度不影响萃取效率, 浓度越高, 甲苯夹带越少。以ChCl萃取含苯酚200 g·L^-1的甲苯溶液, 在萃取温度25℃、ChCl加入量大于0.6(与酚的摩尔比)的条件下, 苯酚萃取率达95%, 甲苯夹带率为15%, 70℃条件下氮气吹扫60 min内可将DES中甲苯完全去除。     

0.3%氯化血红素可湿性粉剂对马铃薯生长及安全性评价

分析了0.3%氯化血红素可湿性粉剂对马铃薯生长的影响及其安全性。结果表明,0.3%氯化血红素可湿性粉剂可以调控马铃薯的生长,随着用量的增加,不仅可以促进植株大薯数和产量增加,其中大薯数增长率为7.2%～15.7%,产量增长率为3.6%～8.8%,还能增强马铃薯的抗病性和叶绿素含量,其中防病率为4.9%～41.0%,叶绿素增长率为19.4%～27.3%。综合分析表明,0.3%氯化血红素可湿性粉剂在马铃薯田间种植中具有较好的应用前景,从用药的经济性和安全性考虑,推荐0.3%氯化血红素可湿性粉剂有效成分用量为0.9～1.35 g/hm²。     

[2,7,12,18-四甲基-3,8-二乙基-13,17-二羧基乙基]-卟啉的简易合成

以氯化血红素(Ⅰ)为原料,在甲酸-铁粉体系下,通过调节铁粉与氯化血红素的摩尔比,一步合成(2,7,12,18-四甲基-3,8-二乙基-13,17-二羧基乙基)-卟啉(双乙基次卟啉,Ⅱ)。探讨了反应过程中铁粉用量、温度、时间对目标产物(Ⅱ)合成的影响。结果表明,当铁粉和氯化血红素的摩尔比为15∶1、反应温度为120℃、反应时间为2 h时,目标产物(Ⅱ)产率达到97.6%。通过1HNMR、MS、UV-vis和IR测试技术对产物结构进行了表征。     

次卟啉(Ⅸ)二甲酯的制备

以氯化血红素为原料,用间苯二酚还原生成次氯化血红素,再经甲醇酯化及干燥HCl气体脱除铁离子,生成次卟啉(Ⅸ)二甲酯.讨论了氯化血红素与间苯二酚配比对反应收率的影响.最终产物进行了精制和表征.     

[EMIM]Br-FeCl2离子液体萃取脱除含硫化合物

考察了1-乙基-3-甲基咪唑溴络合氯化亚铁([EMIM]Br-FeCl2)离子液体对含有噻吩(TS)、苯并噻吩(BT)和二苯并噻吩(DBT)模拟油及FCC汽油的萃取脱硫效果。实验结果表明:在40℃条件下萃取4 h,当剂油质量比为2∶1时,噻吩的脱除率为25.6%;当剂油质量比为2∶5时,苯并噻吩的脱除率达到72.4%,二苯并噻吩的脱除率达到79.9%。按剂油质量比2∶1应用于实际汽油,单级萃取脱硫率为50.3%～54.5%,5级萃取脱硫率为89.3%～91.3%。对使用过的离子液体进行再生处理,再生后离子液体可以使用10次以上。     

磷酸三丁酯和二异丙醚溶剂萃取 体系净化湿法磷酸的研究

以磷酸三丁酯（TBP）与二异丙醚为溶剂,采用溶剂萃取法净化湿法磷酸。研究了萃取剂中TBP体积分数、相比、萃取时间、搅拌转速、反萃取剂加入量对湿法磷酸净化效果的影响,确定了TBP与二异丙醚混合溶剂体系净化湿法磷酸的工艺条件。适宜工艺条件：萃取剂组成为TBP与二异丙醚体积比为1∶1,有机相与水相的体积比为 4∶1,萃取时间为25 min,搅拌转速为300 r/min,反萃取剂加入量为萃取相体积的20%。在此条件下,TBP与二异丙醚萃取体系对金属阳离子和氟离子有较好的分离能力。     

氯化血红素提取新工艺的研究

探讨了从新鲜猪血中提取氯化血红素的新工艺,利用红外光谱对产品进行了定性检验。以上海丽珠东风生物技术有限公司生产的氯化血红素为对照品,利用紫外光谱进行了定量测定,质量分数为对照品的1．03－1．07倍。此工艺简单易行,成本低,经济效益好。     

Insect antifeedant properties of anthranoids from the genusVismia

Vismiones and ferruginins, representatives of a new class of lypophilic anthranoids from the genusVismia were found to inhibit feeding in larvae of species ofSpodoptera, Heliothis, and inLocusta migratoria.     

Methyl 2,4,6-decatrienoates Attract Stink Bugs and Tachinid Parasitoids

Halyomorpha halys (Stål) (Pentatomidae), called the brown marmorated stink bug (BMSB), is a newly invasive species in the eastern USA that is rapidly spreading from the original point of establishment in Allentown, PA. In its native range, the BMSB is reportedly attracted to methyl (E,E,Z)-2,4,6-decatrienoate, the male-produced pheromone of another pentatomid common in eastern Asia, Plautia stali Scott. In North America, Thyanta spp. are the only pentatomids known to produce methyl 2,4,6-decatrienoate [the (E,Z,Z)-isomer] as part of their pheromones. Methyl 2,4,6-decatrienoates were field-tested in Maryland to monitor the spread of the BMSB and to explore the possibility that Thyanta spp. are an alternate host for parasitic tachinid flies that use stink bug pheromones as host-finding kairomones. Here we report the first captures of adult and nymph BMSBs in traps baited with methyl (E,E,Z)-2,4,6-decatrienoate in central Maryland and present data verifying that the tachinid, Euclytia flava (Townsend), exploits methyl (E,Z,Z)-2,4,6-decatrienoate as a kairomone. We also report the unexpected finding that various isomers of methyl 2,4,6-decatrienoate attract Acrosternum hilare (Say), although this bug apparently does not produce methyl decatrienoates. Other stink bugs and tachinids native to North America were also attracted to methyl 2,4,6-decatrienoates. These data indicate there are Heteroptera in North America in addition to Thyanta spp. that probably use methyl 2,4,6-decatrienoates as pheromones. The evidence that some pentatomids exploit the pheromones of other true bugs as kairomones to find food or to congregate as a passive defense against tachinid parasitism is discussed.     

2005～2006年国外塑料工业进展

收集了2005年7月～2006年6月国外塑料工业的相关资料，介绍了2005—2006年国外塑料工业的发展情况。提供了世界塑料产量、消费量及全球各类树脂生产量以及各国塑料制品的进出口情况。作为对比，介绍了中国塑料的生产情况。按通用热塑性树脂（聚乙烯、聚丙烯、聚苯乙烯、聚氯乙烯、ABS树脂）、工程塑料（聚酰胺、聚碳酸酯、聚甲醛、热塑性聚酯、聚苯醚）、通用热固性树脂（酚醛、聚氨酯、不饱和树脂、环氧树脂）、特种工程塑料（聚苯硫醚、液晶聚合物、聚醚醚酮）的品种顺序，对树脂的产量、消费量、供需状况及合成工艺、产品开发、树脂品种的延伸及应用的扩展作了详细的介绍。     

2007～2008年世界塑料工业进展

收集了2007年7月～2008年6月世界塑料工业的相关资料,介绍了2007～2008年国外塑料工业的发展情况,提供了世界塑料产量、消费量及全球各类树脂的需求量及产能情况.按通用热塑性树脂(聚乙烯、聚丙烯、聚苯乙烯、聚氯乙烯、ABS树脂)、工程塑料(尼龙、聚碳酸酯、聚甲醛、热塑性聚酯、聚苯醚)、特种工程塑料(聚苯·硫醚、液晶聚合物、聚醚醚酮)、通用热固性树脂(酚醛、聚氨酯、不饱和聚酯树脂、环氧树脂)不同品种的顺序,对树脂的产量、消费量、供需状况及合成工艺、产品应用开发、树脂品种的延伸及应用的进一步扩展等技术作了详细介绍.     

Inorganic/organic nanocomposite coatings: The next step in coating performance

Inorganic/organic hybrid materials have considerable promise and are beginning to become a major area of research for many coating usages, including abrasion and corrosion resistance. Our primary approach is to prepare the inorganic phase in situ within the film formation process of the organic phase. The inorganic phase is introduced via sol-gel chemistry into a thermosetting organic phase. By this method, the size, periodicity, spatial positioning, and density of the inorganic phase can be controlled. An important aspect of the inorganic/organic hybrid materials is the coupling agent. The initial task of the coupling agent is to provide uniform mixing of the oligomeric organic phase with the sol-gel precursors, which are otherwise immiscible. UV-curable inorganic/organic hybrid systems have the advantages of a rapid cure and the ability to be used on heat sensitive substrates such as molded plastics. Also, it is possible to have better control of the growth of the inorganic phase using UV curing. It is our ultimate goal to completely separate the curing of inorganic and organic phases to gain complete control over the morphology, and hence optimization of “all” the coating properties. Thus far, it has been found that concomitant UV curing of the inorganic and organic phases using titanium sol-gel precursors afforded nanocomposite coatings which completely block the substrate from UV light while maintaining a transparent to visible light. Also, it has been found that the morphology of the inorganic phase is highly dependent on the concentration and reactivity of the coupling agent. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004, in Chicago, IL.     

Ethanol and (−)-α-Pinene: Attractant Kairomones for Some Large Wood-Boring Beetles in Southeastern USA

Ethanol and α-pinene were tested as attractants for large wood-boring pine beetles in Alabama, Florida, Georgia, North Carolina, and South Carolina in 2002–2004. Multiple-funnel traps baited with (−)-α-pinene (released at about 2 g/d at 25–28°C) were attractive to the following Cerambycidae: Acanthocinus nodosus, A. obsoletus, Arhopalus rusticus nubilus, Asemum striatum, Monochamus titillator, Prionus pocularis, Xylotrechus integer, and X. sagittatus sagittatus. Buprestis lineata (Buprestidae), Alaus myops (Elateridae), and Hylobius pales and Pachylobius picivorus (Curculionidae) were also attracted to traps baited with (−)-α-pinene. In many locations, ethanol synergized attraction of the cerambycids Acanthocinus nodosus, A. obsoletus, Arhopalus r. nubilus, Monochamus titillator, and Xylotrechus s. sagittatus (but not Asemum striatum, Prionus pocularis, or Xylotrechus integer) to traps baited with (−)-α-pinene. Similarly, attraction of Alaus myops, Hylobius pales, and Pachylobius picivorus (but not Buprestis lineata) to traps baited with (−)-α-pinene was synergized by ethanol. These results provide support for the use of traps baited with ethanol and (−)-α-pinene to detect and monitor common large wood-boring beetles from the southeastern region of the USA at ports-of-entry in other countries, as well as forested areas in the USA.