腰果酚缩水甘油醚的工艺技术研究

以腰果酚和环氧氯丙烷为主要原料,在催化剂苄基三乙基氯化铵的催化下合成了腰果酚缩水甘油醚。考察了反应条件对环氧值的影响,通过正交试验和单因素试验确定了合成腰果酚缩水甘油醚的适宜工艺条件为:n(腰果酚)∶n(环氧氯丙烷)∶n(氢氧化钠)=1∶5∶1.2,醚化温度为80℃,醚化时间为4 h,闭环温度为60℃,闭环时间为3 h,催化剂为腰果酚质量的2%,腰果酚缩水甘油醚的环氧值高达到0.279并且收率达到85.6%。     

离子液体中苯基缩水甘油醚的合成

合成了，M-正丁基吡啶氟硼酸盐（[BPy]BF4）离子液体，并将（BPy）BF4作为溶剂和催化剂用于苯基缩水甘油醚的合成反应。研究了反应条件对苯基缩水甘油醚产率的影响，探讨了苯基缩水甘油醚的合成反应机理。结果表明，在反应温度为70℃，反应时间为2h，反应物苯酚钠与环氧氯丙烷的物质的量比为1．15：1，离子液体与反应物的质量比为2：1时，苯基缩水甘油醚的产率为96．8％。重复使用结果表明，离子液体具有良好的重复使用性能。     

活性阻燃环氧稀释剂的合成

本文介绍了下列产品的合成过程:(一)甲酚经溴化后与环氧氯丙烷缩合再用氢氧化钠闭环制得二溴代甲苯基缩水甘油醚。(二)二溴代新戊二醇先与环氧氯丙烷缩合再用氢氧化钠闭环制得二溴代新成二醇基二缩水甘油醚。文中还介绍了它们的应用配方。     

聚乙二醇/环氧氯丙烷多羟基聚醚的合成及表征

以聚乙二醇(PEG–600)和环氧氯丙烷(ECH)为原料,四正丁基氯化铵(TBAC)和氢氧化钠为催化剂,制得聚乙二醇缩水甘油醚;再通过聚乙二醇缩水甘油醚的开环反应制得多羟基聚醚。通过正交试验研究了聚乙二醇缩水甘油醚制备过程中反应时间、原料配比、催化剂用量对环氧值的影响。采用红外光谱、环氧值及羟值对产物进行了表征。结果表明:当n(聚乙二醇)︰n(环氧氯丙烷)︰n(氢氧化钠)︰n(催化剂)=1︰2.5︰3︰0.03,反应时间为1.5 h,反应温度为55℃时,产物有较理想的环氧值。     

正癸基缩水甘油醚的合成与工艺优化

研究了相转移催化剂存在下，癸醇与环氧氯丙烷为原料合成癸基缩水甘油醚的工艺条件下，考察了n(癸醇）：n(环氧氯丙烷）、反应温度和反应时间等因素对反应影响，通过正交实验优化了合成工艺条件。实验表明：苄基三乙基氯化铵为相转移催化剂；n(癸醇）：n(环氧氯丙烷）为1：1．15，反应温度为70℃，反应时间为3．5h，癸基缩水甘油醚收率90％以上。     

相转移催化法合成烯丙基缩水甘油醚

以烯丙醇和环氧氯丙烷为原料，采用相转移催化法，合成了烯丙基缩水甘油醚。研究了反应时间、反应温度、投料比及固体碱的用量对反应收率的影响。在n(烯丙醇)∶n(环氧氯丙烷)∶n(固体碱)∶n(催化剂)=1∶1.5∶1.5∶0.005、反应时间1 h、反应温度50～60 ℃时，烯丙醇缩水甘油醚收率可达88%。     

聚乙二醇二缩水甘油醚的制备及表征

以聚乙二醇2000(PEG 2000)、环氧氯丙烷(ECH)和氢氧化钠为原料,四正丁基溴化铵(TBAB)为催化剂,制得聚乙二醇二缩水甘油醚。通过试验研究了聚乙二醇二缩水甘油醚制备过程中反应时间、反应温度、原料配比对转化率的影响。采用红外光谱、环氧指数及液相色谱对产物进行了表征。结果表明:当n(聚乙二醇)︰n(环氧氯丙烷)︰n(氢氧化钠)︰n(催化剂)=1︰5︰2.5︰0.18,反应时间为18 h,反应温度为40℃时,产物有较理想的转化率和环氧指数。     

超声波辐射相转移催化合成十二烷基缩水甘油醚

超声波辐射下三乙基苄基氯化铵相转移催化由十二醇与环氧氯丙烷合成十二烷基缩水甘油醚,产品用FT-IR进行结构表征。考察了催化剂的种类、反应物的摩尔比及其与催化剂和NaOH的摩尔比、超声波辐射功率和辐射时间等因素对产品收率的影响。结果表明,超声波辐射下,三乙基苄基氯化铵具有良好的催化活性,较佳反应条件为:十二醇0.15 mol,n(十二醇):n(环氧氯丙烷):n(三乙基苄基氯化铵):n(NaOH)=1:1.15:0.05:1.05,甲苯15 mL,超声波辐射功率100 W下辐射45 min,此时产品的收率达到93%以上。     

(2-羟基-3-烯丙氧基)丙基肌氨酸钠的合成研究

以肌氨酸和烯丙基缩水甘油醚为主要原料制备标题化合物(AGE-JAC)。通过单因素实验,考察了原料物质的量比、反应温度和反应时间对反应收率的影响,最终确定合成标题化合物的最佳条件为:n(肌氨酸):n(烯丙基缩水甘油醚):n(氢氧化钠)=1. 00:1. 05:1. 00,反应温度为60℃,反应时间为4h,产品收率可达99. 56%,所得化合物结构经过FT-IR和1H-NMR确认。方法具有合成工艺简单、条件温和、产率高,适合工业化生产。     

月桂基缩水甘油醚合成工艺的研究

以月桂醇和二氯丙醇为原料,在相转移催化剂四丁基硫酸氢铵(TBAHS)存在下合成了月桂基缩水甘油醚,通过测定产品环氧值的方法来计算产品的收率。采用单因素实验和正交试验相结合,考察了原料摩尔比、碱加入量、反应时间和反应温度等对月桂基缩水甘油醚收率的影响,并用1HNMR和IR等对产物结构进行了表征。正交试验极差和方差分析表明,因素影响大小依次为:原料摩尔比碱加入量反应时间反应温度,在优化工艺条件n(二氯丙醇)∶n(月桂醇)=1.2∶1,n(氢氧化钠)∶n(月桂醇)=2.2∶1,50℃下反应4 h,月桂基缩水甘油醚的收率可达81.3%。     

Many Drugs of Abuse May Be Acutely Transformed to Dopamine,Norepinephrine and Epinephrine In Vivo

It is well established that a wide range of drugs of abuse acutely boost the signaling of the sympathetic nervous system and the hypothalamic–pituitary–adrenal (HPA) axis, where norepinephrine and epinephrine are major output molecules. This stimulatory effect is accompanied by such symptoms as elevated heart rate and blood pressure, more rapid breathing, increased body temperature and sweating, and pupillary dilation, as well as the intoxicating or euphoric subjective properties of the drug. While many drugs of abuse are thought to achieve their intoxicating effects by modulating the monoaminergic neurotransmitter systems (i.e., serotonin, norepinephrine, dopamine) by binding to these receptors or otherwise affecting their synaptic signaling, this paper puts forth the hypothesis that many of these drugs are actually acutely converted to catecholamines (dopamine, norepinephrine, epinephrine) in vivo, in addition to transformation to their known metabolites. In this manner, a range of stimulants, opioids, and psychedelics (as well as alcohol) may partially achieve their intoxicating properties, as well as side effects, due to this putative transformation to catecholamines. If this hypothesis is correct, it would alter our understanding of the basic biosynthetic pathways for generating these important signaling molecules, while also modifying our view of the neural substrates underlying substance abuse and dependence, including psychological stress-induced relapse. Importantly, there is a direct way to test the overarching hypothesis: administer (either centrally or peripherally) stable isotope versions of these drugs to model organisms such as rodents (or even to humans) and then use liquid chromatography-mass spectrometry to determine if the labeled drug is converted to labeled catecholamines in brain, blood plasma, or urine samples.     

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.     

Direct observation of freeze-thaw instability of latex coatings via high pressure freezing and cryogenic SEM

Despite its industrial importance, the subject of freeze-thaw (F/T) stability of latex coatings has not been studied extensively. There is also a lack of fundamental understanding about the process and the mechanisms through which a coating becomes destabilized. High pressure (2100 bar) freezing fixes the state of water-suspended particles of polymer binder and inorganic pigments without the growth of ice crystals during freezing that produce artifacts in direct imaging scanning electron microscopy (SEM) of fracture surfaces of frozen coatings. We show that by incorporating copolymerizable functional monomers, it is possible to achieve F/T stability in polymer latexes and in low-VOC paints, as judged by the microstructures revealed by the cryogenic SEM technique. Particle coalescence as well as pigment segregation in F/T unstable systems are visualized. In order to achieve F/T stability in paints, latex particles must not flocculate and should provide protection to inorganic pigment and extender particles. Because of the unique capabilities of the cryogenic SEM, we are able to separate the effects of freezing and thawing, and study the influence of the rate of freezing and thawing on F/T stability. Destabilization can be caused by either freezing or thawing. A slow freezing process is more detrimental to F/T stability than a fast freezing process; the latter actually preserves suspension stability during freezing. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004 in Chicago, IL. Tied for first place in The John A. Gordon Best Paper Competition.     

Ethanol and (−)-α-Pinene: Attractant Kairomones for Bark and Ambrosia Beetles in the Southeastern US

In 2002–2004, we examined the flight responses of 49 species of native and exotic bark and ambrosia beetles (Coleoptera: Scolytidae and Platypodidae) to traps baited with ethanol and/or (−)-α-pinene in the southeastern US. Eight field trials were conducted in mature pine stands in Alabama, Florida, Georgia, North Carolina, and South Carolina. Funnel traps baited with ethanol lures (release rate, about 0.6 g/day at 25–28°C) were attractive to ten species of ambrosia beetles (Ambrosiodmus tachygraphus, Anisandrus sayi, Dryoxylon onoharaensum, Monarthrum mali, Xyleborinus saxesenii, Xyleborus affinis, Xyleborus ferrugineus, Xylosandrus compactus, Xylosandrus crassiusculus, and Xylosandrus germanus) and two species of bark beetles (Cryptocarenus heveae and Hypothenemus sp.). Traps baited with (−)-α-pinene lures (release rate, 2–6 g/day at 25–28°C) were attractive to five bark beetle species (Dendroctonus terebrans, Hylastes porculus, Hylastes salebrosus, Hylastes tenuis, and Ips grandicollis) and one platypodid ambrosia beetle species (Myoplatypus flavicornis). Ethanol enhanced responses of some species (Xyleborus pubescens, H. porculus, H. salebrosus, H. tenuis, and Pityophthorus cariniceps) to traps baited with (−)-α-pinene in some locations. (−)-α-Pinene interrupted the response of some ambrosia beetle species to traps baited with ethanol, but only the response of D. onoharaensum was interrupted consistently at most locations. Of 23 species of ambrosia beetles captured in our field trials, nine were exotic and accounted for 70–97% of total catches of ambrosia beetles. Our results provide support for the continued use of separate traps baited with ethanol alone and ethanol with (−)-α-pinene to detect and monitor common bark and ambrosia beetles from the southeastern region of the US.     

ICP-MS法测定地球化学样品中As、Cr、Ge、V等18种微量痕量元素的研究

建立了测定地球化学样品中包括As、Cr、Ge、V等18种微量、痕量元素的ICP-MS方法。地化试样用HF-HNO3混酸分解后,以1 1 HNO3溶解干渣。由于制样不使用盐酸,避免了Cl对As、Cr、Ge、V的质谱干扰。用国家一级地球化学标准物质GBW 07309制备溶液优化仪器工作参数,并用于校准。方法测定限(6s)为:0.007~6.4μg/g,精密度(RSD%,n=12)为:29%~9.4%,经过国家一级地球化学标准物质的分析验证,结果与标准值吻合。方法已应用于国土资源调查的试样分析。