松香-壳聚糖基梳型离子型高分子表面活性剂的制备及性能研究(摘要)

<正>以脱氢枞胺为原料首次合成了3-氯-2-羟丙基脱氢枞基氯化铵(CHPDMDHA)和烯丙基二甲基脱氢枞基氯化铵(ADMDHA),并创新提出以CHPDMDHA和ADMDHA作为活性季铵盐对壳低聚糖(LWCTSs)、N-羧甲基壳聚糖(N-CMC)、N,O-羧甲基壳聚糖(N,O-CMC)、N-羧乙基壳聚糖(N-CEC)和N,O-羧乙基壳聚糖(N,O-CEC)进行改性,分别得到了CHPDMDHA接枝壳低聚糖(CHPDMDHA-g-LWCTSs)、CHPDMDHA接枝羧烷基壳聚糖(CHPDMDHA-g-CACTSs)、ADMDHA接枝壳低聚糖(ADMDHA-g-LWCTSs)和ADMDHA接枝羧烷基壳聚糖(ADMDHA-g-CACTSs)等4个系列松香改性壳聚糖类梳型高分子表面活性剂。采用FT-IR、NMR、元素分析等手段表征了产物结构,并研究了所合成化合物的     

脱氢枞胺及其衍生物的应用研究进展

脱氢枞胺是歧化松香胺的主要成分,具有三环菲骨架结构,是松香重要的改性产品之一。本文综述了脱氢枞胺及其衍生物的应用研究进展,包括脱氢枞胺在手性化合物分离方面的应用和脱氢枞胺衍生物在抑菌、防腐、缓蚀、金属离子浮选、催化、抗癌、抗氧化、抗溃疡、可与雄性激素结合等方面的应用。指出目前脱氢枞胺成盐衍生物及脱氢枞胺N-C衍生物的研究较为广泛,脱氢枞胺B环和C环改性衍生物的研究仍需加强,而且对于B环和C环改性衍生物的深入研究,将进一步促进脱氢枞胺衍生物在生物活性方面的应用。最后对脱氢枞胺衍生物在生物医学工程上的应用前景进行了展望。     

-苯乙酯的合成

通过一种简单易操作的方法合成了脱氢枞酸月桂酯和脱氢枞酸β-苯乙酯,脱氢枞酸首先在甲苯中与SOCl₂反应制得脱氢枞酸酰氯,脱氢枞酸酰氯在室温下与月桂醇和β-苯乙醇反应制得脱氢枞酸月桂酯和脱氢枞酸β-苯乙酯。     

超声波作用下脱氢枞酰甘氨酸表面活性剂的合成与表面活性

以脱氢枞酸与氯化亚砜制得脱氢枞酸酰氯,脱氢枞酸酰氯和甘氨酸在超声波作用下生成脱氢枞酰甘氨酸,超声波的固定功率为120 W,讨论了反应温度、时间及反应物的用量比对反应的影响。结果表明,最佳的反应条件为:脱氢枞酸酰氯和甘氨酸物质的量之比为1∶1(摩尔比),反应温度20~25℃,反应时间70 m in,产率可达73.81%。并且对脱氢枞酰甘氨酸钠和脱氢枞酰甘氨酸钾的表面活性进行了测试。     

脱氢枞基缩水甘油醚的合成及其条件优化

以歧化松香中分离出的脱氢枞酸为原料,经甲酯化和金属钠还原得到脱氢枞醇后,再在BF3-乙醚催化下与环氧氯丙烷加成生成3-氯-2-羟丙基脱氢枞基醚,最后在NaOH存在下环化得脱氢枞基缩水甘油醚(DAGE);用FT IR和GC-MS表征了产物的结构,环氧值分析法测定了产物中DAGE含量,正交实验方法优化了DAGE的合成条件。结果表明,以BF3-乙醚为催化剂催化合成DAGE时,其适宜条件为:加成反应的温度和时间分别为65℃和6.0h,环氧氯丙烷对脱氢枞醇的摩尔比为2.5,BF3-乙醚用量为脱氢枞醇质量的5.0%;在此条件下,DAGE的产率为71.67%。     

超声波协同反应-结晶耦合单离脱氢枞酸

以歧化松香和2-乙醇胺为原料、乙醇为溶剂、超声波协同反应-结晶制备脱氢枞酸乙醇胺盐,经萃取、结晶、重结晶、酸化制得脱氢枞酸。通过正交优化实验,考察了溶剂浓度、反应温度、反应时间、超声波功率、搅拌转速对脱氢枞酸收率的影响,确定最佳单离条件为：反应时间50 min,反应温度35℃,超声波功率500 W,溶剂浓度50%,搅拌转速400 r&#8226;min^-1,在该操作条件下脱氢枞酸的收率达55.37%,纯度达99.53％。并探讨了脱氢枞酸胺化反应-结晶过程相态变化对反应平衡和选择性的影响,当反应温度分别为35℃和70℃时,胺化反应是在非均相和均相下进行,所得脱氢枞酸产品的纯度为99.53%和95.66%。采用GC、GC-MS、元素分析、UV、FT-IR、熔点仪和旋光仪对脱氢枞酸产品进行了分析鉴定,实验值与文献值吻合。     

脱氢枞酸盐透明改性聚丙烯研究

以脱氢枞酸钾和脱氢枞酸钾成核剂对透明聚丙烯（PP）进行改性，研究了脱氢枞酸盐对PP光学性能、力学性能及结晶特性的影响，并与山梨酸类成核剂改性PP的性能进行了比较。实验结果表明，加入脱氢枞酸钾或脱氢枞酸钠后，聚丙烯的雾度大幅度降低，光泽度提高，但透光率变化不大；弯曲模量大幅度提高，而拉伸强度和缺口冲击强度略有下降；球晶尺寸大幅度减小；结晶温度提高，结晶度略有上升。脱氢枞酸盐改性聚丙烯与山梨醇类成核剂改性聚丙烯的性能相当，但脱氢枞酸盐克服了山梨醇类成核剂的缺点，可以作为山梨醇类成核剂的理想替代品。     

手性7-氨基脱氢枞酸乙酯的合成及表征

基于7-氨基脱氢枞酸衍生物在药物开发、手性催化和特殊光学材料等方面的潜在应用,该文以脱氢枞酸为起始原料,通过酯化、氧化、手性辅剂亚胺化、还原以及酸解脱除手性辅剂等反应获得光学纯的7-(S)-氨基脱氢枞酸乙酯Ⅵ和7-(R)-氨基脱氢枞酸乙酯Ⅷ,总产率分别为24.3%和8.7%。产物结构通过1HNMR、13CNMR、MS和HRMS进行表征,绝对构型经X-ray单晶衍射确定。     

脱氢枞酸的单离及其季铵盐表面活性剂合成

采用胺化结晶法单离脱氢枞酸,并以纯化后脱氢枞酸、三乙胺、环氧氯丙烷为原料,常规加热制备脱氢枞基季铵盐表面活性剂N-(3-脱氢枞酸酰氧-2-羟)丙基-N,N,N-三乙基氯化铵。通过单因素实验与正交实验考察了反应温度、n(脱氢枞酸)∶n(三乙胺)∶n(环氧氯丙烷)、反应时间对酯化率的影响,并对产物结构进行FT-IR表征。结果显示,当反应温度=115℃,n(脱氢枞酸)∶n(三乙胺)∶n(环氧氯丙烷)=0.7∶1∶1,反应时间为3h时,酯化率达到97.6%。将产物进行一系列测试,其表面张力为38.02mN/m,临界胶束参数为0.001mol/L,HLB值为8~10,乳化力为48h,泡沫力14cm,泡沫稳定性2cm。     

反应-结晶耦合单离脱氢枞酸过程研究?

以歧化松香和2-乙醇胺为原料,采用超声波强化的方法进行反应-结晶耦合单离脱氢枞酸过程研究.考察了反应时间、反应温度、超声波强度、溶剂浓度、搅拌转速、胺盐结晶溶剂浓度、重结晶次数及结晶方式对脱氢枞酸收率的影响,实验结果表明,超声波可以有效地强化歧化松香胺化反应-结晶过程,适宜的反应时间为40min、反应温度为35℃、超声波功率为300W、溶剂浓度为40%、搅拌转速为300r·min-1、胺盐结晶溶剂浓度为40%、胺盐重结晶次数为2~3次、结晶方式为自然结晶,所制得的脱氢枞酸收率为48.59%,纯度为99.28%.并对脱氢枞酸单离过程的收率、纯度和损失率进行了跟踪分析,其中胺化反应-结晶过程脱氢枞酸产品的损失率最大,其次是溶剂萃取过程,二者损失率分别为36.12%和10.94%.     

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。