嵌段共聚物PS-b-P2VP的合成及表征

采用氮氧稳定自由基聚合技术合成了苯乙烯和2-乙烯吡啶嵌段共聚物(PS-b-P2VP),用凝胶渗透色谱(GPC)表征了聚合物的分子量及其分布,用红外光谱表征了其结构,结果表明,在氮氧稳定自由基(HTEMPO.)存在下,用过氧化苯甲酰(BPO)引发苯乙烯聚合,当[HTEMPO.]/[BPO]配比为1.8/1时为最佳比例,在此比例下所制备聚合物PS的分子量分布在1.17~1.36范围内;再将该聚苯乙烯溶于2-乙烯吡啶,在(130±2)℃时可以继续引发2-乙烯吡啶的聚合反应,且2-乙烯吡啶的聚合反应具有“活性”聚合的特征,共聚物的分子量分布范围在1.16~1.35内,分子量在12 930~19 670 g/mol范围。红外谱图说明共聚物为嵌段共聚物。     

交联PMMA微球表面PS刷子的合成与表征

将含有双键的甲基丙烯酸-2-氨基乙酯化学锚接在交联聚甲基丙烯酸甲酯微球表面,然后用过氧化苯甲酰引发苯乙烯发生氮氧调控自由基原位接枝聚合反应,将聚苯乙烯接枝在交联聚甲基丙烯酸甲酯微球表面,制备了PS刷子层.用凝胶渗透色谱和红外光谱对所合成交联聚苯乙烯接枝聚甲基丙烯酸乙酯共聚物进行了表征,实验结果显示：在2,2,6,6-四甲基哌啶-1-氧自由基存在下,苯乙烯的聚合反应为＂活性＂自由基聚合,所得到的聚苯乙烯分子量分布在1.13～1.28范围,分子量随聚合时间的延长而增大（7 000～68 000 g/mol）.接枝聚合物红外光谱显示聚苯乙烯被接枝到了交联聚甲基丙烯酸甲酯微球表面.AFM 表征显示交联聚甲基丙烯酸甲酯微球尺寸在0.3～1.6 μm 范围.     

H型两亲嵌段共聚物PSt2-PEG-PSt2的合成

设计合成了结构对称的H型两亲嵌段共聚物二(聚苯乙烯)-聚乙二醇-二(聚苯乙烯)(PSt2-PEG-PSt2).聚乙二醇与2,2-二氯乙酰氯通过酯化反应合成的大分子引发剂,引发苯乙烯(St)单体的原子转移自由基聚合反应,得到一系列H-型嵌段共聚物.并表征了产物的分子量及其分布与结构.     

ATRP法合成两亲性三嵌段共聚物

采用原子转移自由基活性聚合(ATRP)的方法,先以苯乙烯(St)为单体,α-溴代异丁酸乙酯(Ei B-Br)为小分子引发剂,Cu Br/PMDETA为催化体系,通过本体聚合制备出大分子引发剂聚苯乙烯(PS-Br)。再以PS-Br为引发剂引发第二单体甲基丙烯酸二甲氨基乙酯(DMAEMA)的本体聚合,得到PS-b-PDMAEMA-Br二嵌段共聚物,接着用PS-b-PDMAEMA-Br分别引发第三单体甲基丙烯酸甲酯(MMA)和甲基丙烯酸叔丁酯(t BMA)的本体聚合,得到三嵌段共聚物PS-b-PDMAEMA-b-Pt BMA,运用GPC、1H-NMR以及FTIR等对三嵌段共聚物进行表征;最后通过酸性水解得到PS-b-PDMAEMA-b-PMAA两亲性嵌段共聚物,并初步探究其表面活性。结果表明所得两亲性三嵌段共聚物具有一定的降低表面张力的能力,但弱于硬脂酸类小分子表面活性剂。     

两亲性苯乙烯嵌段共聚物的合成及结构表征

以α,α'-二甲基-α-乙酸-三硫代碳酸酯(BDATC)为链转移剂,采用可逆-加成-断裂链转移(RAFT)自由基聚合方法合成了末端带有—COOH官能团的两亲性嵌段共聚物聚苯乙烯-b-聚甲基丙烯酸聚乙二醇单甲醚-b-聚苯乙烯(PSt-b-POEOMA-b-PSt),这种含有亲水性端基的嵌段共聚物可以自组装成核-壳结构的纳米微粒,用于载药高分子的模板研究。利用FTIR、1HNMR、GPC对产物结构进行表征,用热失重(TG)和差示扫描量热(DSC)的方法研究了3种不同比例的嵌段共聚物的热性能。实验结果表明,通过RAFT聚合方法得到了所设计的嵌段共聚物,相对分子质量(简称分子量,下同)分布1.35左右;嵌段共聚物的热稳定性较好,通过玻璃化转变温度(Tg)的变化推测出嵌段共聚物中两种嵌段比例对两嵌段相容性的影响。     

H型两亲嵌段共聚物PSt2-PEG-PSt2的合成

设计合成了结构对称的H型两亲嵌段共聚物二(聚苯乙烯)-聚乙二醇-二(聚苯乙烯)(PSt2-PEG-PSt2).聚乙二醇与2,2-二氯乙酰氯通过酯化反应合成的大分子引发剂,引发苯乙烯(St)单体的原子转移自由基聚合反应,得到一系列H-型嵌段共聚物.并表征了产物的分子量及其分布与结构.     

RITP合成含氟两亲性嵌段共聚物PTFEMA-b-HEMA及其表征

使用可逆碘转移聚合(RITP)的方法,以I2作为链转移剂,合成了第一段为甲基丙烯酸2,2,2-三氟乙酯(TFEMA),第二段为甲基丙烯酸羟乙酯(HEMA)的两亲性嵌段共聚物TFEMA-b-HEMA,并对聚合物进行了FT-IR、1H NMR、GPC的表征。结果表明成功合成嵌段共聚物,并且分子量分散系数在1.4~1.6之间,达到活性聚合的效果。     

苯乙烯与甲基丙烯酸含氟酯（FNEMA）嵌段共聚物的合成与表征

用原子转移自由基聚合方法合成了苯乙烯与甲基丙烯酸－２－（全氟壬烯氧基）乙酯的嵌段共聚物。结果表明，共聚物分子量的实验值与计算值接近，且具有低分散性。用红外光谱和核磁共振表征了此共聚物的结构。     

P2VP-b-PS-b-PI三嵌段共聚物的RAFT合成及表征

以S-十二烷基-S’-(α,α’-二甲基-α’’-乙酸)-三硫代碳酸酯(DDMAT)为链转移剂,通过可逆加成-断裂链转移自由基聚合(RAFT)方法制备了窄分布的聚2-乙烯基吡啶。再以该聚合物为大分子链转移剂,引发苯乙烯的RAFT聚合,得到聚2-乙烯基吡啶-b-聚苯乙烯(P2VP-b-PS)的两嵌段共聚物。以P2VP-b-PS为RAFT试剂,合成聚2-乙烯基吡啶-b-聚苯乙烯-b-聚异戊二烯(P2VP-b-PS-b-PI)的三嵌段共聚物。运用1H NMR、IR和凝胶渗透色谱(GPC)等技术对产物的结构和分子量及分子量分布进行表征,采用原子力显微镜(AFM)观察三嵌段共聚物薄膜的微相分离结构。结果表明,所得三嵌段共聚物P2VP72-b-PS136-b-PI300分子量分布较窄(PDI=1.69),合成过程具有活性/可控聚合特征,聚合物薄膜经溶剂退火处理后出现了明显的微观相分离结构。     

RAFT法合成超分散剂PS-b-PAA及其分散性能研究

以苯乙烯(St)和丙烯酸(AA)为单体,二硫代苯甲酸苄酯为链转移剂,偶氮二异丁腈(AIBN)作为引发剂,采用可逆加成-断裂链转移(RAFT)活性自由基聚合方法合成了两亲性嵌段共聚物分散剂聚苯乙烯-b-聚丙烯酸(PS-b-PAA),探讨了影响聚合反应的主要因素,用GPC、IR、1H NMR对其结构进行了表征.结果表明,用RAFT法制得的共聚物分子量分布为1.1～1.3,聚合反应在80℃下24h内转化率达95%.进一步的分散性能研究表明,超分散剂PS-b-PAA对SiO2粉体在水中有着较好的分散效果.     

Sapindaceae,cyanolipids, and bugs

Scentless plant bugs (Heteroptera: Rhopalidae) are so named because adults of the Serinethinae have vestigial metathoracic scent glands. Serinethines are seed predators of Sapindales, especially Sapindaceae that produce toxic cyanolipids. In two serinethine species whose ranges extend into the southern United States,Jadera haematoloma andJ. sanguinolenta, sequestration of host cyanolipids as glucosides renders these gregarious, aposematic insects unpalatable to a variety of predators. The blood glucoside profile and cyanogenesis ofJadera varies depending on the cyanolipid chemistry of hosts, and adults and larvae fed golden rain tree seeds (Koelreuteria paniculata) excrete the volatile lactone, 4-methyl-2(5H)-furanone, to which they are attracted.Jadera fed balloon vine seeds (Cardiospermum spp.) do not excrete the attractive lactone. Loss of the usual heteropteran defensive glands in serinethines may have coevolved with host specificity on toxic plants, and the orientation ofJadera to a volatile excretory product could be an adaptive response to save time.Mention of a commercial product does not consititute an endorsement by the USDA.     

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.     

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.     

2008～2009年世界塑料工业进展

收集了2008年7月～2009年6月世界塑料工业的相关资料,介绍了2008～2009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、环氧树脂、不饱和聚酯树脂)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。     

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.