罗丹明B类Cu~(2+)荧光增强型探针的合成及其选择性识别

设计并合成了一种可用于识别的Cu~(2+)新型荧光探针(3',6'-双(二乙氨基)-2-(4-(二乙氨基)-2-羟基苯胺基-螺(异喹啉-1,9'-氧杂蒽)-3-酮)(RB)。通过红外、元素分析、质谱、~1HNMR、~(13)CNMR等手段表征了探针的结构。其光谱性和离子选择性实验结果表明,RB自身荧光很弱,但是与Cu~(2+)结合后会发生显著的荧光增强,而与其他金属离子结合后,荧光强度变化很小。说明RB对Cu~(2+)具有很好的选择性和较高的灵敏度,可用作Cu~(2+)荧光增强型探针,据此建立了一种测定Cu~(2+)的新型分析方法。     

罗丹明B衍生物荧光探针的合成及其对Fe3 的检测

以罗丹明B与苯胺为原料,经过缩合反应制得一种罗丹明B衍生物的荧光探针F-1[3',6'-二(二乙基氨基)-2-苯基螺[异吲哚-3,9'-氧杂蒽]-1-酮],其结构通过1HNMR、13CNMR、红外光谱和高分辨质谱(HRMS)进行确证。Fe~(3+)加入探针体系后,体系颜色由无色变为紫色,荧光显著增强,而不受其他金属离子(Na~+、K~+、Ca~(2+)、Mg~(2+)、Zn~(2+)、Hg~(2+)、Co~(2+)、Cd~(2+)、Ni~(2+)、Cu~(2+)、Mn~(2+)、Ag+、Pb~(2+)、Cr~(3+)、Fe~(2+))干扰。通过测定探针化合物F-1的离子选择性、离子竞争性、浓度梯度、Job’s曲线和pH对探针分子荧光强度的影响,发现在p H=5～7的环境中,Fe~(3+)浓度在2.0×10~(–6)～1.8×10~(–5) mol/L时,探针F-1对其检测呈较好的线性关系,其具备定性、定量检测生物机体或者环境中痕量Fe~(3+)的潜力。     

一种新型的罗丹明席夫碱探针在水环境中检测铜离子的应用

为快速、高效地检测环境中的Cu~(2+),以罗丹明B酰肼与2-羟基-4-甲基苯甲醛为起始原料,采用一步反应法制备了一种新型的罗丹明席夫碱探针((E)-3',6'-双(二乙氨基)-2-((2-羟基-4-甲基亚苄基)氨基)螺[异二氢吲哚-1,9'-呫吨]-3-酮,简称RHHM),研究表明该探针可以高选择性的识别Cu~(2+)。将该探针应用于湖水和自来水中Cu~(2+)的检测,其加标回收率均在94%以上,检测结果具有很高的准确性和可靠性。幵将该探针制备成一种便携式试纸条,结果表明该试纸条具有检测方便、快速的优点。     

L-色氨酸衍生物的合成及促凝活性

以L-色氨酸为原料,分别与以邻苯二甲酸酐保护的4-氨甲基苯甲酸、4-氨甲基环己基甲酸及6-氨基己酸反应合成了3种酰胺衍生物,分别是(S)-3-(1'H-吲哚-3'-基)-2-{4″-[(1'″,3'″-二氧代异吲哚-2'″-基)甲基]苯甲酰氨基}丙酸(Ⅰ)、(S)-3-(1'H-吲哚-3'-基)-2-{4″-[(1'″,3'″-二氧代异吲哚-2'″-基)甲基]环己基甲酰氨基}丙酸(Ⅱ)及(S)-3-(1'H-吲哚-3'-基)-2-[6″-(1'″,3'″-二氧代异吲哚-2'″-基)己酰氨基]丙酸(Ⅲ)。通过IR、MS、1HNMR及13CNMR对其结构进行了表征。反向筛选出两种与促凝活性相关的蛋白,再将L-色氨酸及3个目标化合物与其分别进行正向对接,通过凝血四项与血浆复钙时间实验表明,化合物Ⅰ及化合物Ⅲ的促凝活性随其质量浓度的增加而增强,化合物Ⅱ具有浓度依赖性调节作用。     

氧代螺环异吲哚啉衍生物的合成及表征

具有手性的氧代螺环异吲哚啉衍生物可作为天然药物的活性结构单元,这些化合物在医药和化工领域具有重要的研究价值。实验以1,4-二氧螺环[4.5]癸烷-8-酮和苯甲酸酐为原料,经过一系列反应制得2-(1-(4-氧代双环[4.1.0]庚基-1-)丙基-2-)异吲哚啉-1,3-二酮,并利用高效液相色谱(HPLC)、液质联用仪(LCMS)、核磁(NMR)对其结构进行表征。     

2-(3-氯-2-氧代基)异吲哚啉-1,3-二酮合成工艺改进

[目的] 2-(3-氯-2-氧代基)异吲哚啉-1,3-二酮是合成5-氨基乙酰丙酸的中间体,用催化氧化方法进行了合成。[方法]以邻苯二甲酰亚胺钾为主要原料,经与和环氧氯丙烷反应制备N-(2,3-环氧丙基)邻苯二甲酰亚胺,再经盐酸水解,TEMPO催化下PhI(OAc)_2氧化得到目标产物。[结果]在优化的反应条件下,2-(3-氯-2-氧代基)异吲哚啉-1,3-二酮的反应收率为93.1%。催化剂TEMPO可回收套用2次。结构经氢谱核磁分析确证。[结论] 2-(3-氯-2-氧代基)异吲哚啉-1,3-二酮合成工艺具有污染小、收率高和易于工业化生产等优点。     

1-吲哚基苯基甲酮的合成及其与牛血清白蛋白相互作用的荧光分析

合成1-吲哚基苯基甲酮,并对其进行了红外光谱、质谱和核磁共振表征,通过荧光光谱法、紫外光谱法研究该药物分子与牛血清白蛋白(BSA)的相互作用。实验结果显示,在309K时,1-吲哚基苯基甲酮与牛血清蛋白(BSA)的猝灭速率常数Kq=1.771×10~(12) L·mol~(-1)·s~(-1),结合常数Ka=3.726 5×10~3 L/mol,结合位点数n=0.884 0,ΔH=2.01kJ/mol,ΔS=36.19J·mol~(-1)·K~(-1)。结果表明:1-吲哚基苯基甲酮对BSA具有荧光猝灭作用,该药物分子与BSA的主要作用力是疏水作用力(ΔH0,ΔS0)。     

盐酸鲁拉西酮的合成工艺研究

合成了抗精神分裂药物盐酸鲁拉西酮。以苯并异噻唑-3(2H)-酮为原料,经氯代、与无水哌嗪缩合得3-(哌嗪-1-基)苯并异噻唑,其和(1R,2R)-环己-1,2-二甲醇二甲磺酸酯反应得反式-3aR,7aR-八氢异吲哚啉-2-螺-1'-[4'-(1,2-苯并异噻唑-3-基)哌嗪]甲磺酸盐,再和顺-降冰片烷-外-2,3-二甲酰亚胺反应得鲁拉西酮,最后经成盐得盐酸鲁拉西酮。目标化合物经光谱确证,三步收率为42%(以苯并异噻唑-3(2H)-酮计)。反应条件温和、操作简便,各步原料价格低廉,采用的工艺操作简便易行。     

阿普斯特有关物质的合成研究

为更好控制阿普斯特产品质量,依据阿普斯特的结构特征与合成工艺,分别合成了其4个可能有关物质,分别为异构体杂质((R)-2-[1-(3-乙氧基-4-甲氧基苯基)-2-甲磺酰基乙基]-4-乙酰基氨基异吲哚啉-1,3-二酮)、有关物质A((S)-2-[1-(3-乙氧基-4-甲氧基苯基)-2-甲磺酰基乙基]-4-硝基异吲哚啉-1,3-二酮)、有关物质B((S)-2-[1-(3-乙氧基-4-甲氧基苯基)-2-甲磺酰基乙基]-4-氨基异吲哚啉-1,3-二酮)、有关物质H((S)-2-[1-(3-乙氧基-4-甲氧基苯基)-2-甲磺酰基乙基]-4-(4-乙酰基氨基异吲哚啉-1,3-二酮)异吲哚啉-1,3-二酮)),并对其结构通过1H-NMR进行了确证,可作为阿普斯特质量标准研究参照。     

氧杂杯[2]芳烃[2]三嗪衍生物的合成及其离子识别性能研究

以间苯二酚、三聚氯氰和(4-羟基苯基)-(吗啉代)甲酮为原料合成了一个新的标题化合物,并经HR-MS、~1HNMR、~(13)CNMR、IR、UV-Vis等手段确证了其结构。接着利用荧光光谱法分别考察了它对8种阴离子和10种金属离子的识别性能,结果表明标题化合物可以专属性地识别Fe~(3+),而对其他测试的阴离子和阳离子没有识别作用,同时其他金属离子不影响标题化合物对Fe~(3+)的识别。利用推导的新非线性拟合方程计算得到标题化合物与Fe~(3+)形成配合比和配合常数分别为1∶1和3.41×10~4mol/L的配合物,并通过核磁共振波谱法初步确证Fe~(3+)是结合在标题化合物的两个三嗪环组成的空腔中。     

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.     

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.