黄皮树果实中的酰胺类化合物

黄皮树（ＰｈｅｌｌｏｄｅｎｄｒｏｎｃｈｉｎｅｎｓｅＳｃｈｎｅｉｄ．）属芸香科黄檗属植物,树皮为中药黄柏。我们曾从其树皮中提取到数种三萜类的昆虫拒食物质［１］,继而从其干果中分离到数种拒食物质［２］。本文报道从干果中分离到的酰胺类化合物,它们是：反,反－２,４－Ｎ－异丁基十四碳二烯酰胺（１）,反,反,顺－２,４,８－Ｎ－异丁基十四碳三烯酰胺（２）,反,反－２,４－Ｎ－异丁基十五碳二烯酰胺（３）和Ｎ－ｍｅｔｈｙｌｆｌｉｎｄｅｒｓｉｎｅ（４）。其中,反,反,顺－２,４,８－Ｎ－异丁基十四碳三烯酰胺是一…     

川黄柏果实中的化学成分及抗肿瘤活性

通过应用多种色谱方法从川黄柏果实的乙醇提取物中分离得到10个单体化合物,运用现代波谱技术鉴定了它们的结构,分别为:23-aldehyde-tirucall-7-ene-3-one(1)、(23R,24S)-21-oxomelianodiol(2)、3β,22S-dihydroxy-tirucalla-7,24-dien-23-one(3)、21,23-lactone-24,25 dihydroxy-tirucall-7-ene-3-one(4)、Aphagranins F(5)、24,25-epoxy-tirucall-7-ene-3,23-dione(6)、木栓酮(Friedelin,7)、吴茱萸次碱(Rutaecarpine,8)、反,反,顺-2,4,8-N-异丁基十四碳三烯酰胺(9)、7-脱甲基软木花椒素(7-Demethylsuberosin,10)。其中化合物1新的天然产物,2-5、7系首次从该植物中分离得到。体外抗肿瘤活性表明,化合物3对乳腺癌MDA细胞的增殖具有较好的抑制作用,化合物5对白血病K562细胞的生长具有较好的抑制作用,其IC_(50)分别为7.38(±3.24)μmol/L、3.86(±2.71)μmol/L。     

植物气味化合物与斜纹夜蛾性信息素的协同作用

为提高现有性信息素对雄蛾的引诱活性, 本研究通过大量的田间试验探索植物气味化合物与斜纹夜蛾Spodoptera litura性信息素（顺9, 反11-十四碳二烯乙酸酯∶顺9, 反12-十四碳二烯乙酸酯=10∶1）的协同作用机制。从斜纹夜蛾寄主植物和花的气味化合物中, 选择9种有代表性的化合物, 并以一定剂量分别加入到斜纹夜蛾性信息素诱芯中, 在田间测试对雄蛾的引诱活性。结果表明: 在测试的9种植源性化合物中, 发现一定剂量(每个诱芯加入0.4 mg)的苯乙醛(PAA), 具有显著提高斜纹夜蛾性信息素的引诱作用, 而高剂量的苯乙醛则强烈抑制性信息素的引诱活性; 此外, 其他各种浓度的测试化合物或混合物对性信息素则没有统计上显著的增效作用。不同剂量的苯乙醛单个化合物及各种植物气味化合物组成的混合物对斜纹夜蛾也有微弱的引诱作用。苯乙醛必须要与性信息素的完整组分(以10∶1比例混合的顺9, 反11-十四碳二烯乙酸酯和顺9反, 12-十四碳二烯乙酸酯)混合才能起作用, 缺少顺9, 反12-十四碳二烯乙酸酯则没有引诱活性。本研究证明, 苯乙醛作为理想的性信息素诱芯增效剂, 可应用于建立更理想的斜纹夜蛾性信息素诱杀技术, 对性诱害虫防治和测报具有应用价值。     

海绵Hyatella sp．中的含氮化合物

本文报道从中国南海湛江硇洲岛海绵Hyatella sp.分离得到5种含氮化合物,经光谱分析鉴定其结构分别为:环脯氨酰-苏氨酸(1),2-N-(1,3,4-三羟基-17-甲基)十八烷基-2′-羟基-18-甲基二十碳酰胺(2),2-N-(1,3,4-三羟基-17-甲基)十八烷基-2′-羟基-19-甲基二十一碳酰胺(3),2-N-(1,3,4-三羟基-17-甲基)十八烷基-2′-羟基-20-甲基二十二碳酰胺(4)和胸腺嘧啶(5),化合物(1)首次从自然界中发现.     

中国印度谷螟性信息素次级组份的研究

印度谷螟是我国危害性较严重的仓储害虫之一,食性很广,几乎危害每一种植物性仓储物.印度谷螟雌虫性信息素主要成份顺9,反12-十四碳二烯醇醋酸酯(TDA)早已被鉴定,并利用TDA单一组份诱捕印度谷螟雄蛾也较为有效,但该虫的完整信息素系统尚不清楚.本研究采用单个雌蛾性信息素腺体抽提技术,利用毛细管气相色谱GC保留时间定性方法和气质联用GC-MS分析鉴定技术,从印度谷螟雌虫腺体提取物中鉴定了顺9,反12-十四碳二烯醇醋酸酯(A),顺9,反12-十四碳二烯醇(B),顺9,反12-十四碳二烯醛(C)和顺9-十四碳醋酸醋(D)4种主要信息素成份,其比例为A∶B∶C∶D=100∶22∶12∶9.风洞试验结果表明,以该4种主要成分按A∶B∶C∶D=8∶2∶1∶0.8比例配制成的诱芯,其引诱雄蛾的活性接近于雌蛾腺体提取物.     

合成性信息素对柑桔潜叶蛾的田间引诱作用

目前柑桔潜叶蛾的防治主要依赖化学农药, 而且生产中缺少有效测报技术。为此, 我们于2009年6月30日至10月6日在浙江宁波通过有机合成柑桔潜叶蛾Phyllocnistis citrella（鳞翅目, 细蛾科）的3种性信息素化合物顺7, 顺11, 反13-十六碳三烯醛、顺7, 顺11-十六碳二烯醛和顺7-十六碳烯醛, 配制成不同浓度比例的混合物, 进行田间试验比较其引诱活性。结果表明, 单一的顺7, 顺11, 反13-十六碳三烯醛对柑桔潜叶蛾雄蛾就可以显示较强的引诱作用, 而顺7, 顺11-十六碳二烯醛单一成分没有引诱活性, 顺7, 顺11, 反13-十六碳三烯醛与顺7, 顺11-十六碳二烯醛的二元混合物30∶1~3∶1之间活性较强, 而在30∶1的质量比例时诱虫量最高。含顺7-十六碳烯醛的三元混合物, 当顺7, 顺11, 反13-十六碳三烯醛∶顺7, 顺11-十六碳二烯醛∶顺7-十六碳烯醛三者比例为100∶10∶3时有显著增效作用。剂量与诱捕活性试验显示每枚诱芯1 mg顺7, 顺11, 反13-十六碳三烯醛的剂量引诱作用最强, 随浓度降低, 引诱作用下降。诱捕器在0.8~1.5 m之间的不同悬挂高度对诱捕数量无显著影响。结果说明, 顺7, 顺11, 反13-十六碳三烯醛、顺7, 顺11-十六碳二烯醛和顺7-十六碳烯醛组成的三元混合物诱芯可以作为柑桔潜叶蛾的诱杀技术并应用于其生物防治和预测测报。     

日本松干蚧性信息素光学异构体的引诱活性

对合成的日本松干蚧Matscoccus matsumurse(kuwana)性信息素4、6、10、12-四甲基-反2、反4-十三碳二烯-7-酮1所有四个光学活性异构体,进行了诱虫活性测定和林间诱捕试验。结果表明,只有6R、10R-4、6、10、12-四甲基-反2 反4-十三碳二烯-7-酮对日本松干蚧雄成虫具有强烈引诱活性,被确定为该虫天然性信息素的绝对构型。     

马尾松毛虫性外激素的新成分:化学结构鉴定和田间试验

马尾松毛虫 Dendrolimus punctatus 性外激素由顺5,反7-十二碳二烯醇(Z5,E7-12:OH)、顺5,反7-十二碳二烯乙酸酯 Z5,E7-12:Ac和顺5,反7-十二碳二烯丙酸酯(Z5,E7-12:Pr)构成。为了确定马尾松毛虫性外激素系统是否含有其它成分,我们对外激素腺体提取物进行分析,以此为基础通过田间诱蛾试验发现了某些增加诱蛾活性的新成分。     

中华山蓼化学成分研究

bk中华山蓼(Dxyria sinensis Hemsl.)全草中首次分离得到十四个化合物,通过波谱学方法分别鉴定为(-)-表没食子儿茶素(1)、(-)-儿茶素没食子酸酯(2)、(-)-表儿茶素(3)、(-)-表儿茶素-3-没食子酸酯(4)、槲皮素-3-O-α-L-鼠李糖苷(5)、tiliroside(6)、山萘酚-3-O-β-D-吡喃葡萄糖苷(7)、桷皮素(8)、2,4-二羟基-6-甲氧基-乙酰基苯-4-O-β-D-吡喃葡萄糖苷(9)、反-N-(4-羟基苯乙基)阿魏酸酰胺(10)、顺-N-(4-羟基苯乙基)阿魏酸酰胺(11)、icariol A2(12)、(+)-松脂素(13)、Helonioside B(14).     

几种橡胶载体对马尾松毛虫性信息素几何构型异构化的影响

马尾松毛虫Dendrolimus punctatus Walker性信息素的主要活性组分为顺5,反7-十二碳二烯醇、顺5,反7-十二碳二烯基乙酸酯、顺5,反7-十二碳二烯基丙酸酯,在橡胶塞诱芯载体上很快发生异构化。半月后以顺反式为主的三组分已改变为以反反式为主体,反顺式和顺顺式也增加了。因而,此类材料不宜作为共轭二烯类信息素的载体。本文报告了一种硅橡胶材料对共轭双键具有相当小的影响,并可望成为含有共轭双键结构的昆虫信息素的载体材料。     

INSECTICIDAL COMPOUNDS FROM THE FRUITS OF PHELUlDENDRON CHINENSE AGAINST HOUSEFLY

Abstract Three N-isobutylamides were isolated from the fruits of Phellodendron chinense . (2E, 4E)-N-isobutyl tetradecadienamide and (2E, 4E1-N-isobutyl pentadecadienamide were responsible for the in-secticidal activity against Musca domestica . However, (2E, 4E, 82)-N-isobutyl tetradecatrienamide was not active.     

(4E)-dehydrocitrals [(2E,4E)- and (2Z,4E )-3,7-dimethyl-2,4,6-octatrienals] from acarid mite Histiogaster sp. A096 (Acari: Acaridae)

A mixture of two monoterpenes was obtained as the opisthonotal gland secretion from unidentified Histiogaster sp. A096 (Acari: Acaridae), and their structures were elucidated to be (4E)-dehydrocitrals [(2E,4E)- and (2Z,4E)-3,7-dimethyl-2,4,6-octatrienals] by GC/MS, GC/FT-IR, UV and 1H-NMR spectra. Both isomers of (4E)-dehydrocitral prepared by syntheses in 4 steps from 3-methyl-2-butenal with 34.2% yields (based on the ylide) were separated by column chromatography into the (2E,4E)- and (2Z,4E)-3,7-dimethyl-2,4,6-octatrienal. Mass spectra together with GC retention times of the purified natural (4E)-dehydrocitrals were identical with those of synthetic (2E,4E)-3,7-dimethyl-2,4,6-octatrienal and (2Z,4E)-3,7-dimethyl-2,4,6-octatrienal. The geometry at the 2-C position of both synthetic (4E)-dehydrocitrals was confirmed by NOESY analyses. This is the first identification of (4E)-dehydrocitrals from the animal kingdom.     

Precursor role of 15alpha-hydroxyestradiol and 15alpha-hydroxyandrostenedione in the formation of estetrol

Studies were designed to elucidate the origin of estetrol (15alpha-hydroxyestriol (estra-1,3,5(10)triene-3,15alpha,17beta-tetrol) or E4) during late human pregnancy. 3H-Labelled 15alpha-hydroxyestradiol (3,15alpha-dihydroxyestra-1,3,5(10)-trien-17-one or 15E2) and 14C-labelled 17beta-estradiol (estra-1,3,5(10)-triene-3,17beta-diol or E2) were infused into the fetus during transfusion in utero for erythroblastosis fetalis, and in another study the same substrates were injected intravenously into the maternal circulation. In a third study, 3H-labelled 15alpha-hydroxyandrostenedion (15alpha-hydroxyandrost-4-ene-3,17-dione or 15delta4) and 14C-labelled E2 were infused into the fetus. Maternal urine was collected for 5--6 days, and after Glusulase hydrolysis, the following metabolites were isolated: estriol (estra-1,3,5(10)-triene-3,16alpha,17beta-triol or E3) containing 14C only and 15alpha-hydroxyestrone (3,15alpha-dihydroxyestra-1,3,5(10)-trien-17-one or 15E1), 15E2, and E4, all containing both labels. From the isotope content of these metabolites, it was concluded that E4 was derived from both fetal E2 and 15delta4 and only partially via 15E2. When administered to the fetus E2 and 15delta4 contributed approximately equal amounts to urinary E4. The yield of 15alpha-hydroxylated estrogens from E2 injected into the mother was very low indicating the predominantly fetal origin of the 15alpha-hydroxylase. 15delta4 was a better precursor than E2 for urinary 15E2.     

Apolipoprotein E polymorphism in Saudis

Apolipoprotein E (apoE) genotypes were determined in 165 Saudis. The prevalence of genotype, E3/E3, E3/E4 and E4/E4 was found to be 71, 27 and 2% respectively. The E3/E3 was the most prevalent genotype among the Saudis followed by E3/E4. However, other genotypes E2/E2, E2/E3 and E2/E4 were absent showing the absence of E2 allele in the test population. The high frequencies of the E3 allele (0.845) and E3/E3 genotype (0.71) and absence of E2 allele in Saudis under study are similar to those reported earlier for Native Americans, Mexican-Americans, Mayans, Cayapa, Mazatecan Indians and Mexican Mestizos populations.     

Antioxidative compounds isolated from the rhizomes of smaller galanga (Alpinia officinarum Hance)

Antioxidative compounds were isolated from the methanol extract of fresh rhizome of smaller galanga (Alpinia officinarum Hance). Seven phenylpropanoids (1-7) were obtained and their structures were elucidated by MS and NMR analyses. They comprised the two known compounds, (E)-p-coumaryl alcohol gamma-O-methyl ether (1) and (E)-p-coumaryl alcohol (6); and the five novel compounds, stereoisomers of (4E)-1,5-bis(4-hydroxy-phenyl)-1-methoxy-2-(methoxymethyl)-4-pentene (2a and 2b), stereoisomers of (4E)-1,5-bis(4-hydroxyphenyl)-1-ethoxy-2-(methoxymethyl)-4-pentene (3a and 3b), (4E)-1,5-bis(4-hydroxy-phenyl)-1-[(2E)-3-(4-acetoxyphenyl)-2-propenoxy]-2-(methoxymethyl)-4-pentene (4), (4E)-1,5-bis(4-hydroxyphenyl)-2-(methoxymethyl)-4-penten-1-ol (5), and (4E)-1,5-bis(4-hydroxyphenyl)-2-(hydroxymethyl)-4-penten-1-ol (7). Compounds 1-7 were detected for the first time as constituents of galanga rhizomes and exhibited antioxidative activities against the autoxidation of methyl linoleate in bulk phase.     

Apolipoprotein E polymorphism in Saudis

Apolipoprotein E (apoE) genotypes were determined in 165 Saudis. The prevalence of genotype, E3/E3, E3/E4 and E4/E4 was found to be 71, 27 and 2% respectively. The E3/E3 was the most prevalent genotype among the Saudis followed by E3/E4. However, other genotypes E2/E2, E2/E3 and E2/E4 were absent showing the absence of E2 allele in the test population. The high frequencies of the E3 allele (0.845) and E3/E3 genotype (0.71) and absence of E2 allele in Saudis under study are similar to those reported earlier for Native Americans, Mexican-Americans, Mayans, Cayapa, Mazatecan Indians and Mexican Mestizos populations.     

Study on anaerobic and aerobic degradation of different non-ionic surfactants

Six alcohol ethoxylates (C5E2, C6E4, C7E4, C8E2, C8E4, C10E4) and two fatty acid esters were tested at lab-scale for degradation in anaerobic and aerobic conditions and oxygen uptake rate (OUR). Anaerobic removal of C5E2, C6E4 and C7E4 improved with increasing number of ethoxy groups (E) and decreasing length of the alkyl chain (C). Their aerobic removal was also great but lower than the anaerobic values. C8E2, C8E4 and C10E4 were adsorbed on sludge but not degraded in anaerobic conditions, while they were efficiently removed under aerobiosis. The fatty acid esters were removed to a level between the two alcohol ethoxylates groups in both anaerobiosis and aerobiosis. The measured OUR confirmed the different behaviours of the three groups of compounds.     

A natural recessive resistance gene against potato virus Y in pepper corresponds to the eukaryotic initiation factor 4E (eIF4E)

We show here that the pvr2 locus in pepper, conferring recessive resistance against strains of potato virus Y (PVY), corresponds to a eukaryotic initiation factor 4E (eIF4E) gene. RFLP analysis on the PVY-susceptible and resistant pepper cultivars, using an eIF4E cDNA from tobacco as probe, revealed perfect map co-segregation between a polymorphism in the eIF4E gene and the pvr2 alleles, pvr2(1) (resistant to PVY-0) and pvr2(2) (resistant to PVY-0 and 1). The cloned pepper eIF4E cDNA encoded a 228 amino acid polypeptide with 70-86% nucleotide sequence identity with other plant eIF4Es. The sequences of eIF4E protein from two PVY-susceptible cultivars were identical and differed from the eIF4E sequences of the two PVY-resistant cultivars Yolo Y (YY) (pvr2(1)) and FloridaVR2 (F) (pvr2(2)) at two amino acids, a mutation common to both resistant genotypes and a second mutation specific to each. Complementation experiments were used to show that the eIF4E gene corresponds to pvr2. Thus, potato virus X-mediated transient expression of eIF4E from susceptible cultivar Yolo Wonder (YW) in the resistant genotype YY resulted in loss of resistance to subsequent PVY-0 inoculation and transient expression of eIF4E from YY (resistant to PVY-0; susceptible to PVY-1) rendered genotype F susceptible to PVY-1. Several lines of evidence indicate that interaction between the potyvirus genome-linked protein (VPg) and eIF4E are important for virus infectivity, suggesting that the recessive resistance could be due to incompatibility between the VPg and eIF4E in the resistant genotype.     

Characterization of noncovalent complexes of recombinant human monoclonal antibody and antigen using cation exchange, size exclusion chromatography, and BIAcore.

The binding of fully human monoclonal antibodies (MAbs) D2E7 and 2SD4 to their antigen, human tumor necrosis factor-alpha (TNFalpha), was investigated by BIAcore, cation exchange (CIEX), and size exclusion liquid chromatography (SEC) using ultraviolet and laser light scattering detectors. D2E7 has a higher affinity for TNFalpha than 2SD4 and the two antibodies (Abs) differ by 12 amino acids in the antigen (Ag) binding regions. A BIAcore biosensor instrument was used to determine the association, k(on) and dissociation, k(off), rate constants for the binding of TNFalpha to D2E7 and 2SD4. The HPLC methods were used to resolve and to study D2E7, 2SD4, and TNFalpha molecules and the noncovalent complexes of D2E7 and 2SD4 with TNFalpha. The CIEX method demonstrated that all D2E7 charged-variants bound TNFalpha equally well. There was no preferential binding for any one of D2E7 charged-variants to TNFalpha. D2E7 and 2SD4 Abs were resolved by the CIEX method. When a mixture of D2E7 and 2SD4 was mixed with excess TNFalpha, D2E7. TNFalpha complexes were formed before any 2SD4. TNFalpha complexes. Thus, the CIEX method was able to rank the affinities of the MAbs. D2E7 and TNFalpha formed complexes of 600-5000 kDa. The molecular weights of various D2E7. TNFalpha complexes were determined by a SEC method with light scattering (LS) and refractive index (RI) detectors. Upon overnight incubation, a 598-kDa complex emerged as the most stable and the only D2E7. TNFalpha complex. The molar ratio of D2E7 to TNFalpha in this complex was approximately 1:1. Based on molecular weights and the molar ratio, an immune complex, consisting of alternating three D2E7 and three TNFalpha molecules, is proposed as the most stable complex.     

Synthesis and immunomodulatory properties of selected oxazolone derivatives

Eleven oxazolone derivatives were synthesized and characterized by (1)H NMR, EI, IR and UV spectroscopic and CHN analysis. Three compounds, 4-[(E)-(4-nitrophenyl)methylidene]-2-phenyl-1,3-oxazol-5(4H)-one (11), 4-[(E)-(4-methoxyphenyl)methylidene]-2-methyl-1,3-oxazol-5-one (12) and 4-[(E)-(4-nitrophenyl)methylidene]-2-methyl-1,3-oxazol-5(4H)-one (13) were screened for phagocyte chemiluminescence, neutrophil chemotaxis, T-cell proliferation, cytokine production from mononuclear cells and cytotoxicity. 4-[(E)-(4-Nitrophenyl)methylidene]-2-methyl-1,3-oxazol-5(4H)-one (13) was found to be the most potent immunomodulator in the series.