淡黄杜鹃植物挥发油化学成分的研究

利用毛细管气相色谱保留指数定性、标准样品叠加和色谱质谱计算机联用技术,对淡黄杜鹃植物挥发油的化学成分进行了分离和鉴定,共鉴定出单萜烃１８个、倍半萜烃４１个,并测得了各化合物的相对含量,其主要成分是：β蒎烯、α蒎烯、乙酸冰片酯、柠檬烯、β榄香烯、香桧烯、香茅醇和月桂烯     

雷公藤新的降倍半萜成分

从贵州产雷公藤（ＴｒｉｐｔｅｒｙｇｉｕｍｗｉｌｆｏｒｄｉＨｏｋＦ．）中分离得到８个化合物,其中一个为新的降倍半萜化合物雷公藤酮（１）,根据光谱（ＩＲ,１ＨＮＭＲ,１３ＣＮＭＲ,ＨＲＭＳ,ＣＤ等）数据分析并通过Ｘ射线晶体分析确定了结构;另外７个化合物分别鉴定为雷公藤素（２）,（±）６氧２（４′羟基３′,５′二甲氧苯基）３,７二氧杂二环［３．３．０］辛烷（３）,ｔｒｉｐｔｅｒｉｆｏｒｄｉｎ（４）,雷公藤内酯酮（５）,雷公藤内酯醇（６）,雷公藤内酯甲（７）和对乙氧基乙酰替苯胺（８）．其中,３和８均为首次从该植物中分离得到．用二维核磁共振谱对３的氢谱和碳谱进行了指定     

耐盐(CaCl2)皂素废水降解菌的分离及特性

从湖北省某皂素生产废水池底污泥中分离出2株耐高盐（CaCl2）皂素废水降解菌，编号分别为B723—1和B723—3，并进行菌株的鉴定和生长特性以及不同盐度迫胁下胞内游离氨基酸、蛋白质、膜的相对透性的研究，结果发现：（1）菌株B723—1与扩展短杆菌的同源性为98．0％～99．0％，B723—3与松鼠葡萄球菌的同源性为98．0％～99．0％：（2）两菌株均能在0．0％～9．0％CaCl2范围内生长良好；（3）菌株B723—1和B723—3的适宜生长温度分别是20～35oC和25～37oC，两者均在pH7．0～10．0生长；（4）当耐盐菌株受到1．8％、3．6％、5．4％和9．0％CaCl2盐迫45min时，其胞内会迅速积累大量氨基酸来平衡外界的高盐渗透压，且其胞内蛋白质含量均高于对照组（未受盐迫），而其膜的相对通透性低于非耐盐菌株．图4表1参11.     

部分取代苯类在江水中的生物降解与结构相关性研究^1）

测定了27种取代苯类化合物在松花江江水中的生物降解性，采用量子化学MOPAC6．0－AM1法计算了化合物的分子量（MW），生成热（Hf)，分子总表面积（TSA）及高占有轨道能（EHOMO），结合辛配醇／水分配系数lgP及酸解离常数pKa对其中22种化合物BOD值进行了多元线性回归分析，得到如下模型：BOD＝105.73-0.439MW-0.076Hf-6.660lgP n=22,R^2=0.821,SE=8.250,F=27.56,P=0.000应用所得模型对其余5个化合物的生物降解性进行了预测，只有一个化合物相的相对预测误差大于20％，为20．8％，平均预测误差为12．4％。     

腺叶香茶菜的化学成分研究

从腺叶香茶菜［Rabdosiaadenoloma（Hand．－Mazz．）Hara］地上部分的乙醇提取物中共分离出10个化合物．经EIMS、1HNMR和13CNMR等波谱和化学方法分别鉴定为：effusaninA（1）、effusaninE（2）、洋芹素－4＇，7－二甲醚（3）、β－谷甾醇（4）、柳杉二醇（5）、Uvaol（6）、白桦酸（7）、齐墩果酸（8），乌苏酸（9），齐墩果酸－3－O－α－L－鼠李吡喃糖基（1→2）［β－D－葡萄吡喃糖基－（1→4）］－α－L－阿拉伯吡喃糖甙（10）．其中8的含量高达1％以上．上述化学成分均为首次从该植物中分离得到．     

牡丹皮、川芎和石菖蒲挥发油提取工艺研究

目的确定牡丹皮、川芎和石菖蒲挥发油最适宜的提取工艺方法．方法用共水回流冷凝法研究了三种药材混合提取及分开提取挥发油的工艺方法,以挥发油的重量为指标来评价提取工艺．结果混合提取及分开提取所获得的挥发油的重量,经统计学分析无显著性差异（P〉0．05）．结论共水回流冷凝法混合提取牡丹皮、川芎和石菖蒲挥发油的工艺可行、简便,适合工业化大生产．表5,参3     

刺红珠根中的生物碱

从利红珠根中分离到7个生物碱：8-氧小檗碱（1），巴马亭（2），小檗碱（3）．非洲防己碱（4），8-氧巴马亭（5），（±）-oblongine（6）和小檗胺（7）．通过波谱数据鉴定了它们的结构.首次用二维核磁对8-氧小檗碱和小檗胺的氢谱与碳谱进行了指定．     

酸雨,降尘对莴苣和小白菜3种抗氧化酶活性的影响

用酸雨（A）、降尘（D）、酸雨和降尘（A＋D）处理生长在紫色中性土和紫色酸性土上的莴苣和小白菜，以研究3种处理对2种蔬菜中超氧物歧化酶（SOD）、过氧化氢酶（CAT）和过氧化物酶（POD）活性的影响．结果表明：3种处理可提高莴苣中的SOD和CAT的活性，且以（A＋D）处理最为明显．与CK相比，在酸性土中，（A＋D）处理可使SOD活性提高11．1％～21．2％，CAT活性提高15．5％～22．7％；3种处理可使小白菜POD活性提高，其中中性土（A＋D）处理可使POD活性比CK提高50％～52％．     

有机肥中4类典型兽药抗生素的多残留测定

建立了固相萃取-超高效液相色谱-串联质谱（SPE—UPLC—MS／MS）法同时测定有机肥中7种磺胺类、4种氟喹诺酮类、4种四环素类和3种大环内酯类抗生素残留的方法。采用乙腈和磷酸盐缓冲液（pH=3）的混合液作为有机肥样品的提取溶液,用强阴离子交换柱（SAX）-亲水亲脂平衡萃取柱（HLB）串联进行提取液的富集和纯化。以甲醇-φ=0．1％的甲酸溶液作为流动相,进行液相质谱分析。18种抗生素在5—500μg·kg-1的浓度范围内线性关系良好,决定系数（r2）1〉0．99。以3倍信噪比估算磺胺类、氟喹诺酮类、四环素类和大环内酯类的检测限分别为0．37～4．65、0．43—2．42、0．94～2．78和0．83～4．20μg·kg-1,这4类抗生素50和500μg·kg。2个添加水平的样品平均加标回收率分别为71．6％～94．3％、72．3％～86．7％、71．0％～102．2％和70．7％～93．3％,相对标准偏差在2．1％～11．4％之间。采用所建方法对南京地区市售8种有机肥中18种抗生素含量的测定结果显示,除磺胺类外,其他抗生素均有不同程度的检出。     

取代芳烃的生物降解性与结构相关性研究

采用量子化学MOPAC－AM1法计算了42种取代芳烃的生成热Hf、分子最高占有轨道能EHOMO、分子量MW、分子总表面积TSA及偶极矩μ。分别采用线性回归分析法和人工神经网络法对所研究化合物的生物降解性参数BOD进行QSBR研究。对训练组而言，线性方法和神经网络法的平均预测误差分别为15．9％和11．4％；而测试组化合物的平均百分误差分别为14．5％和13．0％。无论对于测试组还是训练组，神经网络法的预测都更精确。     

Tolerance and accumulation of lead in Vetiveria zizanioides and its effect on oil production

Experiments were conducted to evaluate lead tolerance and accumulation in vetiver grass Vetiveria zizanioides (L.), grown in hydroponics and a pot study and to examine the effect of lead on vetiver oil production. Elevated concentrations of lead decreased the length of shoots and roots of plants. However, vetiver grown in highly contaminated soils showed no apparent phytotoxicity symptoms. Lead concentrations in the shoots and roots of vetiver plants grown in hydroponics were up to 144 and 19530 mg kg(-1) and those grown in soil were 38 and 629 mg kg(-1), respectively. Lead had an effect on vetiver oil production and composition by stimulating oil yield and the number of its constituents. Oil yield ranged from 0.4-1.3%; the highest yields were found in plants grown in nutrient solution with 100 mg Pb l(-1) for 5 weeks (1.29%) and 7 weeks (1.22%). The number of total constituents of vetiver oil also varied between 47-143 compounds when lead was presentin the growth medium. The highest number (143) was found in plants grown in soil spiked with 1000 mg Pb kg(-1). The predominant compound was khusimol (10.7-18.1%) followed by (E)-isovalencenol (10.3-15.6%). Our results indicated that lead could increase the oil production of vetiver.     

荧光假单胞菌高效广谱载体的构建及分析

为促进高GC含量基因在荧光假单胞菌(Pseudomonas fluorescens)中表达效果更加理想、操作更加简便,本研究首先采用不依赖基因序列和连接反应的克隆(Sequence and ligation independent cloning,SLIC)方法将载体pCIBhis上与复制相关的序列和标记基因片段构建成克隆载体pCIBS1.然后优化荧光假单胞菌转化方法,用电转化法将pCIBS1导入荧光假单胞菌BL915中,随后又将T7和tac基因启动子分别插入pCIBS1中,成功构建了表达载体pCIBS3和pCIBS2.研究发现载体pCIBS1在大肠杆菌和荧光假单胞菌中均较为稳定,并且将绿色荧光蛋白基因插入表达载体中,在大肠杆菌BL21(DE3)中获得表达,验证了表达载体功能.本研究构建的表达载体和建立的荧光假单胞菌BL915电转化方法,为高GC含量基因在荧光假单胞菌中的表达奠定了基础.     

Neurotoxicity and oxidative stress induced by permethrin in gills of the freshwater mussel Unio ravoisieri

Pyrethroids are contaminants found in the aquatic environment, and their toxicological effects on aquatic organisms have received extensive attention. However, the impact on freshwater bivalve of exposure to these chemicals is still largely unknown. Freshwater mussels Unio ravoisieri were exposed to two nominal permethrin (PM) concentrations C1?=?50?µg/L and C2?=?100?µg/L during 7 days. The measured concentrations of PM using gas chromatography (GC/ECD) in the treated aquariums were, respectively, 28.7–62.3?µg/L. Catalase (CAT), Glutathione-S-transferase (GST), and Acetylcholinesterase (AChE) activities, Glutatione (GSH) and Malondialdehyde (MDA) levels were determined in gills of U. ravoisieri. Significant increase in CAT activity by the lowest concentration and decrease by highest concentration were observed. Additionally, GST activity was increased in a concentration-dependent manner. However, statistically significant decrease in GSH levels (about 39%) was observed only at high concentration of this compound (100?µg/L). PM generated an increase in MDA levels reaching the highest value at the high concentration. AChE activity of mussel ranging from 51% inhibition at lowest concentration 50?µg/L to 89% inhibition at highest concentration 100?µg/L. The results indicated that oxidative stress and cell damage might be one of the main mechanisms of PM toxicity to freshwater mussels.     

气相色谱-质谱联用测定母乳中合成麝香

建立了凝胶渗透色谱(GPC)柱和硅胶柱净化,气相色谱-质谱(GC/MS)测定母乳中合成麝香的分析方法.实验结果表明:GC/MS在0.01μg.ml-1到1μg.ml-1的浓度范围内对4种常见合成麝香(佳乐麝香HHCB、吐纳麝香AHTN、二甲苯麝香MX和酮麝香MK)均有良好的线性响应,4种合成麝香的基质加标回收率为76%—115%,相对标准偏差为2.8%—7.4%.利用信噪比(5/1)确定该方法的定性检测限,HHCB,AHTN,MX为5ng.g-1脂重,MK为4ng.g-1脂重,定量检测限为定性检测限的2倍.采用上述方法分析了上海母乳样品中合成麝香的浓度和分布特征,发现母乳中普遍存在这4种合成麝香,浓度分别为HHCB92±70;AHTN16±12;MX26±22;MK16±14ng.g-1脂重,与欧美国家的污染水平相比,总体含量偏低.     

Comparison of chemical composition of the essential oil of Laurus nobilis L. leaves and fruits from different regions of Hatay, Turkey

The essential oils of the leaves and fruits from bay (Laurus nobilis L.) grown in Antakya, Yayladagi and Samandagi were isolated by solvent extraction and analysed by capillary gas chromatography (GC), gas chromatography and mass spectrometry (GC/MS). In Antakya, Yayladagi and Samandagi the chemical compositions of the fruits and leaves were similar according to qualitative and quantitative analysis. Although in both fruits and leaves the major component was found to be 1.8-Cineole a concentration of about 50% compared with essential oils. The composition of the essential oil from the leaves has high content of 1.8-Cineole, Sabinene and alpha-Terpinyl acetate, but a low content of a-Pinene, alpha-Phellandrene and trans-/beta-osimen. 1.8-Cineole was found major component of the leaves essential oil collected from Samandagi (59.94%) which is sea coast of region. Interestingly alpha-Pinene, beta-Pinene, alpha-Phellandrene, 1.8-Cineole and trans-beta-osimen were found the major components of fruits of Laurus nobilis L. harvested from Antakya, Yayladagi and Samandagi Trans-beta-osimen was detected as the major component of fruits essential oil collected again from Samandagi (28.35%)     

Bestimmung von Mineralölkohlenwasserstoffen im Boden

The infra-red (IR) and the gas Chromatographic (GC) methods for the determination of mineral oil hydrocarbons in soils were examined in collaborative trials with regard to their accuracy and reproducibility. Natural, homogenized soils and soils spiked with mineral oil were used as standards. The soil matrix was composed relatively simply. The repeatability and reproducibility values obtained were about 5 % und 23 %, respectively. In contrast, the GC method revealed a considerably higher error range, especially by using the split/splitless technique. The degradation of mineral oil hydrocarbons in soils under different temperatures was investigated by IR throughout one year. The degradation rate at room temperature was about 25 %; at lower temperatures no degradation was detected. Thus, the spiked soils may be used as calibration standards for the mineral oil analysis.     

Removal of pesticides from water samples by adsorption with fatty acids supported on barium sulphate

Oleic or linoleic acid supported on barium sulphate was used to remove atrazine and terbuthylazine in the range of 0.1–2.0 μg/L using spiked water samples. The sorption of atrazine depends on the stirring time and the best value is 150 min. Terbuthylazine is removed well with a stirring time of 60 min and its adsorption is about 90%. Detection of the residual pesticide in treated waters, after solid phase extraction (SPE), was carried out by GC‐MS operating in selected ion monitoring (SIM) using a calibration curve by direct injection of standard solutions of herbicide.     

Investigation of naphthalene contamination in olive oil from Greece

Abstract

Incidents of using naphthalene in olive orchards as a repellent of olive fly (Bactrocera oleae) have recently been recorded. Naphthalene, the primary ingredient of mothballs, is described to be diluted in plastic bottles and hanged on the trees releasing its characteristic odor which is supposed to repel olive fly. Since naphthalene has been characterized as possibly carcinogenic to humans and animals, it was considered essential to monitor olive oils regarding their potential contamination with this specific pollutant. To this goal, a simple, sensitive and reliable analytical method for the determination of naphthalene in olive oil has been developed. The method involves extraction with ethyl acetate: acetonitrile (1:1) and determination of naphthalene using gas chromatography triple quadrupole mass spectrometry. The method was validated in four fortification levels, 0.005, 0.01, 0.05, and 0.1?mg/kg in accordance with the EU requirements. The obtained results were acceptable as far as validation criteria are concerned, given recoveries between 71% and 87% and RSDs between 5% and 24%. The limit of determination for naphthalene was set at 0.005?mg/kg based on the lowest concentration level being validated with acceptable accuracy. The analytical technique was successfully applied to 75 olive oil samples collected from oil mills in Greece and no positive results of naphthalene were detected.     

煤飞灰环境标准参考物中PAHs的表征

本文采用不同提取方法以及不同溶剂对煤飞灰环境标准参考物质样品中PAHs的提取效率进行了考察.采用HPLC,毛细管GC以及GC-MS对飞灰样品中的PAHs进行了分析表征,并对前两种分析方法的精密度、准确性和所得结果的一致性进行了研究.     

杭州市居室空气中芳香族化合物污染研究

用热解吸/气质联用技术研究了杭州市居室空气中芳香族化合物的组成。结果表明:杭州市居室空气中共存在60种芳香族化合物,其中苯系化合物48种,非苯芳香族化合物12种,检出率大于50%的23种;在10种非苯芳香族化合物,茚、二氢甲基-1H-茚、二氢二甲基-1H-茚、六氢四甲基亚甲基奥、戊基呋喃等5种化合物的总含量之比为77%-96%,是主要的非苯芳香族化合物污染物,在48种苯系化合物中,苯、甲苯、乙苯、苯乙烯、邻二甲苯、间(对)二甲苯、1,2,4-三甲苯、1,3,5-三甲苯、乙基甲苯、丙烯基苯、乙基二甲苯、二乙基苯、萘等13种的总含量之比大于97%,是室内空气中最主要的苯系污染物。