3-(3′-羟基)丁基苯酞氨基酸酯衍生物的设计与合成

3-(3′-羟基)丁基苯酞是丁苯酞在体内的代谢产物,具有多种药理作用,可以作为一种新的活性成分应用于药物开发中。本文以甘氨酸、甲硫氨酸和亮氨酸为起始原料,经过Boc保护,再与3-(3′-羟基)丁基苯酞进行缩合,脱保护3步反应合成了3-(3′-羟基)丁基苯酞的氨基酸酯。以期提高水溶性和改善药代动力学性质,获得3-(3′-羟基)丁基苯酞的前药。     

Sedimentary Steryl Chlorin Esters (SCEs) and Other Photosynthetic Pigments as Indicators of Paleolimnological Change Over the Last 28,000 Years from the Buguldeika Saddle of Lake Baikal

Detailed depth profiles of photosynthetic pigments in a sediment core (G-12) collected at the BDP93 site, the Buguldeika saddle, of south Lake Baikal, along with depth profiles of total organic carbon (TOC) and biogenic silica, were studied to elucidate the temporal changes of phytoplankton assemblages in the lake during the past 28 kyr. In addition to the quantification of carotenoids by high-performance liquid chromatography with photodiode-array detection (HPLC-PDA), steryl chlorin esters (SCEs) were analyzed by HPLC-PDA, HPLC-mass spectrometry (LC-MS) and sterols in SCEs by gas chromatography–mass spectrometry (GC–MS) to enrich the taxonomical information on the phytoplankton composition. Allochthonous input of organic matter from the Selenga River resulted in the higher TOC contents in core G-12 than in a previously reported core (G-6) collected at another site from the southern basin. The poorer correlation in core G-12 than in G-6 between TOC and chlorophyll-a-originating pigments, which are indicative of autochthonous production, also indicated a significant allochthonous input at the site. The abundance of lutein among the carotenoids detected, and the good correlation of total chlorophyll a and b shows that green algae represented a significant portion of the phytoplankton, accompanying the diatoms at the G-12 site, after the last glacial period. The presence of cryptomonads and cyanobacteria were confirmed from marker carotenoids in the sediment core. GC–MS analysis of sterols in SCEs detected marker sterols of diatoms, green algae, chrysophytes and dinoflagellates. The depth profiles of the measured indicators gave consistent features for temporal changes in phytoplankton assemblage at the G-12 site of Lake Baikal after the last glacial maximum. Notably, the profile of a chrysophyte-specific sterol in SCEs was consistent with the reported distribution of chrysophyte cysts during the Holocene. The presence of phytoplankton, such as green algae, diatoms and chrysophytes, in Lake Baikal during the late last glacial period was indicated by the analysis of sterols in SCEs. Sedimentary carotenoids and sterols in SCEs were found to give complementary information about phytoplankton composition. These molecular indicators allow us to reconstruct past lake phytoplankton assemblages responding to environmental changes with a time resolution as high as age–depth relationship in sediments attainable at present.     

超声波萃取-高效液相色谱法测定土壤中邻苯二甲酸酯

邻苯二甲酸酯类(PAEs)是环境激素类物质中的一类化合物。文章对土壤中6种被美国EPA列入"优先监测污染物名单"的PAEs类物质邻苯二甲酸二甲酯(DMP)、二乙酯(DEP)、二丁酯(DBP)、邻苯二甲酸二(2-乙基己基)酯(DEHP)、二辛酯(DOP)、丁基苄基酯(BBP)邻苯二甲酸酯经超声波萃取、柱层析净化后,采用高效液相色谱法测定。对影响加标回收率的实验条件如萃取溶剂比例、萃取时间和萃取溶剂的选择等进行优化。方法回收率为94.1%～108.2%,相对标准偏差(RSD,n=7)为0.70%～2.42%,方法检出限为0.003～0.009μg/g。建立的方法样品前处理简单、快速,溶剂用量少,液相色谱法分析6种PAEs类物质仅用10 min,适用于大批量土壤样品中PAEs类物质的测定。     

Biogenic Volatile Organic Compounds (VOC): An Overview on Emission, Physiology and Ecology

This overview compiles the actual knowledge of the biogenic emissions of some volatile organic compounds (VOCs), i.e., isoprene, terpenes, alkanes, alkenes, alcohols, esters, carbonyls, and acids. We discuss VOC biosynthesis, emission inventories, relations between emission and plant physiology as well as temperature and radiation, and ecophysiological functions. For isoprene and monoterpenes, an extended summary of standard emission factors, with data related to the plant genus and species, is included. The data compilation shows that we have quite a substantial knowledge of the emission of isoprene and monoterpenes, including emission rates, emission regulation, and biosynthesis. The situation is worse in the case of numerous other compounds (other VOCs or OVOCs) being emitted by the biosphere. This is reflected in the insufficient knowledge of emission rates and biological functions. Except for the terpenoids, only a limited number of studies of OVOCs are available; data are summarized for alkanes, alkenes, carbonyls, alcohols, acids, and esters. In addition to closing these gaps of knowledge, one of the major objectives for future VOC research is improving our knowledge of the fate of organic carbon in the atmosphere, ending up in oxidation products and/or as aerosol particles.     

Assessment of storage lipid accumulation patterns in eucalanoid copepods from the eastern tropical Pacific Ocean

Members of the copepod family Eucalanidae are widely distributed throughout the world׳s oceans and have been noted for their accumulation of storage lipids in high- and low-latitude environments. However, little is known about the lipid composition of eucalanoid copepods in low-latitude environments. The purpose of this study was to examine fatty acid and alcohol profiles in the storage lipids (wax esters and triacylglycerols) of Eucalanus inermis, Rhincalanus rostrifrons, R. nasutus, Pareucalanus attenuatus, and Subeucalanus subtenuis, collected primarily in the eastern tropical north Pacific near the Tehuantepec Bowl and Costa Rica Dome regions, noted for its oxygen minimum zone, during fall 2007 and winter 2008/2009. Adult copepods and particulate material were collected in the upper 50 m and from 200 to 300 m in the upper oxycline. Lipid profiles of particulate matter were generated to help ascertain information on ecological strategies of these species and on differential accumulation of dietary and modified fatty acids in the wax ester and triacylglycerol storage lipid components of these copepods in relation to their vertical distributions around the oxygen minimum zone. Additional data on phospholipid fatty acid and sterol/fatty alcohol fractions were also generated to obtain a comprehensive lipid data set for each sample. Rhincalanus spp. accumulated relatively large amounts of storage lipids (31–80% of dry mass (DM)), while E. inermis had moderate amounts (2–9% DM), and P. attenuatus and S. subtenuis had low quantities of storage lipid (0–1% DM). E. inermis and S. subtenuis primarily accumulated triacylglycerols (>90% of storage lipids), while P. attenuatus and Rhincalanus spp. primarily accumulated wax esters (>84% of storage lipids). Based on previously generated molecular phylogenies of the Eucalanidae family, these results appear to support genetic predisposition as a major factor explaining why a given species accumulates primarily triacylglycerols or wax esters, and also potentially dictating major fatty acid and alcohol accumulation patterns within the more highly modified wax ester fraction. Comparisons of fatty acid profiles between triacylglycerol and wax ester components in copepods with that in available prey suggested that copepod triacylglycerols were more reflective of dietary fatty acids, while wax esters contained a higher proportion of modified or de novo synthesized forms. Sterols and phospholipid fatty acids were similar between species, confirming high levels of regulation within these components. Similarities between triacylglycerol fatty acid profiles of E. inermis collected in surface waters and at >200 m depth indicate little to no feeding during their ontogenetic migration to deeper, low-oxygen waters.     

菹草(Potamogeton crispus L.)对酞酸酯污染沉积物的净化作用

酞酸酯是一类典型的内分泌干扰物,在我国城区河湖中污染超标相对严重,且污染呈上升趋势.本文采用根袋法,模拟海河干流水体建立了室内菹草微宇宙,同时设置无菹草微宇宙为对照,研究了沉水植物菹草对沉积物中酞酸二丁酯(DBP)和酞酸二异辛酯(DEHP)的去除作用.实验连续运行27 d.结果表明:系统运行结束时,菹草体内DBP和DEHP含量分别升高了133%和68%;水中,有草组和对照组中DBP的浓度始终低于定量限(8μg/L),而DEHP的浓度则由初始的65μg/L和70μg/L逐渐降低,至第3 d后低于定量限(8μg/L);对照组和有草组非根际沉积物中DBP浓度差异不显著,结束时去除率为32.2%~36.5%,根际沉积物中DBP去除率达50.0%;对照组和非根际沉积物中DEHP浓度差异也不显著,始终在一定范围内波动,结束时去除率为10.3%~11.4%,根际沉积物中DEHP则在第27 d时迅速下降,去除率达80.9%.微生物的结果进一步表明,实验过程中根际土中微生物量明显高于对照组和非根际沉积物,实验后期根际沉积物中微生物群落结构变化较大,这与根际中这两种酞酸酯的去除数据相一致.可见,沉水植物菹草可以通过根际效应有效去除沉积物中酞酸酯类化合物.     

太湖沉积物中长链脂肪酸甲酯化合物的检出及意义

在太湖表层沉积物中检测出丰度较高的一系列长链脂肪酸甲酯化合物,采用标准图谱与质谱解析相结合的方法进行鉴定,长链脂肪酸甲酯化合物有类似正构烷烃的分布型式,碳数分布范围为Ｃ１４－Ｃ３４,主峰碳为Ｃ１６,具有明显的偶碳优势。     

原位微区X射线荧光光谱分析装置与技术研究进展

原位微区X射线荧光(Micro-XRF)光谱分析技术是X射线光谱学领域一重要分支。近年来X射线毛细管光学透镜聚焦技术不断进步,以实验室X光源为基础的原位微区X射线光谱分析装置与应用技术快速发展,已成功应用于多领域样品的原位、多维、动态和非破坏性微区分析。文章介绍了近年来X射线毛细管光学透镜技术发展和原位微区X射线光谱分析装置研制进展,对近年来micro-XRF光谱分析技术在大气气溶胶颗粒物分析与来源识别、考古样品产地和真伪鉴别、古气候古环境重建研究中沉积纹层样品元素分析,以及刑侦科学中指纹样品的鉴定等应用领域进行了系统介绍,阐述了micro-XRF光谱分析技术性能的影响因素(空间分辨率和强度增益)。micro-XRF光谱分析技术不仅可以获取样品表面的信息,还能够获取样品内部的信息,成为目前国际上一门迅速发展的竞争技术。我国在毛细管透镜制造技术与性能研究,以及micro-XRF应用领域取得了重要进展。由于X射线焦斑尺寸对能量的依赖性以及样品基质对X射线的吸收效应,在微区定量分析中易引入较大误差,利用X射线毛细管透镜获取更小光斑尺寸与高稳定性的X射线光束,提高micro-XRF分析技术的空间高分辨率性能和对基体效应进行校正实验将是今后一个重要的研究目标和分析研究难点。     

高效液相色谱-串联质谱法同时测定海洋沉积物中27种有机磷酸酯

应用广泛且具有毒性的有机磷酸酯(organophosphate esters,OPEs)类阻燃剂,通过水、气输送等多种途径进入海洋环境,可能会导致人类和海洋生物面临潜在的健康风险。因此,建立高效可靠的分析方法对于揭示OPEs在海洋环境中的赋存状况,评估其生态风险具有重要的科学意义。文章建立了同时测定沉积物中27种OPEs的超声提取、固相萃取(SPE)净化以及高效液相色谱-串联质谱(HPLC-MS/MS)检测的分析方法。结果表明:30mL乙酸乙酯(EA)和乙腈(ACN)混合溶剂(体积比为3︰7)的提取效果明显优于单独使用甲醇(MeOH)、二氯甲烷(DCM)、EA和ACN;用5mL EA经LC-C18固相萃取小柱洗脱两次回收率最好;以MeOH和含0.0025%甲酸的水溶液作为流动相时,质谱离子丰度最高。27种OPEs的线性范围为5~500 ng/g (R²>0.99),方法检出限(MDL)范围为0.004~1.250 ng/g,定量限(LOQ)为0.01~4.17 ng/g。三个加标水平(低、中、高)基质加标样品的平均回收率在45%~130%之间,相对标准偏差(RSD)最高11.0%,表明此方法可靠,精密度和灵敏度较高。采用优化的方法分析我国长江口、杭州湾入海口以及东海和黄海交界处海域表层沉积物中OPEs的含量,共检出了21种OPEs,浓度范围为9.83~48.70 ng/g,平均浓度为28.40 ng/g。该方法检测结果高效准确,可用于海洋沉积物中27种OPEs的同时测定。     

海洋及其上空大气中有机磷酸酯的研究进展

基于全球海洋及其上空大气中关于有机磷酸酯(OPEs)的数据,分析了目前OPEs在全球海洋及其上空大气的分布特征、影响因素以及当前研究存在的不足。总结发现,海水中的OPEs主要来自河流输送,且浓度分布特征表现为由近及远、由浅及深逐渐递减。磷酸三(2-氯乙基)酯(TCEP)、磷酸三(1-氯-2-丙基)酯(TCPP)和磷酸三(1,3-二氯异丙基)酯(TDCPP)三种卤化OPEs是海水中主要污染物;输入到海水中的OPEs经过颗粒沉降等作用沉积到海洋沉积物中,随之,沉积物中的OPEs可能反析出或直接累积,在海洋沉积物中形成一个大的OPEs储存库。分析北太平洋到北冰洋表层沉积物中OPEs的浓度发现,从白令海峡到北冰洋,随着纬度的增加OPEs的浓度也普遍增加,且相对于非卤化OPEs,卤化OPEs更易被运输到偏远海域。总有机碳(TOC)与大洋沉积物中OPEs的浓度无相关性,但与近海海洋沉积物中OPEs的浓度呈正相关,TCEP和磷酸三异丁酯(TiBP)为海洋沉积物中主要污染物;海洋上空大气与水体中的OPEs是不可分割的,海洋上空大气中的OPEs一部分通过大气沉降进入海水,一部分继续迁移到更偏远区域,气团...