Sequential ultrastructural and biochemical changes induced in vivo by the hepatotoxic microcystins in liver of the phytoplanktivorous silver carp Hypophthalmichthys molitrix

Up to now, in vivo studies on the toxic effects of microcystins (MCs) on the ultrastructures of fish liver have been very limited. The phytoplanktivorous silver carp was injected i.p. with extracted hepatotoxic microcystins (mainly MC-RR and -LR) at a dose of 1000 mu g MC-LReq. kg(-1) body weight, showing a time-dependent ultrastructural change in liver as well as significant increases in enzyme activity of plasma alanine aminotransferase (ALT), aspartate aminotransferase (AST) and lactate dehydrogenase (LDH). We observed for the first time the occurrence of a large amount of activated secondary lysosomes, which might be an adaptive mechanism to eliminate or lessen cell damage caused by MCs through lysosome activation. Quantitative and qualitative determinations of MCs in the liver were conducted by HPLC and LC-MS2, respectively. MCs concentration in the liver reached the maximum (114.20 mu g g(-1) dry weight) after 3 h post-injection, and then rapidly dropped to 7.57 mu g g(-1) dry weight at 48 h, indicating a deputation of 99% accumulated MC-LReq. On the other hand, a decrease trend in glutathione (GSH) concentration was observed in the liver of silver carp while the activity of glutathione S-transferase (GST) increased significantly after injection. The high tolerance of silver carp to MCs might be due to the high basic GSH level in their liver, and/or an increased GSH synthesis. (C) 2007 Elsevier Inc. All rights reserved.

附子及乌头属植物中二萜类生物碱的电喷雾质谱研究

电喷雾质谱是一种软电离技术，生物碱分子中均含有氮原子，具有很高的质子亲合势和气相碱度，特别适合电喷雾质谱分析。本文利用电喷雾质谱系统研究了乌头属的几种植物中二菇类生物碱的质谱行为。并且对中药复方中的生物碱成分的化学变化进行探讨，在串联质谱中，乌头碱类生物碱的裂解方式相似。双酷型、三醋型、脂类生物碱在MS2中容易丢失C8乙酸或长链脂肪酸形成特征子离子峰，在进一步CID谱中，在C15位失去CO为其特征。但是单酷型生物碱在串联质谱中碎裂方式与上述几种生物碱有很大差别，例如，在MSZ中主要失去甲醇，还会失去C3位经基，但是不会失去CS轻基。利用这些规律分析了附子及草乌中的生物碱，发现了多种具有特殊取代基的新化合物。以电喷雾质谱为检测手段分析了附子在炮制过程中的成分变化；并且发现了分离提取脂类生物碱的方法。高乌头中的生物碱以C18型为主，同时也包含少量C19乌头碱骨架的生物碱。这两种类型的生物碱在串联质谱中的碎裂规律相似，都容易失去取代基，而生物碱骨架比较稳定，难以碎裂。但是不同位置的取代基失去时所形成的子离子的丰度有很大差别，经过串联质谱可以获取重要的结构信息。并且通过串联质谱确定了刺乌头碱环糊精的包合位点，更正了文献中的错误。关白附的CZ。型海替生型生物碱在串联质谱中的行为与上述生物碱相似，容易失去取代基，但是在失去取代基的同时，常常伴随骨架中C-C键的断裂。由于这些生物碱的结构存在较强的规律，所以很容易表征其中的结构相似的新生物碱。另一方面，我们发现导致白术与附子配伍将导致共煎液中有毒生物碱成分增加，从而解释了八味地黄丸与人参汤导致中毒的原因。并且通过对八味地黄汤的配伍研究，发现起解毒作用的药材为山茱英，解毒机理为抑制了有毒生物碱的溶出。方中的山药能够抑制双酷型生物碱的水解。

几种中药材的化学成分及其定性定量检测方法研究

本论文由四部分组成。第一部分报道了佛手参提取物的化学成分研究，建立了活性成分含量测定的高效液相测定和指纹图谱研究，采用液质联用技术鉴定了主要色谱峰；第二部分报道了丹参及其复方制剂的特征图谱研究；第三部分探讨了两面针生物碱的电喷雾质谱裂解规律，并采用液质联用技术分离鉴定了提取物中的多种生物碱。第四部分概述了液质联用在药物代谢研究中的运用。 第一部分包括第一、第二和第三章。第一章针对佛手参（Gymnadeniaconopsea）块茎的甲醇提取物，采用大孔树脂和反相硅胶柱层析等各种分离方法，共分离鉴定出4 个化合物，通过波谱分析将它们的结构确定为dactylorhin B (1)、loroglossin (2)、dactylorhin A (3)和militarine (4)。这4 个化合物均是首次从佛手参中分离得到的琥珀酸葡萄糖苷类成分。第二章采用高效液相色谱法对西藏、四川、河北、青海和尼泊尔等不同地区产的十个佛手参样品进行腺嘌呤核苷和对羟基苯甲醇的定量分析，结果表明这2 个成份可视为佛手参的特征成分，但也注意到产地不同该2 个特征成分的含量也有所不同。第三章采用标准中药指纹图谱相似度计算软件，以10 个佛手参样品HPLC 图谱的平均值为相似性评价对照模板，对10 个样品进行了相似度评价，并经液质联用分析指认了7 个共有峰，分别为腺嘌呤核苷(1)、对羟基苯甲醇(2)、对羟基苯甲醛(3) 、dactylorhin B(4) 、loroglossin(5)、dactylorhin A(6)和militarine(7)。 第二部分包括第四、第五、第六和第七章。第四章运用电喷雾质谱检测了对照药材和五个不同产地的丹参药材中脂溶性和水溶性成分，系统地探讨了多种成分的电喷雾质谱规律，并以对照药材为标准建立了特征指纹图谱。五个产地的药II材通过与对照药材相对比，采用聚类分析的方法，得到了定性的鉴别与判断。并采用液质联用技术对丹参药材提取液中的化学成份进行分析，推测了九个特征峰，并对六样品的液相色谱图进行了聚类分析。第五章探讨了三七皂苷的电喷雾质谱电离和裂解规律，并采用电喷雾质谱法对三七标准药材，血通片中的皂苷成分进行了分析。第六章运用电喷雾质谱研究复方丹参片提取液的特征图谱，并和单味药材丹参和三七的特征图谱进行了对比研究。并运用HPLC-ESI MSn 分析鉴定了复方丹参片提取液中的化学成分，推测了12 个色谱峰。第七章总结了电喷雾质谱和液质联用技术在丹参药材，三七药材及复方丹参制剂中的运用的优势和局限性。 第三部分（第八章）研究了两面针生物碱中二氢白屈菜红碱(1)、二氢两面针碱(2)、8-酮基二氢白屈菜红碱(3)、8-丙酮基二氢两面针碱(4)、两面针碱(5)、和1,3-二(8-二氢两面针碱)丙酮(6)等六个苯并菲啶型生物碱的电喷雾质谱裂解规律，其中二氢两面针碱和二氢白屈菜红碱，8-丙酮基二氢两面针碱和8-酮基二氢白屈菜红碱是两对二个甲氧基分别在C-9 和C-10，C-10 和C-11 的同分异构体。实验结果表明，在相同的碰撞能下，这类位置异构体的ESI MS2 质谱二级碎片离子的相对峰度存在很大差异，这可以用于区分该类同分异构体，采用液-质联用可以对两面针的总生物碱提取物中的这些同分异构体加于区分。同时在本实验采用的液相色谱条件下，多种生物碱得到较好的分离，通过和对照品的保留时间，紫外吸收光谱及电喷雾质谱图对照，鉴定了11 个主要色谱峰。 第四部分（第九章）对液质联用技术在药物代谢中的运用进行了综述。 This dissertation consisted of four sections. The first two sections elaborated thephytochemical investigation of the rhizomes Gymnadenia conopsea R. Br., methoddevelopment for rapid identifying and qutifying the chemical condtituent of thistibetant medicine, and the chemical fingerprint analysis of rhizomes of G. conopsea,Salviae miltiorrhiza and P. notoginseng. The third section studied the fragmentationmechanism of six alkaloids from Zanthoxylum nitidium and method development forrapid identifying varieties of alkaloids from the extract of this herbal medicine. Thefourth section reviewed HPLC- MS method in drug metabolism studies. The first section consisted of chapters 1, 2, 3. Chapter 1 elaborated the phytochemicalinvestigation of Gymnadenia conopsea R. Br. Four succinate derivative esters wereisolated from the methanol extract of the rhizomes of G. conopsea through repeatedcolumn chromatography on normal and reversed phase silica gel, their structures weredetermined by ESI-MS, 1D and 2D NMR evidence. They were firstly discoveredfrom this species. In chapter 2, a high-performance liquid chromatography.diodearray detection (HPLC-DAD) method has been firstly developed for quantitation oftwo characteristic constituents, adenosine and 4-hydroxybenzyl alcohol, from theextract of rhizomes of G. conopsea. All 10 samples of G. conopsea contained differentamount of adenosine and 4-hydroxybenzyl alcohol. Adenosine and the4-hydroxybenzyl alcohol can be applied in identification and quality control for theroots of G. conopsea. In chapter 3, a high-performance liquid chromatography.diodearray detection.tandem mass spectrometry (HPLC-DAD-MSn) method has been firstly developed for chemical fingerprint analysis of rhizomes of G. conopsea andrapid identification of major compounds in the fingerprints. Comparing the UV andMS spectra with those of authentic compounds, seven main peaks in the fingerprintswere identified as adenosine, 4-hydroxybenzyl alcohol, 4-hydroxybenzyl aldehyde,dactylorhin B, loroglossin, dactylorhin A and militarine. The Computer AidedSimilarity Evaluation System for Chromatographic Fingerprint of TraditionalChinese Medicine (CASES) was employed to evaluate the similarities of 10 samplesof the rhizomes of G. conopsea collected from Sichuan, Qinghai and Hebei provincesand Tibet autonomous region of China, and Nepal. These samples from differentsources had similar chemical fingerprints to each other. The second section consisted of chapters 4, 5, 6 and 7. In chapter 4，both thecharacteristic spectra of liposoluble tanshinones and aqueous-soluble salvianolic acidswere established by the electrospray ionization mass spectrometry (ESI MS)technique and the differences between standard and crude rhizomes of Salviaemiltiorrhiza Bge. from 5 sources were analyzed. The law of electrospray ion trap mass(ESI ITMS) of typical tanshinones and salvianolic acids is studied.The analysis of the chemical constituent of rhizomes of Salviae miltiorrhiza Bge. byliquid chromatography coupled with mass spectrum (LC/MS) technique wasestablished，and the distances among standard herb and crude herb from 5 sourceswere calculated by clustering analysis. According the DAD spectra and MS2 data，9tanshinones could be speculated. In chapter 5, the character spectra of total saponinsin P. notoginseng extracts were established by ESI ITMS and selective ion monitoring(SIM) technology. The law of notoginsenosides by ESI MS2 was studied. In chapter 6,the characteristic spectra of Compound Danshen Tablet established and compared byESI-MS and HPLC/DAD/MS, 6 known tanshinones and 3 saponins were speculated.In chapter 7, the advantage and disadvantage of the strategy, using the ESI ITMS andLC/MS techniques for study of characteristic spetra of danshen and Compound Danshen Tablet, were summerized. The third section (chapter 8) studied the fragmentation mechanism of six alkaloids,dihydronitidine, dihydrochelerythrine, 8-acetonyl dihydronitidine,8-acetonyldrochelerythrine, nitidine and 1,3-bis (8-dihydronitidinyl)-acetone, by ESIMSn. Tandem mass spectrometry experiments indicated that different substitutionsites of the methoxyl groups at C-9 and C-10 or at C-10 and C-11 determined thedifferent abundances of the MS2 fragmentation ions using the same collision energy.According to the different abundances of MS2 product ions, positional isomericbenzo[c] phenanthridine alkaloids can be differentiated. Moreover, ten constituents inthe crude alkaloids extract from the roots of Zanthoxylum nitidium were rapidlyidentified by high-performance liquid chromatography coupled with tandem massspectrometry (HPLC-MSn), through comparing the retention times and ESI MSn spectra with the authentic standards. The fourth section (chapter 9) is a review on HPLC-MS method development in drug metabolism studies.

余甘子、细叶草乌及土荆皮化学成分研究

本论文由三部分共6 章组成。第一部分报道了余甘子、细叶草乌和土荆皮等三种药用植物的化学成分研究成果；第二部分报道了细叶草乌和土荆皮中分离得到的化合物的活性测试，以及这两种植物的质谱分析；第三部分概述了土荆皮的研究现状。第一部分包括1－3 章。在第1 章、第2 章和第3 章中分别报道了余甘子(Phyllanthus emblica L.) 、细叶草乌(Aconitum richardsonianum var.pseudosessiliflorum) 和土荆皮( pseudolarix kaempferi) 的化学成分。采用正、反相硅胶柱层析等各种分离方法，从余甘子中共分离出10 个化合物，其中1 个为新化合物，另外还有2 个为首次从该植物中分离得到。细叶草乌的化学成分研究尚未见报道，我们从该植物中共分离出15 个化合物，其中6 个为二萜生物碱，9个为非生物碱成分。从土荆皮中分离得到16 个化合物，其中8 个二萜、1 个三萜和7 个其它类型化合物，其中有4 个化合物为首次在该植物中分离得到；从土荆皮挥发油中分离鉴定出了22 个化合物，占挥发油总量的90%。第二部分包括4－5 章。第4 章报道了从细叶草乌和土荆皮中分离得到的13个化合物的药理活性研究，结果显示，展花乌头宁和土荆乙酸葡萄糖苷等表现出较高的组织蛋白酶K 抑制活性；土荆乙酸葡萄糖苷表现出较高的组织蛋白酶B抑制活性；8-去乙酰滇乌碱表现出较高的蛋白质酪氨酸磷酸酶抑制活性。第5 章报道了细叶草乌和土荆皮总浸膏的质谱( ESI-MS ) 分析，研究结果表明，ESI-MS 法可以简单快速地检测这两种植物的主要成分；通过ESI-MS2 分析初步探讨了一些化合物的裂解规律，尝试质谱在其结构测定中的具体应用。第三部分为第6 章。从化学成分、药理、构效关系、主要成分的定量分析、及其合成研究等方面概述了土荆皮的研究进展。 This dissertation consists of three parts. The first part elaborate thephytochemical investigation of three medicinal plants, Phyllanthus emblica L.,Aconitum richardsonianum var. pseudosessiliflorum and pseudolarix kaempferi. Thesecond part reported the bioassay of 13 constituents from Aconitum richardsonianumvar. pseudosessiliflorum and pseudolarix kaempferi, and ESI-MS analysis of these twoplant . The third part is a review on the research progress of pseudolarix kaempferi.The first part is composed of three chapters. Chapters 1-3 focus on the isolationand identification of chemical constituents from Phyllanthus emblica L., Aconitumrichardsonianum var. pseudosessiliflorum and pseudolarix kaempferi. 10 compoundsincluding a new tannin were isolated from the fruits of Phyllanthus emblica by repeatcolumn chromatography over normal and reversed phase silica gel, 2 of them werefirstly reported in this plant. The chemical constituents of Aconitum richardsonianumvar. pseudosessiliflorum never reported before, 15 compounds including 6 diterpenealkaloids were isolated and identified from the roots of this plant. 16 compoundsincluding 8 diterpenes , 1 triterpene and 7 other compounds were isolated from the bark of pseudolarix kaempferi, among them, 4 compounds were firstly reported fromthe EtOH extracts of this plant, and 22 compounds were identified from its essentialoil, representing 90% of the total essential oil.The second part includes chapters 4 and 5. Chapter 4 reported thepharmacological activities of 13 compounds isolated from Aconitum richardsonianumvar. pseudosessiliflorum and pseudolarix kaempferi. Results demonstrated that chasmanine and pseudolaric acid B-β-D-glucoside exhibit relatively high anti-Cathepsin K activities; pseudolaric acid B-β-D-glucoside exhibits relatively highanti-Cathepsin B activity; 8-deacetyl-yunaconitine exhibits relatively high anti-PTP1Bactivity. Chapter 5 reported the ESI-MS analysis of extractions from Aconitumrichardsonianum var. pseudosessiliflorum and pseudolarix kaempferi, it was showedthat ESI-MS can be used as an useful tool in analyzing the major constituents of thesetwo plant much quick and easy, in addition, the fragmentation rules of somecompounds were discussed, in order to find some applications of ESI-MS2 method in their structure determination.The third part is a review on the research progress of pseudolarix kaempferi,including the chemical constituents, pharmacology, structure-activity relationship(SAP), quantitative analysis and synthesis of the major constituents.

共基质对10株细菌降解苯并芘的作用研究

从石油污染的污泥中分离驯化出10株细菌(SB01～SB10),利用生物摇床实验对其降解苯并芘(BaP)的效能进行试验,研究了有(或无)共基质(葡萄糖Glu,或菲PHE)对细菌降解BaP的影响,并采用ANOVA和Tukey多重比较进行分析。结果表明(,1)当以BaP为惟一碳源和能源且BaP初始浓度为50mg·L-1时(MS1),SB01的降解率最高,5d可降解31.0%;以Glu为共代谢基质时(MS2),SB09的降解率最高,可达36.9%;以PHE为共代谢基质时(MS3),SB01对BaP的降解率为46.0%。(2)Glu对SB01、SB02、SB03、SB07、SB10降解BaP有抑制作用,对SB01抑制作用最明显,使SB01的降解率降低了13.1%,Glu对SB05,SB08降解率无明显促进或抑制作用。(3)PHE对细菌降解BaP均表现出促进作用,对SB01的促进作用最明显,使其降解率提高15.0%。(4)Glu对SB09的促进作用大于PHE的促进作用,而对SB06,PHE的促进作用大于Glu。

共基质对10株细菌降解芘的作用

从石油污染的污泥中分离出10株细菌(SB01-SB10),研究了有(或无)共基质(葡萄糖Glu,或菲PHE)对细菌降解芘(PYR)的影响.结果表明:当以PYR为唯一碳源和能源时(MS1),SB01的PYR降解率最高,5d可降解30.4%;以Glu为共代谢基质时(MS2),SB09的PYR降解率最高,可达37.7%;以PHE为共代谢基质时(MS3),SB10的PYR降解率为50.2%.Glu抑制SB01、SB03对PYR的降解,对SB01抑制作用最明显,使SB01的PYR降解率降低7.9%;Glu对SB02、SB07、SB08、SB10降解率无明显促进或抑制作用.PHE对细菌降解PYR均有促进作用,对SB10的促进作用最明显,使其降解率提高29.8%.Glu与PHE对SB04和SB09降解PYR的促进作用无显著差异,而对其它各菌株而言,PHE对PYR降解的促进作用大于Glu.

两种黄酮醇苷同分异构体的电喷雾质谱区分

Two flavonol glycoside isomers of Icariside Ⅰ and Caohuoside C were differentiated by electrospray ionization tandem mass spectrometry (ESI-MSn) method.In the negative ion mode,the two compounds with different glycosyl moieties showed the same ESI-MS spectrum,but obvious different MS2 spectra and thus they can be distinguished rapidly,accurately and easily by ESI-MS.

Analysis of strychnos alkaloids using electrospray ionization Fourier transform ion cyclotron resonance multi-stage tandem mass spectrometry

The fragmentations of four strychnos alkaloids have been investigated by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) in the positive ion mode. Experiments using multi-stage tandem mass spectrometry (ESI-FT-ICR-MSn) allowed us to obtain precise elemental compositions of product ions at high mass resolution. The experimental data demonstrated that the nitrogen bridge and the coordinated oxygen atom on the nitrogen bridge in the alkaloid compounds were the active sites in the MS2 fragmentations. The loss of CH3 or the OCH3 group in those alkaloids, which have an OCH3 substituent, was the dominant fragmentation mode in the MS3 fragmentations. Logical fragmentation schemes for strychnos alkaloids have been proposed and these should be useful for the identification of these compounds.

Characterization of aconitine-type alkaloids in the flowers of Aconitum kusnezoffii by electrospray ionization tandem mass spectrometry

The fragmentation mechanism of aconitine-type alkaloids in the flowers of Aconitum kusnezoffii (FAK) was investigated using electrospray ionization tandem mass spectrometry (ESI-MSn) firstly. The analysis of the collision-induced dissociation (CID) spectra of three purified aconitine standards and six previously reported aconitines indicated that the fragmentation of the protonated aconitines at low-energy CID follows a similar pathway. The elimination of a C-8-substituent such as an acetic acid or a fatty acid is the dominant fragmentation mode in MS2. Successive losses of CH3COOH, CH3OH, H2O, BzOH, and CO are the main fragmentation pathways of aconitine-type alkaloids in MS3 spectra. Based on these features, a rapid method for the direct detection and characterization of alkaloids from an ethanolic extract of FAK is described. All the known aconitum alkaloids are detected and a series of lipo-aconitines has been found for the first time in this plant.

Electrospray ionization tandem mass spectrometric study of the aconitines in the roots of aconite

Fragmentation pathways of aconitine-type alkaloids were investigated by electrospray ionization/ion trap multistage tandem mass spectrometry. Low-energy collision-induced dissociation of protonated aconitines follows a dominant first step, the elimination of the C-8-substituent as acetic acid or fatty acid in MS2 spectra. Successive losses of 1-4 CH3OH molecules, 1-3 H2O, CO, benzoic acid, and CH3 or C2H5 (N-substituents) are all fragmentation pathways observed in MS3 and MS4 spectra. By applying knowledge of these fragmentation pathways to the aconitines in the ethanolic extract of aconite roots, all the known aconitines were detected and also 23 unknown aconitine-type alkaloids, in which the lipo-alkaloids containing residues of 15C, 17C and 19C saturated or unsaturated fatty acids were characterized. These odd-carbon-number fatty acid substituents have not been reported previously.

白山草乌中二萜生物碱的电喷雾串联质谱分析

利用电喷雾串联质谱 ( ESI-MS2 )对吉林省白山市地产草乌的乙醇提取液进行了直接分析 ,方法简便 ,直观 ,用样量少。ESI-MS可以给出分子量信息 ,MS2 方法则可以从复杂体系中获得结构信息。在该植物中发现中乌头碱、次乌头碱乌头碱及中乌头碱的水解产物和脂类生物碱等九种二萜生物碱

Electrospray ionization multiple-stage tandem mass spectrometric analysis of diglycosyldiacylglycerol glycolipids from the bacteria Bacillus pumilus

Electrospray ionization (ESI) combined with multiple-stage tandem mass spectrometry (MSn) was used to directly analyze the glycolipid mixture from bacteria Bacillus pumilus without preliminary separation. Full scan ESI-MS revealed the composition of picomole quantities of glycerolglycolipid species containing C-14-C-19 fatty acids, some of which were monounsaturated, Two main components were identified from their molecular masses and fragmentation pathways. The fragmentation pathway of the known compound compared with the investigated compound verified the proposed structure as 1(3)-acyl-2-pentadecanoyl-3(1)-O-[beta-D-glucopyranosyl-(1-->6)-O-beta-D-glucopyranosyl]-sn-glycerols. A comparison of the multiple tandem mass spectra of the different alkali-metal cation adducts indicates that the intensity of fragments and the dissociation pathways are dependent on the alkali-metal type, The basic structures of glycerolglycolipids were reflected clearly from the fragmentation patterns of the sodium cations, The intense fragments of the sugar residue from the precursor ions were obtained from the lithiated adduct ions. ESI-MSn spectra of [M + K](+) ions did not provide as much fragmentation as [M + Na](+) and [M + Li](+) adducts, but their spectra allow the position of glycerol acylation to be determined. On the basis of MS2 spectra of[M + K](+) ions, it was established that all components have a C-15:0 fatty acid at the sn-2 position of the glycerol backbone and C-14-C-19 acids at the sn-1 position of the glycerol backbone. Copyright (C) 1999 John Wiley & Sons, Ltd.

南极格罗夫山陨石磁性分类研究

陨石分类是一项基础性的工作，是开展深入研究的前提。磁化率(χ)的测量提供了一种快速简单、无损的陨石分类方法，国外已有一些学者开始对陨石的磁性分类开展了研究，但国内尚无这方面研究的报导。本文主要对从南极格罗夫山回收的陨石开展了磁性分类的初步研究，论文主要工作包括以下几个方面： 1) 进行了磁化率测量模拟实验：由于陨石样品具有不规则和大小不等的形状，通过对模拟样品测量，了解上述几何因素对磁化率测量精度和准确性的影响，并作出MS2磁化率测量系统MS2D探头与MS2B传感器测量值之间的校正曲线。对模拟样品测量结果的分析表明，不同形状和大小的样品(所含磁性矿物分布均一)在进行MS2D测量时，测量相对偏差可控制在2%以内，表明上述测量系统可以用于陨石的磁化率测量。 2) 对所选600块南极格罗夫山陨石用MS2D探头进行了磁化率测量，得出这600块陨石的磁化率㏒χ(10-9m3/kg)数据，并用MS2B探头测量其中375块用来作岩石矿物学分类用的小块劈分样品的磁化率㏒χ(10-9m3/kg)。这600块格罗夫山陨石磁化率分布模式与南极其他区域收集的陨石较吻合，对应H、L、LL群呈3个明显的峰分布。相同的陨石用MS2D与MS2B两种探头测量，将它们的磁化率数据进行对比，显示它们的结果相当一致(相关系数R2=0.97)，也同时证明MS2D用于磁化率测量是行之有效的。 3)测量了44块沙漠陨石和9块降落型陨石的磁化率，在此基础上对南极格罗夫山陨石、沙漠陨石及降落型陨石数据做了对比讨论。格罗夫山陨石、沙漠陨石及降落型陨石磁化率值分布出现不同程度的偏移，总体来说磁化率㏒χ平均值为降落型陨石>南极陨石>沙漠陨石，这主要是由于陨石所受风化程度的差异造成的。风化作用使陨石部分金属发生氧化，因而降低了磁化率。 4)基于陨石的岩石矿物学分类，172块平衡型普通球粒陨石的磁化率分布，与文献上南极陨石磁化率分布基本一致，不过格罗夫山H、L、LL型普通球粒陨石磁化率分布范围更为狭窄，反映了南极不同地区陨石风化程度的差异。 5)讨论了陨石磁化率分类的有效性，分析了部分异常值出现的原因。磁化率分类结果与部分格罗夫山陨石的岩石矿物学分类(申请者作为陨石分类小组成员完成了其中的部分工作)结果相当吻合，仅在群之间约有5%的重叠，表明磁化率可作为化学群分类的重要参考数据。由于各陨石所受风化程度的差异，风化程度较强的少量陨石在磁性分类的基础上，还需其他工作加以证实。部分小质量(小于3g)且有部分或完整熔壳的陨石，磁化率受熔壳的影响达10%以上，偏离了其初始矿物的磁化率值，不能反映其真实的化学群类型，这部分磁化率数据仅供参考。

D4.2 – Full Design Document

This deliverable outlines the design blueprints for the RAGE application scenario games and forms the rest of the scope for WP4’s tasks. The game designs have been developed in collaboration with application scenario partners in WP5, and informed by WP1, 2 & 3. Additionally peer-feedback has been provided by game developers across WP4. The designs outline the integration of the RAGE assets developed in WP2 and WP3. Each section provides in detail the game play descriptions, game dynamics and mechanics, pedagogies and technical implementation of the RAGE assets into the game applications as described in detailed in WP5’s application documents. The full description of the application objectives and associated learning outcomes has been provided in the project’s MS2 Application Scenario Outlines document.

Atmospheric pressure chemical ionisation liquid chromatography/mass spectrometry of the ultraviolet screening pigment scytonemin: characteristic fragmentations

Atmospheric pressure chemical ionisation reversed-phase high-performance liquid chromatography/multistage mass spectrometry has been used to study the mass spectral fragmentation of the cyanobacterial sheath pigment scytonemin and its reduced counterpart. The two pigments exhibit characteristic fragment ions in their MS2 and MS3 spectra that are of value in confirming the identification of the structures in extracts from natural environments.