西藏多不杂铜矿床稀土元素地球化学特征研究

探讨稀土元素地球化学对多不杂铜矿床成矿物质及流体来源的指示意义。选择相关岩矿石及金属矿物样品,测试其稀土元素组成。研究表明,岩矿石及金属矿物均具有轻稀土富集的特征,这是地幔流体作用成矿的标志。由磁铁矿→浸染状黄铁矿→脉状黄铁矿→黄铜矿演化,δEu值逐步从大于1过渡为小于1,即由正铕异常→负铕异常演化,这是含矿地幔流体作用导致熔浆→热液演化,引发交代蚀变,促使壳幔物质混染叠加成矿的依据。从花岗闪长斑岩→变质砂岩→玄武安山岩,总稀土元素呈现出逐步上升的趋势;花岗闪长斑岩和变质砂岩均为含矿地质体,构成了接触带成矿体系,它们的δEu值分别表现为大于1和小于1,即分别呈现出正铕异常和负铕异常;玄武安山岩不含矿,无明显的铕异常。     

河南省洛宁龙门店银铅矿稀土元素地球化学特征及地质意义

龙门店银铅矿片麻岩和中性喷出岩具有相似的稀土配分模式,轻稀土富集,曲线右倾。前者稀土总量较低,平均105.99×10~(-6),δEu=0.71~5.59,总体呈正异常;后者稀土总量略高,平均194.81×10~(-6),δEu=0.84~1.08;花岗岩稀土总量较高,平均231.06×10~(-6),具Eu负异常,混合花岗岩及辉绿岩呈正异常;矿石稀土总量相对较低,平均108.5×10~(-6),Eu正异常和负异常交替出现。岩石和矿石均有轻重稀土分异明显的特征。从片麻岩→矿石→辉绿岩→混合花岗岩→安山岩类→花岗岩,稀土元素总量递增,显示了成矿热液对岩浆岩体的淋滤萃取和对围岩的叠加改造。矿体中的Y/Ho=26.29~37.16,集中于27~31,接近陨石比值,表明矿床形成过程中应该有岩浆热液加入,体现后期岩浆热液的特征,稀土元素总量变大。燕山期岩浆热液对矿石组分有一定的改造,Eu正异常和负异常同时出现,矿石稀土元素特征体现出后期叠加岩浆流体的部分反映。结合石英、黄铁矿、方铅矿及围岩的稀土元素配分模式对比,基本确定成矿物质主要来自岩浆热液,即与蒿坪沟岩体关系密切。     

河南省董家埝银矿稀土元素地球化学特征及地质意义

为研究董家埝银矿稀土元素组成特征及其地质意义,对矿区岩浆岩、地层、构造角砾岩、蚀变岩及银矿石等的稀土元素进行了ICP-MS分析测试。从沉积岩系→片麻岩→构造角砾岩→小河花岗岩→银矿石→蚀变花岗质碎裂岩→闪长岩、辉绿岩,ΣREE逐渐增加,显示了成矿流体对岩浆岩、地层的淋滤改造作用。各类岩矿石的Y/Ho比值均与球粒陨石接近,且在La/Ho-Y/Ho图解上呈近水平分布,表明它们之间具有同源性,存在一定的成因联系。银矿石的稀土元素可分为两组:一组表现为Eu正异常和Ce负异常,反映了原始成矿热液稀土元素特征,指示成矿流体有具相对高温和相对还原的流体特征,且在成矿过程中可能有海水参与;另一组银矿石表现出Eu负异常和Ce负异常,为岩浆热液叠加改造的反映。综合分析认为,董家埝银矿属于中高温裂隙填充型矿床。     

滇西北北衙金多金属矿床稀土元素地球化学

北衙金多金属矿床是三江特提斯成矿域中喜马拉雅期斑岩-矽卡岩型矿床的典型代表。对该矿床钾质斑岩、蚀变斑岩、斑岩型矿石、矽卡岩、矽卡岩矿石、灰岩内热液脉型矿石、蚀变灰岩到灰岩的稀土元素进行了系统的分析测试。结果表明:斑岩型铜金矿石的稀土配分模式为轻稀土富集的右倾型,具Eu弱的负异常,总体继承钾质斑岩体稀土元素特征,成矿流体主要为岩浆热液。矽卡岩稀土配分模式变化较大,可分为三种类型:直线型稀土配分模式、折线型稀土配分模式及平坦型稀土配分模式,其中折线形稀土配分模式呈现Eu正异常。本区矽卡岩属接触交代成因,稀土配分模式的特征与变化特征说明矽卡岩型铁金矿石主要形成于矽卡岩化后期,成矿环境总体上为水-岩比值较大的高温氧化环境。灰岩内热液脉型矿石稀土配分模式为轻稀土富集的右倾型,具Eu正异常,表明热液型矿石形成于较为开放的氧化环境,大气降水与岩浆热液的混合是矿石沉淀的主要机制。北衙金多金属矿床的矿石稀土元素配分曲线变化较大、类型多样,充分显示了成矿流体的多来源和多阶段成矿特征。为北衙矿区成矿作用过程与机制研究提供了稀土元素方面的证据。     

河南老湾金矿床稀土元素地球化学对成矿物质来源的示踪

采用ICP-MS方法测定了河南桐柏老湾金矿床成矿期主成矿阶段石英和黄铁矿的稀土元素组成,以及老湾花岗岩中石英的稀土元素组成,并结合矿床矿石、老湾花岗岩和赋矿围岩全岩的稀土元素组成的对比研究,以期示踪成矿物质来源。分析结果显示,矿床石英和黄铁矿的稀土元素平均总量为13.39×10-6,花岗岩中的石英为6.68×10-6,显著低于矿床矿石、花岗岩和围岩全岩,而矿床石英和黄铁矿的δEu,δCe,轻重稀土分异程度以及稀土元素配分模型都与花岗岩中的石英非常相似,显著不同于赋矿围岩。矿床相关地质体的稀土元素特征表明,成矿流体主要源自老湾花岗岩浆分异的岩浆流体,而非变质流体。     

云南镇康芦子园铅锌多金属矿床稀土元素地球化学特征及意义

芦子园铅锌矿床位于"三江成矿带"南段保山-镇康地块,矿体赋存于上寒武统沙河厂组第二、三段(∈3s2,∈3s3)中的一套碳酸盐岩系中,矿体呈似层状、透镜状、脉状,严格受构造控制,矿体及其周围发育大量的矽卡岩矿物。矿区大理岩和矿石的稀土元素配分模式为轻稀土元素相对富集,具有中等Eu亏损异常及无明显的Ce异常;矽卡岩的稀土元素配分模式可分为两类:一类为中等Eu亏损异常;另一类为无明显Eu异常或较弱的Eu正异常。大理岩、矽卡岩和矿石具有相似的REE配分模式,均为轻稀土元素相对富集型,具有一定的负Eu异常及无明显Ce异常,向右倾斜,通过各类岩(矿)石稀土元素特征分析,并结合矿床地质特征,认为成矿作用主要是在相对还原的环境下进行,其成矿物质来源于深部热液,可能部分来源于赋矿地层(∈3s2,∈3s3)。研究认为,该矿床为赋存于碳酸盐岩地层中明显受构造控制的热液充填交代矽卡岩型铅锌矿床。     

滇东南南秧田钨矿床含矿矽卡岩地球化学特征及成因初探

南秧田矽卡岩型白钨矿床是滇东南老君山W,Sn多金属成矿区的重要组成部分之一。该矿床由多个白钨矿体组成,以层状、似层状矽卡岩型矿石为主。本文在系统野外工作的基础上,对含矿矽卡岩的主量元素和稀土元素地球化学特征进行了研究。测试结果表明,该矿床的矽卡岩具有富铝、富钙、相对富镁、贫碱的特点;稀土元素具有LREE富集的右倾型特征,Eu具有中等负异常,Ce无明显异常。与不同类型矽卡岩相比,南秧田矿区矽卡岩与典型岩浆热液交代成因矽卡岩稀土元素特征类似。结合年代学研究成果,认为南秧田钨矿床和矽卡岩的形成可能经历了加里东期喷流沉积作用、印支期区域变质作用,但最终成型于与燕山期老君山花岗岩相关的岩浆热液交代作用。     

吉林夹皮沟金矿带的稀土元素地球化学研究

为了解吉林夹皮沟金矿带的成矿期次,利用稀土元素的示踪性,对夹皮沟金矿带含矿石英脉、花岗岩及变质地层斜长角闪岩等21个样品进行稀土元素含量测定。测定结果表明,石英脉ΣREE=19.12×10-6～147.57×10-6,δEu=0.61～1.22,平均值0.89,具弱的负Eu异常;太古代花岗岩ΣREE=121.40×10-6～157.32×10-6,δEu=0.87～1.09;中生代花岗岩ΣREE=69.78×10-6～90.95×10-6,δEu=0.94～1.02,LREE/HREE比值分别为11.51～14.12和14.16～16.73,后者轻重稀土分馏程度略高于前者;变质围岩ΣREE=22.40×10-6～275.86×10-6,δEu=0.75～5.79,平均值2.30,具明显的正Eu异常。三者都具有轻稀土富集的平滑稀土配分模型。结合其区域地质背景、流体包裹体和稀土元素特征,得出夹皮沟金矿存在两期成矿作用,分别对应于太古代成矿花岗岩岩浆作用及中生代燕山期花岗岩岩浆作用。太古代首次富集成矿,中生代燕山期叠加成矿并扩大成矿规模,成矿时代分别为2475～2469 Ma和170～160 Ma;结合稀土特征研究及包裹体研究,成矿流体以岩浆热液流体为主,遭受轻微地层变质热液混染,中生代成矿流体混染作用更强烈。     

铜陵狮子山矿田岩浆岩及金矿床的稀土元素地球化学

研究了铜陵狮子山矿田岩浆岩及金矿床矿石和蚀变岩石的稀土元素地球化学特征。矿田内3种代表性的岩浆岩稀土元素含量及Eu异常特征相似,轻重稀土元素比值有规律地变化,反映其具有相同的来源,是同源岩浆演化的结果,稀土元素特征显示岩浆的形成机制为分离结晶作用。金矿床矿石和蚀变岩石的稀土元素球粒陨石配分模式呈右倾斜型式,与矿区岩浆岩基本一致;稀土元素含量界于岩浆岩和围岩大理岩之间,显示成矿流体对岩浆岩的淋滤迁移和对围岩灰岩的叠加改造,反映成矿物质主要来源于岩浆作用;矿石Eu异常特征表明成矿热液为地壳浅部低压下岩浆分异的还原性富Cl-的流体;从成矿早期矽卡岩化到晚期块状硫化物矿石的形成,轻重稀土元素分异和Eu异常特征均显示岩浆热液演化的特征。     

蒙古查干苏布尔加(Tsagaan Suvarga)大型斑岩型铜钼矿床含矿蚀变岩常量、微量和稀土元素地球化学特征及意义

蒙古Tsagaan Suvarga大型斑岩型铜钼矿床围岩蚀变类型主要有网脉状硅化、泥化、石英-绢云母化、钾硅酸岩化和青盘岩化。从热液成矿中心向外的矿化蚀变分带特征为含铜网脉状硅化蚀变带→含铜泥化带→含铜钼石英-绢云母化带→含铜钼钾硅酸岩化带→青盘岩化带。早期为钾硅酸岩化带,中期为石英-绢云母化和硅化,晚期为泥化带和碳酸盐化(方解石)。含矿蚀变岩明显受不同级次构造-裂隙带控制,北东向和北西向裂隙带可能是斑岩成矿热液体系的运移通道。随着接近循环热液成矿体系的成矿中心和硅化不断增强,REE,LREE和HREE含量降低,轻和重稀土元素之间分异程度增强;轻和重稀土元素之间分异程度与硅化-钾硅酸盐化之间关系具有指数关系。随着(Na2O K2O)含量逐渐增高,从负Eu异常→无Eu异常→正Eu异常→明显正Eu异常,说明Eu异常受循环热液成矿体系的碱交代程度控制明显,因此,正Eu异常、轻和重稀土元素之间分异程度明显及其相关围岩蚀变特征是寻找与蒙古Tsagaan Suvarga斑岩型铜钼矿床类似的找矿预测指标。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.