个旧超大型锡多金属矿稀土元素地球化学特征

对比研究了个旧不同类型岩(矿)石(蚀变花岗岩、钙质泥岩、大理岩、矽卡岩矿石、层状矿石和脉状矿石)的稀土元素、微量元素地球化学特征,借以示踪不同类型矿床的成矿物质来源。研究表明不同类型矿石中的稀土元素配分曲线较为相似,成矿物质具有同源性,并与本区的花岗岩具有一定的成因联系。由于其成矿方式的不同,不同类型矿石中的稀土元素特征和矿物组合特征略有差异,脉状矿石和层状矿石中稀土含量相对较少且富集轻稀土,而矽卡岩矿石中稀土含量相对较多且轻、重稀土的含量变化较大。     

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。     

皖南西坑Ag-Pb-Zn矿床稀土元素地球化学研究

对比研究了皖南西坑银多金属矿床中赋矿围岩蓝田组地层、成矿有关的花岗岩、矿石、矿床蚀变岩等地质体的稀土元素地球化学特征 ,借以示踪成矿物质来源。结果表明 ,西坑银多金属矿床成矿热液、成矿物质主要来源于花岗岩浆作用 ,成矿热液和富碳酸盐岩地层水岩反应使蚀变岩相对富集重稀土。     

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。     

皖南西坑Ag—Pb—Zn矿床烯土元素地球化学研究

对比研究了皖南西坑银多金属矿床中赋矿围岩蓝田组地层、成矿有关的花岗岩、矿石、矿床蚀变岩等地质体的稀土元素化学特征,借以示踪成矿物来源。结果表明,西坑银多金属矿床成矿热液、成矿物质主要来源于花岗岩浆作用,成矿热液和富碳酸盐岩地层水岩反应使蚀变岩相对富集重稀土。     

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。     

万洋山-诸广山加里东期花岗岩的物质来源——Ⅱ.同位素多维空间的拓扑分析

Sr-Nd-O-Pb~3六维同位素空间的拓扑分析结果表明,万洋山-诸广山加里东期花岗岩的源岩主要由三端元物质组成,混合模式判别证明花岗岩是由三端元组分不同比例混合的产物,多元同位素体系和元素地球化学综合示踪研究表明,这三端元地壳成分为陆源沉积物、地槽沉积物和蚀变的基性火山岩。     

贵东花岗杂岩体的稀土元素特征及与铀成矿关系

贵东花岗杂岩体是一个由鲁溪岩体、下庄岩体、帽峰岩体、笋洞岩体、隘子岩体和司前岩体等组成的印支-燕山期复式花岗岩体，不同的岩体不仅在主要元素含量、铝过饱和指数等方面存在差异，而且在一系列稀土元素特征方面，如稀土总量、δEu值以及LREE／HREE、（La／Yb）N、（La／Sm）N、（Gd／Yb）N比值等，也存在很大的不同。铀矿体常常赋存在强过铝质、并且后期发生了强烈的流体．岩石相互作用的花岗岩体中，这些岩体典型的稀土元素特征是稀土总量、δEu、LREE／HREE、（La／Yb）N、（La／Sm）N、（Gd/Yb）N比值等均较低，并具有M型四分组效应。     

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。     

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%.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

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.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

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.