黑山热液型矿床稀土元素的地球化学行为

通过对岩石,矿石的稀土组成研究,揭示含矿热液稀土总旧为２．４８４－１１．７７８μｇ．ｇ＾－１,富集轻稀土型分布模式及铕,铈负异常。δＥｕ和δＣｅ表明从早至晚热液体系向氧化程度增加的方向演化。     

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。     

二道沟金矿床中的稀土元素地球化学特征

通过对未蚀变流纹岩，蚀变流纹岩和金矿石中稀土元素组成及分布模式的研究，表明岩浆热液与以大气降水为来源的地下水相混合后形成的成矿热液中稀土元素具有富集ＬＲＥ、稀土元素总量低以及Ｅｕ具有明显负异常的特征。     

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。     

鄂尔多斯盆地油气伴生水的REE地球化学特征

研究了鄂尔多斯盆地油气伴生水的稀土元素地球化学特征.结果表明,油气伴生水的稀土元素含量明显偏高,物质来源具有多源性;油气伴生水普遍形成强度不等的Eu和Ce负异常,表明其主要形成于还原环境,但在后期演化过程中经历了氧化环境的改造,并与围岩发生过相互作用,且受后期改造程度较高.该油气伴生水的稀土元素球粒陨石标准化曲线具有4种基本模式,其中,SH-4样品的稀土总量∑REE极高,稀土总量介于上地幔和下地壳的岩石之间,稀土模式图及稀土比值特征接近下地壳,显示其中有深部物质加入.在基底断裂发育、构造活动相对强烈的区域所赋存的油气伴生水中,深部物质组分相对较多,表明其在运移过程中可能与深部岩石有过相互作用,抑或有深都流体物质加入.     

稀土二元系相图的基本类型和二元化合物的生成规律

以周期表中各元素与稀土形成的化合物组成与结构为依据,讨论了化合物组成范围与组元X的d、S、SP电子组态的关系、化合物的稳定性及镧系收缩现象。对某一给定化合物类型,化合物单胞体积的立方根与三价稀土离子半径存在着线性关系。由化合物生成时的体积收缩找到化合物稳定性和组元X在周期表中位置的关系,与电子组态的影响一致。总结了铈、铕、镱的价态行为与组元X在周期表中的位置的关系。     

离子吸附型稀土矿床的成矿机制

研究表明在弱酸性条件下,单一稀土元素在风化壳内的迁移能力常随原子序数的增大而增强(铈与铕例外);粘土对稀土元素的吸附率常随pH上升而增高,地下水的渗流、淋溶作用与环境pH是控制稀土总量呈“抛物线”型富集的主导因素,稀土元素在地下水中可能与HCO_3~(3-)、SO_4~(2-)、NO_3~-、Cl~-等结合迁移或呈自由离子形式运移。     

AZ91镁合金表面稀土转化膜的制备及耐蚀性能研究

采用在镁合金表面形成无毒、无污染的稀土铈转化膜的方法解决AZ91镁合金表面的腐蚀问题。确定了最佳成膜工艺参数，讨论了处理液的浓度、成膜温度和成膜时间等因素对转化膜耐蚀性的影响。利用湿热实验、阳极极化曲线的测定等实验方法评价了转化膜对镁合金表面的防护作用。结果表明，在潮湿温热条件下稀土铈转化膜试样仍能保持膜层的完整性并具有较高的覆盖度，腐蚀现象不明显。腐蚀电势升高，出现钝化现象，腐蚀电流密度下降，稀土铈转化膜可以提高AZ91镁合金的耐蚀性能。用扫描电镜观察了膜的微观形貌，稀土铈转化膜是由基膜和附着的细小颗粒组成，最佳工艺形成的铈转化膜无破碎现象，对AZ91镁合金表面的腐蚀过程的发生有明显的抑制作用。     

苏皖四处凹凸棒石粘土矿床稀土元素地球化学研究

研究了苏皖四处凹凸棒石粘土矿床不同类型矿石的烯土元素组成及其变化特征。研究表明玄武岩首先风化形成蒙皂石族粘土矿物，在此过程中稀土元素没有明显的分馏作用，强风化的玄武岩重稀土元素强烈亏损；如果玄武岩在地表进一步风化形成红土型蒙脱石粘土，则发生明显的铈正异常，中稀土亏损而轻稀土和重稀土又重新富集，这反映了当时大陆地表特殊的氧化条件和盆地湖水溶液的胶体吸附作用。玄武岩在原地进行水－岩作用，发生递进化学风化，其稀土元素地球化学特征与玄武岩及其风化产物的稀土元素化学特征基本一致，总量略低，显示REE没有大量迁移流失，沉积型凹凸棒石粘土的稀土元素地球化学特征也与玄武岩及其风化产物的稀土元素地球化学特征相似，但同时表现出轻重稀土比值磁大，铕正异常，表明沉积型凹凸棒石粘土的物源基本上是来源于玄武岩的风化产物，但REE配分模型受玄武岩风化残积物的制约。     

滇东北矿集区茂租铅锌矿床萤石的稀土元素特征及其指示意义

巧家茂租铅锌矿床是滇东北矿集区的代表矿床之一,除矿石矿物闪锌矿、方铅矿、黄铁矿外,萤石是其主要的脉石矿物。通过萤石的稀土元素地球化学特征研究,发现其中REE含量变化较大,特征参数也有差别,但其球粒陨石标准化曲线分配模式基本一致,不同矿化带萤石均具有明显的Ce负异常、中稀土富集、分配曲线相对平缓的特征。从铅锌矿体中心到外围矿化带,萤石稀土元素呈现∑REE逐渐减少、LREE富集变为HREE富集,δEu正异常变为δEu负异常,δCe逐渐变小的变化特征。表明该矿床萤石的形成是一个连续过程,不同矿化带的萤石是同一体系经历不同阶段的产物。通过萤石的形成机制分析,认为该矿床萤石是热液作用的产物,是由富含F的成矿流体沿构造活动带从下向上运移,与灯影组地层的白云岩发生水-岩的相互作用,使流体中的CaF_2产生过饱和而大规模沉淀析出形成的,且随着热液向两侧围岩迁移,不断与围岩发生水岩反应,分别形成了不同矿化带的萤石。本文研究对揭示矿床铅锌成矿机制具有重要意义。     

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%.     

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.     

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.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

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.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.