云南腾冲土官寨离子吸附型稀土矿床地球化学特征

运用岩石地球化学方法,对云南腾冲土官寨矿区离子吸附型稀土矿床的地球化学特征进行研究。结果显示:风化层较基岩明显富集Al_2O_3, Fe_2O_3, FeO等,贫化CaO, Na_2O, MgO, K_2O等元素,绝大多数微量及稀土元素均有不同程度的富集;垂向上从上到下稀土含量总体呈现"低-高-低"的抛物线形态, Ce元素与其他元素之间发生了明显的分异现象,个别样品中表土层稀土含量较高且含矿层较厚可能是由于风化历史时期的构造沉降作用造成的;由半风化层到全风化层, REE元素均为迁入,其中∑LREE迁入程度较∑HREE高,与不同稀土元素的水解能力和黏土矿物吸附选择性有关,而由全风化层到表土层, REE元素则发生了不同程度的降低。     

岩溶地下河系统中表层土壤稀土元素含量及分布特征

以桂林寨底地下河系统中表层土壤为研究对象,采用激光剥蚀电感耦合等离子体质谱(LA-ICP-MS)进行稀土元素测试分析,开展了稀土元素地球化学研究,研究结果表明:研究区内土壤稀土元素总量∑REE分布范围为117.82~451.98μg·g~(-1),平均为312.30μg·g~(-1),变化范围属中等分异型,高于中国大陆的土壤稀土元素总量背景值。轻稀土总量LREE高于中国大陆土壤LREE背景值,重稀土总量HREE略低于中国大陆土壤HREE背景值。LREE/HREE平均值为7.86,与北美页岩LREE/HREE值7.47相接近。土壤样品的北美页岩标准化曲线具有略轻稀土富集的右倾特征,Ce和Eu均表现出微弱的负异常特征,与研究区内成土母岩有一定的关系。虽然成土母岩决定着土壤中稀土元素的初始含量,但最终含量还受到其他因素的影响。     

黔西南卡林型金矿床稀土元素地球化学特征

分析了黔西南地区板其、、丫他及戈塘等卡林型金矿床的(La/Yb)N、(La/Sm)N、∑REE及LREE/HREE等稀土元素的含量及参数特征.结果表明,该区金矿床相对富集LREE;该区戈塘金矿具有明显的MREE富集及正Eu异常的特点,表明成矿热液应该是一种还原性流体,来源于深部或至少经历过对富含斜长石源区的水-岩反应矿...     

桂林寨底地下河系统中地下水稀土元素含量及分异特征

对寨底地下河系统中地下水样品进行水化学指标测试和稀土元素测试分析,开展了稀土元素地球化学研究,研究结果表明:寨底地下河系统中地下水∑REE质量浓度偏低,大部分水点表现出LREE亏损、HREE富集的特点。∑REE质量浓度与地下水pH,Eh的相关性不明显,地下水中HCO_3~-和Ca~(2+)对∑REE浓度的影响程度相似,地下水中HREE富集与pH有一定关系。采用北美页岩标准化后大部分地下水稀土元素分布表现出Ce负异常和Eu正异常;Ce负异常与Fe,Mn有一定的相关性,Eu正异常与地下水系统氧化还原条件有关。整个地下河系统包含的子系统中,地下河子系统与岩溶泉子系统稀土元素富集、分异特征存在差异。     

乌江流域沉积岩风化过程中稀土元素的富集与释放

以乌江流域石灰岩、白云质灰岩、白云岩、硅质岩、页岩和砂岩等沉积岩的13条风化剖面为对象，运用R型分层聚类分析和质量平衡计算方法，研究了这些岩石风化过程中稀土元素（REE）的富集与释放及其对植物生长和河水REE分布的影响，目的是为河水物质来源研究和为农业生产提供依据。结果表明：（1）乌江流域石灰土中REE的富集程度显著高于各自母岩、黄壤、上陆壳（UCC）、中国土壤（CS）和世界土壤（WS）；（2）沉积岩风化过程中REE的富集特征和机制可能与母岩中REE分布特征以及风化剖面中有机质、铁（氢）氧化物和粘土矿物的吸附有关；（3）沉积岩风化过程中释放的REE可为植物吸收利用；（4）石灰岩等沉积岩风化过程中REE和F。等元素的释放对河水溶解态REE的分布有重要影响。     

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。     

云南鹤庆盆地岩溶地下水稀土元素地球化学特征

为揭示云南鹤庆盆地岩溶地下水中稀土元素地球化学特征,对该盆地内主要岩溶泉水和地下河水样进行了水化学常规指标测试和稀土元素测试,分析研究了该地区地下水中稀土元素质量浓度、配分模式以及分异特征和影响因素。结果表明:由于含水岩组的截然不同,造成盆地东部岩溶地下水比西部岩溶地下水ΣREE质量浓度高,该地区岩溶地下水中ΣREE浓度与Eh,HCO_3~-,Ca~(2+)有负相关性,与pH,DO,Fe和Mn有较好的正相关关系,高含量HCO_3~-和Ca~(2+)在一定程度上制约了REE在水中的溶解,铁锰氧化物矿物的还原性溶解是REE进入地下水的主要途径。地下水中LREE有富集、有亏损,还有部分既不富集也不亏损,盆地东部地区地下水中HREE富集程度远远大于西部地区地下水。该地区岩溶地下水表现出明显的Ce负异常和Eu正异常,可能与含水岩组岩性和还原环境有关,同时高Ca~(2+)和HCO_3~-的环境中,Eu~(2+)更容易被释放出来进入地下水中。在地下河管道中,地下水经过长距离的地下径流后,地下河出口∑REE质量浓度高于岩溶泉水,且与入口相比,出口地下水中轻稀土富集和Eu正异常有所增强,Ce负异常程度减少。     

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.     

酸雨胁迫及稀土农用条件下菠菜及其土壤中稀土元素的赋存

利用盆栽实验研究了酸雨胁迫、稀土农用条件下 ,菠菜及其土壤中稀土元素的含量及分布特征。结果表明 :菠菜地上部分的REE含量为 0 .5 2 7～ 0 .696μg·g- 1 之间 ,地下部 2 .668～ 3 .0 0 3 μg·g- 1 。土壤 2 2 9.0 9～ 2 5 0 .3 μg·g- 1 。酸雨明显地影响作物对REE的吸收和利用 ,酸度越大 ,影响越明显。随着酸雨酸度的增大、植株体内、土壤中的REE受淋洗的作用加强而表现出REE的总量随着pH的减小而逐渐减少。施用稀土后 ,植株的地上或地下部分及其土壤中的REE含量均与对照的土壤中的REE分配模式基本相同 ,遵循稀土元素分布丰度的奇偶 (Oddo Harkins)规则、轻稀土富集 ,Eu弱负异常 ,富铈配分型 ,表明稀土元素仍然主要来自土壤并受其影响。     

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.     

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.     

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.     

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.     

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.