南黄海表层沉积物稀土元素分布与物源关系

对南黄海295个表层沉积物样品稀土元素的电感耦合等离子体质谱法分析,结果表明,南黄海表层沉积物稀土元素平均含量为188.39μg.g-1,稀土富集与重矿物有密切关系;稀土元素的球粒陨石配分模式均呈现Eu负异常,模式具负斜率,表明表层沉积物物质主要来源于大陆地壳。从稀土元素地球化学特征的区域变化来看,南黄海东部沉积物来源于朝鲜半岛,西部沉积物来源于黄河和长江物质输入,中部细粒沉积物主要与黄河及长江物质东南、东北扩散有关,东南部为朝鲜半岛及黄河、长江物质共同作用的结果。     

东海内陆架沉积物稀土元素地球化学特征及物源意义

对位于东海内陆架浙.闽沿岸泥质带的EC2005孔进行了岩性、粒度、稀土元素以及AMS14C年代分析,探讨了研究区自末次冰消期以来的物源变化及其原因.该孔岩性、粒度和稀土元素含量垂向上变化较大,平均粒径变化范围为8-121 μm,∑REE为152.8～227.9μg·g-1.沉积物球粒陨石和世界页岩标准化配分模式均表明研究区物质的陆源属性.根据稀土元素配分模式、稀土内部分馏差异以及与平均粒径的关系,分析认为,研究区17.3～12.3 kaBP期间主要物质来源是湖盆流域物质;12.3～9.8 ka BP是以湖盆流域物质为主向长江物质为主转变的过渡阶段;自大约10～9.8 ka BP开始,长江物质对研究区形成了主导.海平面的升高以及沿岸流的形成是物质来源发生变化的重要原因.     

湟水河西宁段表层沉积物稀土元素地球化学特征及其物源分析

采样测定了湟水河西宁段表层沉积物28个样品的14种稀土元素地球化学含量,分析其含量、特征参数及配分模式,探讨其影响因素及物质来源。结果表明：湟水河西宁段表层沉积物中稀土元素总含量为89.75～217.58 mg·kg^-1,平均值为153.56 mg·kg^-1;28个样品的稀土元素含量变化较为一致,组成特征变化较小,轻稀土元素相对富集,重稀土元素相对亏损,Eu呈中等程度亏损,Ce呈无异常;沉积岩源岩及矿物组成对湟水河西宁段表层沉积物中稀土元素的组成起到控制作用,化学风化对稀土元素的组成无影响;湟水河西宁段表层沉积物的稀土元素特征参数、大陆上地壳和球粒陨石标准化配分模式与青海土壤、黄河沉积物接近,暗示了湟水河西宁段表层沉积物中稀土元素主要来源于湟水河河流侵蚀搬运物,同时其为黄河沉积物中稀土元素提供部分物源。     

稀土元素在长江口及邻近陆架表层沉积物中的分布及物源示踪研究

长江口邻近陆架表层沉积物中稀土元素含量及组成表明其主要来源为中国大陆陆源物质.轻重稀土元素比值对于区分长江和黄河流域来源物质具有一定的示踪意义,古黄河三角洲以较低的轻重稀土元素比值为特征,而长江来源物质以相对较高的轻重稀土比值为特征,沉积物粒度和Cl含量不是控制沉积区内稀土元素分馏的主要因素.通过聚类分析将研究区域划分为长江口近岸区和东海北部陆架区两个分区,黄海沿岸流、长江冲淡水以及台湾暖流是造成分区的关键水动力因素.分区内常量和微量元素以及同位素组成皆表现为不同程度差异,长江口近岸区化学组成和长江流域物质基本一致,东海北部陆架区与黄河流域物质比较接近.     

深海富稀土沉积研究的若干问题

深海富稀土沉积是指稀土元素含量(包含Y)≥400×10~(-6)的一类深海沉积物,以中-重稀土富集、与钙十字沸石紧密共生而区别于其他深海沉积类型。深海富稀土沉积在太平洋和印度洋广泛分布,其稀土氧化物资源量可达1000亿t,其中重稀土资源量约为325亿t,引起了国际学术界的普遍关注。在系统总结深海富稀土沉积的调查研究历史和现状基础上,对其分布特征和规律、地球化学特征、载体矿物、富集机制、物质来源等研究进展进行了阐述,并指出了目前在稀土元素富集机制研究方面存在的几个重要问题:稀土元素的物质来源;沉积物孔隙水对于稀土元素富集的作用;钙十字沸石等共生矿物的成矿指示意义。     

天津沿海潮间带沉积物中稀土元素的地球化学特征

研究了天津沿海潮间带沉积物中稀土元素(REE)的地球化学特性以及污染条件下稀土元素的环境行为特征,通过稀土分布模式特征探讨了潮间带沉积物的物质来源.结果表明(1)潮间带沉积物中14种稀土含量总和的均值为164.5mg@kg-1,但各岸段又有不同.大致以海河口为界,北部明显高于南部,均值分别为182和150mg@kg-1,均明显高于海洋沉积物稀土含量;(2)海岸带沉积物稀土形态分布特征是自北向南残渣态比例逐渐下降,铁锰氧化物态和有机结合态比例逐渐增高,与黄河、长江等大河相比,残渣态和碳酸盐态比例都显著偏低;(3)稀土元素分布模式均为轻稀土富集、铕中度亏损型,与沿海排污河及内陆大河沉积物稀土分布模式相似,而与海洋大陆架沉积物稀土分布模式有显著差别.     

三亚近岸海域表层沉积物稀土元素地球化学特征及物源分析

为充分了解三亚海岸带表层沉积物的物源状况,对三亚近岸海域331个站位表层沉积物的稀土元素进行了分析.结果表明:研究区表层沉积物稀土元素含量略低于南海大陆架和南海全区表层沉积物的平均水平,ΣREE含量分布特征与沉积物粒径有很好的相关性,符合"元素粒度控制律";δEu值也与沉积物粒度有关,与Mz(Φ)为较显著的负相关关系....     

天津沿海排污河中稀土元素的地球化学特征

选择天津沿海的南、北排污河为对象，研究了城市排污河中稀土元素的某些地球化学特征。结果表明，在排污河水体中溶解态稀土含量仍很低，但与其他天然大河相比，Eu和重稀土溶解态含量明显偏高。原水中稀土元素含量较高，以悬浮态为主。轻稀土的溶解态与悬浮态分布模式随原子序递增有相反的变化趋势。沉积物与悬浮物中的稀土含量明显低于其他天然河流，而悬浮物中的稀土含量又明显低于沉积物。沉积物与悬浮物中的稀土分布模式相似，均为轻稀土富集、重稀土亏损、Eu正异常型。这种分布模式与其他天然河流不同，而与本地区含有机质丰富的土壤相似，表明其外源为附近土壤。排污河稀土元素地球化学特性与天然河流的差异可能主要由于其水体中含有大量有机污染物造成的。     

长江下游下蜀黄土的稀土元素物源判别

通过对长江下游镇江、福家湾、新港、芜湖、福路镇等地区下蜀黄土中稀土元素的研究,结合长江古漫滩堆积物及北方黄土沉积物,对下蜀黄土进行了物源判别,得出：下蜀黄土与长江河漫滩之间的各稀土元素的 DF 值绝大部分小于0．2,表现出在各个稀土元素上与河漫滩的接近程度较大,而与北方黄土接近程度较小;由物源指数 PI 计算得出,新港、福路镇、镇江下蜀黄土 PI 值均在0．2附近,表现出下蜀黄土与河漫滩在稀土元素总体上的相似程度极高,物源判别为长江河漫滩;福家湾下蜀黄土物源判别为北方黄土,北方黄土对其有一定影响。总体上,长江下游下蜀黄土受到北方黄土与河漫滩的影响,其中以长江河漫滩影响为主。     

南大西洋中脊表层沉积物中稀土元素的含量及分布模式分析

以HNO3-H2O2-HF为消解体系,对南大西洋中脊16个站位表层沉积物进行消解,应用电感耦合等离子体质谱测定了沉积物中稀土元素(Rare earth elements,REE)的含量,并分析了稀土元素的分布特征。结果表明,微波消解-ICP-MS方法测定稀土元素,各元素的线性关系良好(r=0.9997~1.0000),检出限可达ng/L,精密度好、准确度高,相对标准偏差(RSD,n=3)不大于3.0%,相对误差在6.0%以内。16个站位沉积物样品中稀土总量(∑RE)变化范围为37.25~134.77μg/g,轻重稀土元素含量比值(LRE/HRE)的变化范围是0.61~1.70,平均值为1.27,沉积物中富集轻稀土略明显;从稀土配分模式看出,各个站位REE分布模式基本一致,轻重稀土元素之间有明显的分馏;不同来源沉积物中稀土元素分布模式类似,陆地和海洋沉积物稀土存在稍微差异;沉积物中δEu和δCe均出现负异常,说明了稀土元素主要是来自于海水。本研究分析了南大西洋中脊稀土元素的含量和分配规律,为深入研究大西洋中稀土元素的分布提供技术支撑和参考数据。     

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.