重庆市江津区表层土壤中稀土元素含量与分布特征

为研究重庆市江津区表层土壤中稀土元素(REE)含量和空间分布特征,采集156件土壤样品,用电感耦合等离子体质谱仪(ICP-MS)测定其稀土元素含量。采用统计学和地质统计学分析了表层土壤中稀土元素含量和空间分布特征,结果表明:江津区表层土壤中REE含量范围为99.06～222.28μg·g~(-1),平均值149.07μg·g~(-1),低于中国土壤REE背景值(163.86μg·g~(-1))。江津区表层土壤的球粒陨石标准化曲线呈现向右倾斜的轻稀土富集型。δEu和δCe平均值分别为0.57和0.91,表现出明显的Eu负异常和微弱的Ce负异常。不同地质时代地层上覆表层土壤中REE含量具有显著差异性(p=0.0350.05),下白垩统窝头山组(K_(1w))和侏罗系(J)地层上覆表层土壤中稀土元素含量高于三叠系(T)地层。江津区中西部地区表层土壤中稀土元素总量较高。     

南方离子型稀土矿区马尾松稀土元素的分布与富集

为探讨南方离子型稀土矿区马尾松地上部分各器官稀土元素的分布与富集特征,采集福建省长汀县濯田镇马尾松下的土壤样品和地上部分各器官(树皮、树干、树枝和树叶)样品,测定其稀土元素。结果表明:马尾松下的土壤稀土元素含量平均值为275.15 mg·kg~(-1),轻重稀土元素分异明显, Ce元素富集明显, Eu元素相对亏损;马尾松地上部分各器官稀土元素含量普遍较低, LREE高于HREE,轻重稀土元素分异。马尾松地上部分各器官稀土元素球粒陨石分布模式中, Ce元素和Eu元素明显正异常,马尾松树干、树叶重稀土元素标准化后明显波动分布,呈锯齿状,马尾松树皮和树枝波动幅度小;其δCe(δEu)均大于1, Ce和Eu元素明显富集。马尾松地上部分各器官稀土元素的吸收系数均较小,该地区稀土元素由土壤到植物的迁移程度低,马尾松地上部分各器官对稀土元素的富集能力弱,但其生物量和提取稀土元素的能力不容忽视,可尝试将植物提取技术运用于该地区的稀土净化。     

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。     

密云县潮河流域沿岸铁矿集中区土壤中稀土元素的地球化学特征及粒度效应

研究评价了原土及粒级土壤中稀土元素地球化学特征以及粒度效应。采用ICP-MS对原土和各个粒级土壤中15种稀土元素,包括La,Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb,Lu和Y进行了测定。结果表明:研究区内土壤中稀土元素的含量高于中国大陆土壤稀土元素背景值,平均值变化较大;15种稀土元素含量与不同粒级的关系趋势一致,即随着粒径的减小而呈现增大的趋势;原土及各粒级土壤经Masuda(1973)的6个Leedy球粒陨石平均值标准化后,REEs的配分模式一致,呈富集轻稀土的右倾型,明显的Eu负异常,Ce弱亏损,主要受陆源控制。潮河流域沿岸土壤中REE随粒度的变化特征与粘土矿物对其吸附及不同粒级中的矿物成分密切相关。该研究结论为选取稀土元素作为示踪剂提供了科学依据,并为不同粒径组分中稀土元素的进一步研究提供一定的参考价值。     

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。     

厦门西海域表层沉积物中稀土元素分布特征

以厦门西海域表层沉积物为对象,研究了沉积物中稀土元素(REE)的分布特征.结果表明:厦门西海域沉积物中REE含量为125.71～206.02 μg·g-1,西部港湾区的8号和九龙江口的2号采样点REE含量较高,且轻稀土占绝对优势.REE含量随沉积物粒级呈有规律的变化,REE含量最高的是＜63μm的粒级,最低的是250 μm的粒级;沉积物经球粒陨石标准化后,各粒级REE总体配分曲线相近,均表现为明显的Eu亏损和Ce亏损,且＜63μm粒级亏损尤为严重.Eu与Ce异常平均值均小于黄河流域和长江流域沉积物;＜63μm粒级的沉积物中轻重稀土分馏程度最高,但在其他三种粒级沉积物中由粗到细分馏程度逐渐降低.分馏现象表明细粒级沉积物轻重分馏较粗粒级明显.与当地土壤稀土元素背景值比较,沉积物主要来自厦门西海域本地的土壤.     

赣南小流域水体中溶解态稀土元素地球化学特征

以亚热带富稀土背景区的赣南水系为研究对象,通过ICP-MS测定,探讨了赣南小流域水体中溶解态稀土元素的含量及分布模式,结果表明：赣南小流域溶解态稀土（DREE）含量均值为1.2845μg·L^-1,其浓度高于长江、珠江等内陆天然河流,这反映了其富稀土背景的特点。该区溶解态稀土元素分布模式表现出Ce明显的负异常和Eu正异常,这与同一背景下表土层中的Ce正异常和Eu负异常是相对应的。溶解态稀土元素的页岩标准化分布模式表现为中重稀土（MREE/HREE）富集型,这是由于该区富含重稀土矿物的易风化的氟碳钙钇矿的存在引起的。     

宁都盆地典型脐橙园土壤稀土元素地球化学特征研究

为研究宁都盆地典型脐橙园土壤稀土元素地球化学特征,在宁都盆地内共采集30组土壤样品,对REE组成特征、配分模式、参数特征、Eu亏损原因进行分析和讨论。结果表明：土壤样品总稀土含量平均值为346.16 mg·kg^-1,分别是江西土壤稀土背景值、中国南方红土土壤稀土平均值、中国土壤背景值、北美页岩值、地壳值含量的1.64倍、1.97倍、1.84倍、1.85倍、1.83倍。园内所有样点配分曲线均呈现出右倾的几何形态,∑Ce/∑Y平均值为4.26,显示出土壤中轻稀土相对富集的特点,具有明显的Eu负异常。(La/Yb)_N,(Gd/Yb)_N参数值表明轻稀土元素具有更为显著的分馏作用。δCe,δEu计算结果显示,Ce负异常点主要集中在基岩岩性为花岗岩的土壤中;30组样品Eu则全部呈现出明显的负异常,表明区内土壤具有共同的陆源属性,以酸性岩为主,与区内大面积分布花岗岩相一致。土壤中Eu亏损的主要原因是成土母质存在一定的亏损及土壤发育过程中Eu发生氧化还原反应淋失产生的亏损叠加。La/Yb-∑REE图解显示白垩纪砂岩、砾岩基岩区土壤7组样...     

黄土高原表层土壤中稀土元素含量及其对稀土农用效果的影响

用中子活化法（ＩＮＡＡ）测定了黄土高原地区主要类型土壤（表层）１０４个样品中８个稀土元素（Ｌａ，Ｃｅ，Ｎｄ，Ｓｍ，Ｅｕ，Ｔｂ，Ｙｂ，Ｌｕ），初步探讨了该区土壤中稀土元素的区域分布及对稀土农用效果的影响。结果表明，黄土高原土壤中稀土元素的含量接近全国土壤中的平均含量：主要类型土壤的稀土元素含量分布规律为：灰褐土，娄土＞黑垆土，黄绵土＞灰钙土，与土壤粘粒含量相似，由东南向西北呈下降趋势：该区较适合于农用稀土的推广应用。     

湖南辰溪特高有机硫煤的稀土元素特征及其成因

采用高分辨率电感耦合等离子质谱(HR-ICP-MS)技术测定辰溪晚二叠世高有机硫(7.75%)煤中的稀土元素(REEs)。辰溪煤中∑REE变化较大,从38.84 μg/g至305.85 μg/g,加权平均值为104.57 μg/g,高于世界煤均值,与中国煤相近。辰溪煤中有明显的Ce负异常(δCe=0.74~0.84)和Eu的负异常(δEu=0.55~0.69)。煤层剖面上稀土元素含量和分布模式的变化反映了成煤环境的波动,从底板到顶板陆源物质的影响减弱,而海水的影响增强。沉积环境的阶段性变化是导致剖面上下有机硫与黄铁矿硫比值相差悬殊的原因。辰溪煤中稀土元素与铁呈现了显著的正相关性(n=11,r=0.95),说明其物质来源和富集条件有一定相似性,即陆源物质和海水共同影响的结果。稀土元素的分布模式以及∑REE与灰分、Si、Al的相关性说明了其主要来源于陆源物质;辰溪煤中δCe与δEu在剖面上变化很小,说明海水对煤中的稀土元素存在重新改造的作用。     

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%.     

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.     

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.     

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 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.     

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.     

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.     

Microwave-assisted copper-catalyzed stereoselective ring expansion of three-membered heterocycles with α-diazo-β-dicarbonyl compounds

Microwave-assisted copper-catalyzed ring expansions of three-membered heterocycles with α-diazo-β-dicarbonyl compounds were investigated. Thiiranes generated 3-acyl-5,6-dihydro-1,4-oxathiines in the presence of copper sulfate and trans-3-acyl-5,6-dihydro-1,4-oxathiines as stereospecific products for 1,2-disubstituted cis-thiiranes through an intramolecular S_N2 process. Oxiranes gave rise to 2-acyl-5,6-dihydro-1,4-dioxines under the catalysis of copper hexafluoroacetylacetonate and cis-3-acyl-5,6-dihydro-1,4-dioxines as stereospecific products for 1,2-disubstituted cis-oxiranes via an intimate ion-pair mechanism. The current method provides a direct and simple strategy in efficient preparation of 3-acyl-5,6-dihydro-1,4-oxathiines and 2-acyl-5,6-dihydro-1,4-dioxines, important agents in medicinal and agricultural chemistry, from readily available thiiranes and oxiranes, respectively.