Eu(Ⅲ)在蒙脱石上的吸附及碳酸根和磷酸根对其吸附的影响

锕系核素在处置库围岩和缓冲回填材料中的吸附和迁移参数是处置库安全评价的重要数据模块之一，而Eu(Ⅲ)由于其与三价锕系元素An(Ⅲ)相似的离子半径和化学性质常被用于模拟三价锕系元素的化学行为。本文通过批式吸附实验研究了固液比、接触时间、离子强度、pH、碳酸根及磷酸根等对Eu(Ⅲ)在蒙脱石上吸附的影响，重点关注了吸附机理和表面种态。研究结果表明，低pH时Eu(Ⅲ)在蒙脱石上的吸附方式为外层配位吸附，近中性时为内层配位吸附，高pH时则以表面沉淀的方式被吸附。离子强度的增大对Eu(Ⅲ)在低pH时的吸附产生抑制作用。低pH时碳酸根对Eu(Ⅲ)吸附的影响不明显，但在高pH时其会改变Eu(Ⅲ)的表面吸附种态。尽管磷酸根本身的吸附非常弱，但磷酸根会显著增强Eu(Ⅲ)的吸附。X射线光电子能谱结果和磷酸根吸附实验说明Eu(Ⅲ)在蒙脱石表面上形成了EuPO₄沉淀。本工作研究了蒙脱石/Eu(Ⅲ)二元体系和蒙脱石/Eu(Ⅲ)/阴离子三元体系的吸附行为，并用光谱技术探究了其吸附种态，为理解三价锕系核素在蒙脱石上的吸附行为提供了重要参考。     

大孔膦酸树脂吸附铟的研究

研究了大孔膦酸型树脂对铟(Ⅲ)的吸附、洗脱条件;不同金属离子对铟吸附的影响;树脂吸附铟的容量及配位比。并用化学分析法及红外光谱探讨了膦酸树脂吸附铟的机理。     

聚合物支载的甘氨酸与Cu^2＋离子的络合性能

本文用N-（3-聚苯乙烯磺酰基-2-羟基丙基）甘氨酸为模型，研究了聚合物支载的氨基酸与Cu2 离子的络合作用性能。树脂与铜离子络合的介质最佳pH值在2～3之间。按照方程：－1n（1－F）=KTt处理求得吸附速率下数K288＝2．47X10－4sec－1。根据Boyd液膜扩散理论，这一吸附过程主要受液膜扩散控制。而且这个反应过程是一种Freundlish吸附过程。G=－30．91KJ／mole和S=129．90J／moleK表明，吸附反应是自发进行的。用斜率法和容量法求得树脂支载的氨基酸基因与铜离子之间的配位比为2:1。     

氨基膦酸树脂对钕(Ⅲ)的吸附性能

研究了氨基膦酸树脂对钕(Ⅲ)的吸附行为。当pH=5.70时,氨基膦酸树脂对钕(Ⅲ)的静态饱和吸附容量为199.74 mg/g,用1moL/L HCl溶液可以定量洗脱,当T=298 K时,表观吸附速率常数为1.68×10~(-4)s~(-1),吸附热力学参数△H=60.68 kJ/mol,△G=-14.91 kJ/mol,△S=253.65 J/(mol·K),等温吸附服从Freundlich曲线,氨基膦酸树脂功能基与钕(Ⅲ)的配位比为2:1。用红外光谱探讨了氨基膦酸树脂与钕(Ⅲ)的成键情况。     

3-N-乙酰基-2-取代芳基-5-[5''-甲基-异噁唑-3'']-Δ3-1,3,4－噁唑啉类化合物的合成

保护氨基的壳聚糖微球经环氧氯丙烷交联得到不溶于酸的吸附剂，与氯乙酸在碱性条件下反应，合成了羧甲基壳聚糖树脂，并用FT-IR对树脂进行了表征。其吸附Pb^2 的实验结果表明，在1h内有最快的吸附速率，吸附受pH值影响。在pH=5时，对Pb^2 的吸附量为1．12mmol／g，比壳聚糖树脂提高了70％。     

pH值对海藻吸附镍离子的影响研究

采用3种大型海藻－裙带菜，海黍子，马尾藻对重金属镍离子进行吸附，研究了溶液的pH值对Ni^2 吸附特性的影响，得到最佳pH值，发现了相同浓度，不同pH值的溶液吸附镍离子后pH值的变化规律及不同浓度。相同pH值的溶液吸附镍离子后pH值得变化规律，为进一步探讨海藻吸附重金属的吸附机理提供了依据。     

几种吸附树脂对硝基化合物吸附性能的研究

研究NJ－8、AM－1、Amberlite XAD-4、JX－101 4种吸附树脂对对硝基苯乙酮和对硝基苯甲酸的静态吸附行为。结果表明：江苏南大戈德环保科技有限公司研制的NJ－8和AM－1两种吸附树脂对硝基化合物的吸附效果较好。并研究NJ－8型吸附树脂的动态吸附和脱附行为，结果显示：NJ－8型吸附树脂对对硝基苯甲酸的吸附容量为128mg/g干树脂，对对硝基苯乙酮的吸附容量为383mg/g干树脂。用8%NaOH:乙醇（体积比1：1）洗脱吸附酸的树脂，用甲醇或乙醇洗脱吸附酮的树脂，体积为5BV时，温度分别为333K和313K，脱附率均接近100％。     

巯基树脂对重金属离子的吸附性能

研究了自合成的巯基树脂对重金属离子Pb^2 、Cu^2 、Cd^2 ．Ni^2 、Co^2 的吸附容量、吸附动力学、等温吸附过程等静态吸附性能，同时研究了影响吸附的因素和吸附机理．结果表明，该树脂对软酸型重金属离子吸附容量高．pH=5．0-5．7，低温有利于吸附，树脂对各重金属离子等温吸附在实验浓度范围内均符合Langmuir和Freundnch方程．吸附机理研究表明，巯基与重金属离子发生了离子交换和配位反应，化学吸附起支配作用。     

大孔聚丙烯醛-呋喃-2-硫代酰腙螯合树脂的合成及其性能的初步研究

合成了一新型高分子骨架，大孔内烯醛－苯乙烯－二乙烯苯三元共聚物树脂骨架，通过其含有的活泼醛基与呋喃－2－硫代酰肼螯合剂进行高分子反应，制备了一种含氮、硫配位原子的螯合树脂，聚丙烯醛－呋喃－2－硫代酰腙。对其与贵金属离子的吸附性能进行了初步研究，结果表明，该树脂对金、钯及铂具有选择性吸附作用，吸附容量分别为1.20mmol/g干树脂，0.37mmol/g干树脂及0.28mmol/g干树脂。     

两性离子交换树脂吸附L-苹果酸热力学研究

本文研究了两性离子交换树脂柱吸附分离L－苹果酸的热力学行为，在分析柱上测定了不同温度时的吸附等温线热力学性能的变化，结果表明，当温度对20℃至80℃变化时，该树脂对L－苹果酸的吸附量显著减小。故可采用热水作为洗脱剂进行脱附。进一步计算得该树脂吸附热△H为－34.89KJ/mol，该值远大于一般的酸／碱离子交换树脂，因而温度对其平衡产生很大的影响。     

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.     

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.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

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.