笼形聚偕胺肟树脂的研究──酸处理树脂吸附H_2PdCl_4

考查了无机酸、羧酸和酚类化合物处理的笼形聚偕胺肟树脂吸附酸性溶液中H_2PdCl_4的能力，其中H_3BO_3/ACAO、HSCH_2CO_2H/ACAO和p－NH_2C_6H_4H/ACAO树脂对H_2PdCl_4的吸附容量分别是2．023、2．368和2．083mmol/g-R或215、252和222mgPd／g－R。优于相同条件下的碱处理树脂（BCAO吸附容量为1．828mmol/g-R）。研究了吸附动力学，讨论了吸附机理。     

二维TiC 层表面H2的化学吸附与物理吸附

第一性原理计算研究发现由于二维TiC单原子层具有高的比表面积与大量的暴露在表面的Ti原子,其是一种非常有潜力的储氢材料.计算结果显示H2可以在二维TiC单原子层表面进行物理吸附与化学吸附.其中化学吸附能为每个氢分子0.36 eV,物理吸附能是每个氢分子0.09 eV.覆盖度为1和1/4层(ML)时,H2分子在二维TiC单原子层表面的离解势垒分别为1.12和0.33 eV.因此,除了物理吸附与化学吸附,TiC表面还存在H单原子吸附.最大的H2储存率可以达到7.69%(质量分数).其中,离解的H原子、化学吸附的H2、物理吸附的H2的储存率分别为1.54%、3.07%、3.07%.符合Kubas吸附特征的储存率为3.07%.化学吸附能随覆盖度的变化非常小,这有利于H2分子的吸附与释放.     

二维TiC层表面H2的化学吸附与物理吸附

第一性原理计算研究发现由于二维TiC单原子层具有高的比表面积与大量的暴露在表面的Ti原子,其是一种非常有潜力的储氢材料.计算结果显示H2可以在二维TiC单原子层表面进行物理吸附与化学吸附.其中化学吸附能为每个氢分子0.36 eV,物理吸附能是每个氢分子0.09 eV.覆盖度为1和1/4层(ML)时,H2分子在二维TiC单原子层表面的离解势垒分别为1.12和0.33 eV.因此,除了物理吸附与化学吸附,TiC表面还存在H单原子吸附.最大的H2储存率可以达到7.69％(质量分数).其中,离解的H原子、化学吸附的H2、物理吸附的H2的储存率分别为1.54％、3.07％、3.07％.符合Kubas吸附特征的储存率为3.07％.化学吸附能随覆盖度的变化非常小,这有利于H2分子的吸附与释放.     

笼形聚偕胺肟树脂的研究─—H_2PtCl_6在酸处理树脂上的吸附过程

H2PtCl6可被一系列的酸处理定形聚偕胺肟树脂所吸附，吸附容量的大小与处理树脂的质子酸的Pka值有关．认为是解高度低的酸所处理的树脂上的伯胺基成盐的机会较少，即树脂的吸附中心保留着较多的空穴，有利于H2PtCl6的接近而被吸附下来．吸附动力学的研究表明化学反应是吸附速度的控制因素。     

两种吸附树脂对4B酸吸附行为的比较研究

研究了新型复合功能吸附树脂NDA-99和超高交联大孔吸附树脂JX-101对水溶液中4B酸(对甲苯胺-2-磺酸)的静态吸附行为和热力学特性，结果表明，NDA-99树脂对4B酸的吸附量明显大于JX-101树脂，两种树脂对4B酸的吸附均符合Freundlich吸附等温方程．其中，JX-101对4B酸的吸附属于物理吸附：NDA-99由于树脂表面存在弱碱性官能团，对4B酸的吸附表现为物理吸附和化学络合协同作用。     

笼形聚偕胺肟树脂的研究──(NH_4)_2IrCl_6在酸处理树脂上的吸附及还原过程

研究了酸处理树脂对（NH4）2IrCl6的吸附行为。吸附动力学数据表明（NH4）2IrC6在酸处理树脂上通过物理吸附生成1：1配合物，并被还原为Ir（0）。     

P204-TBP浸渍树脂对硫酸介质中Sc3+的吸附行为研究及其应用

通过溶剂挥发法制备了含双萃取剂(TBP-P204)的浸渍树脂，利用静态法、动态法研究其在硫酸介质中对钪的吸附行为，测得静态吸附容量21．75mg／g，绘制了吸附等温线．应用于钛白废酸，用H2O2 H2SO4洗涤铁、钛，4％HCl洗脱钪，可实现钪和铁、钛的完全分离,钪的回收率96．2％。     

O,O'-二(苯基)二硫代磷酸-N,N-二乙铵对Q235钢在硫酸溶液中的缓蚀性能研究

合成了O,O'-二(苯基)二硫代磷酸-N,N-二乙铵(DEDDP),采用失重,电化学和SEM技术共同研究了DEDDP在H2SO4溶液中对Q235钢的缓蚀性能。失重法研究表明:DEDDP在H2SO4溶液中能有效地抑制Q235钢腐蚀,25℃的5%H2SO4溶液中,DEDDP浓度为160 mg.L-1时,其缓蚀率为94.67%;电化学研究结果表明:DEDDP在5%H2SO4溶液中属混合型缓蚀剂。同时,研究了温度,H2SO4浓度和浸泡时间对缓蚀率的影响。吸附规律研究表明:DEDDP在Q235钢表面的吸附符合Langmuir吸附等温式,其吸附自由能为-32.32kJ/mol,吸附为自发进行的物理和化学吸附。     

D301R树脂对Keggin型铁取代杂多阴离子的吸附性能研究

详细研究了D301R弱碱性阴离子交换树脂对Keggin型铁取代杂多阴离子PW11O39Fe(III)(H2O)4－ (PW11Fe)的吸附作用, 考察了不同pH和温度对吸附量和吸附速率的影响, 测定了不同温度下吸附的动力学曲线和吸附等温线, 提出吸附动力学模型和计算了吸附的热力学函数, 结果表明, 在pH 2～8的范围内, PW11Fe的吸附量随溶液pH值的升高而增加, 随溶液温度的升高而降低; 吸附动力学符合表面过程控制的准二级反应模型, 其速率常数k2在298 K时为 9.33×10－4 g•mg－1•min－1, 并随温度的升高而减小. 吸附等温线符合Freundlich吸附模型, 吸附热约为40 kJ•mol－1, 因此, 吸附为物理吸附.     

纤维素基磁性聚偕氨肟树脂吸附Mn（Ⅶ）

用酸处理的纤维素基磁性聚偕氨肟树脂（AMAO）在溶液中吸附KMnO4，发生氧化还原反应的几率在2％以下；用碱处理的树脂（BMAO）作吸附剂，KMnO4还原为Mn（OH）4的比例剧增，达到或超过10％，并且与溶液的pH有关。但是，Mn（Ⅶ）被还原为Mn（Ⅳ）的量基本上不受KMnO4起始浓度、吸附剂添加量和吸附时间变化的影响。BMAO树脂吸附KMnO4的量是树脂偕氨肟基含量的5倍以上。超当量吸附现象反映了物理吸附的本质。     

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.