苯并咪唑基金属有机骨架/氧化石墨烯复合材料对罗丹明B的吸附

通过对溶剂热“一锅法”合成中碱性溶剂的调整,成功制备了2种形貌不同的Cd(Ⅱ)苯并咪唑基金属有机骨架(Cd-MOF)与氧化石墨烯(GO)的复合材料,利用扫描电子显微镜(SEM)、X射线粉末衍射(XRD)、X射线光电子能谱(XPS)、紫外可见吸收光谱(UV-Vis)和傅里叶红外光谱(FT-IR)对复合材料的结构和性能进行了表征,并研究了其对水中罗丹明 B(rhodamine B,RhB)的吸附性能。结果表明：GO的加入增强了Cd-MOF在水中的稳定性,提高了吸附能力;当溶液pH为3.5,吸附时间为60 min时,吸附率可达约95%。     

Fe3O4/PEI/GO复合材料的制备及其吸附效果研究

以氧化石墨烯(GO)和聚乙烯亚胺(PEI)为反应物,采用共混法制备PEI/GO,然后将Fe_3O_4纳米颗粒分散沉积到PEI/GO表面,得到了复合材料Fe_3O_4/PEI/GO。利用傅里叶红外光谱(FT-IR)、透射电子显微镜(TEM)、X射线衍射(XRD)和X射线光电子能谱(XPS)等方法对该材料进行表征,并研究了其对Cu~(2+)的吸附性能。结果表明,PEI与GO的羧基反应生成了酰胺键,Fe_3O_4成功沉积在GO表面,GO层状结构的规整性被破坏。Freundlich等温吸附模型和准二级动力学模型能更好地拟合Cu~(2+)在Fe_3O_4/PEI/GO表面的吸附过程,说明该吸附主要受化学作用控制,可能是Fe_3O_4/PEI/GO表面的胺基、羧基、羟基等活性基团与Cu~(2+)发生了离子交换或络合反应所致。     

磁性氧化石墨烯/聚苯胺纳米复合材料的制备 及再生循环吸附性研究

由氧化法和原位合成法成功制备了磁性氧化石墨烯/聚苯胺(Fe_3O_(4 )/GO/PANI,MPGO)纳米复合材料,使用X射线衍射、热重分析、红外光谱、VSM、BET等对所得材料进行了结构表征和性能测试,研究了复合材料对甲基橙染料的吸附性能。结果表明:pH为4时,MPGO吸附量最大,为198 mg·g~(-1);450 min达到吸附平衡,吸附量为211.08 mg·g~(-1)。MPGO对甲基橙的吸附行为符合Langmuir等温模型和准二级动力学模型;经过7次再生循环后,MPGO对甲基橙的吸附量保持为初始吸附量的72.2%,具有较好的重复利用性。     

GO/Fe3O4/有机胺复合材料的制备及对结晶紫染料的吸附性能

用改进的Hummers法制备了氧化石墨烯,用乙二胺、乙二胺与丁二胺/己二胺混溶来改性氧化石墨烯。用水热法制备了Fe3O4,并用物理混合法制备了GO/Fe3O4/有机胺的三元复合体系。用透射电镜、扫描电镜、红外光谱、热重分析、X射线衍射、VSM和XPS等对所制得的样品进行了结构表征和性能测试,研究了三元复合粒子对结晶紫染料的吸附性能及影响结晶紫染料吸附效果的因素。结果表明:所制备的Fe3O4的平均粒径约为200 nm,粒径分布均匀;复合物中GO为典型的片状结构,GO及有机胺的掺杂没有影响Fe3O4的尖晶石结构;复合物为超顺磁性,Ms为53.0 emu·g~(-1)。吸附结果表明:石墨烯/Fe3O4/有机胺的三元复合材料对结晶紫染料的最大吸附量随浓度增大而增大,而吸附结晶紫染料的移除率却随结晶紫染料浓度增大而减小,并趋向一定值;乙二胺和己二胺混溶比例为5∶1的GO/Fe3O4复合材料吸附性能最佳:结晶紫浓度为400 mg·L~(-1),最大吸附量为164.3 mg·L~(-1)。     

Fe3O4/GO/PPy复合材料的制备及其对2-硝基-1,3-苯二酚的吸附性能

采用改进的Hummers法制备了氧化石墨烯,用水热法首次制备了Fe_3O_4/GO/PPy(聚吡咯)三元复合粒子用于处理含2-硝基-1,3-苯二酚(NRC)的废水,研究了其对水中NRC的吸附性能。采用紫外-可见吸收光谱(UV-Vis)、透射电子显微镜(TEM)、傅里叶变换红外光谱(FT-IR)、X射线衍射(XRD)、振动样品磁强计及ζ电位等对所制备复合粒子的结构进行了表征;研究了溶液pH值、吸附剂用量、NRC的初始浓度、吸附时间和温度对吸附NRC的吸附性能的影响,并对吸附过程进行了吸附动力学模拟。结果表明:制备的Fe_3O_4/GO/PPy复合材料为层状分散结构,PPy及Fe_3O_4颗粒无规则地镶嵌在石墨烯片层之间。Fe_3O_4颗粒为多面体晶体结构,尺寸为100～300 nm。Fe_3O_4/GO/PPy具有超顺磁性,40 s可以磁分离,NRC移除率达91.6%;在NRC浓度为200 mg·L~(-1)、pH=5±0.05、温度T=318 K、吸附剂用量10 mg·L~(-1)和吸附时间6 h的条件下Fe_3O_4/GO/PPy对NRC的吸附量最大,达到163.3mg·g~(-1)。NRC吸附动力学符合二级动力学模型,吸附等温线符合Langmuir模型。循环使用5次后,NRC的移除率由最初的91.6%下降至77.6%,说明Fe_3O_4/GO/Ppy磁性复合物的结构具有较好的稳定性,且可以再重复利用。     

C/粉煤灰复合吸附材料的制备及表征

以粉煤灰和蔗糖为原料,浓硫酸为炭化剂,制备了一种新型的C/粉煤灰复合吸附材料。 采用X光电子能谱、红外吸收光谱、场发射扫描电子显微镜、X射线衍射及N2气吸附实验对所制备复合材料进行了表征。 结果表明,粉煤灰表面被类石墨态炭纳米颗粒所包裹,复合材料表面密集分布着大量的介孔,Brunauer-Emmett-Teller(BET)比表面积SBET=5.4 m2/g,并且在该复合材料表面含有丰富的-SO3H、-COOH和-OH等含氧官能团。 考察了所制备的复合材料对典型阳离子型染料亚甲基蓝及重金属离子的吸附能力,结果表明,该复合材料具有优异的吸附性能,其对亚甲基蓝的吸附能力达到活性炭的83.7%,对典型重金属离子的吸附能力优于市售活性炭。 所制备复合材料可作为活性炭的一种替代品,用于水中有机染料和重金属离子的吸附处理。     

二氧化硅/氧化锌复合体系的制备及其去除亚甲基蓝和罗丹明B研究

利用溶剂热法,以正硅酸乙酯为硅源,硝酸锌为锌源一次性合成了二氧化硅/氧化锌(SiO₂/ZnO)复合材料,利用傅里叶红外光谱和X射线衍射对其结构进行了表征分析,研究了该复合材料对亚甲基蓝和罗丹明B的吸附性能。结果表明,SiO₂/ZnO可快速去除水中的亚甲基蓝和罗丹明B,并在20 min内达到吸附平衡,SiO₂/ZnO对亚甲基蓝的吸附速率和吸附量均高于罗丹明B。吸附动力学研究表明,SiO₂/ZnO对亚甲基蓝和罗丹明B的吸附动力学均符合准二级动力学方程。等温吸附数据分析表明,Langmuir比Freundlich模型能更好地拟合亚甲基蓝和罗丹明B的吸附过程,由Langmuir计算得到亚甲基蓝和罗丹明B的单层饱和吸附量分别为235.3 mg/g和100.1 mg/g。此外,SiO₂/ZnO具有良好的重复使用性能,经过5次吸附-脱附循环后,其对亚甲基蓝的吸附能力仍保持在80%以上。     

膦酸化氧化石墨烯-壳聚糖复合材料对Eu(Ⅲ)的富集性能

本文定向合成了一种新型的膦酸化氧化石墨烯(GO)-壳聚糖(CS)复合材料(GO-CS-P),并将其应用于水体中三价Eu(Ⅲ)的高效富集.宏观实验结果显示,这一复合材料对Eu(Ⅲ)的吸附在5 min内即可达到平衡,在pH5.5和293 K条件下的最大吸附容量(106.14 mg/g)高于先前文献中报道的一系列吸附材料.此外, GO-CS-P能够高效、选择性地从高盐度和多组分金属离子共存的水溶液中捕获Eu(Ⅲ). X射线衍射(X-ray diffraction, XRD)、傅里叶变换红外光谱(Fourier transform infrared spectrometry, FTIR)、X射线吸收光谱(X-ray absorption spectroscopy,XAS)和X射线光电子能谱(X-ray photoelectron spectroscopy, XPS)的分析结果表明, Eu(Ⅲ)与GO-CS-P表面的膦酸酯基团和羧基发生共价结合,形成稳定的内层络合物.基于本文的研究发现, GO-CS-P复合材料在修复被三价镧系/锕系元素污染的地下水方面具有很大的应用潜力.     

超弹性石墨烯气凝胶的制备及其性能

以多胺小分子二乙烯三胺(DETA)为还原剂和结构增强剂,采用水热还原法,制备了具有三维交联网络结构的高弹性石墨烯气凝胶(GA)。通过X射线衍射仪(XRD)、四探针测试仪、扫描电子显微镜(SEM)、万能拉力机和吸附实验等手段对GA的微观结构和性能进行了表征和测试。研究了氧化石墨烯(GO)和DETA的质量浓度对GA性能的影响。结果表明:GA的密度和导电率随着GO和DETA的质量浓度变化而变化,压缩强度随着GO和DETA质量浓度的升高而增大。当GO的质量浓度为8mg/mL,GO与DETA的质量浓度之比为1 000∶7.5时,其最大压缩强度高达6.8 MPa。GA被压缩后,其形貌可基本完全回复,表现出较好的抗疲劳性能。GA对7种常见有机溶剂的吸附量为自身质量的41~83倍,其中对二氯甲烷的吸附量最大,达到了自身质量的83倍。     

β-环糊精/磁性氧化石墨烯对氧氟沙星的吸附

以自制的氧化石墨烯(GO)、β-环糊精(β-CD)为原料,通过化学共沉淀法合成了β-环糊精/磁性氧化石墨烯复合材料(β-CD/MGO),并用扫描电镜、透射电镜、X射线衍射、拉曼光谱、BET和VSM等对其进行形貌态表征和性能测试.结果 表明,Fe4 O3被成功负载到GO上,并枝接上β-环糊精;β-CD/MGO的比表面积为...     

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.