酸性黄25插层水滑石薄膜的制备及其性能研究

采用原位生长法在铝片基底表面制备了ZnAl-NO3-LDHs水滑石薄膜,以其为前驱体,在弱酸性条件下通过离子交换反应将酸性黄25阴离子插层至ZnAl-LDHs/Al薄膜层间,制备了酸性黄25插层水滑石薄膜,并采用XRD、SEM、FTIR、TG-DTA、UV-Vis和色差计等手段对薄膜进行了表征。XRD和FTIR表征结果表明,酸性黄25阴离子成功地插层到了水滑石薄膜层间,ZnAl-LDHs的层间距由0.87 nm增加到2.96 nm,NO3-阴离子在1 384 cm-1处的特征吸收峰消失,同时出现了酸性黄25阴离子的特征吸收峰。SEM照片显示,水滑石晶片主要以c轴平行于铝片基底生长。TG-DTA分析、UV-Vis分析、色差分析和紫外光老化结果表明,插层后酸性黄25阴离子的耐热性和耐光性均得到了提高。     

金属氢氧化物直接制备对苯二甲酸插层水滑石及其应用

以新制备的Mg(OH)_2和Al(OH)_3滤饼与对苯二甲酸通过水热反应制备了对苯二甲酸插层水滑石(TALDHs).使用X射线衍射(XRD)、热重-差热分析、扫描电镜(SEM)等技术对TA-LDHs与碳酸根型水滑石(CO3-LDHs)进行对比研究,结果显示,对苯二甲酸离子成功插入到LDHs层间,产物结构完整、晶相单一,所制得的TA-LDHs为片状.CO3-LDHs和TA-LDHs分别作为纳米填料,以两种不同的添加方式制备聚对苯二甲酸乙二醇酯(PET)/LDHs纳米复合材料.对复合材料进行XRD和SEM研究,结果表明在酯交换反应前添加2%TA-LDHs所制备的PET/LDHs纳米复合材料的层板被部分剥离,分散性最好.     

MgAl-EDTA柱撑水滑石的制备及其应用

以MgAl-CO3型水滑石为前体,由离子交换法进行插层组装,合成了EDTA柱撑的MgAl-EDTA水滑石,并用X射线衍射、红外光谱对样品进行了表征。探讨了n(Mg)/n(Al)摩尔比、pH、反应温度、EDTA与前体水滑石配比对插层反应的影响,结果表明,当n(Mg)/n(Al)摩尔比为2～3、pH在4.5左右、反应温度控制在150℃以上、同时保证过量的EDTA时,EDTA可以插入MgAl-CO3水滑石层间,取代CO23-,形成结构完好的EDTA柱撑水滑石。MgAl-EDTA柱撑水滑石通过层间EDTA对Cu2+的螯合作用,可以在较短的时间内吸附溶液中的Cu2+,溶液中Cu2+的去除率在96%以上。     

PE膜中层状双羟基复合氢氧化物的红外吸收性能

水滑石;聚乙烯薄膜;PE膜中层状双羟基复合氢氧化物的红外吸收性能     

镧离子掺杂纳米TiO2光催化降解聚乙烯薄膜的研究

La3 掺杂纳米TiO2光催化剂后,用于固相光催化降解聚乙烯(PE)薄膜。在紫外线辐射288h后,0.1%La2O3/TiO2使薄膜失重14.5%,产生更多石蜡和CO2,SEM表明其对PE的光氧化腐蚀能力更强,在薄膜表面形成更大更多的凹坑和空洞,红外光谱表明PE薄膜中的-CH2和支链-CH3基团的吸收明显减少,0.1%La2O3/TiO2光催化剂使PE的C=O的吸收增大。La3 掺杂后,提高了纳米TiO2的光催化活性。     

新型锌铝水滑石紫外吸收剂的制备及其紫外吸收性能

以有机紫外吸收剂2-苯基苯并咪唑-5-磺酸(PBSA)、N,N-二甲氨基苯甲酸(DABA)为有机原料,采用共沉淀法,合成了有机紫外吸收剂插层水滑石Zn2Al-LDH/PBSA和Zn2Al-LDH/DABA,并测定了所得到的样品的XRD、FT IR、薄膜紫外吸收性质和氧化催化活性。结果表明,当有机紫外吸收剂以阴离子的形式进入水滑石层间后,仍有良好的紫外吸收性能并在可见光区有很好的透光性;通过测定插层水滑石的氧化催化活性,与纯有机物相比,Zn2Al-LDH/PBSA和Zn2Al-LDH/DABA的氧化催化活性明显降低。合成的新型的插层水滑石有望在防晒产品中得到应用。     

新型锌铝水滑石紫外吸收剂的制备及其紫外吸收性能

以有机紫外吸收剂2-苯基苯并咪唑-5-磺酸(PBSA)、N,N-二甲氨基苯甲酸(DABA)为有机原料,采用共沉淀法,合成了有机紫外吸收剂插层水滑石Zn2Al-LDH/PBSA和Zn2Al-LDH/DABA,并测定了所得到的样品的XRD、FT IR、薄膜紫外吸收性质和氧化催化活性。结果表明,当有机紫外吸收剂以阴离子的形式进入水滑石层间后,仍有良好的紫外吸收性能并在可见光区有很好的透光性;通过测定插层水滑石的氧化催化活性,与纯有机物相比,Zn2Al-LDH/PBSA和Zn2Al-LDH/DABA的氧化催化活性明显降低。合成的新型的插层水滑石有望在防晒产品中得到应用。     

新型锌铝水滑石紫外吸收剂的制备和紫外性能研究

以有机紫外吸收剂2-苯基苯并咪唑-5-磺酸(PBSA)、N,N-二甲氨基苯甲酸(DABA)为有机原料,采用共沉淀法,合成了有机紫外吸收剂插层水滑石Zn2Al-LDH/PBSA和Zn2Al-LDH/DABA,并测定了所得到的样品的XRD、FT IR、薄膜紫外吸收性质和氧化催化活性。结果表明,当有机紫外吸收剂以阴离子的形式进入水滑石层间后,仍有良好的紫外吸收性能并在可见光区有很好的透光性;通过测定插层水滑石的氧化催化活性,与纯有机物相比,Zn2Al-LDH/PBSA和Zn2Al-LDH/DABA的氧化催化活性明显降低。合成的新型的插层水滑石有望在防晒产品中得到应用。     

基于氟碳表面活性剂插层水滑石的聚酰亚胺纳米复合材料的制备与性能

以氟碳表面活性剂全氟辛基磺酸钾为插层剂, 通过离子交换制备插层水滑石, 并以其为填料, 通过原位插层聚合方法, 制备了水滑石/氟碳表面活性剂/聚酰亚胺纳米复合材料. 用X射线衍射、 红外光谱和热失重等方法分析插层水滑石结构. 结果表明, 全氟辛基磺酸钾插层水滑石后, 水滑石的层间距由0.76 nm增加到2.52 nm, 在水滑石层间构建了氟碳链的微环境. 这种氟化水滑石可剥离分散于聚酰亚胺基体中, 改善了纳米复合材料的气体阻隔性能、 介电性能和机械性能. 这种影响不仅体现无机纳米片层的杂化效果, 而且展示出氟碳链的特点.     

焦磷酸根嵌入后形成的交联水滑石的研究

合成了焦磷酸根交联水滑石，用XRD，FT－IR，DTA－TG，MASNMR等手段研究了焦磷酸根嵌入后形成的水滑后，提出了嵌入水滑石层间最多的离子为H2P2O7^2-，高温灼烧，P2O7^4-柱子交联到层上，且焦磷酸根离子链垂直位于水滑石层中，产物表面积为87m^2/g。     

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.     

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.     

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.     

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.     

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.     

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.