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.     

PVC/插层稀土类水滑石的热稳定性能研究

以山梨酸、La(NO_3)_3,Al(NO_3)_3,Mg(NO_3)_2和Na OH为主要原料合成了山梨酸插层镁铝镧类水滑石(Mg Al La-SA LDHs),通过X射线衍射(XRD)、红外光谱(FT-IR)进行结构表征。采用刚果红法、热老化烘箱法、转矩流变法、电导率法等研究了山梨酸插层类水滑石及与季戊四醇、硬脂酸锌复合后添加到聚氯乙烯(PVC)的热稳定性能。结果表明:山梨酸插层类水滑石可有效地延长PVC热稳定时间,抑制初期着色,降低加工能耗,热降解活化能较纯PVC提高了6.59 k J·mol~(-1)。按质量份数1/4/1与季戊四醇、硬脂酸锌复合后,热降解活化能较复合前提高了13.96 k J·mol~(-1),热稳定效果更优。     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

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.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.     

Synthesis of N-substituted carbazolones from α-iodo enaminones via Pd(0)-catalyzed intramolecular coupling under microwave irradiation

A variety of N-aryl and N-alkyl carbazolones were conveniently achieved in good to high yields via Pd₂(dba)₃-mediated intramolecular coupling of N-substituted α-iodo enaminones under microwave irradiation. The Pd(0)-catalyzed cyclization was found to proceed favorably with the more electron-deficient phenyl ring during the reactions involving unsymmetrical N,N-diaryl α-iodo enaminones. This unique property enables the construction of carbazolone skeleton containing nitro substituted benzenoid ring.     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles by intramolecular nitrilimine cycloaddition

Both substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles have been synthesized by the 3+2 intramolecular dipolar cycloaddition of nitrilimines to alkynes. This cyclization has been extended to more versatile 3-bromo derivatives by the use of alkynylbromides as dipolarophiles.