CXN天然沸石的研究1: 离子交换与结构性质表征

采用离子交换和焙烧等方法,对我国CXN天然沸石(STI型)进行改性。应用化学分析,粉末XRD,TG/DTA,^2^7AlMASNMR,^2^9SiMASNMR,低温N~2吸附等方法表征相关的结构、离子交换等性质。CXN沸石的晶胞组成Na~0~.~2Mg~0~.~1Ca~8~.~4[Al~1~7~.~2Si~5~4~.~8O~1~4~4].65H~2O,属富钙型。经离子交换脱Ca^2^+后的沸石在焙烧过程中伴随有骨架脱铝,骨架的热稳定性已由原样的500℃以下提高到700℃以上。交换改性后的沸石,呈现反映该沸石微孔特性的I型氮吸附等温线。     

CXN天然沸石的研究1: 离子交换与结构性质表征

采用离子交换和焙烧等方法,对我国CXN天然沸石(STI型)进行改性。应用化学分析,粉末XRD,TG/DTA,^2^7AlMASNMR,^2^9SiMASNMR,低温N~2吸附等方法表征相关的结构、离子交换等性质。CXN沸石的晶胞组成Na~0~.~2Mg~0~.~1Ca~8~.~4[Al~1~7~.~2Si~5~4~.~8O~1~4~4].65H~2O,属富钙型。经离子交换脱Ca^2^+后的沸石在焙烧过程中伴随有骨架脱铝,骨架的热稳定性已由原样的500℃以下提高到700℃以上。交换改性后的沸石,呈现反映该沸石微孔特性的I型氮吸附等温线。     

天然CXN沸石分子筛水热稳定性研究 I. 水热稳定性影响因素

以天然CXN沸石为基底材料, 通过离子交换、焙烧和酸处理等方法研究了影响该沸石水热稳定性的因素. XRD, XRF和27Al MAS NMR等结果表明阳离子种类和位置均会影响沸石水热稳定性, 其中铵型CXN沸石的水热稳定性最高. 高温焙烧铵型CXN沸石虽能提高骨架硅铝比, 但骨架缺陷增多导致其水热稳定性下降. 还研究了水蒸汽量、处理温度和时间对沸石骨架结构变化的影响, 结果表明提高温度和水蒸汽量均会降低沸石结晶度, 但处理时间则对结晶度的影响较小.     

天然CXN沸石分子筛水热稳定性研究Ⅰ.水热稳定性影响因素

以天然CXN沸石为基底材料,通过离子交换、焙烧和酸处理等方法研究了影响该沸石水热稳定性的因素.XRD,XRF和27Al MAS NMR等结果表明阳离子种类和位置均会影响沸石水热稳定性,其中铵型CXN沸石的水热稳定性最高.高温焙烧铵型CXN沸石虽能提高骨架硅铝比,但骨架缺陷增多导致其水热稳定性下降.还研究了水蒸汽量、处理温度和时间对沸石骨架结构变化的影响,结果表明提高温度和水蒸汽量均会降低沸石结晶度,但处理时间则对结晶度的影响较小.     

CXN天然沸石的研究 V. 结构超稳化

以离子交换结合控制焙烧的方法分别制得结构超稳化高硅H-STI-I和H-STI-II沸石. EDX, ²⁹Si MAS NMR, ²⁷Al MAS NMR, FT-IR等表征证明, 其骨架硅铝原子比分别为4.43和10.62. 分段程序升温焙烧后的沸石样品经粉末XRD表征表明, 其结构热稳定性达到1000 ℃以上. 结构稳定化沸石呈现反映微孔特性的I型吸附等温线, 吸附孔道完美、开放. 经历过酸处理的H-STI-II沸石, 结构缺陷增多, 其热稳定性、比表面积及孔容积略低于H-STI-I.     

天然CXN沸石分子筛水热稳定性研究 II. 水蒸汽处理温度对铵型沸石物化性质的影响

在前文研究天然Stilbite沸石(CXN沸石)水热稳定性影响因素的基础上, 以27Al与29Si MAS NMR, NH3-TPD和低温氮吸附等详细研究了铵型CXN沸石骨架铝配位状态和硅配位状态, 表面酸性与孔性质等与水蒸汽处理温度的关系. 随温度升高, 沸石骨架硅铝比逐渐提高, 并伴随硅羟基缺陷增多. 经750 ℃水蒸汽处理3 h后沸石骨架硅铝比可达到21.3. 沸石总酸量随水蒸汽处理温度的提高而降低, 沸石骨架铝脱除造成沸石孔道部分被堵塞, 但同时形成有利于分子扩散的介孔.     

CXN天然沸石的研究Ⅶ.骨架高硅超稳化改性

以高硅超稳化辉沸石(STI)为基底沸石,分别经盐酸脱铝或氟硅酸铵脱铝补硅处理后制备的改性H-STI沸石,其非骨架铝含量明显减少,而后者骨架硅铝比进一步提高.X射线荧光散射光谱(XRF),27Al高分辨率魔角旋转固体核磁共振(MAS NMR),红外(FT-IR)光谱等表征证明改性后的沸石骨架硅铝原子比分别为6.8和11.4.低温氮吸附表明,经盐酸处理的高硅STI沸石孔道开放完美,但经氟硅酸铵处理的样品孔道被部分堵塞.分段程序升温焙烧表明前者骨架热稳定性略差,1000℃焙烧后结构基本被破坏,而后者热稳定性较好,经相同温度段焙烧后仍保持较高的结晶度和热稳定性,其结构基本实现超稳化.     

CXN天然沸石的研究VII. 骨架高硅超稳化改性

以高硅超稳化辉沸石(STI)为基底沸石, 分别经盐酸脱铝或氟硅酸铵脱铝补硅处理后制备的改性H-STI沸石, 其非骨架铝含量明显减少, 而后者骨架硅铝比进一步提高. X射线荧光散射光谱(XRF), ²⁷Al高分辨率魔角旋转固体核磁共振(MAS NMR), 红外(FT-IR)光谱等表征证明改性后的沸石骨架硅铝原子比分别为6.8和11.4. 低温氮吸附表明, 经盐酸处理的高硅STI沸石孔道开放完美, 但经氟硅酸铵处理的样品孔道被部分堵塞. 分段程序升温焙烧表明前者骨架热稳定性略差, 1000 ℃焙烧后结构基本被破坏, 而后者热稳定性较好, 经相同温度段焙烧后仍保持较高的结晶度和热稳定性, 其结构基本实现超稳化.     

THF-FER沸石的系列研究Ⅰ.晶体结构稳定性

四氢呋喃(THF)-Na2O-SiO2-Al2O3-H2O体系水热合成的THF-FER沸石,经酸交换-焙烧脱THF(Ⅰ)或焙烧脱THF-酸交换(Ⅱ)的不同方式处理,均可制得低钠H-FER沸石.经XRD,27Al与29Si MAS NMR,低温氮吸附等表征证明,通过1273 K高温的热处理和1073 K饱和水蒸气下的水热处理,H-FER沸石骨架保持高度稳定.在高温水蒸气作用下,Si(2Al)容易从骨架上脱离,而Si(1Al)则保持相对稳定.以(Ⅱ)方式处理,制备的H-FER沸石在水热条件下易产生较多的硅羟基缺陷.经高温热和水热处理后,H-FER沸石孔道结构基本保持完美、开放.     

CXN天然沸石的研究 VI. 耐酸性及不同阳离子型沸石结构的热稳定性

以X射线粉末衍射(XRD)结晶度测定法观测CXN (STI型)天然沸石在不同浓度盐酸(HCl)热溶液中的结构耐酸性, 以及比较和研究用不同方法制备的结构超稳化高硅H-STI-I和H-STI-II沸石及其不同阳离子交换型M-STI (M＝Li, Na, K, Ca, Ag) 系列沸石在程序阶梯升温过程中的结构热稳定性. 用X射线荧光散射(XRF), ²⁹Si与²⁷Al固体核磁共振(MAS NMR)表征超稳化高硅H型沸石的组成与结构性质. 结果表明该天然沸石在浓度低于2 mol/L盐酸中可较长时间保持结构完美. 视阳离子类型不同, 经1173 K焙烧后M-STI-I系列沸石与M-STI-II系列沸石相对结晶度降低百分数分别为2.5%～18% 与0～35%. 在M-STI-I系列沸石中, 焙烧前后相对结晶度下降幅度的次序为K型＜(H, Li, Na)型＜(Ca, Ag)型, 而M-STI-II系列沸石, (Na, K)型＜(Li, H, Ca)型＜Ag型. 从沸石骨架硅铝比、结构缺陷、阳离子种类及其氧化物形成热等方面讨论影响沸石结构热稳定性的因素.     

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%).     

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 pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.