Synthesis and properties of 1,3,5-benzene periodic mesoporous organosilica (PMO): novel aromatic PMO with three point attachments and unique thermal transformations

A new aromatic periodic mesoporous organosilica material containing benzene functional groups that are symmetrically integrated with three silicon atoms in an organosilica mesoporous framework is reported. The material has a high surface area, well-ordered mesoporous structure and thermally stable framework aromatic groups. The functional aromatic moieties were observed to undergo sequential thermal transformation from a three to two and then to a one point attachment within the framework upon continuous thermolysis under air before eventually being converted to periodic mesoporous silica devoid of aromatic groups at high temperatures and longer pyrolysis times. The mesoporosity of the material was characterized by powder X-ray diffraction (PXRD), transmission electron microscopy (TEM), and nitrogen porosimetry, whereas the presence and transformation of the aromatic groups in the walls of the materials were characterized by solid-state NMR spectroscopy, mass spectrometry, and thermogravimetric analysis. The attachment of a benzene ring symmetrically onto three siloxanes of the framework was used advantageously as a cross-linker to enhance the thermal stability of the organic group. Some of these properties are investigated in comparison with other aromatic PMOs that have only two point attachments and an amorphous phenylsilica gel that has only one point attachment. The successful synthesis of the first aromatic PMO with its organic group attached within the framework through more than two points is an important step toward the synthesis of PMOs having organic groups with more complex and multiple attachments within the framework.     

Metamorphosis of ordered mesopores to micropores: periodic silica with unprecedented loading of pendant reactive organic groups transforms to periodic microporous silica with tailorable pore size

Ordered porous silicas with unprecedented loadings of pendant vinyl groups have been synthesized via co-condensation of tetraethyl orthosilicate (TEOS) and triethoxyvinylsilane (TEVS) under basic conditions in the presence of cetyltrimethylammonium surfactant. The resulting organosilicate-surfactant composites exhibited at least one low-angle X-ray diffraction (XRD) peak up to the TEVS:TEOS molar ratio of 7:3 (70% TEVS loading) in the synthesis gel. The surfactant was removed from these composites without any structural collapse. Nitrogen adsorption provided strong evidence of the presence of uniformly sized pores and the lack of phase separation up to TEVS:TEOS ratios as high as 13:7 (65% TEVS loading), whereas (29)Si MAS NMR and high-resolution thermogravimetry showed essentially quantitative incorporation of the organosilane. Thus, a hitherto unachieved loading level for pendant groups, considered by many to be impossible to achieve for stable organosilicas because of the expected framework connectivity constraints, has been obtained. The resulting vinyl-functionalized silicas exhibited gradually decreasing pore diameter (from 2.8 to 1.7 nm for TEVS loadings of 25-65%) and pore volume as the loading of pendant groups increased, but the specific surface area was relatively constant. Because of the reactivity of vinyl groups, ordered silicas with very high loadings of these groups are expected to be robust starting materials for the synthesis of other organic-functionalized ordered microporous materials. Herein, we demonstrate that these starting materials can also be transformed via calcination into ordered microporous silicas with pore diameters tailorable from 2.5 to as little as 1.4 nm simply by using an appropriate loading of the vinyl-functionalized precursor. This ease of the micropore size adjustment and the attained degree of structural ordering (as judged from XRD) have not been reported before. The novel ordered microporous materials reported herein are promising as adsorbents and catalyst supports.     

Infrared and raman spectra,and stereochemistries of 1:2 trimethylphosphine complexes of group V trihalides,MX3 · 2P(CH3)3 and MX3 · 2P(CD3)3 (where M = P or As and X = Cl or Br); spectra of 1,2-bisdimethylphosphinoethane and chelate complexes with group v trihalides

The 1 : 2 trimethylphosphine (deuterated and non-deuterated) adducts of the Group V trihalides MX₃ (where M = P or As and X = Cl or Br) are prepared and examined by vibrational spectroscopy. The forced cis-configuration complexes MX₃ · bdpe where bdpe is the bidentate ligand 1,2-bisdimethylphosphinoethane are also prepared and examined spectroscopically. Comparison of the Raman and IR spectra of these complexes shows the monodentate adducts to be covalent monomers having a trans-stereochemistry in the solid state. Normal coordinate calculations in C_2v symmetry (trans-stereochemistry) are performed for all monodentate adducts reported.     

Synthesis and Crystal Structures of Two Novel Anionic Aluminophosphates: A One-Dimensional Chain, UT-7 ([Al(3)P(5)O(20)H](5-)[C(7)H(13)NH(3)(+)](5)), and a Layer Containing Two Cyclic Amines, UT-8 ([Al(3)P(4)O(16)](3-)[C(4)H(7)NH(3)(+)](2)[C(5)H(10)NH(2)(+)])

UT-7 and UT-8 (University of Toronto, structure numbers 7 and 8) are two novel aluminophosphate materials prepared under non-aqueous conditions. Their structures, extended in one and two dimensions, respectively, have been solved by single-crystal X-ray diffraction and characterized by a variety of methods including powder X-ray diffraction (PXRD), insitu high-temperature PXRD, thermogravimetric analysis (TGA), energy dispersive X-ray analysis (EDX), and scanning electron microscopy (SEM). UT-7 ([Al(3)P(5)O(20)H](5)(-)[C(7)H(13)NH(3)(+)](5), triclinic space group P&onemacr;, Z = 2, a = 10.118(3) ?, b = 15.691(4) ?, c = 18.117(3) ?, alpha = 72.91(2) degrees, beta = 85.18(2) degrees, gamma = 79.49(2) degrees ) is built of polymeric one-dimensional chain units, hydrogen-bonded into anionic layers that are charge-compensated by interlamellar cycloheptylammonium cations. UT-7 is isostructural to our previously discovered UT-3 chain structure, isolated in the analogous cyclopentylamine system. UT-8 ([Al(3)P(4)O(16)](3-)[C(4)H(7)NH(3)(+)](2)[C(5)H(10)NH(2)(+)], monoclinic space group P2(1), Z = 2, a = 8.993(4) ?, b = 14.884(8) ?, c = 9.799(9) ?, beta = 103.52(3) degrees ) is a two-dimensional net isostructural to several previously reported [Al(3)P(4)O(16)](3)(-) layers. The interlayer region of UT-8 is occupied by two different cyclic organic amine species, namely piperidinium and cyclobutylammonium. To our knowledge, this is the first report of the crystal structure of an aluminophosphate material containing cyclobutylammonium or a mixture of cyclic amines. Interestingly, UT-7 is observed to thermally transform in the solid state to an as yet unknown layered material that can be independently synthesized in a similar synthetic system. In the same way as UT-3 transforms to the UT-4 layered phase, we believe UT-7 transforms to a layered material by means of a chain to layer transformation.     

种植沙生植物--沙棘改善内蒙古地区生态环境

结合内蒙古地区现状，对沙棘的生物学和生态学特性、沙棘属植物化学成分和微量元素及种植沙生植物——沙棘的重要性和必要性进行了详细的研究和探讨。研究表明，沙棘属植物具有极强的生态适应性并富含多种营养成分和生物活性物质，并以耐干旱、耐瘠薄、萌蘖及固氮能力强等特点被称为治理非宜林地水土流失、改善生态环境的先锋树种。种植沙棘是治理内蒙古脆弱生态环境最经济、最有效的措施，是贫瘠的不毛之地发展经济、增加收入的经济树种。另外．种植沙棘的技术简便，容易掌握，投资少，见效快。     

内蒙古地区天然植物沙棘果中黄色素的提取工艺及性质研究

以内蒙古地区沙棘果实为原料，研究了提取黄色素的工艺条件，同时对该色素的性质进行了初步探讨。结果表明，以95％的乙醇溶液作浸提剂，提取的黄色素浓度最高，工艺流程简单易行，且无毒，无污染。对提取的黄色素进行的性质试验表明，沙棘黄色素对光、热具有较好的稳定性，适用于酸性或弱碱性的食品中，葡萄糖、氧化剂(H2O2)、还原剂(Na2SO3)等食品添加剂均无明显影响以上结果为这种优良天然色素的开发与应用提供了参考。     

The zeolate ligand; zeolite encapsulated semiconductor nanomaterials

Consolidation of the results of structural, spectroscopic and kinetic studies of a range of intrazeolite guests and their reactions have led to the development of the “crown ether-zeolite ligand analogy” and the concept of the “zeolate” as a macrospheroidal or macrocylindrical multidentate anionic ligand. This view of a zeolite cavity or channel as a collection of interconnected aluminosilicate crown ether-like building blocks, permits a coordination chemistry approach to the understanding of metal-ligand bonding (capping, anchoring, complexing, stabilizing and structure-directing phenomena) in a variety of zeolite guest-host inclusion systems. In this paper we focus attention on the role that the zeolate ligand plays in the organization of semiconductor precursors and their assembly to semiconductor nanoclusters with particular reference to II-VI nanomaterials.