合成吡啶类化合物用催化剂的再生行为研究

对合成吡啶类化合物用的失活催化剂上的结焦物进行了元素分析 ,并着重对失活催化剂的再生行为进行了研究。得到了不同失活程度催化剂的再生曲线及相同失活程度、不同再生条件下的再生曲线。经回归求得了一简单的再生反应动力学经验方程式 ,其中反应级数为碳含量的 1.16 5级 ,活化能为 4 2 .5 72kJ/mol,计算值与实验值的平均相对误差为 6 .5 %。     

Steric requirements for coal swelling by amine bases

A set of six coals ranging in rank from lignite to hvA bituminous was swollen with a series of alkyl-substituted pyridines and a smaller set of 4-alkylanilines. The size and branching of the alkyl groups was varied and the effect of this variation on the dissolution of the amines in the coal and the resulting coal swelling was measured volumetrically. In a few cases, substituents which hindered the amine nitrogen were studied. The lignite and subbituminous coal have a much higher tolerance to branched, bulky groups than do the bituminous coals. The presence of tertiary groups in a solute strongly inhibits their dissolution in bituminous coals. Bituminous coals behave as if extensive parallel packing of structures occurs. Often, they can accept very large planar groups but have a low capacity for branched groups.     

Synthesis and Spectral Properties of Mixed-Ligand Complexes of Lanthanide Perchlorate with Bis-(phenylsulfinyl)ethane and Organic Lewis Bases

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Laplace spectra as fingerprints for image recognition

In the area of image retrieval from data bases and for copyright protection of large image collections there is a growing demand for unique but easily computable fingerprints for images. These fingerprints can be used to quickly identify every image within a larger set of possibly similar images. This paper introduces a novel method to automatically obtain such fingerprints from an image. It is based on a reinterpretation of an image as a Riemannian manifold. This representation is feasible for gray value images and color images. We discuss the use of the spectrum of eigenvalues of different variants of the Laplace operator as a fingerprint and show the usability of this approach in several use cases. Contrary to existing works in this area we do not only use the discrete Laplacian, but also with a particular emphasis the underlying continuous operator. This allows better results in comparing the resulting spectra and deeper insights in the problems arising. We show how the well known discrete Laplacian is related to the continuous Laplace-Beltrami operator. Furthermore, we introduce the new concept of solid height functions to overcome some potential limitations of the method.     

取代水杨醛Schiff碱金属配合物催化氧化脱硫性能

以水杨醛类Schiff碱为配体,与Co(NO_3)_2、Cu(NO_3)_2反应合成6种Salen(M)型配合物Ⅰ～Ⅵ。以1-己硫醇、二丁基硫醚和2-甲基噻吩为模型化合物配制模拟油体系,考察了配合物Ⅰ～Ⅵ的催化氧化脱硫性能,并分析了配合物结构与氧化脱硫性能的关系。结果表明,6种配合物在75 min时的总脱硫效果为Ⅵ>Ⅴ>Ⅳ>Ⅰ>Ⅲ>Ⅱ,Ⅵ的总脱硫率为31.9%。对1-己硫醇及二丁基硫醚脱除效果最佳的是Ⅴ,脱除率分别为74.2%和65.1%;对2-甲基噻吩脱除效果最好的是Ⅰ,脱除率为26.8%。构效关系研究表明,中心金属离子与O_2的配位能力越强,配体的共轭体系越大、电子云密度越高,配合物的脱硫性能越好;通过IR和离子色谱对单一硫化物模拟油体系氧化前后的产物进行分析发现,硫化物氧化后皆生成相应的砜类或亚砜类,且1-己硫醇和二丁基硫醚被进一步氧化生成SO_3~(2–)或SO_4~(2–)。     

A ratiometric fluorescent sensor for zinc(II) with high selectivity

Spectroscopic studies revealed that the compound [N,N′-di(quinoline-2-methylene) -1,2-phenylenediimine] (1) exhibited a rather high selectivity toward Zn²⁺ over other metal ions, even Cd²⁺. In acetonitrile, the red shift of fluorescent emission from 396 nm to 426 nm upon zinc binding is due to the formation of a 1:1 metal/ligand complex.     

Formation of Polymeric Lewis Acid–Lewis Base Complexes with Well-defined Organoboron Polymers

The binding of Lewis bases to organoboron polymeric Lewis acids has been studied and the parameters that determine the complexation equilibrium have been investigated, which include (i) the strength of the individual Lewis acids and Lewis bases, (ii) concentration, and (iii) temperature. While the strongly Lewis acidic borane polymers poly(4-bis(pentafluorophenyl)borylstyrene) (PS-BPf) and poly(4-(di-2-thienylboryl)styrene) (PS-BTh) form isolable complexes with strong Lewis bases such as 4-t-butylpyridine (^tPy), a temperature dependent equilibrium is established with weaker bases such as THF. Similarly, the weakly Lewis acidic boronate polymer poly(4-diethoxyborylstyrene) (PS-BOEt) undergoes a temperature dependent equilibrium with the strong Lewis base 4-dimethylaminopyridine (DMAP), while poly(4-pinacolatoborylstyrene) (PS-BPin) does not significantly bind to pyridine bases. Decomplexation of PS-BTh· ^t Py is achieved by treatment with the stronger Lewis acid, B(C₆F₅)₃, thereby confirming the reversible nature of the polymeric Lewis acid–base adducts. This paper is dedicated to Professor Ian Manners in gratitude of his guidance throughout the years and recognition of his scientific accomplishments     

Novel lanthanide salicylaldimine complexes with unusual coordination mode

The one-step metal promoted reaction between salicylaldehyde and 4-methyl-1,3-phenylenediamine in the presence of lanthanum(III) or gadolinium(III) nitrate yields new salicylaldimine complexes containing N,N′-bis(salicylidene)-4-methyl-1,3-phenylenediamine as a result of the [2 + 1] Schiff base condensation. The crystal structure of the gadolinium complex reveals a dinuclear species with four unionized ligands coordinating in the monodentate and bridging bidentate fashion, using exclusively the oxygens as donor atoms with the nitrogen atoms not being involved in coordination. The coordination number of nine is achieved by involving three bidentate nitrate counterions in the coordination sphere.     

Effect of pH on a gossypol complex with phospholipids: Gossypol-PE

PE, one of the major phospholipids in oilseed soapstock, may react with gossypol to form Schiff bases. PE amounts to 20–30% of the phosphorus compounds in soap-stock. In this report, the dependence on pH of the Schiff base products between PE and gossypol was investigated using a spectrophotometer, an HPLC equipped with an ELSD, and an LC-MS system. We observed that at pH 7 the Schiff reaction product and reactants were clearly detected by ELSD, absorption, and LC-MS spectra. The absorption spectra displayed the characteristic peak for the Schiff bases around 430–440 nm. The absorption spectra also indicated that the reaction was pH dependent. The reaction temperatures were 60 and 90°C. The LC-MS spectra supported the formation of Schiff bases as well as methyl ether derivatives of gossypol in alcohol at the elevated temperatures. The implications of these experimental findings are presented in this paper.     

一类特殊本原不可幂定号有向图的广义基

考虑了一类含有三个n—2圈和一个n圈本原不可幂定号有向图的广义基,通过分析图中是否存在寻求的途径及SSSD途径对,运用本原不可幂定号有向图的一些定义和性质,给出了此类图的广义本原指数及广义基.