近年来国内高碳烯烃氢甲酰化反应研究进展

介绍了近年来国内高碳烯烃氢甲酰化反应研究与开发进展，内容涉及高碳烯烃氢甲酰化反应的三个主要催化体系：均相催化体系、水／有机两相催化体系、固载水相催化体系。国内近年来研究进展表明，尽管运用三个主要催化体系所进行的研究取得一定进展。但就各个催化体系的不同特点，又都面临一些亟待解决的问题，实现反应的工业化尚待时日。     

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     

Well defined CuI(NO), CuI(NO)2 and CuII(NO)X (X = O− and/or NO 2 − ) complexes in CuI-ZSMS prepared by interaction of H-ZSM5 with gaseous CuCl

In this note an exchange procedure of the acidic protons of H-ZSM5 by Cu^I ions through reaction with CuCl in the gas phase is described. In the so obtained Cu^I-ZSM5 exchanged zeolite the Cu^I ions are in well defined configuration and form with NO mono and di-nitrosyl complexes of high structural and spectroscopic quality. The Cu^I(NO)₂ species are transformed at RT into Cu^II(NO)X (X=O^– and/or NO ₂ ^– ) species which could represent an intermediate in NO decomposition.     

Preparation and characterization of multi-walled carbon nanotubes supported PtRu catalysts for proton exchange membrane fuel cells

A series of PtRu nanocomposites supported on H₂O₂-oxidized multi-walled carbon nanotubes (MWCNTs) were synthesized via two chemical reduction methods—one used aqueous formaldehyde (HCHO method) and the other used ethylene glycol (EG method) as the reducing agents. The effects of the solvents (water and ethylene glycol) and the surface composition of the MWCNTs on the deposition and the dispersion of the metal particles were investigated using N₂ adsorption, TEM, ICP-AES, FTIR and TPD. The wetting heats of the MWCNTs in corresponding solvents were also measured. The characterizations suggest that combination of the surface chemistry of the MWCNTs with the solvents decides the deposition and the dispersion of the metal nanoparticles. These nanocomposites were evaluated as proton exchange membrane fuel cell anode catalysts for oxidation of 50 ppm CO contaminated hydrogen and compared with a commercial PtRu/C catalyst. The data reveal superior performances for the nanocomposites prepared by the EG method to those by the HCHO method and even to that for the commercial analogue. Structure–performance relationship of the nanocomposites was also studied.     

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.     

一种蛋白质复合体模块度函数及其识别算法

蛋白质复合体对于研究细胞活动具有重要意义.随着新的生物实验技术的不断出现,产生了大量的蛋白质相互作用网络.通过对蛋白质相互作用网络进行聚类识别蛋白质复合体是当前研究热点.然而,目前大多数蛋白质复合体识别算法的性能不够理想.为此,提出了蛋白质复合体模块度函数(PQ),并在此基础上提出了基于蛋白质复合体模块度函数的模块合并(based on protein complexes modularity function for merging modules,BMM)算法.BMM算法首先识别网络中一些稠密子图作为初始模块,然后依据PQ函数对这些初始模块进行合并,最终得到了质量较高的蛋白质复合体.将识别出的复合体分别与2种已知的蛋白质复合体数据集进行比对,结果表明BMM算法具有很好的识别性能.此外,与其他最新的识别算法相比,BMM算法的识别准确率较高.     

Origin of rate bistability in Mn–O/Al2O3 catalysts for carbon monoxide oxidation: role of the Jahn–Teller effect

Peculiarities in catalytic activity in carbon monoxide oxidation as well as some structure, electronic and magnetic properties of the three oxide catalysts, Mn³⁺–O/Al₂O₃ (1), Mn³⁺–O–Fe/Al₂O₃ (Mn-substituted spinel, 2) and -Fe₂O₃/Al₂O₃ (3), were studied by kinetic measurements and by Mössbauer spectroscopy. The catalysts 1 and 2 showed a kinetic bistability with a sharp transition towards more reactive state at 200°C (ignition point). In contrast, for catalyst 3, at 200–250°C, the behavior of reaction rate against temperature did not display noticeable hysteresis. On cooling the catalysts 1 and 2, extinction was observed at about 170 and 120°C, respectively, i.e., at 30–80°C lower than the corresponding ignition points. Proximity of activation energy for the high and low activity (15–19 kJ/mol) for both Mn-containing catalysts suggests an increase in the number of active sites at high temperature with no changes in the reaction mechanism. The considerable difference between Mn-containing catalysts 1, 2 and Fe-containing catalyst 3 may be caused by Jahn–Teller (JT) type distortions of the oxygen polyhedron around Mn³⁺. A significant spontaneous axial bond stretching within the local polyhedron seems to diminish Mn–O binding energy, facilitate the participation of surface oxygen species, O_S, in the oxidation of CO by a redox mechanism and promote oxygen vacancies at the surface that would cause considerable effect on the activity. An increase in the width of the counterclockwise hysteresis loop for the catalyst 2 compared to the catalyst 1 indicates that clusters of mixed spinel provide more active sites and more labile O_S species than clusters of the binary Mn oxide.     

芴甲氧羰基酪氨酸苄醚的合成研究

研究了硫酸铜存在下溴苄与酪氨酸反应生成酪氨酸苄醚,收率45%。反应中,铜盐先与酪氨酸的羧基作用,生成4∶1的酪氨酸铜配合物,从而有效地保护了酪氨酸的羧基,使苄基化反应选择性地发生在侧链酚基氧原子上。酪氨酸苄醚与芴甲氧羰酰氯在THF中反应得标题化合物,收率98%。     

不同二辛基二硫代磷酸金属配合物促进剂对NR性能的影响

研究了5种二辛基二硫代磷酸稀土配合物（REDODP）对天然橡胶（NR）硫化特性、力学性能和老化性能的影响，并与二辛基二硫代磷酸钾（KDODP）和二辛基二硫代磷酸锌（ZnDODP）进行了对比。结果表明，含REDODP的NR胶料的正硫化时间介于含ZnDODP和KDODP的胶料之间，但抗返原性比KDODP的好，而与ZnDODP的相近。由于REDODP促进剂中RE是三配位，胶料中RE含量较低，降低了硫化胶的交联密度，对力学性能有一定的影响，但硫化胶老化前后拉伸强度及拉断伸长率下降幅度低于含KDODP和ZnDODP的硫化胶，表明REDODP有利于提高NR硫化胶的耐老化性能。     

Studies on syntheses and properties of novel CeO2/polyimide nanocomposite films from Ce(Phen)3 complex

A series of cerium dioxide (CeO₂)/polyimide (PI) nanocomposites were successfully prepared from Ce(Phen)₃ and polyamic acid (PAA) via the solution direct-dispersing method, followed by a step thermal imidization process. TGA and XPS studies showed that the cerium complex decomposed to form CeO₂ during the thermal imidization process at 300 °C. SEM observation showed that the formed CeO₂ as nanoparticles was well dispersed in polyimide matrix with a size of about 50-100 nm for samples with different contents of CeO₂. Thermal analysis indicated that the introduction of CeO₂ decreased the thermal stability of nanocomposite films due to the decomposition of Ce(Phen)₃ in the imidization process, while the glass transition temperature (T_g) increased obviously, especially nanocomposite films with high loading of CeO₂ exhibited a trend of disappearance of T_g. DMTA and static tensile measurements showed that the storage modulus of nanocomposite films increased, while the elongation at break decreased with increasing CeO₂ content.