TBAB修饰的负载型Wacker催化剂催化甲醇羰基化合成碳酸二甲酯

自 1 95 9年 Smidt等 [1]发现均相 Pd Cl2 - Cu Cl2 体系可高效率直接选择性氧化乙烯制乙醛以来 ,Wacker催化过程已成为乙醛工业生产的主要方法 .为解决 Wacker催化体系腐蚀性强及催化体系与产物难以分离等弊端 ,将均相 Wacker(Pd Cl2 - Cu Cl2 )催化剂固载化成为备受关注的研究课题[2 ] .多相Wacker催化剂不仅成功地应用于选择性氧化低碳烯烃制醛和酮 [3 ,4 ] ,还用于 CO深度氧化 [5～ 7] .碳酸二甲酯 (DMC)的合成与应用研究是目前绿色化学前沿课题 .在众多的 DMC合成方法中 ,常压气相法因其工艺简单、对设备无腐蚀以及产品易分离…     

《分子催化》征稿启事

《分子催化》是由中国科学院主管、科学出版社出版,由中国科学院兰州化学物理研究所主办的向国内外公开发行的学术刊物.主要报导有关分子催化方面的最新进展与研究成果.辟有学术论文、研究简报、研究快报及进展评述等栏目.内容侧重于络合催化、酶催化、光助催化、催化过程中的立体化学问题、催化反应机理与动力学、催化剂表面态的研究及量子化学在催化学科中的应用等.工业催化过程中均相催化剂、固载化的均相催化剂、固载化的酶催化剂等的活化、     

《分子催化》征稿启事北大核心CSCD

《分子催化》是由中国科学院主管、科学出版社出版,由中国科学院兰州化学物理研究所主办的向国内外公开发行的学术刊物.主要报导有关分子催化方面的最新进展与研究成果.辟有学术论文、研究简报、研究快报及进展评述等栏目.内容侧重于络合催化、酶催化、光助催化、催化过程中的立体化学问题、催化反应机理与动力学、催化剂表面态的研究及量子化学在催化学科中的应用等.工业催化过程中均相催化剂、固载化的均相催化剂、固载化的酶催化剂等的活化、     

《分子催化》简介

《分子催化》是由中国科学院兰州化学物理研究所主办、中国科学院主管、科学出版社出版的向国内外公开发行的学术性刊物.主要报道有关分子催化方面最新进展与研究成果.辟有学术论文、研究简报、研究快报及综合述评等栏目.内容侧重于配位催化、酶催化、光助催化、催化过程中的立体化学问题、催化反应机理与动力学、催化剂表面态的研究及量子化学在催化学科中的应用等.工业催化过程中的均相催化剂、固载化学的均相催化剂、固载化的酶催化剂等活化、失活和再生;用于新催化过程的催化剂的优选与表征等方面的内容,本刊亦有报道.读者对象主要是科研单位及工矿企业中从事催化工作的科技人员、研究生、高等院校化学系和化工系的师生.     

欢迎订阅《分子催化》

《分子催化》是由中国科学院主管、科学出版社出版,由中国科学院兰州化学物理研究所主办的向国内外公开发行的学术刊物.主要报导有关分子催化方面的最新进展与研究成果.辟有学术论文、研究简报、研究快报及进展评述等栏目.内容侧重于络合催化、酶催化、光助催化、催化过程中的立体化学问题、催化反应机理与动力学、催化剂表面态的研究及量子化学在催化学科中的应用等.工业催化过程中均相催化剂、固载化的均相催化剂、固载化的酶催化剂等的活化、失活和再生,以及用于新催化过程的催化剂的优选     

水溶性膦配体络合金属催化剂的进展

均相催化剂与多相催化剂相比有许多优点,如在均相催化剂中,全部中心金属原子均参与构成活性种;具有确定均一的结构;催化剂浓度低,具有高活性、高选择性;反应条件温和;不存在扩散问题;传热易于解决等.但是,均相催化剂与产物的分离问题给工业生产带来了困难,特别是对产品沸点高的均相催化过程,显得更为突出,加之所用催化剂大多是贵重金属,因此,均相催化剂的分离回收一直是催化剂研究领域的一个热点.如均相催化多相化的研究,即通过高分子锚定,无机载体固定、双重固载及液相担载等方法,使均相催化剂多     

离子液体载催化剂和载试剂在有机合成中的应用

综述了离子液体载催化剂和载试剂在有机合成中的应用进展. 离子液体载催化剂是针对离子液体中催化剂难以回收利用的问题提出来的, 它不仅可以实现均相催化, 而且反应产物容易分离, 催化剂可以循环使用. 离子液体载有机试剂合成, 又称为离子液体相有机合成, 具有固相反应产物纯度高和液相反应反应快的优点. 在离子液体载无机试剂的反应中, 反应物毒性降低, 反应条件温和, 产物选择性好.     

以聚乙二醇为载体的催化剂及为反应介质的催化反应体系

聚乙二醇(PEG)负载的催化剂具有较高的催化活性, 易于回收和循环使用, 因此受到人们极大的关注. 此外, PEG可以用作催化反应的流动相动态地担载催化剂, 通过“均相反应, 两相分离”实现均相催化剂的简单分离. 对这一领域的研究进展作一综述.     

《分子催化》简介

《分子催化》是由中国科学院兰州化学物理研究所主办、中国科学院主管、科学出版社出版的向国内外公开发行的学术性刊物。主要报道有关分子催化方面最新进展与研究成果。辟有学术论文、研究简报、研究快报及综合述评等栏目。内容侧重于配位催化、酶催化、光助催化、催化过程中的立体化学问题、催化反应机理与动力学、催化剂表面态的研究及量子化学在催化学科中的应用等。工业催化过程中的均相催化剂、固载化学的均相催化剂、固载化的酶催化剂等活化、失活和再生;用于新催化过程的催化剂的优选与     

《分子催化》征稿启事

正《分子催化》是由中国科学院主管、科学出版社出版,由中国科学院兰州化学物理研究所主办的向国内外公开发行的学术刊物.主要报导有关分子催化方面的最新进展与研究成果.辟有学术论文、研究简报、研究快报及进展评述等栏目.内容侧重于络合催化、酶催化、光助催化、催化过程中的立体化学问题、催化反应机理与动力学、催化剂表面态的研究及量子化学在催化学科中的应用等工业催化过程中均相催化剂固载化的均相催化剂固载化的酶催化剂等的活化失活     

Regioselectivity of olefin oxidation by iodosobenzene catalyzed by metalloporphyrins : control by the catalyst

The regioselectivity of the oxidation of three monosubstituted olefins, 6-phenoxyhex-1-ene, hex-1-ene and styrene, by iodosobenzene in the presence of various Fe-, Mn- or Cr-tetraaryl-porphyrins, was studied. It was found that, besides epoxides, known products from such systems, allylic alcohols and aldehydes were formed, the latter not being derived from the corresponding epoxides. The relative importance of these reactions greatly depends upon both the metal and porphyrin constituents of the catalyst. More particularly, the competition between epoxidation and allylic hydroxylation can be efficiently controlled by non-bonded interactions between the olefin and porphyrin substituents. No hydroxylation of the aromatic rings and no oxidative dealkylation of the ether function was detected.     

Enantiomer separation by CEC——Enantiomer separation by packed-capillary electrochromatography

Three chiral compounds were successfully separated in a short time with two enantiomer separation models on packed-capillary electrochromatography (CEC). (i) 75 μm I.D. capillaries were packed with 5 μm β-cyclodextrin (β-CD) chiral stationary phase (CSP). Effects of voltage, pH and concentration of organic modifier on electroosmotic flow (EOF) and chiral separations were investigated systematically. Enantiomers of a neutral compound (benzoin) and a neutral drug (mephenytoin) were separated within a short time with high efficiency. Efficiency of 32 000 theoretical plates per meter and resolution (R_s) of 1.42 were achieved for enantiomers of benzoin using a βCD packed column with 6.2 cm packed length. Efficiency of 45 000 theoretical plates per meter and R_s of 3.40 were obtained for enantiomers of mephenytoin. Especially, the enantiomer separation of mephenytion was performed in just 3.4 min with R_s of 2.60. (ⅱ) 75 μm I.D. capillary was packed with octadecylsilica particles (ODS). Chiral separat     

Membrane solubilization by detergent: resistance conferred by thickness

The commonly held model for membrane dissolution by detergents/surfactants requires lipid transport from the inner to the outer bilayer leaflet ('flip-flop'). Although applicable to many systems, it fails in cases where cross-bilayer transport of membrane components is suppressed. In this paper we investigate the mechanism for surfactant-induced solubilization of polymeric bilayers. To that end, we examine the dissolution of a series of increasingly thick, polymer-based vesicles (polymersomes) by a nonionic surfactant, Triton X-100, using dynamic light scattering. We find that increasing the bilayer thickness imparts better resistance to dissolution, so that the concentration required for solubilization, after a fixed amount of time, increases nearly linearly with membrane thickness. Combining our experimental data with a theoretical model, we show that the dominant mechanism for the surfactant-induced dissolution of polymeric vesicles, where polymer flip-flop across the membrane is suppressed, is the surfactant transport through the bilayer. This mechanism is different both qualitatively and quantitatively from the mechanisms by which surfactants dissolve pure lipid vesicles.     

Antibiotic recognition by binuclear metallo-beta-lactamases revealed by X-ray crystallography

Metallo-beta-lactamases are zinc-dependent enzymes responsible for resistance to beta-lactam antibiotics in a variety of host bacteria, usually Gram-negative species that act as opportunist pathogens. They hydrolyze all classes of beta-lactam antibiotics, including carbapenems, and escape the action of available beta-lactamase inhibitors. Efforts to develop effective inhibitors have been hampered by the lack of structural information regarding how these enzymes recognize and turn over beta-lactam substrates. We report here the crystal structure of the Stenotrophomonas maltophilia L1 enzyme in complex with the hydrolysis product of the 7alpha-methoxyoxacephem, moxalactam. The on-enzyme complex is a 3'-exo-methylene species generated by elimination of the 1-methyltetrazolyl-5-thiolate anion from the 3'-methyl group. Moxalactam binding to L1 involves direct interaction of the two active site zinc ions with the beta-lactam amide and C4 carboxylate, groups that are common to all beta-lactam substrates. The 7beta-[(4-hydroxyphenyl)malonyl]-amino substituent makes limited hydrophobic and hydrogen bonding contacts with the active site groove. The mode of binding provides strong evidence that a water molecule situated between the two metal ions is the most likely nucleophile in the hydrolytic reaction. These data suggest a reaction mechanism for metallo-beta-lactamases in which both metal ions contribute to catalysis by activating the bridging water/hydroxide nucleophile, polarizing the substrate amide bond for attack and stabilizing anionic nitrogen intermediates. The structure illustrates how a binuclear zinc site confers upon metallo-beta-lactamases the ability both to recognize and efficiently hydrolyze a wide variety of beta-lactam substrates.     

Substitution of 2-phosphaindolizines by bromine and by chlorophosphines

Bromine does not add to phosphorus in a 2-phosphaindolizine 1 but substitutes its 1-position. The 1-bromo derivatives 2 are best prepared with Br₂/NEt₃ or N-bromosuccinimide. Their hydrolysis is remarkable; it involves a debromination of C-1, an oxidation of P and a selective opening of the P/C-3 bond. PCl₃ also causes a substitution of the 1-position. The resulting 1-dichlorophosphino derivatives 5 easily undergo a substituent exchange at the exocyclic phosphorus. More 1-phosphino derivatives are formed in the reaction of 1 with phenyl and diazaphospholyl dichlorophosphine.     

DNA damage by sulfite autoxidation catalyzed by cobalt complexes

DNA damage was investigated in the presence of sulfite, dissolved oxygen and cobalt(II) complexes with glycylglycylhistidine, glycylhistidyllysine, glycylglycyltyrosylarginine and tetraglycine. These studies indicated that only Co(II) complexed with glycylglycylhistidine (GGH) induced DNA strand breaks at low sulfite concentrations (1-80 microM) via strong oxidants formed in the reaction. In the presence of the other complexes, some damage occurred only in the presence of high sulfite concentrations (0.1-2.0 mM) after incubation for 4 h. In the presence of GGH, Co(II) and dissolved O2, DNA damage must involve a reactive high-valent cobalt complex. The damaging effect was increased by adding S(IV), due to the oxysulfur radicals formed as intermediates in S(IV) autoxidation catalyzed by the complex. SO3 -, HO and H radicals were detected by EPR-spin trapping experiments with DMPO (5,5-dimethyl-1-pyrroline N-oxide). The results indicate that Co(II) binds O2 in the presence of GGH, and leads to the formation of a DMPO-HO adduct without first forming free superoxide or hydroxyl radical, supporting the participation of a reactive high-valent cobalt complex.     

Multitargeting by curcumin as revealed by molecular interaction studies

Curcumin (diferuloylmethane), the active ingredient in turmeric (Curcuma longa), is a highly pleiotropic molecule with anti-inflammatory, anti-oxidant, chemopreventive, chemosensitization, and radiosensitization activities. The pleiotropic activities attributed to curcumin come from its complex molecular structure and chemistry, as well as its ability to influence multiple signaling molecules. Curcumin has been shown to bind by multiple forces directly to numerous signaling molecules, such as inflammatory molecules, cell survival proteins, protein kinases, protein reductases, histone acetyltransferase, histone deacetylase, glyoxalase I, xanthine oxidase, proteasome, HIV1 integrase, HIV1 protease, sarco (endo) plasmic reticulum Ca(2+) ATPase, DNA methyltransferases 1, FtsZ protofilaments, carrier proteins, and metal ions. Curcumin can also bind directly to DNA and RNA. Owing to its β-diketone moiety, curcumin undergoes keto-enol tautomerism that has been reported as a favorable state for direct binding. The functional groups on curcumin found suitable for interaction with other macromolecules include the α, β-unsaturated β-diketone moiety, carbonyl and enolic groups of the β-diketone moiety, methoxy and phenolic hydroxyl groups, and the phenyl rings. Various biophysical tools have been used to monitor direct interaction of curcumin with other proteins, including absorption, fluorescence, Fourier transform infrared (FTIR) and circular dichroism (CD) spectroscopy, surface plasmon resonance, competitive ligand binding, Forster type fluorescence resonance energy transfer (FRET), radiolabeling, site-directed mutagenesis, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS), immunoprecipitation, phage display biopanning, electron microscopy, 1-anilino-8-naphthalene-sulfonate (ANS) displacement, and co-localization. Molecular docking, the most commonly employed computational tool for calculating binding affinities and predicting binding sites, has also been used to further characterize curcumin's binding sites. Furthermore, the ability of curcumin to bind directly to carrier proteins improves its solubility and bioavailability. In this review, we focus on how curcumin directly targets signaling molecules, as well as the different forces that bind the curcumin-protein complex and how this interaction affects the biological properties of proteins. We will also discuss various analogues of curcumin designed to bind selective targets with increased affinity.