助剂对低碳醇合成熔铁催化剂的影响

用ＸＲＤ，ＴＧ－ＤＴＡ－ＤＴＧ和ＣＯ加氢反应装置，对某些难熔氧化物助剂改性的熔铁催化剂的结构、还原和合成醇活性、选择性进行了研究。结果表明，催化剂的氧化态物相主要是Ｆｅ３Ｏ４，难熔氧化物助剂的加入可使还原温度提高。Ｖ２Ｏ５助剂有利于提高低温催化活性和Ｃ２＾＋ＯＨ选择性，Ｃｒ２Ｏ３助剂对提高高温活性有利。ＴｉＯ２助剂的最佳含量约为２．５％。当采用复合助剂时，不仅可提高催化活性和选择性，而且可降低催化     

Covalent Anchor Positions Play an Important Role in Tuning Catalytic Properties of a Rationally Designed MnSalen-containing Metalloenzyme

Two questions important to the success in metalloenzyme design are how to attach or anchor metal cofactors inside protein scaffolds, and in what way such positioning affects enzymatic properties. We have previously reported a dual anchoring method to position a nonnative cofactor, MnSalen (1), inside the heme cavity of apo sperm whale myoglobin (Mb) and showed that the dual anchoring can increase both the activity and enantioselectivity over the single anchoring methods, making this artificial enzyme an ideal system to address the above questions. Here we report systematic investigations of the effect of different covalent attachment or anchoring positions on reactivity and selectivity of sulfoxidation by the MnSalen-containing Mb enzymes. We have found that changing the left anchor from Y103C to T39C has an almost identical effect of increasing rate by 1.8-fold and increasing selectivity by +14% for S, whether the right anchor is L72C or S108C. At the same time, regardless of the identity of the left anchor, changing the right anchor from S108C to L72C increases rate by 4-fold and selectivity by +66%. The right anchor site was observed to have a greater influence than the left anchor site on the reactivity and selectivity in sulfoxidation of a wide scope of other ortho-, meta- and para- substituted substrates. The 1?Mb(T39C/L72C) showed the highest reactivity (TON up to 2.31 min(-1)) and selectivity (ee% up to 83%) among the different anchoring positions examined. Molecular dynamic simulations indicate that these changes in reactivity and selectivity may be due to the steric effects of the linker arms inside the protein cavity. These results indicate that small differences in the anchor positions can result in significant changes in reactivity and enantioselectivity, probably through steric interactions with substrates when they enter the substrate-binding pocket, and that the effects of right and left anchor positions are independent and additive in nature. The finding that the anchoring arms can influence both the positioning of the cofactor and steric control of substrate entrance will help design better functional metalloenzymes with predicted catalytic activity and selectivity.     

Chiral bis(oxazoline)-copper complex catalyzed Diels-Alder reaction in ionic liquids: remarkable reactivity and selectivity enhancement, and efficient recycling of the catalyst

Ionic liquid was found to be an excellent medium for asymmetric Diels-Alder reaction catalyzed by chiral bis(oxazoline)-copper complex. The reactivity and selectivity of reactions were highly dependent upon the property of the ionic liquids. Reactions of β-substituted acryloyl dienophiles in [Bmim]SbF₆ at ambient temperature provided remarkably enhanced reactivity and stereoselectivity compared to homogeneous reactions in non-ionic liquid solvent at −78 °C. Due to the increased reactivity, the amount of metal catalyst could be reduced down to 0.6 mol % without any significant selectivity compromise. Additionally, recycling of the ligand-metal complex was achieved efficiently up to 18 times.     

The reactivity-selectivity principle: an imperishable myth in organic chemistry

The reactivity-selectivity principle (RSP), once a tenet of organic chemistry, eroded during the 1970s and was more or less abandoned by 1980. Although it has been clear for more than 25 years that a decrease in selectivity with increasing reactivity can only be expected with certainty if diffusion control is approached, the RSP has survived as an intuitively appealing rule. This Minireview shows why selectivity cannot generally decrease with increasing reactivity and highlights the weaknesses of the theoretical foundations of the RSP.     

Modelling of Enzyme Properties in Organic Solvents

 In this article we review how molecular modeling techniques can be used to shed some light on the influence of organic solvents on the molecular characteristics of proteins and enzymes. Molecular dynamic simulations on bovine pancreas trypsin inhibitor, chymotrypsin, and subtilisin make it possible to get a deeper understanding into how increased intramolecular interactions improve conformational rigidity, thus explaining the lower reactivity and the higher thermostability of enzymes in non-aqueous media. The application of thermodynamics-based models allows first qualitative predictions on the selectivity of many reaction types; however, the application of quantum mechanical/molecular mechanical methods is required for the development of quantitative models of actual reactivity patterns.     

Modelling of Enzyme Properties in Organic Solvents

Summary.  In this article we review how molecular modeling techniques can be used to shed some light on the influence of organic solvents on the molecular characteristics of proteins and enzymes. Molecular dynamic simulations on bovine pancreas trypsin inhibitor, chymotrypsin, and subtilisin make it possible to get a deeper understanding into how increased intramolecular interactions improve conformational rigidity, thus explaining the lower reactivity and the higher thermostability of enzymes in non-aqueous media. The application of thermodynamics-based models allows first qualitative predictions on the selectivity of many reaction types; however, the application of quantum mechanical/molecular mechanical methods is required for the development of quantitative models of actual reactivity patterns. Received November 18, 1999. Accepted (revised) February 8, 2000     

H+反应对土壤重金属分级提取形态分析的影响

探讨了普遍存在于重金属分级提取形态分析体系中的H+浓度的影响因素,分析了H+反应与提取剂的选择性、金属离子的重分配现象的关系,以及H+浓度对分级提取法数据结果的影响,并对分级提取方法作了进一步的改进.研究表明提取剂pH、提取体系、土壤理化性质及土壤/溶液比是影响H+反应的主要因素;H+反应可降低提取剂选择性,减弱金属离子的重分配能力,影响分析结果的有效性,且对于不同的重金属离子、不同的提取体系,H+反应所造成的影响不同.     

H+反应对土壤重金属分级提取形态分析的影响

探讨了普遍存在于重金属分级提取形态分析体系中的H 反应的影响因素,分析了H 反应与提取剂的选择性、金属离子的重分配现象的关系,以及H 反应对分级提取法数据结果的影响,并对分级提取方法作了进一步的改进。研究表明提取剂pH、提取体系、土壤理化性质及土壤 溶液比是影响H 反应的主要因素;H 反应可降低提取剂选择性,减弱金属离子的重分配能力,影响分析结果的有效性,且对于不同的重金属离子、不同的提取体系,H 反应所造成的影响不同。     

铋钒钼复合氧化物催化剂结构与丙烷选择氧化催化性能

用X射线衍射（XRD）、激光拉曼光谱（LRS）、程序升温还原（TPR）和微型反 应测试等手段研究了Bi-V-Mo-O复合氧化物催化剂组成、结构与丙烷选择性氧化催 化性能。结果表明不同组成的Bi-V-Mo-O复合氧化物催化剂可形成白钨矿型晶体结 构,丙烷选择氧化催化性能与催化剂组成和结构密切相关。Mo组分的引入使催化剂 的丙烷安全氧化催化性能受到抑制,丙烯醛选择性增加且在Mo/（V+Mo）原子比为 0.45时达极大值。Mo含量进一步增加,催化剂的丙烯选择性增加而丙烯醛选择性下 降。LRS和TPR结果表明,不同组成的Bi-V-Mo-O复合氧化物催化剂的丙烷选择氧化 催化性能与催化剂的金属氧物种性质相关联。     

Ligand Design for Electrochemically Controlling Stoichiometric and Catalytic Reactivity of Transition Metals

Changing the oxidation state of redox-active ligands is a powerful method for electrochemically controlling the reactivity and selectivity of bound transition metals (see drawing on the right). In some cases reaction rates can be increased by many orders of magnitude simply by removing an electron from a metal–ligand complex. In the case of polymeric redox-active ligands, a continuous range of properties can be achieved for the transition metal complex.     

Ru助剂对Co/SiO2催化剂费托合成反应性能的影响

 考察了 Ru 助剂 (0.17%?9.96%) 对 Co/SiO2 催化剂结构及其费托合成反应性能的影响. 结果表明, Ru 助剂可降低 Co/SiO2 催化剂的还原温度, 从而提高其还原度. 光电子能谱和扩展 X 吸收射线精细结构研究表明, 即使 Ru 含量高达 9.96%, 在 Co/SiO2 催化剂焙烧过程中也未观察到 Ru 物种与 Co 物种作用形成的化合物. 还原后催化剂中 Ru 趋向于与 Co 物种紧密接触且分散在催化剂表面. H2 程序升温脱附结果表明, 随着 Ru 含量的增加, 位于反应温度附近的 H2 脱附峰面积增加, 即此时催化剂吸附 H2 能力提高, 因此反应活性单调增加, 但存在最佳 Ru 含量, 此时 C5+选择性最高.     

Model reaction for the synthesis of polyhydroxyurethanes from cyclic carbonates with amines: Substituent effect on the reactivity and selectivity of ring‐opening direction in the reaction of five‐membered cyclic carbonates with amine

This article focuses on the substituent effect on the reactivity and selectivity of the ring‐opening direction in the reaction of five‐membered cyclic carbonates with n‐hexylamine. The reactivity of the cyclic carbonate and the formation selectivity of the adduct with a secondary hydroxyl group increased as a stronger electron‐withdrawing group was introduced at the α‐methylene of the cyclic carbonate. These results are discussed on the basis of the stability of intermediates, primary and secondary alcoholate anions, Mulliken charges on carbonyl carbon, and the bond lengths and orders of the O? C?O single bond. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3678–3685, 2001     

Effect of Micropores of a Porous Coordination Polymer on the Product Selectivity in RuII Complex-catalyzed CO2 Reduction

To develop an efficient CO2 reduction catalyst, hybridizing a molecular catalyst and a porous coordination polymer (PCP) is a promising strategy because it can combine both advantages of the precise reactivity control of the former and the CO2 adsorption property of the latter. Although several PCP hybrid catalysts have been reported to date, the CO2 sorption behavior and the CO2 reduction reactivity have been investigated separately, and the CO2 enrichment during the catalysis is still unclear. We report CO2 photoreduction under different temperatures and pressures using a PCP-RuII complex hybrid catalyst. The product selectivity (CO or HCOOH) varied depending on the reaction conditions. The altered selectivity could be interpreted in terms of the CO2 capture in the micropores of a PCP.     

Ethynylation of Cysteine Residues: From Peptides to Proteins in Vitro and in Living Cells

Current approaches to introduce terminal alkynes for bioorthogonal reactions into biomolecules still present limitations in terms of either reactivity, selectivity, or adduct stability. We present a method for the ethynylation of cysteine residues based on the use of ethynylbenziodoxolone (EBX) reagents. The acetylene group is directly introduced onto the thiol group of cysteine and can be used for copper‐catalyzed alkyne‐azide cycloaddition (CuAAC) without further processing. Labeling proceeded with reaction rates comparable to or higher than the most often used iodoacetamide on peptides or maleimide on the antibody trastuzumab, and high cysteine selectivity was observed. The reagents were also used in living cells for cysteine proteomic profiling and displayed improved coverage of the cysteinome compared to previously reported iodoacetamide or hypervalent iodine reagents. Fine‐tuning of the EBX reagents allows optimization of their reactivity and physical properties.     

A bispericyclic transition structure allows for efficient relief of antiaromaticity enhancing reactivity and endo stereoselectivity in the dimerization of the fleeting cyclopentadienone

B3LYP/6-31G calculations account for the enhanced reactivity and endo stereoselectivity in the dimerization of the fleeting antiaromatic cyclopentadienone. Secondary orbital interactions promote endo stereoselectivity and a full merging of 4+2 and 2+4 allowed paths in an endo bispericyclic transition structure. Electrostatic effects increase reactivity and selectivity but the driving force to enhanced reactivity is the loss of antiaromaticity in the dimerization TSs while enhanced selectivity derives from the more efficient relief of antiaromaticity in the bispericyclic array.     

Metal‐Mediated Functionalization of Natural Peptides and Proteins: Panning for Bioconjugation Gold

Selective modification of natural proteins is a daunting methodological challenge and a stringent test of selectivity and reaction scope. There is a continued need for new reactivity and new selectivity concepts. Transition metals exhibit a wealth of unique reactivity that is orthogonal to biological reactions and processes. As such, metal‐based methods play an increasingly important role in bioconjugation. This Review examines metal‐based methods as well as their reactivity and selectivity for the functionalization of natural proteins and peptides.     

Expanded substrate scope and catalyst optimization for the catalytic kinetic resolution of N-heterocycles

The scope, reactivity, and selectivity of the chiral hydroxamic acid-catalyzed kinetic resolution of chiral amines are improved by a new catalyst structure and a more environmentally friendly reaction protocol. In addition to increasing selectivity across all substrates, these conditions make possible the resolution of N-heterocycles containing lactams or other basic functional groups that can inhibit the catalyst.     

New Perspectives in Living/Controlled Anionic Polymerization

Summary: Control of the reactivity and selectivity of active species remains a major challenge in the course of living/controlled polymerizations of vinyl and heterocyclic monomers. We have found that alkyl metal derivatives such as dialkylmagnesium or trialkylaluminum derivatives or the corresponding alkoxyakyl metal derivatives, when added to conventional anionic polymerization systems, are very effective mediators for the controlled anionic polymerization of both styrenic and oxirane monomers. When used as additives to alkali metal alkyl initiators (alkyl lithium, alkyl sodium) for the styrene anionic polymerizations, they strongly retard the reactivity of the propagating species and allow controlling the polymerization in very unusual conditions (bulk, very high temperature). On the contrary, when used in combination to the same alkali metal based initiators for the anionic polymerization of ethylene oxide or propylene oxide, these additives can drastically enhance the reactivity and the selectivity of the propagating species allowing a fast living-like polymerization to proceed already at low temperature in hydrocarbon media.     

Regioselective and high-yielding bromination of aromatic compounds using hexamethylenetetramine-bromine

A regioselective and highly efficient method for bromination of aromatic compounds in the presence of a stoichiometric amount of hexamethylenetetramine-bromine (HMTAB) as an efficient reagent in dichloromethane is reported. The selectivity depends on the temperature and nature of the substituent on the substrate. The reactivity of this reagent was increased by supporting it to silica gel for bromination of less activated compounds.