Local Least Product Relative Error Estimation for Varying Coefficient Multiplicative Regression Model

Acta Mathematicae Applicatae Sinica, English Series - In this article, we consider the varying coefficient multiplicative regression model, which is very useful to model the positive response. The...     

含分布时滞的时滞微分系统多步龙格-库塔方法的时滞相关稳定性

本文研究了一类含分布时滞的时滞微分系统的多步龙格-库塔方法的稳定性.基于辐角原理，本文给出了多步龙格-库塔方法弱时滞相关稳定性的充分条件，并通过数值算例验证了理论结果的有效性.     

Phosphorescent κ3-(N^C^C)-Gold(III) Complexes: Synthesis,Photophysics, Computational Studies and Application to Solution-Processable OLEDs

Efficient OLED devices have been fabricated using organometallic complexes of platinum group metals. Still, the high material cost and low stability represent central challenges for their application in commercial display technologies. Based on its innate stability, gold(III) complexes are emerging as promising candidates for high-performance OLEDs. Here, a series of alkynyl-, N-heterocyclic carbene (NHC)- and aryl-gold(III) complexes stabilized by a κ³-(N^C^C) template have been prepared and their photophysical properties have been characterized in detail. These compounds exhibit good photoluminescence quantum efficiency (η_PL) of up to 33 %. The PL emission can be tuned from sky-blue to yellowish green colors by variations on both the ancillary ligands as well as on the pincer template. Further, solution-processable OLED devices based on some of these complexes display remarkable emissive properties (η_CE 46.6 cd.A⁻¹ and η_ext 14.0 %), thus showcasing the potential of these motifs for the low-cost fabrication of display and illumination technologies.     

Room temperature suzuki cross‐coupling polymerizations of aryl dihalides and aryldiboronic acid/acid esters with t‐Bu3P‐coordinated 2‐phenylaniline‐based palladacycle complex as the precatalyst

Room temperature Suzuki cross‐coupling polymerization of aryl dibromides/diiodides with aryldiboronic acids/acid esters with t‐Bu₃P‐coordinated 2‐phenylaniline‐based palladacycle complex, [2′‐(amino‐kN)[1,1′‐biphenyl]‐2‐yl‐kC]chloro(tri‐t‐butylphosphine)palladium, as a general precatalyst is described. Such room temperature Suzuki cross‐coupling polymerization is achieved by employing six equivalents or more of the base and affords polymers within an hour, with the yields and the molecular weights in general comparable to or higher than reported results that required higher reaction temperature and/or longer polymerization time. Our study provides a general catalyst system for the room temperature Suzuki cross‐coupling polymerization of aryl dibromides/diiodides with aryldiboronic acids/acid esters and paves the road for the investigation of employing other monodentate ligand‐coordinated palladacycle complexes including other electron‐rich monophosphine‐coordinated ones for room temperature cross‐coupling polymerizations. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1606–1611     

Strategies Towards Capturing Nitrogenase Substrates and Intermediates via Controlled Alteration of Electron Fluxes

Nitrogenase utilizes an ATP-dependent reductase to deliver electrons to its catalytic component to enable two important reactions: the reduction of N₂ to NH₄⁺, and the reduction of CO to hydrocarbons. The two nitrogenase-based reactions parallel the industrial Haber–Bosch and Fischer–Tropsch processes, yet they occur under ambient conditions. As such, understanding the enzymatic mechanism of nitrogenase is crucial for the future development of biomimetic strategies for energy-efficient production of valuable chemical commodities. Mechanistic investigations of nitrogenase has long been hampered by the difficulty to trap substrates and intermediates relevant to the nitrogenase reactions. Recently, we have successfully captured CO on the Azotobacter vinelandii V-nitrogenase via two approaches that alter the electron fluxes in a controlled manner: one approach utilizes an artificial electron donor to trap CO on the catalytic component of V-nitrogenase in the resting state; whereas the other employs a mismatched reductase component to reduce the electron flux through the system and consequently accumulate CO on the catalytic component of V-nitrogenase. Here we summarize the major outcome of these recent studies, which not only clarified the catalytic relevance of the one-CO (lo-CO) and multi-CO (hi-CO) bound states of nitrogenase, but also pointed to a potential competition between N₂ and CO for binding to the same pair of reactive Fe sites across the sulfur belt of the cofactor. Together, these results highlight the utility of these strategies in poising the cofactor at a well-defined state for substrate- or intermediate-trapping via controlled alteration of electron fluxes, which could prove beneficial for further elucidation of the mechanistic details of nitrogenase-catalyzed reactions.     

Copper‐Catalyzed Reaction Cascade of Thiophenol Hydroxylation and S‐Arylation through Disulfide‐Directed C−H Activation

Copper‐catalyzed thiophenol C?H activation is described. Through an initial attempt to conduct C‐arylation with arylboronic acid, a rather surprising sequential C?H activation and S‐arylation was discovered. Mechanistic investigation revealed the disulfide intermediate as the key component in directing C?H oxidation. The overall reaction proceeded under mild conditions with molecular oxygen as the oxidant. Discovery of disulfide as the directing group provides a potential new direction for catalytic C?H functionalization under mild conditions.     

An Unprecedented Two‐Fold Nested Super‐Polyrotaxane: Sulfate‐Directed Hierarchical Polythreading Assembly of Uranyl Polyrotaxane Moieties

The hierarchical assembly of well‐organized submoieties could lead to more complicated superstructures with intriguing properties. We describe herein an unprecedented polyrotaxane polythreading framework containing a two‐fold nested super‐polyrotaxane substructure, which was synthesized through a uranyl‐directed hierarchical polythreading assembly of one‐dimensional polyrotaxane chains and two‐dimensional polyrotaxane networks. This special assembly mode actually affords a new way of supramolecular chemistry instead of covalently linked bulky stoppers to construct stable interlocked rotaxane moieties. An investigation of the synthesis condition shows that sulfate can assume a vital role in mediating the formation of different uranyl species, especially the unique trinuclear uranyl moiety [(UO₂)₃O(OH)₂]²⁺, involving a notable bent [O=U=O] bond with a bond angle of 172.0(9)°. Detailed analysis of the coordination features, the thermal stability as well as a fluorescence, and electrochemical characterization demonstrate that the uniqueness of this super‐polyrotaxane structure is mainly closely related to the trinuclear uranyl moiety, which is confirmed by quantum chemical calculations.     

Sulfur and Nitrogen Codoped Carbon Tubes as Bifunctional Metal‐Free Electrocatalysts for Oxygen Reduction and Hydrogen Evolution in Acidic Media

Invited for the cover of this issue is the group of Qiang Wu and Zheng Hu at Nanjing University. The image depicts sulfur and nitrogen codoped carbon tubes as bifunctional metal‐free electrocatalysts for oxygen reduction and hydrogen evolution in acidic media. Read the full text of the article at 10.1002/chem.201601535 .     

Palladium‐Catalyzed Insertion of an Allene into an Aminal: Aminomethylamination of Allenes by C?N Bond Activation

A new and atom‐economic palladium‐catalyzed aminomethylamination of allenes with aminals by C N bond activation is described. This direct and operationally simple method provides a fundamentally novel approach for the synthesis of 1,3‐diamines. Mechanistic studies suggest that a unique cationic π‐allylpalladium complex containing an aminomethyl moiety is generated as a key intermediate through the carbopalladation of the allene with a cyclometalated palladium–alkyl species.