Catalytic Nitrene Transfer by an FeIV-Imido Complex Generated by a Comproportionation Process

Nitrene transfer reactions have emerged as one of the most powerful and versatile ways to insert an amine function to various kinds of hydrocarbon substrates. However, the mechanisms of nitrene generation have not been studied in depth albeit their formation is taken for granted in most cases without definitive evidence of their occurrence. In the present work, we compare the generation of tosylimido iron species and NTs transfer from Fe^II and Fe^III precursors where the metal is embedded in a tetracarbene macrocycle. Catalytic nitrene transfer to reference substrates (thioanisole, styrene, ethylbenzene and cyclohexane) revealed that the same active species was at play, irrespective of the ferrous versus ferric nature of the precursor. Through combination of spectroscopic (UV-visible, Mössbauer), ESI-MS and DFT studies, an Fe^IV tosylimido species was identified as the catalytically active species and was characterized spectroscopically and computationally. Whereas its formation from the Fe^II precursor was expected by a two-electron oxidative addition, its formation from an Fe^III precursor was unprecedented. Thanks to a combination of spectroscopic (UV-visible, EPR, Hyscore and Mössbauer), ESI-MS and DFT studies, we found that, when starting from the Fe^III precursor, an Fe^III tosyliodinane adduct was formed and decomposed into an Fe^V tosylimido species which generated the catalytically active Fe^IV tosylimide through a comproportionation process with the Fe^III precursor.     

Visible light-driven acridone catalysis for atom transfer radical polymerization

Acridone as a new kind of visible light photocatalyst has been developed to catalyze metal free atom transfer radical polymerization (ATRP). The photocatalyst possess low excited state potential as can undergo an oxidative quenching pathway to initiate ATRP of vinyl monomers. Kinetic study and light on/off reaction demonstrate the “living”/controlled nature of the polymerization by light. Block copolymers can be achieved by using PMMA as macroinitiator to reinitiate polymerization of other vinyl monomers, which shows highly preserved Br chain-end functionality in the synthesized polymers. Moreover, the polymerization can be conducted under air atmosphere as most photocatalysts need anaerobic condition, which may give inspiration of further application of this kind of photocatalyst.     

Wave turbulence and intermittency in directional wave fields

The evolution of surface gravity waves is driven by nonlinear interactions that trigger an energy cascade similarly to the one observed in hydrodynamic turbulence. This process, known as wave turbulence, has been found to display anomalous scaling with deviation from classical turbulent predictions due to the emergence of coherent and intermittent structures on the water surface. In the ocean, waves are spread over a wide range of directions, with a consequent attenuation of the nonlinear properties. A laboratory experiment in a large wave facility is presented to discuss the sensitivity of wave turbulence on the directional properties of model wave spectra. Results show that the occurrence of coherent and intermittent structures become less likely with the broadening of the wave directional spreading. There is no evidence, however, that intermittency completely vanishes.     

Wave-based vibration control of large cable net structures

Large cable net structures have been widely applied in aerospace engineering due to the feature of light-weight, high packaging efficiency, and high thermal stability. Structural vibrations induced by a variety of disturbances are inevitable in the space environment, resulting in the requirement of effective vibration control strategies for large cable net structures. Since the large cable net structures have many closely spaced vibrational modes in the range of low frequencies, traditional modal based control may cause modal truncation and spillover problems. In this paper, a wave-based boundary control strategy is adopted and its effectiveness to control the vibration of cable net structures is investigated, by transfer function analysis and numerical methods. It is found that the structural vibration can be absolutely resisted by applying the wave-based boundary controllers onto all the exterior nodes, when disturbances come from the external boundaries of the cable net. Our results in this paper can provide a theoretical basis for the vibration control of large cable net structures.     

Plasmon Coupling-Induced Hot Electrons for Photocatalytic Hydrogen Generation

We present the fabrication of core-shell-satellite Au@SiO₂-Pt nanostructures and demonstrate that LSPR excitation of the core Au nanoparticle can induce plasmon coupling effect to initiate photocatalytic hydrogen generation from decomposition of formic acid. Further studies suggest that the plasmon coupling effect induces a strong local electric field between the Au core and Pt nanoparticles on the SiO₂ shell, which enables creation of hot electrons on the non-plasmonic-active Pt nanoparticles to participate hydrogen evolution reaction on the Pt surface. In addition, small SiO₂ shell thickness is required in order to obtain a strong plamon coupling effect and achieve efficient photocatalytic activities for hydrogen generation.     

Generalized Jacobi spectral Galerkin method for fractional pantograph differential equation

This work is concerned with the extension of the Jacobi spectral Galerkin method to a class of nonlinear fractional pantograph differential equations. First, the fractional differential equation is converted to a nonlinear Volterra integral equation with weakly singular kernel. Second, we analyze the existence and uniqueness of solutions for the obtained integral equation. Then, the Galerkin method is used for solving the equivalent integral equation. The error estimates for the proposed method are also investigated. Finally, illustrative examples are presented to confirm our theoretical analysis.     

Experimental and numerical analysis of cylindrical turbulators in a double pipe heat exchanger under turbulent flow conditions

In the present work, the use of cylindrical turbulators in a double pipe heat exchanger has been investigated. Cylindrical fin type of turbulators has been placed circumferentially separated by 90° on the outer side of an inner pipe at a regular pitch. Experimental studies were undertaken for different air flow rates in a turbulent regime whose Reynolds number range between 2500 and 10000. Heat transfer characteristics like Nu and friction factor have been experimentally determined. Parametric studies were conducted by changing the pitch and also the orientation of the turbulators. Nu and friction factor were found to increase as the pitch is reduced. A model with alternatively changed orientation outperformed others by exhibiting highest Nu and reduced friction factor.     

A paper-based resonance energy transfer nucleic acid hybridization assay using upconversion nanoparticles as donors and quantum dots as acceptors

Monodisperse aqueous upconverting nanoparticles (UCNPs) were covalently immobilized on aldehyde modified cellulose paper via reduction amination to develop a luminescence resonance energy transfer (LRET)-based nucleic acid hybridization assay. This first account of covalent immobilization of UCNPs on paper for a bioassay reports an optically responsive method that is sensitive, reproducible and robust. The immobilized UCNPs were decorated with oligonucleotide probes to capture HPRT1 housekeeping gene fragments, which in turn brought reporter conjugated quantum dots (QDs) in close proximity to the UCNPs for LRET. This sandwich assay could detect unlabeled oligonucleotide target, and had a limit of detection of 13 fmol and a dynamic range spanning nearly 3 orders of magnitude. The use of QDs, which are excellent LRET acceptors, demonstrated improved sensitivity, limit of detection, dynamic range and selectivity compared to similar assays that have used molecular fluorophores as acceptors. The selectivity of the assay was attributed to the decoration of the QDs with polyethylene glycol to eliminate non-specific adsorption. The kinetics of hybridization were determined to be diffusion limited and full signal development occurred within 3 min.     

New Phenomena in Organometallic‐Mediated Radical Polymerization (OMRP) and Perspectives for Control of Less Active Monomers

The impact of reversible bond formation between a growing radical chain and a metal complex (organometallic‐mediated radical polymerization (OMRP) equilibrium) to generate an organometallic intermediate/dormant species is analyzed with emphasis on the interplay between this and other one‐electron processes involving the metal complex, which include halogen transfer in atom transfer radical polymerization (ATRP), hydrogen‐atom transfer in catalytic chain transfer (CCT), and catalytic radical termination (CRT). The challenges facing the controlled polymerization of “less active monomers” (LAMs) are outlined and, after reviewing the recent achievements of OMRP in this area, the perspectives of this technique are analyzed.