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.     

基于耦合声场建模的膨胀腔消声器声学性能分析及试验

针对圆柱形膨胀腔消声器三维建模及声学性能分析问题, 提出一种基于切比雪夫变分原理的耦合声场建模方法, 建立三维圆柱形膨胀腔消声器理论模型并搭建试验台架, 传递损失试验结果验证了理论模型的准确性. 将膨胀腔消声器内部声场分解为多个子声场, 基于子声场间压力与质点振速连续性条件, 推导声场耦合变分公式, 构建子声场拉格朗日泛函. 将子声场声压函数展开为切比雪夫-傅里叶级数形式, 通过瑞利-里兹法求解膨胀腔消声器频率、声压响应及传递损失. 计算并对比分析扩张比、扩张腔长度、进出口管偏置对膨胀腔消声器消声性能的影响. 结果表明: 扩张比增大会有效提高消声器在低频段的消声性能, 进出口管的偏置对消声器消声性能影响很小.     

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.     

Numerical study of unsteady flow and heat transfer of circular tangential direction jets flowing over the inner cylinder surface in the annular chamber

In order to understand the dynamics of vortices on heat transfer, the unsteady flow field of tangential direction jets flowing in the annular chamber is numerically investigated by scale-adaptive simulation (SAS). The jet Reynolds number is 332,000 based on the jet’s diameter and inflow velocity for a specific geometric model. The analogy theory is used to obtain the convective heat transfer coefficient distribution on the hub surface. Spectral analysis via fast Fourier transform (FFT) is used to analyze frequency information that flows inside the chamber. The proper orthogonal decomposition (POD) method is performed on the velocity field in the chamber and the convective heat transfer coefficient on the hub surface using a snapshot method. The fast Fourier transform helps find the dominant frequency of the unsteady flow in the chamber. The time sequence of velocity fields on the radial plane shows the presence of cyclic flapping of the jet. The proper orthogonal decomposition analysis indicates that the unsteady periodic flow phenomenon in the chamber and unsteady heat transfer on the hub surface are mainly related to the dynamics of the counter-rotating vortices caused by the jet.     

Fluid‐structure coupling of linear elastic model with compressible flow models

Cavitation erosion is caused in solids exposed to strong pressure waves developing in an adjacent fluid field. The knowledge of the transient distribution of stresses in the solid is important to understand the cause of damaging by comparisons with breaking points of the material. The modeling of this problem requires the coupling of the models for the fluid and the solid. For this purpose, we use a strategy based on the solution of coupled Riemann problems that has been originally developed for the coupling of 2 fluids. This concept is exemplified for the coupling of a linear elastic structure with an ideal gas. The coupling procedure relies on the solution of a nonlinear equation. Existence and uniqueness of the solution is proven. The coupling conditions are validated by means of quasi‐1D problems for which an explicit solution can be determined. For a more realistic scenario, a 2D application is considered where in a compressible single fluid, a hot gas bubble at low pressure collapses in a cold gas at high pressure near an adjacent structure.     

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.     

Metabolomics techniques applied in the investigation of phenolic acids from the agro-industrial by-product of Carapa guianensis Aubl

Processing of Carapa guianensis seeds to obtain oil on an industrial scale generates a significant amount of by-product, approximately 66% w/w, which is called cake and is a potential source of biomolecules, including simple phenolic structures. For this reason, studies were carried out on the chemical profiles of hydrolyzed extract from this agro-industrial by-product through High Performance Thin-Layer Chromatography (HPTLC) and Gas Chromatography coupled to Mass Spectrometry (GC–MS). These techniques were used to detect metabolic classes and/or groups, and to identify, for the first time, thirteen simple phenolic acids in this by-product. The sample antioxidant capacity was determined by methods of 2,2-diphenyl-1-picrylhydrazyl (DPPH)and 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS⁺) radicals direct sequestration. The hydrolyzed fraction showed a total of 63.47% in the relative abundance of the total of compounds, standing out: p-hydroxybenzoic acid (39.19%) and protocatechuic acid (3,4-dihydroxybenzoic acid) (5.62%), both from hydroxybenzoic acids and 3-(3,4-dihydroxyphenyl)lactic acid, (7.76%) hydroxycinnamic acids derivatives. In these results, the fraction rich in simple phenolic acids was obtained, attributing the prominent behavior of this matrix antioxidant activity, expressed by (IC₅₀: of 16.42 µg/mL and 6.52 µg/mL for DPPH and ABTS⁺ radicals, respectively). The research demonstrated an alternative to applicability that involves sustainability from agro-industrial. These techniques were used to detect metabolic classes and/or groups, and to identify, for the first time, thirteen simple phenolic acids in this by-product, generating a process capable of converting biomass into a bioproduct, consisting of bioactive compounds, in addition to adding value to the industrial chain.     

Formation of low-temperature deformation-induced segregations of nickel in Fe–Ni-based austenitic alloys

ABSTRACT

The authors present the results of an investigation in Fe–Ni-Cr austenitic alloys of the low-temperature deformation-induced segregations of nickel that form in the micro regions being (i) located close to grain- and subgrain boundaries and (ii) characteristic of the concentration and magnetic inhomogeneities indicated by the appearance of a dark diffraction contrast at the electron diffraction patterns taken from these regions typical (at the same time) of an enhanced value of Curie temperature. The observed effects were connected with the micro distortions caused by the local change of lattice parameter because of an increase in nickel concentration, as well as in the result of a magnetostriction dilatation. Using methods of the X-ray energy dispersive spectroscopy (XEDS) and atomic-probe body-section radiography (tomography – APT) has made it possible to determine the borders of those regions of austenite that were characteristic of an enhanced concentration of nickel in the fields of the localisation of a deformation-induced segregation of nickel in the vicinity of grain (subgrain) boundaries of austenitic alloys of the types Fe–13Cr–30Ni and Fe–37Ni–3Ti.