Ultrahigh Loading Copper Single Atom Catalyst for Palladium-free Wacker Oxidation

Wacker oxidation is an industry-adopted process to transform olefins into value-added epoxides and carbonyls. However, traditional Wacker oxidation involves the use of homogeneous palladium and copper catalysts for the olefin addition and reductive elimination. Here, we demonstrated an ultrahigh loading Cu single atom catalyst(14% Cu, mass fraction) for the palladium-free Wacker oxidation of 4-vinylanisole into the corresponding ketone with N-methylhydroxylamine hydrochloride as an additive under mild conditions. Mechanistic studies by ¹⁸O and deuterium isotope labelling revealed a hydrogen shift mechanism in this palladium-free process using N-methylhydroxylamine hydrochloride as the oxygen source. The reaction scope can be further extended to Kucherov oxidation. Our study paves the way to replace noble metal catalysts in the traditional homogeneous processes with single atom catalysts.     

基于内聚力模型的快速荷载下CFRP-混凝土界面剪切剥离模拟

鉴于纤维增强复合材料(Fiber Reinforced Polymer, FRP)已在混凝土结构加固中普遍应用, 能有效提高结构的承载和变形能力. 为揭示动载作用下FRP-混凝土界面的剥离机理, 本文基于ABAQUS平台, 采用内聚力模型模拟CFRP-混凝土界面层, 实现了快速荷载下CFRP-混凝土界面剥离的高效模拟. 结果表明: CFRP表面应变在加载过程中由加载端向自由端方向传递, 随着加载速率的提高, 界面承载能力也随之提高; 界面峰值剪应力也存在显著的应变率效应; 模拟结果与试验结果基本吻合, 说明了新方法的有效性.     

Rate sensitivity and deformation mechanism of semi-crystalline polymers during instrumented indentation

Instrumented indentation tests using both constant loading rate (CLR) and continuous stiffness measurement (CSM) operation modes were performed to investigate the deformation mechanism and their sensitivity to the deformation rate in semi-crystalline polymers through the quantitative analysis of load-depth loading and unloading curves. The strain rate was constant during the CSM tests, while the strain rate decreased with the increasing of loading time in CLR tests. The mechanical response mechanism of the semi-crystalline polymers to these tests was very complicated because of the combined effects of strain-hardening in the crystal phase and strain-softening in the amorphous phase. Results show that the loading index m reflects the strain-hardening or strain-softening response during indentation. When m > 2, the mechanical response was due to the strain-hardening, and when m < 2, the response was due to strain-softening. A method based on the measured contact hardness was proposed to obtain the unloading stiffness, and the other mechanical parameters could then be determined according to the unloading stiffness.     

Flume testing of passively adaptive composite tidal turbine blades under combined wave and current loading

The tidal energy industry is progressing rapidly, but there are still barriers to overcome to realise the commercial potential of this sector. Large magnitude and highly variable loads caused by waves acting on the turbine are of particular concern. Composite blades with in-built bend-twist elastic response may reduce these peak loads, by passively feathering with increasing thrust. This could decrease capital costs by lowering the design loads, and improve robustness through the mitigation of pitch mechanisms. In this study, the previous research is extended to examine the performance of bend-twist blades in combined wave–current flow, which will frequently be encountered in the field. A scaled 3 bladed turbine was tested in the flume at IFREMER with bend-twist composite blades and equivalent rigid blades, sequentially under current and co-directional wave–current cases. In agreement with previous research, when the turbine was operating in current alone at higher tip speed ratios the bend-twist blades reduced the mean thrust and power compared to the rigid blades. Under the specific wave–current condition tested the average loads were similar on both blade sets. Nevertheless, the bend-twist blades substantially reduced the magnitudes of the average thrust and torque fluctuations per wave cycle, by up to 10% and 14% respectively.     

An experimental investigation into non-linear wave loading on horizontal axis tidal turbines

Tidal turbines are subject to large hydrodynamic loads from combinations of currents and waves, which contribute significantly to fatigue, extreme loading and power flow requirements. Physical model testing enables these loads and power fluctuations to be assessed and understood in a controlled and repeatable environment. In this work, a 1:15 scale tidal turbine model is utilised to further the fundamental understanding of the influence of waves on tidal turbines. A wide range of regular waves are generated in both following-current and opposing-current conditions. Wave frequencies range from 0.31 Hz to 0.55 Hz & wave heights from 0.025 m to 0.37 m in a fixed 0.81 m/s current velocity. Waves are selected and programmed specifically to facilitate frequency domain analysis, and techniques are employed to isolate the effect of non-linear waves on turbine power and thrust.Results demonstrate that wave action induces large variations in turbine power and thrust compared to current only conditions. For the range of conditions tested, peak values of thrust and power exceed current-only values by between 7%–65% and 13%–160% respectively. These wave-induced fluctuations are shown to increase with wave amplitude and decrease with wave frequency. Following wave conditions exhibit greater variations than opposing for waves with the same wave height and frequency due to the lower associated wavenumbers.A model is developed and presented to aid the understanding of the high-order harmonic response of the turbine to waves, which is further demonstrated using steady state coefficients under assumptions of pseudo-stationarity. This approach is proven to be effective at estimating wave-induced power and thrust fluctuations for the combinations of waves, currents and turbine state tested. The outcome of which shows promise as a rapid design tool that can evaluate the effect of site-specific wave–current conditions on turbine performance.     

基于八面体理论的岩石循环加-卸载本构模型及修正

探究岩石的受力特点及破坏特性是研究岩石地下工程安全性的关键,诸多学者都期望能在岩石本构模型的研究上取得突破性进展。在此背景下,提出了一种能够描述循环加-卸载条件下岩石的本构模型。首先,假设岩石的微元强度服从八面体剪应力理论并且微元破坏服从Weibull概率公式,将岩石本构中的损伤变量以及岩石微元强度表达式里包含的损伤因子进行本构变换,得到关于应力、应变等其他表现加-卸载下岩石损伤本构模型的参数,表示出岩石微元强度和损伤变量,再将得到的岩石微元强度和损伤变量代入所提出的岩石本构模型中,并进行等式变换得到一个函数表达式。通过将其与实验数据进行拟合对比分析,得出修正后的拟合参数,将其代入函数式中,得到损伤本构模型的修正式。最后将拟合参数进行必要的敏感性分析,得出各拟合参数的实际物理意义。     

Increased Stress Resistance and Lifespan in Chaenorhabditis elegans Wildtype and Knockout Mutants—Implications for Depression Treatment by Medicinal Herbs

Depression and anxiety disorders are widespread diseases, and they belong to the leading causes of disability and greatest burdens on healthcare systems worldwide. It is expected that the numbers will dramatically rise during the COVID-19 pandemic. Established medications are not sufficient to adequately treat depression and are not available for everyone. Plants from traditional medicine may be promising alternatives to treat depressive symptoms. The model organism Chaenorhabditis elegans was used to assess the stress reducing effects of methanol/dichlormethane extracts from plants used in traditional medicine. After initial screening for antioxidant activity, nine extracts were selected for in vivo testing in oxidative stress, heat stress, and osmotic stress assays. Additionally, anti-aging properties were evaluated in lifespan assay. The extracts from Acanthopanax senticosus, Campsis grandiflora, Centella asiatica, Corydalis yanhusuo, Dan Zhi, Houttuynia cordata, Psoralea corylifolia, Valeriana officinalis, and Withania somnifera showed antioxidant activity of more than 15 Trolox equivalents per mg extract. The extracts significantly lowered ROS in mutants, increased resistance to heat stress and osmotic stress, and the extended lifespan of the nematodes. The plant extracts tested showed promising results in increasing stress resistance in the nematode model. Further analyses are needed, in order to unravel underlying mechanisms and transfer results to humans.     

Anti-TNF-α Compounds as a Treatment for Depression

Millions of people around the world suffer from psychiatric illnesses, causing unbearable burden and immense distress to patients and their families. Accumulating evidence suggests that inflammation may contribute to the pathophysiology of psychiatric disorders such as major depression and bipolar disorder. Copious studies have consistently shown that patients with mood disorders have increased levels of plasma tumor necrosis factor (TNF)-α. Given these findings, selective anti-TNF-α compounds were tested as a potential therapeutic strategy for mood disorders. This mini-review summarizes the results of studies that examined the mood-modulating effects of anti-TNF-α drugs.     

Kinematics of layered reinforced-concrete planar beam finite elements with embedded transversal cracking

In this work crack formation and development is addressed and implemented in a planar layered reinforced-concrete beam element. The crack initiation and growth is described using the strength criterion in conjunction with exact kinematics of the interlayer connection. In this way a novel embedded-discontinuity beam finite element is derived in which the tensile stresses in concrete at the crack position reaching the tensile strength will trigger a crack to open. Since the element is multi-layered, in this way the crack is allowed to propagate through the depth of the beam. The cracked layer(s) will involve discontinuity in the cross-sectional rotation equal to the crack-profile angle, as well as a discontinuity in the position vector of the layer’s reference line. A bond–slip relationship is superimposed onto this model in a kinematically consistent manner with reinforcement being treated as an additional layer of zero thickness with its own material parameters and a constitutive law implemented in the multi-layered beam element.     

混凝土轴拉加卸载随机损伤模型的建立与试验验证

为了分析及深入探讨混凝土在受拉加载及卸载情况下的力学特性,基于随机损伤本构关系提出了一种混凝土轴拉加卸载模型,推导出了混凝土加卸载的应力 应变关系表达式.为了印证理论表达式,进行了混凝土轴向拉伸及加卸载的试验研究,测得了混凝土的材料参数及其相应的轴拉加卸载应力-应变曲线.结合模型的计算结果,对混凝土的轴拉加卸载试验结果进行了对比分析,结果表明:混凝土轴拉加卸载模型能够预测混凝土的极限强度,同时能描述混凝土的强度软化、加载过程中的弹模折减及卸载后的塑性变形.