Controllable Si−C Bond Activation Enables Stereocontrol in the Palladium‐Catalyzed [4+2] Annulation of Cyclopropenes with Benzosilacyclobutanes

A novel and unusual palladium‐catalyzed [4+2] annulation of cyclopropenes with benzosilacyclobutanes is reported. This reaction occurred through chemoselective Si?C(sp²) bond activation in synergy with ring expansion/insertion of cyclopropenes to form new C(sp²)?C(sp³) and Si?C(sp³) bonds. An array of previously elusive bicyclic skeleton with high strain, silabicyclo[4.1.0]heptanes, were formed in good yields with excellent diastereoselectivity under mild conditions. An asymmetric version of the reaction with a chiral phosphoramidite ligand furnished a variety of chiral bicyclic silaheterocycle derivatives with good enantioselectivity (up to 95.5:4.5 er). Owing to the mild reaction conditions, the good stereoselectivity profile, and the ready availability of the functionalized precursors, this process constitutes a useful and straightforward strategy for the synthesis of densely functionalized silacycles.     

Supramolecular self‐assembly modification of ammonium polyphosphate and its flame retardant application in polypropylene

In order to improve its water resistance and compatibility with polymer matrix, ammonium polyphosphate (APP) is modified with melamine‐trimesic acid (MEL‐TA) aggregates by supramolecular self‐assembly technology. Chemical structure and morphology of APP@MEL‐TA are investigated by Fourier transform infrared spectroscopy and scanning electron microscopy (SEM), respectively. Intumescent flame retardant system of APP@MEL‐TA and charring‐foaming agent is introduced into polypropylene (PP) matrix. The flammability and combustion behavior of PP composites are investigated by limiting oxygen index (LOI), UL‐94 vertical burning, and cone calorimetry tests. In terms of LOI values and cone combustion results, APP@MEL‐TA performs better than pristine APP. Char residue of PP composites is investigated by SEM and Raman spectra. Flame retardant mechanisms are proposed based on thermal decomposition, combustion results, and analysis on char residue.     

Engineering Platinum–Oxygen Dual Catalytic Sites via Charge Transfer towards Highly Efficient Hydrogen Evolution

A dual‐site catalyst allows for a synergetic reaction in the close proximity to enhance catalysis. It is highly desirable to create dual‐site interfaces in single‐atom system to maximize the effect. Herein, we report a cation‐deficient electrostatic anchorage route to fabricate an atomically dispersed platinum–titania catalyst (Pt₁^O1/Ti_1?xO₂), which shows greatly enhanced hydrogen evolution activity, surpassing that of the commercial Pt/C catalyst in mass by a factor of 53.2. Operando techniques and density functional calculations reveal that Pt₁^O1/Ti_1?xO₂ experiences a Pt?O dual‐site catalytic pathway, where the inherent charge transfer within the dual sites encourages the jointly coupling protons and plays the key role during the Volmer–Tafel process. There is almost no decay in the activity of Pt₁^O1/Ti_1?xO₂ over 300 000 cycles, meaning 30 times of enhancement in stability compared to the commercial Pt/C catalysts (10 000 cycles).     

New cytotoxic constituents in the water-soluble fraction from Momordicae Semen

Abstract

Two new lignans mubezhisol (1) and mubezhisal (2), together with twenty six known compounds (3–28) were isolated from water-soluble fraction from the semens of Momordica cochinchinensis. In the subsequent action evaluation, four saponins (4, 6, 13, 27), six lignans (1, 2, 16, 17, 22, 23), and one naphthoquinone (24) exhibited the significant cytotoxicity. The results indicated that various saponins and lignans were mainly responsible for the antitumor activities of Momordicae Semen.     

17.1%-Efficiency organic photovoltaic cell enabled with two higher-LUMO-level acceptor guests as the quaternary strategy

Quaternary blended organic solar cells utilize four blended material components(one donor plus three acceptors, two donors and two acceptors, or three donors plus one acceptor) as the active layer materials. The use of four material components allows us to have more material selections and more mechanism choices to improve the photon-to-electron conversion efficiency. In this contribution, we present a new case of quaternary material system, that shows 17.1% efficiency obtained by adding IDIC and PC_(71)BM as the guest acceptors of the host binary of PM6:Y6. The lowest unoccupied molecular orbital(LUMO) levels of IDIC and PC_(71)BM are both higher than that of Y6, which is one reason to obtain increased open-circuit voltage(V_(oc)) in the quaternary device. Upon introduction of IDIC and PC_(71)BM as the acceptor guests, the hole and electron mobilities are both increased, which contributes to the increased short-circuit current-density(J_(sc)). Effects of the weight ratios of the three acceptor components are investigated, which demonstrates that the increased hole and electron mobilities, the accelerated hole-transfer, and the reduced monomolecular recombination are the factors contributing to the increased J_(sc)and fill-factor. This case of quaternary device demonstrates the applicability of the quaternary strategy in increasing the device functions and hence the efficiencies in the field of organic photovoltaic cells.     

移动载荷作用下浮冰的非线性动力学响应

本文考虑非线性、惯性和阻尼的影响, 研究了任意深度二维理想流体顶部浮冰的振动. 对相关的拟微分算子进行展开并将非线性项保留至三阶后, 完全非线性问题被简化为仅与自由面上的变量相关的三阶截断模型. 为了验证简化模型的准确性, 重点关注了自由孤立波解. 在不考虑阻尼的情况下, 采用多重尺度方法推导了三阶非线性薛定谔方程(NLS), 利用该方程预测了任意水深下原始欧拉方程中自由波包型孤立波解的存在性及三阶截断模型的准确性. 相比于Dinvay等所提出的二阶模型, 三阶截断模型的优势在于其对应的三阶NLS具有准确的非线性项系数, 能够在最小相速度附近更好地模拟冰层的动力学响应. 进一步地对自由孤立波解进行数值计算, 数值结果表明三阶截断模型在分岔曲线和孤立波波形上均与完全欧拉方程吻合良好, 准确性高于二阶截断模型. 基于三阶截断模型, 探究了匀速局域化载荷作用下的浮冰非线性动力学响应并将时间依赖解与实验测量数据进行比较, 数值计算结果与实验记录吻合良好.      

Chaotic resonance in Izhikevich neural network motifs under electromagnetic induction

Nonlinear Dynamics - Chaotic resonance (CR) is the response of a nonlinear system to weak signals enhanced by internal or external chaotic activity (such as the signal derived from Lorenz system)....     

Twiston vs. random fluctuation as the source of the rapid motion of polyethylene in the inclusion complex with perhydrotriphenylene

Recently molecular dynamics simulations were performed for polyethylene in the inclusion complex with perhydrotriphenylene. The system contained ninety molecules of perhydrotriphenylene, arranged in six stacks of fifteen molecules each, and one molecule of n-tetracontane, C₄₀H₈₂. The internal CH₂-CH₂ bonds in n-tetracontane have a very strong preference for the trans state. Nevertheless, the chain exhibits a high degree of internal flexibility. This motion produces a characteristic pattern in δ|ψ N + i ψi| vs. N, where ψ_i describes the instantaneous angle of a C-H bond vector at carbon atom i about the axis defined by the channel, and δ denotes the fluctuation. The pattern expected for δ|ψ N + i ψi| vs. N is derived for the case where the rapid internal motion is produced by a twiston. It is compared with the results from the simulation and from the expectation for the case where the rapid motion arises from uncorrelated internal fluctuations within the trans state at each CH₂-CH₂ bond.     

Newly Emerging Strategies in Antiviral Drug Discovery: Dedicated to Prof. Dr. Erik De Clercq on Occasion of His 80th Anniversary

Viral infections pose a persistent threat to human health. The relentless epidemic of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) has become a global health problem, with millions of infections and fatalities so far. Traditional approaches such as random screening and optimization of lead compounds by organic synthesis have become extremely resource- and time-consuming. Various modern innovative methods or integrated paradigms are now being applied to drug discovery for significant resistance in order to simplify the drug process. This review provides an overview of newly emerging antiviral strategies, including proteolysis targeting chimera (PROTAC), ribonuclease targeting chimera (RIBOTAC), targeted covalent inhibitors, topology-matching design and antiviral drug delivery system. This article is dedicated to Prof. Dr. Erik De Clercq, an internationally renowned expert in the antiviral drug research field, on the occasion of his 80th anniversary.     

Perfect state transfer on weighted graphs of the Johnson scheme

Letters in Mathematical Physics - We characterize quantum perfect state transfer on real-weighted graphs of the Johnson scheme $${\mathcal {J}}(n,k)$$ , which represent spin networks with...