Visible-Light Augmented Lithium Storage Capacity in a Ruthenium(II) Photosensitizer Conjugated with a Dione-Catechol Redox Couple

Controlling redox activity of judiciously appended redox units on a photo-sensitive molecular core is an effective strategy for visible light energy harvesting and storage. The first example of a photosensitizer - electron donor coordination compound in which the photoinduced electron transfer step is used for light to electrical energy conversion and storage is reported. A photo-responsive Ru-diimine module conjugated with redox-active catechol groups in [Ru(II)(phenanthroline-5,6-diolate)₃]⁴⁻ photosensitizer can mediate photoinduced catechol to dione oxidation in the presence of a sacrificial electron acceptor or at the surface of an electrode. Under potentiostatic condition, visible light triggered current density enhancement confirmed the light harvesting ability of this photosensitizer. Upon implementation in galvanostatic charge-discharge of a Li battery configuration, the storage capacity was found to be increased by 100 %, under 470 nm illumination with output power of 4.0 mW/cm⁻². This proof-of-concept molecular system marks an important milestone towards a new generation of molecular photo-rechargeable materials.     

Biomimetic Approach for Highly Selective Artificial Water Channels Based on Tubular Pillar[5]arene Dimers

Artificial water channels mimicking natural aquaporins (AQPs) can be used for selective and fast transport of water. Here, we quantify the transport performances of peralkyl-carboxylate-pillar[5]arenes dimers in bilayer membranes. They can transport ≈10⁷ water molecules/channel/second, within one order of magnitude of the transport rates of AQPs, rejecting Na⁺ and K⁺ cations. The dimers have a tubular structure, superposing pillar[5]arene pores of 5 Å diameter with twisted carboxy-phenyl pores of 2.8 Å diameter. This biomimetic platform, with variable pore dimensions within the same structure, offers size restriction reminiscent of natural proteins. It allows water molecules to selectively transit and prevents bigger hydrated cations from passing through the 2.8 Å pore. Molecular simulations prove that dimeric or multimeric honeycomb aggregates are stable in the membrane and form water pathways through the bilayer. Over time, a significant shift of the upper vs. lower layer occurs initiating new unexpected water permeation events through toroidal pores.     

平面波输入下海水-海床-结构动力相互作用分析

海洋工程结构的地震反应分析是保证海洋工程结构地震安全的重要环节.由于其所处的复杂环境, 该问题涉及到流固耦合和土-结相互作用.本文基于海水、饱和海床、基岩流固耦合统一计算框架,采用Davidenkov模型和修正的Masing准则考虑饱和海床的非线性,在脉冲SV波垂直入射下, 进行了海域场地和海洋工程结构的动力响应分析. 首先,对比分析了线性自由场和非线性自由场输入情形的海域场地非线性反应,结果表明线性自由场输入时反应不合理,自由场分析和场地分析应该采用相一致的本构模型. 然后,对比分析了海床分别为线性和非线性情形时,海域场地以及海水-海床-结构体系的反应特征. 与线性海床情形相比,非线性对海床反应的影响主要由如下两方面因素控制: 一方面,非线性导致饱和海床模量减小, 饱和海床与基岩间的波阻抗比减小,由基岩到饱和海床间的反射系数和透射系数增加, 导致反应增大; 另一方面,非线性导致阻尼加大, 使海床反应减小. 对于本文算例而言,阻尼对非线性海床结果的影响占主导作用.      

Synthesized AI LMI-based Criterion for Mechanical Systems

This paper proposes a novel artificial intelligence sythethized controller in the mechanical system which has high speed computation because of the LMI type criterion. The proposed membership functions are adopted and stabilization criterion of the closed-loop T-S fuzzy systems are obtained through a new parametrized LMI (linear matrix) inequality which is rearranged by machine learning membership functions.     

Review on the Use of Artificial Intelligence to Predict Fire Performance of Construction Materials and Their Flame Retardancy

The evaluation and interpretation of the behavior of construction materials under fire conditions have been complicated. Over the last few years, artificial intelligence (AI) has emerged as a reliable method to tackle this engineering problem. This review summarizes existing studies that applied AI to predict the fire performance of different construction materials (e.g., concrete, steel, timber, and composites). The prediction of the flame retardancy of some structural components such as beams, columns, slabs, and connections by utilizing AI-based models is also discussed. The end of this review offers insights on the advantages, existing challenges, and recommendations for the development of AI techniques used to evaluate the fire performance of construction materials and their flame retardancy. This review offers a comprehensive overview to researchers in the fields of fire engineering and material science, and it encourages them to explore and consider the use of AI in future research projects.     

A Selective Sulfide Oxidation Catalyzed by Heterogeneous Artificial Metalloenzymes Iron@NikA

Performing a heterogeneous catalysis with proteins is still a challenge. Herein, we demonstrate the importance of cross-linked crystals for sulfoxide oxidation by an artificial enzyme. The biohybrid consists of the insertion of an iron complex into a NikA protein crystal. The heterogeneous catalysts displays a better efficiency-with higher reaction kinetics, a better stability and expand the substrate scope compared to its solution counterpart. Designing crystalline artificial enzymes represents a good alternative to soluble or supported enzymes for the future of synthetic biology.     

半导体纳米复合材料的制备及其光电催化CO2还原

本实验通过模拟植物光合作用,设计制备了新颖的光电联合催化池3D-ZnO/Ni BiVO4/FTO,用电化学沉积法制备了泡沫镍负载的ZnO纳米棒光电阴极和BiVO4光电阳极,以0.1 mol·L^−1 KHCO3水溶液作为电解质,1 mmol·L^−1曙红Y为光敏剂,在−0.6 V硅太阳电池的电压下光电催化还原CO2得到了乙醇、乙酸和甲醇,总产率22.5μmol·L^−1·h^−1·cm^−2。实现了将太阳能贮存为化学能并减少了空气中的CO2,加深了学生对绿色化学和植物Calvin循环机理的理解。     

核电结构土-结相互作用分析分区混合计算方法

土-结构相互作用分析是核电结构进行抗震设计和安全评估的重要环节.在核电结构的土-结相互作用分析中,阻尼和非线性是影响结构反应的重要因素. 若采用频域分析,可以方便考虑阻尼,但需通过等效线性化来考虑非线性,不适合于强震作用下的土体非线性.若采用时域分析的逐步积分方法,适合于考虑非线性,但材料阻尼一般采用瑞利阻尼模型,除了紧靠指定阻尼比的少数几个振型外,其他振型的反应将受到瑞利阻尼模型所确定的大阻尼所抑制,造成地震反应与真实情形有较大差异.若采用时域分析的模态叠加法,可合理计入阻尼效应,但模态叠加法不能考虑非线性.因此,如何合理考虑阻尼和非线性是核电结构土-结相互作用分析需要关注的问题.基于此,本文提出一种模态叠加和时步积分结合的土-结相互作用分区算法.其中,出于安全性考虑,地震作用下核电主体结构一般不允许进入非线性,因此结构可采用模态叠加方法,以便合理考虑结构阻尼;土体和基础采用显式时步积分法,可考虑土体非线性;通过人工边界条件考虑无限域的影响 (辐射阻尼).通过简单算例对该方法进行了验证,并用于CAP1400核电结构的土-结相互作用分析中,对比分析了采用模态阻尼和瑞利阻尼时核电结构和场地反应的差异,结果表明结构阻尼模型对场地的反应影响不大,但对结构反应影响明显,在实际工程中应合理选取阻尼模型.