Adenine-functionalized conjugated polymer as an efficient photocatalyst for hydrogen evolution from water

Conjugated polymers have emerged as a promising class of organic photocatalysts for photocatalytic hydrogen evolution from water splitting due to their adjustable chemical structures and electronic properties. However, developing highly efficient organic polymer photocatalysts with high photocatalytic activity for hydrogen evolution remains a significant challenge. Herein, we present an efficient approach to enhance the photocatalytic performance of linear conjugated polymers by modifying the surface chemistry via introducing a hydrophilic adenine group into the side chain. The adenine unit with five nitrogen atoms could enhance the interaction between the surface of polymer photocatalyst and water molecules through the formation of hydrogen bonding, which improves the hydrophilicity and dispersity of the resulting polymer photocatalyst in the photocatalytic reaction solution. In addition, the strong electron-donating ability of adenine group with plentiful nitrogen atoms could promote the separation of light-induced electrons and holes. As a result, the adenine-functionalized conjugated polymer PF6A-DBTO2 shows a high photocatalytic activity with a hydrogen evolution rate (HER) of 25.21 mmol g^?1 h^?1 under UV-Vis light irradiation, which is much higher than that of its counterpart polymer PF6-DBTO2 without the adenine group (6.53 mmol g^?1 h^?1). More importantly, PF6A-DBTO2 without addition of a Pt co-catalyst also exhibits an impressive HER of 21.93 mmol g^?1 h^?1 under visible light (λ > 420 nm). This work highlights that it is an efficient strategy to improve the photocatalytic activity of conjugated polymer photocatalysts by the modification of surface chemistry.     

Changes in polyphenol fractions and bacterial composition after in vitrofermentation of apple peel polyphenol by gut microbiota

The changes in polyphenol fractions after in vitro fermentation of apple peel polyphenol (APP) by gut microbiota as well as the effects of APP on the growth, pH value, short-chain fatty acids (SCFAs) production and intestinal flora composition of gut microbiota fermentation were firstly explored in this study. The relative abundance of Lactobacillus in the APP group was 49.55% with an increment of 49.40% compared with the blank group, while that of Bifidobacterium was 13.32%. Moreover, the flora produced 37.093 ± 0.478 mM of SCFAs including acetic acid, propionic acid, butyric acid and valeric acid during the process of fermentation, thus reduced the environmental pH value. In addition, polyphenol fractions in APP were altered by gut microbiota fermentation to some extent, for example, glycosides were hydrolysed to aglycones. These findings suggested APP as a potential prebiotic agent to alleviate the disorder of intestinal flora.     

An infinite chain, {[Ni(tn)2]3[Fe(CN)4(μ-CN)2]2}n,a new catalyst for electrochemical-driven water splitting and photochemical-driven hydrogen evolution from water under blue light

A new catalyst for both water reduction and oxidation, based on an infinite chain, {[Ni(tn)₂]₃ [Fe(CN)₄ (μ-CN)₂]₂}_n, is formed by the reaction of NiCl₂, 1,3-propanediamine (tn) and K₃ [Fe(CN)₆]. {[Ni(tn)₂]₃ [Fe(CN)₄ (μ-CN)₂]₂}_n can electro-catalyze hydrogen evolution from a neutral aqueous buffer (pH 7.0) with a turnover frequency (TOF) of 1561 mol of hydrogen per mole of catalyst per hour (H₂/mol catalyst/h) at an overpotential (OP) of 837 mV {[Ni(tn)₂]₃ [Fe(CN)₄ (μ-CN)₂]₂}_n also can electro-catalyze O₂ production from water with a TOF of ～45 mol O₂ (mol cat)^?1s^?1 at an OP of 591 mV. Under blue light (λ = 469 nm), together with CdS nanorods (CdS NRs) as a photosensitizer, and ascorbic acid (H₂A) as a sacrificial electron donor, {[Ni(tn)₂]₃ [Fe(CN)₄ (μ-CN)₂]₂}_n can photo-catalyze hydrogen generation from an aqueous buffer (pH 4.0) with a turnover number (TON) of 11,450 mol H₂ per mole of catalyst (mol of H₂ (mol of cat)^?1) during 10 h irradiation. The average of apparent quantum yield (AQY) is as high as 40.96% during 10 h irradiation. Studies indicate that {[Ni(tn)₂]₃ [Fe(CN)₄ (μ-CN)₂]₂}_n exists in two forms: a cyano-bridged chain ({[Ni(tn)₂]₃ [Fe(CN)₄ (μ-CN)₂]₂}_n) in solid, and a salt ([Ni(tn)₂]₃ [Fe(CN)₆]₂) in aqueous media; Catalytic reaction occurs on the nickel center of [Ni(tn)₂]²⁺, and the introduction of [Fe(CN)₆]^3- can improve the catalytic efficiency of [Ni(tn)₂]²⁺ for H₂ or O₂ generation. We hope these findings can afford a new method for the design of catalysts for both water reduction and oxidation.     

基于滚动摩擦作用下玉米颗粒在模拟筒仓卸料中的力链分析（网络首发、推荐阅读）

针对颗粒滚动摩擦作用对筒仓中玉米颗粒的力链空间分布进行研究，通过EDEM离散元软件建立筒仓模型与仿真玉米颗粒模型进行卸粮仿真模拟，并与筒仓卸料实验作流态对比，验证模型与仿真结果的准确性。通过对模拟仓进行切片观察和数据处理，对比分析了不同摩擦情况下力链的细观参数随时间演化规律。模拟结果表明：颗粒间摩擦系数越大，卸粮完成的最终时间越长；颗粒间滚动摩擦系数越小，颗粒由整体流转变为管状流的时间越早。对于有漏斗的筒仓来说，减小颗粒间摩擦会改变整体流和管状流之间的极限，从而增加产生管状流的面积。标准滚动摩擦系数下玉米颗粒在卸料过程中会出现起拱-塌陷效应；减小滚动摩擦，玉米颗粒卸料较稳定，未出现起拱的应力突增、以及拱塌陷的应力衰减；增大颗粒间滚动摩擦不但会增加拱效应，且出现成拱高度距离漏斗口更高。     

数控多轴正逆向制造实训基地建设探索

本文阐述了多轴正逆向制造发展趋势,基地建设的必要性,以五轴加工中心、五轴仿真模拟面板、三维扫描仪、3D打印机等为主的加工、逆向、快速成形先进前沿设备,形成多元化的先进制造实习链,满足、丰富实训内容,提升学生社会就业竞争力。     

一种5 重real-time PCR筛查转基因水稻方法的建立

以转基因水稻中最常用的CaMV35S启动子、NOS终止子、Cry1Ab/Ac基因、HPT基因及SPS水稻内标基因为研究对象，利用5 种不同的荧光信号（FAM、HEX、Taxas Red、Cy5、Cy5.5）进行多重实时聚合酶链式反应（real-time polymerase chain reaction，real-time PCR）检测方法的研究。通过引物组合筛选、反应体系优化、特异性测试、灵敏度测试、适用性测试等一系列实验，建立了5 重real-time PCR方法，灵敏度可达0.032%。此方法具有灵敏度高、结果准确、通量大等优点，可实现水稻中转基因成分的快速、高效检测。     

煤矿冲击地压与冒顶复合灾害研究

随着煤矿向深部发展,矿井动力灾害既表现出冲击地压的部分特征,又表现出冒顶的部分特征。2种典型的灾害打破以往冒顶与冲击地压的发生具有一种互为逆向性的认知规律,在深部高应力煤巷,特别是留顶煤巷道中出现了相互诱导、复合发生的新灾害类型。在总结山东、山西和新疆矿区典型巷道冲击致顶板(顶煤)动力灾害特征的基础上,提出了深部巷道冲击地压与冒顶复合灾害的概念、机理与分类,指出复合灾害机理关键点在于揭示巷道整体系统和破碎区子系统的稳定原理及其2者间的相互影响。建立了巷道发生复合灾害的力学模型,根据扰动响应失稳判据,提出并得到了巷道发生复合灾害的临界应力Pcr、临界软化区半径ρ_cr和最大容许采扰应力增量σ_max,厘清了灾害发生的主控因素,分析了煤岩冲击倾向指数K、支护强度ps、巷道半径ρ₀、煤岩强度σ_c等对灾害发生的影响规律,同时阐明了围岩塑性软化、破碎深度随地应力增加的发育规律。研究结果表明,破碎发育巷道的动力失稳主体为弹性区、软化区与破碎区构成的不稳定系统,垮落主体为破碎区;稳定的破碎区提升了巷道冲击启动临界值,使其启动难度增大,但破碎区的发育又易引起顶煤垮落;巷道稳定支护是解决复合灾害的关键,科学合理支护既能有效调控围岩破碎防冒,又能提升冲击启动临界值。通过理论研究,揭示了巷道冲击地压与冒顶复合灾害的发生机理,阐明了巷道软化与破碎区及其稳控支护对深部破碎发育巷道动力灾害防治的重要性。     

Influence of thermal runaway in styrene–acrylonitrile bulk copolymerization revealed by computational fluid dynamics modeling

The computational fluid dynamics (CFD) and kinetic-based moment methods coupled approach is adopted to simulate the bulk copolymerization of styrene–acrylonitrile (SAN) in a stirred tank reactor. Numerical simulations are carried out to investigate the impacts of impeller speed, monomer ratio, initiator ratio, and initial reaction temperature on the copolymerization process and product properties. Particularly, the Chaos theory is selected as a criterion for evaluating the occurrence of the thermal runaway. The Flory's and Stockmayer's distributions are employed to calculate chain length distribution and copolymer composition distribution of copolymer. The simulation results highlight that the appearance of thermal runaway can be postponed by properly increasing the rotation speed, decreasing the initiator loadings, initial acrylonitrile contents and initial reactor temperature. Furthermore, significant differences exist in the product properties that predicted by the ideal and non-ideal models, which demonstrates that the temperature heterogeneity plays a crucial role in SAN copolymerization. This study could offer references for the safe operation and design of polymerization processes.