Poly(1,4‐Diethynylbenzene) Gradient Homojunction with Enhanced Charge Carrier Separation for Photoelectrochemical Water Reduction

As appealing photoelectrode materials for photoeletrochemical hydrogen evolution reaction (PEC HER), conjugated polymers still show poor PEC HER performance as a result of their serious recombination of photogenerated electrons and holes. Herein, a novel design of gradient homojunction is demonstrated by controlled copolymerization of 1,4‐diethynylbenzene (DEB) and 1,3,5‐triethynylbenzene (TEB). The as‐built gradient distribution of TEB monomer in poly(1,4‐diethynylbenzene) (pDEB) leads to continuous band bending engineering, which constitutes a gradient homojunction. Under AM 1.5G irradiation and in 0.1 m Na₂SO₄ aqueous solution, the as‐fabricated pDEB gradient homojunction exhibits a charge separation efficiency of 0.27% at 0.3 V versus reversible hydrogen electrode (RHE), which is 3.4 and 1.7 times higher than those for pure pDEB and the traditionally designed pDEB homojunction. As a result, the photocurrent of the pDEB gradient homojunction unprecedentedly reaches 55 µA cm^?2 at 0.3 V versus RHE, which is much higher than 19 µA cm^?2 for pure pDEB, 32 µA cm^?2 for the pDEB homojunction, and state‐of‐the‐art organic photocathodes, e.g., g‐C₃N₄ (≈1?32 µA cm^?2). This work opens up a new window for the design of gradient homojunctions and will advance the exploration of high‐performance organic photoelectrodes.     

A Small‐Molecule “Charge Driver” enables Perovskite Quantum Dot Solar Cells with Efficiency Approaching 13%

Halide perovskite colloidal quantum dots (CQDs) have recently emerged as a promising candidate for CQD photovoltaics due to their superior optoelectronic properties to conventional chalcogenides CQDs. However, the low charge separation efficiency due to quantum confinement still remains a critical obstacle toward higher‐performance perovskite CQD photovoltaics. Available strategies employed in the conventional CQD devices to enhance the carrier separation, such as the design of type‐Ⅱ core–shell structure and versatile surface modification to tune the electronic properties, are still not applicable to the perovskite CQD system owing to the difficulty in modulating surface ligands and structural integrity. Herein, a facile strategy that takes advantage of conjugated small molecules that provide an additional driving force for effective charge separation in perovskite CQD solar cells is developed. The resulting perovskite CQD solar cell shows a power conversion efficiency approaching 13% with an open‐circuit voltage of 1.10 V, short‐circuit current density of 15.4 mA cm^?2, and fill factor of 74.8%, demonstrating the strong potential of this strategy toward achieving high‐performance perovskite CQD solar cells.     

High‐Resolution 3D NIR‐II Photoacoustic Imaging of Cerebral and Tumor Vasculatures Using Conjugated Polymer Nanoparticles as Contrast Agent

Exogenous contrast‐agent‐assisted NIR‐II optical‐resolution photoacoustic microscopy imaging (ORPAMI) holds promise to decipher wide‐field 3D biological structures with deep penetration, large signal‐to‐background ratio (SBR), and high maximum imaging depth to depth resolution ratio. Herein, NIR‐II conjugated polymer nanoparticle (CP NP) assisted ORPAMI is reported for pinpointing cerebral and tumor vasculatures. The CP NPs exhibit a large extinction coefficient of 48.1 L g^?1 at the absorption maximum of 1161 nm, with an ultrahigh PA sensitivity up to 2 µg mL^?1. 3D ORPAMI of wide‐field mice ear allows clear visualization of regular vasculatures with a resolution of 19.2 µm and an SBR of 29.3 dB at the maximal imaging depth of 539 µm. The margin of ear tumor composed of torsional dense vessels among surrounding normal regular vessels can be clearly delineated via 3D angiography. In addition, 3D whole‐cortex cerebral vasculatures with large imaging area (48 mm²), good resolution (25.4 µm), and high SBR (22.3 dB) at a depth up to 1001 µm are clearly resolved through the intact skull. These results are superior to the recently reported 3D NIR‐II fluorescence confocal vascular imaging, which opens up new opportunities for NIR‐II CP‐NP‐assisted ORPAMI in various biomedical applications.     

Conjugated Polymer Actuators and Devices: Progress and Opportunities

Conjugated polymers (CPs), as exemplified by polypyrrole, are intrinsically conducting polymers with potential for development as soft actuators or “artificial muscles” for numerous applications. Significant progress has been made in the understanding of these materials and the actuation mechanisms, aided by the development of physical and electrochemical models. Current research is focused on developing applications utilizing the advantages that CP actuators have (e.g., low driving potential and easy to miniaturize) over other actuating materials and on developing ways of overcoming their inherent limitations. CP actuators are available as films, filaments/yarns, and textiles, operating in liquids as well as in air, ready for use by engineers. Here, the milestones made in understanding these unique materials and their development as actuators are highlighted. The primary focus is on the recent progress, developments, applications, and future opportunities for improvement and exploitation of these materials, which possess a wealth of multifunctional properties.     

不同进洞高程隧道洞口段大型振动台模型试验研究

随着我国“一带一路”战略对中西部铁路建设投资力度的进一步加大,黄土地震区隧道安全问题日渐突出。如目前已建成的宝兰客运专线、兰渝铁路,正在修建的成兰铁路、银西铁路等都穿越黄土地震带。长期以来,进洞高程作为影响黄土隧道洞口段边坡隧道系统动力响应的重要参数,很少得到关注。因此,将进洞高程作为一个关键参数,借助振动台模型试验与数值模拟分析,定性研究了坡-隧系统动力响应的特点,设计了相似比为1∶70的隧道洞口段边坡隧道系统大型振动台模型试验。坡脚进洞和1/2倍坡高进洞模型试验震害观测结果表明:坡-隧系统坡高、坡角、入射地震波、岩土体材料、填筑方式、衬砌结构相同,进洞高程不同,洞口段破坏形态不同,破坏程度各异。进洞高程对衬砌结构加速度响应的影响与激振幅值的大小密切相关,坡脚进洞的加速度响应远远小于1/2倍坡高处进洞衬砌结构的加速度响应。     

Constructing a hybrid hierarchical value map to understand young people’s perceptions of social networking sites

ABSTRACT

Based on the means–end chains (MECs) and push–pull–mooring (PPM) model, this study aims to reveal the functional attributes of Facebook (FB) and Instagram (IG), classify them into the PPM model (i.e. push, pull, and mooring effect) and integrate the nature of MECs (i.e. attribute–consequence–value linkages) to examine young people’s perceptions of FB and IG and their switching intentions. Mixed methods, including qualitative and quantitative approaches are employed to gather data in Taiwan. Sixty-two one-on-one in-depth interviews were content-analysed to design the survey questionnaire. A total of 457 valid samples were collected to establish a hybrid hierarchical value map (HVM) for MEC and PPM analyses. The hybrid HVM shows that ‘privacy protection’ and ‘information collection’ are push effects, which are the unfavourable factors of FB that push users to migrate to IG. By contrast, ‘visual interaction’, ‘relationship maintenance’, and ‘expanding friendship ties’ are pull effects favourable to IG that encourage FB users to migrate. Moreover, ‘self-expression’ and ‘message seeding’ belonging to mooring effects are factors that discourage FB users from migrating. Valuable insights may be provided for the design and improvement of social networking sites by understanding the hybrid HVM.     

Effect of side slope of main channels on formation and penetration of scour hole in confluences

In an open‐channel confluence, deep scour holes and depositional point bars are usually formed due to high bed‐shear stresses and secondary circulations. In the present study, presuming the effectiveness of channel geometry on the flow dynamics at the confluence, some variables including different side slope angles of the main channel (θ = 45°, 60°, 75°, 90°), lateral to downstream discharge ratio (Q_r), and downstream densimetric Froude number (Fr_g3) were experimentally studied under clear‐water condition for the confluence angle α = 90°. According to the results, the increase of θ led to a greater penetration of scour hole across the main and tributary channels, whereas a little scour development was observed along those channels. Meanwhile, an increase in Q_r and Fr_g3 caused further scouring, but their effects on the dimensions of scour hole diminished with increase of θ. Thus, with increase of Q_r from 0.194 to 0.552, the mean penetration rate of scour hole to all directions for θ = 45°, 60°, 75°, and 90° was obtained 42.8%, 32.4%, 25%, and 20.5%, respectively. In addition, considering the effect of θ, Q_r, and Fr_g3, some empirical relationships were obtained for estimating the penetration length of scour hole. The derived relationships show that Fr_g3 plays more important role on the dimensions of scour hole than θ.     

基于 Reed-Solomon 编码的抗边信道攻击云数据安全去重方法

跨用户数据去重技术, 通过在用户端减少重复数据上传来提高云端数据存储效率和用户的带宽使用效率。然而, 在数据上传过程中, 云服务商反馈给用户的确定性去重响应为攻击者建立了一个极具安全风险的边信道, 攻击者利用该边信道可推断出目标数据在云端的存在性隐私。现有的抗边信道攻击跨用户去重方法, 采用各种混淆策略试图扰乱攻击者的判断, 然而, 这些方法难以实现完全混淆, 攻击者仍然可通过字典攻击、附加块攻击等方式达到数据窃取的目的。目前, 如何防止攻击者利用边信道窃取数据的存在性隐私, 成为了跨用户数据去重技术亟待解决的重要问题。为应对这一挑战, 本文采用了一种基于广义去重的新型跨用户安全去重框架, 将原始数据从字节层面分解为基和偏移量, 对基进行跨用户去重, 并对偏移量进行云端去重。特别地, 本文采用 Reed-Solomon 纠删码编码思想实现基的提取, 使得从相似的数据中可以较高概率提取出相同的基。不仅可以实现对攻击者的混淆, 还可以有效节省通信开销和云端存储开销。此外, 为了进一步提高效率, 本文在偏移量上传前, 引入数据压缩算法, 减少偏移量间的冗余数据量。实验结果表明, 在实现有效抵抗边信道攻击的前提下, 本方法相比该领域最新工作在通信和存储效率等方面具有显著优势。     

Linking Glass-Transition Behavior to Photophysical and Charge Transport Properties of High-Mobility Conjugated Polymers

The measurement of the mechanical properties of conjugated polymers can reveal highly relevant information linking optoelectronic properties to underlying microstructures and the knowledge of the glass transition temperature (T_g) is paramount for informing the choice of processing conditions and for interpreting the thermal stability of devices. In this work, we use dynamical mechanical analysis to determine the T_g of a range of state-of-the-art conjugated polymers with different degrees of crystallinity that are widely studied for applications in organic field-effect transistors. We compare our measured values for T_g to the theoretical value predicted by a recent work based on the concept of effective mobility ζ. The comparison shows that for conjugated polymers with a modest length of the monomer units, the T_g values agree well with theoretically predictions. However, for the near-amorphous, indacenodithiophene–benzothiadiazole family of polymers with more extended backbone units, values for T_g appear to be significantly higher, predicted by theory. However, values for T_g are correlated with the sub-bandgap optical absorption suggesting the possible role of the interchain short contacts within materials’ amorphous domains.     

The Effect of Alkyl Spacers on the Mixed Ionic-Electronic Conduction Properties of N-Type Polymers

Conjugated polymers with mixed ionic and electronic transport are essential for developing the complexity and function of electrochemical devices. Current n-type materials have a narrow scope and low performance compared with their p-type counterparts, requiring new molecular design strategies. This work presents two naphthalene diimide-bithiophene (NDI-T2) copolymers functionalized with hybrid alkyl-glycol side chains, where the naphthalene diimide unit is segregated from the ethylene glycol (EG) units within the side chain by an alkyl spacer. Introduction of hydrophobic propyl and hexyl spacers is investigated as a strategy to minimize detrimental swelling close to the conjugated backbone and balance the mixed conduction properties of n-type materials in aqueous electrolytes. It is found that both polymers functionalized with alkyl spacers outperform their analogue bearing EG-only side chains in organic electrochemical transistors (OECTs). The presence of the alkyl spacers also leads to remarkable stability in OECTs, with no decrease in the ON current after 2 h of operation. Through this versatile side chain modification, this work provides a greater understanding of the structure-property relationships required for n-type OECT materials operating in aqueous media.