Light-emitting self-assembled metallacages

Coordination-driven self-assembly of metallacages has garnered significant interest because of their 3D layout and cavity-cored nature. The well-defined, highly tunable metallacage structures render them particularly attractive for investigating the properties of luminophores, as well as for inducing novel photophysical characters that enable widespread applications. In this review, we summarize the recent advances in synthetic methodologies for light-emitting metallacages, and highlight some representative applications of these metallacages. In particular, we focus on the favorable photophysical properties—including high luminescence efficiency in various physical states, good modularity in photophysical properties and stimulus responsiveness—that have resulted from incorporating ligands displaying aggregation-induced emission (AIE) into metallacages. These features show that the synergy between carrying out coordination-driven self-assembly and using luminophores with novel photophysical characteristics like AIE could stimulate the development of supramolecular luminophores for applications in fields as diverse as sensing, biomedicine and catalysis.     

Enantioselective assembly of multi-layer 3D chirality

The first enantioselective assembly of sandwich-shaped organo molecules has been achieved by conducting dual asymmetric Suzuki-Miyaura couplings and nine other reactions. This work also presents the first fully C-C anchored multi-layer 3D chirality with optically pure enantiomers. As confirmed by X-ray diffraction analysis that this chiral framework is featured by a unique C₂-symmetry in which a nearly parallel fashion consisting of three layers: top, middle and bottom aromatic rings. Unlike the documented planar or axial chirality, the present chirality shows its top and bottom layers restrict each other from free rotation, i.e., this multi-layer 3D chirality would not exist if either top or bottom layer is removed. Nearly all multi-layered compounds showed strong luminescence of different colors under UV irradiation, and several randomly selected samples displayed aggregation-induced emission (AIE) properties. This work is believed to have broad impacts on chemical, medicinal and material sciences including optoelectronic materials in future.     

Molecular design and application of luminescent materials composed of group 13 elements with an aggregation-induced emission property

Complexation of π-conjugated ligands by metal or semimetal ions leads to the enhancement of the planarity and rigidity of π-conjugated systems. Boron, especially, has played a central role in the design of luminescent main-group complexes. However, these complexes still suffer the disadvantage of aggregation-caused quenching as well as typical organic fluorophores. It has recently been reported that some types of boron complexes exhibit the aggregation-induced emission (AIE) property. Moreover, AIE behavior from complexes and organometallic compounds composed of the other group 13 elements, such as aluminum and gallium, has emerged in this decade. These observations greatly encourage us to develop advanced functional materials based on the group 13 elements. Indeed, recent research has demonstrated that these classes of materials are potentially versatile scaffolds for constructing chromic luminophores, efficiently emissive π-conjugated polymers and so on. This review mainly describes AIE-active group 13 complexes with four-coordinate structures and their application as photo-functional materials. Proposed mechanisms of the origins of AIE behavior are briefly discussed.     

关于我国稀土产业发展的战略性思考

稀土是全球争夺的重要战略资源,稀土功能材料更是战略性新兴产业发展的催化剂,应用前景广阔。然而,稀土产业附加值的高低取决于是否掌握核心技术。分析我国稀土产业发展面临的问题,提出系统谋划我国稀土产业发展、瞄准价值链高端、加快我国稀土产业的技术创新体系建设等发展我国稀土产业的几点思考。     

Collective prompt tuning with relation inference for document-level relation extraction

Document-level relation extraction (RE) aims to extract the relation of entities that may be across sentences. Existing methods mainly rely on two types of techniques: Pre-trained language models (PLMs) and reasoning skills. Although various reasoning methods have been proposed, how to elicit learnt factual knowledge from PLMs for better reasoning ability has not yet been explored. In this paper, we propose a novel Collective Prompt Tuning with Relation Inference (CPT-RI) for Document-level RE, that improves upon existing models from two aspects. First, considering the long input and various templates, we adopt a collective prompt tuning method, which is an update-and-reuse strategy. A generic prompt is first encoded and then updated with exact entity pairs for relation-specific prompts. Second, we introduce a relation inference module to conduct global reasoning overall relation prompts via constrained semantic segmentation. Extensive experiments on two publicly available benchmark datasets demonstrate the effectiveness of our proposed CPT-RI as compared to the baseline model (ATLOP (Zhou et al., 2021)), which improve the 0.57% on the DocRED dataset, 2.20% on the CDR dataset, and 2.30 on the GDA dataset in the F1 score. In addition, further ablation studies also verify the effects of the collective prompt tuning and relation inference.     

Trapping endoplasmic reticulum with amphiphilic AIE-active sensor via specific interaction of ATP-sensitive potassium (KATP)

The current aggregation-induced emission luminogens (AIEgens) sometimes suffer from poor targeting selectivity due to undesirable aggregation in the hydrophilic biosystem with ‘always-on’ fluorescence or unspecific aggregation in the lipophilic organelle with prematurely activated fluorescence. Herein, we report an unprecedented ‘amphiphilic AIEgen’ sensor QM-SO₃-ER based on the AIE building block of quinoline-malononitrile (QM). The introduced hydrophilic sulfonate group can well control the specific solubility in a hydrophilic system with desirable initial ‘fluorescence-off’ state. Moreover, the incorporated p-toluenesulfonamide group plays two roles: enhancing the lipophilic dispersity, and behaving as binding receptor to the adenosine triphosphate (ATP)-sensitive potassium (K_ATP) on the endoplasmic reticulum (ER) membrane to generate the docking assay confinement effect with targetable AIE signal. The amphiphilic AIEgen has for the first time settled down the predicament of unexpected ‘always-on’ fluorescence in the aqueous system and the untargetable aggregation signal in the lipophilic organelle before binding to ER, thus successfully overcoming the bottleneck of AIEgens'' targetability.     

A stimuli-responsive pillar[5]arene-based hybrid material with enhanced tunable multicolor luminescence and ion-sensing ability

Tunable luminescent materials are becoming more and more important owing to their broad application potential in various fields. Here we construct a pillar[5]arene-based hybrid material with stimuli-responsive luminescent properties and ion-sensing abilities from a pyridine-modified conjugated pillar[5]arene and a planar chromophore oligo(phenylenevinylene) upon coordination of Cd (II) metal cores. This new material not only shows an optimized luminescence due to the minimized π–π stacking and efficient charge transfer properties benefitting from the existence of pillar[5]arene rings, but also exhibits tunable multicolor emission induced by different external stimuli including solvent, ions and acid, indicating great application potential as a fluorescent sensory material, especially for Fe³⁺. With this pillar[5]arene-based dual-ligand hybrid material, valid optimization and regulation on the fluorescence of the original chromophore have been achieved, which demonstrates a plausible strategy for the design of tunable solid-state luminescent materials and also a prototypical model for the effective regulation of fluorescent properties of planar π systems using synthetic macrocycle-based building blocks.     

More is different: how aggregation turns on the light

The reductionist approach to science seeks to understand the behaviour of systems by studying their individual components. It has been an enormously productive approach, but it is also widely acknowledged now that in some systems the behaviour of interest is an emergent property that cannot be discerned in the separate parts. Biology is replete with such examples, from the flocking of birds to the way metabolic processes in cells rely on a dynamic interplay of proteins and other components.Yet molecular systems do not have to be particularly complex before their properties become more than the sum of the parts. A classic example is the appearance of bulk-like metallic behaviour in small clusters of metal atoms only once they exceed a certain critical size. One of the most striking instances became apparent in 2001, when Ben Zhong Tang of the Hong Kong University of Science and Technology and his co-workers found that heterocyclic silicon-containing molecules called siloles become luminescent as nanoscopic aggregates even though the individual molecules in dilute solution do not emit light [1]. This looked like the opposite of the well-known phenomenon of concentration quenching, in which energy transfer between fluorescent (generally organic) molecules quenches the emission, an effect explained in 1955 [2]. Aggregation-induced ‘switching off’ is intuitively understandable, but ‘switching on’ due to aggregation was more surprising.Yet this effect of ‘aggregation-induced emission’ (AIE), as Tang and colleagues called it, was apparently seen, but not understood, much earlier [3]. In the 1850s, George Stokes noted that some inorganic complexes were fluorescent in the condensed, solid state but not in solution. At first, AIE was seen as a curiosity and deemed likely to be rare. However, subsequent research has shown not only that it is a rather common effect but also that it can be considered just one manifestation of a wide range of behaviours that arise from aggregation—leading to the proposed field of ‘aggregate science’, manifesting at the supramolecular level of small clusters or groups of molecules held together by relatively weak interactions. The field might be considered to illustrate George Whitesides’ notion of a chemistry ‘beyond the molecule’ [4], which bridges disciplines ranging from colloid science to crystal growth, nanotechnology, liquid crystals, photochemistry and molecular biology. At the same time, it echoes the famous insight of physicist Philip Anderson about emergent phenomena and the hierarchical nature of science: ‘More is different’ [5]. An ability to switch properties on and off by controlling intermolecular interactions and aggregation suggests various applications, from optical device technologies to targeted drugs for cancer therapy [6].NSR spoke to Ben Zhong Tang about the origins and possibilities of the field.

NSR: It seems you noticed AIE in 2001 by accident. How did it come about? Tang: Yes, it was serendipity. Development of new light emitters for the fabrication of organic light-emitting diodes was a hot topic at that time. We were trying to make new luminophores [light-emitting molecules] with high efficiencies and novel structures. Attracted by the aesthetically pleasing molecular structures of siloles, I asked my students to prepare various silole compounds. One day, a student told me that he could not see any luminescence when he used a UV lamp to excite the solution of the silole compound he had made. This surprised me, because I myself prepared a silole compound when I was a PhD student and I remember that its crystal was luminescent. I sensed something strange and immediately rushed to the lab. After careful verification and discussion with the student, we concluded that both of us were correct: the silole solution was not luminescent (his observation was right) but the silole powder was emissive (my memory was right). The non-luminescent molecular species in the dilute solution were induced to emit light through formation of aggregates in the solid state. We termed the process aggregation-induced emission or AIE.

A mesoscopic aggregate can have a property that its molecular species does not exhibit at all.—Ben Zhong Tang

Open in a separate windowBen Zhong Tang of the Hong Kong University of Science and Technology, China (Courtesy of Ben Zhong Tang). NSR: The phenomenon seemed to defy conventional expectations. Did you have trouble persuading others—or yourselves!—that it was real? Tang: I initially thought the student might have done something wrong, for the phenomenon he observed was totally unexpected. The common belief in the community of photophysics research is that luminescence from an organic dye generally weakens when its molecules are aggregated, an effect often referred to as aggregation-caused quenching or ACQ. I was shocked when I realized that the silole luminogen was showing an anti-ACQ effect. Still, I felt lucky to encounter something ‘abnormal’. No matter how odd a phenomenon seems, if it can be repeatedly observed, it must be real. We repeated our experiments many times and we were eventually convinced that the AIE effect was true. We had trouble, however, to understand why the silole luminogen behaved in such a way that was diametrically opposed to conventional ACQ. NSR: Are there any historical precedents—experiments in which this effect might have been glimpsed previously, but not recognized as such? Tang: When we published our first AIE paper in 2001, we thought the photophysical effect was unprecedented. However, we gradually found out that similar phenomena had been previously observed by other scientists. For example, in 1853 George Stokes reported in a paper that some inorganic platinocyanide salts ‘are sensitive’ (meaning luminescent in modern terminology) ‘only in the solid state’ but ‘their solutions look like mere water’. Sadly, he didn’t follow it up. Other people have made similar observations in different dye systems, which were, however, not recognized as AIE processes. Partially because of this, we had great difficulty in finding relevant reference papers. As a matter of fact, Stokes’ report, published in the mid-19th century, was not known to us until the middle of 2018. However, we are not surprised by those early works, for we understand that science progresses not in an abrupt but in a continuous way. George Smith articulated this: ‘Very few research breakthroughs are novel. Virtually all of them build on what went on before.’ A discovery is often a happenstance. We happened to have ‘rediscovered’ a very old but largely unnoticed phenomenon. Luckily, we grasped the opportunity to see more and farther by standing on the shoulders of giants.     

Solid-state intramolecular motions in continuous fibers driven by ambient humidity for fluorescent sensors

One striking feature of molecular rotors is their ability to change conformation with detectable optical signals through molecular motion when stimulated. However, due to the strong intermolecular interactions, synthetic molecular rotors have often relied on fluid environments. Here, we take advantage of the solid-state intramolecular motion of aggregation-induced emission (AIE) molecular rotors and one-dimensional fibers, developing highly sensitive optical fiber sensors that respond to ambient humidity rapidly and reversibly with observable chromatic fluorescence change. Moisture environments induce the swelling of the polymer fibers, activating intramolecular motions of AIE molecules to result in red-shifted fluorescence and linear response to ambient humidity. In this case, polymer fiber provides a process-friendly architecture and a physically tunable medium for the embedded AIE molecules to manipulate their fluorescence response characteristics. Assembly of sensor fibers could be built into hierarchical structures, which are adaptive to diverse-configuration for spatial-temporal humidity mapping, and suitable for device integration to build light-emitting sensors as well as touchless positioning interfaces for intelligence systems.     

Robust sulfonated poly (ether ether ketone) nanochannels for high-performance osmotic energy conversion

The membrane-based reverse electrodialysis (RED) technique has a fundamental role in harvesting clean and sustainable osmotic energy existing in the salinity gradient. However, the current designs of membranes cannot cope with the high output power density and robustness. Here, we construct a sulfonated poly (ether ether ketone) (SPEEK) nanochannel membrane with numerous nanochannels for a membrane-based osmotic power generator. The parallel nanochannels with high space charges show excellent cation-selectivity, which could further be improved by adjusting the length and charge density of nanochannels. Based on numerical simulation, the system with space charge shows better conductivity and selectivity than those of a surface-charged nanochannel. The output power density of our proposed membrane-based device reaches up to 5.8 W/m² by mixing artificial seawater and river water. Additionally, the SPEEK membranes exhibit good mechanical properties, endowing the possibility of creating a high-endurance scale-up membrane-based generator system. We believe that this work provides useful insights into material design and fluid transport for the power generator in osmotic energy conversion.     

Variance reduction in large graph sampling

The norm of practice in estimating graph properties is to use uniform random node (RN) samples whenever possible. Many graphs are large and scale-free, inducing large degree variance and estimator variance. This paper shows that random edge (RE) sampling and the corresponding harmonic mean estimator for average degree can reduce the estimation variance significantly. First, we demonstrate that the degree variance, and consequently the variance of the RN estimator, can grow almost linearly with data size for typical scale-free graphs. Then we prove that the RE estimator has a variance bounded from above. Therefore, the variance ratio between RN and RE samplings can be very large for big data. The analytical result is supported by both simulation studies and 18 real networks. We observe that the variance reduction ratio can be more than a hundred for some real networks such as Twitter. Furthermore, we show that random walk (RW) sampling is always worse than RE sampling, and it can reduce the variance of RN method only when its performance is close to that of RE sampling.     

基于Davinci的嵌入式网络视频监控系统的设计与实现

介绍了一种基于TMS320DM368处理器的网络视频监控系统的实现方案,该系统支持扩展多种视频采集前端接口,支持包括以太网、3G网络和WIFI的多种通信方式。基于RTP/RTSP框架设计了多线程流媒体服务器,并在Web服务器端设计了动态页面,使用CGI技术实现了用户与服务器的交互。测试结果显示系统在低带宽和复杂网络条件下仍能获得很好的监控画面效果,实时性和稳定性好。     

The data-filtering based bias compensation recursive least squares identification for multi-input single-output systems with colored noises

For the multi-input single-output (MISO) system corrupted by colored noise, we transform the original system model into a new MISO output error model with white noise through data filtering technology. Based on the newly obtained model and the bias compensation principle, a novel data filtering-based bias compensation recursive least squares (BCRLS) identification algorithm is developed for identifying the parameters of the MISO system with colored noise disturbance. Unlike the exiting BCRLS method for the MISO system (see, in Section 3), without computing the complicated noise correlation functions, still the proposed method can achieve the unbiased parameters estimation of the MISO system in the case of colored process noises. The proposed algorithm simplifies the implementation of and further expands the application scope of the existing BCRLS method. Three numerical examples clearly illustrate the validity of and the good performances of the proposed method, including its superiority over the BCRLS method and so on.     

Bioinspired hierarchical helical nanocomposite macrofibers based on bacterial cellulose nanofibers

Bio-sourced nanocellulosic materials are promising candidates for spinning high-performance sustainable macrofibers for advanced applications. Various strategies have been pursued to gain nanocellulose-based macrofibers with improved strength. However, nearly all of them have been achieved at the expense of their elongation and toughness. Inspired by the widely existed hierarchical helical and nanocomposite structural features in biosynthesized fibers exhibiting exceptional combinations of strength and toughness, we report a design strategy to make nanocellulose-based macrofibers with similar characteristics. By combining a facile wet-spinning process with a subsequent multiple wet-twisting procedure, we successfully obtain biomimetic hierarchical helical nanocomposite macrofibers based on bacterial cellulose nanofibers, realizing impressive improvement in their tensile strength, elongation and toughness simultaneously. The achievement certifies the validity of the bioinspired hierarchical helical and nanocomposite structural design proposed here. This bioinspired design strategy provides a potential platform for further optimizing or creating many more strong and tough nanocomposite fiber materials for diverse applications.     

Light-driven directional ion transport for enhanced osmotic energy harvesting

Light-driven ion (proton) transport is a crucial process both for photosynthesis of green plants and solar energy harvesting of some archaea. Here, we describe use of a TiO₂/C₃N₄ semiconductor heterojunction nanotube membrane to realize similar light-driven directional ion transport performance to that of biological systems. This heterojunction system can be fabricated by two simple deposition steps. Under unilateral illumination, the TiO₂/C₃N₄ heterojunction nanotube membrane can generate a photocurrent of about 9 μA/cm², corresponding to a pumping stream of ∼5500 ions per second per nanotube. By changing the position of TiO₂ and C₃N₄, a reverse equivalent ionic current can also be realized. Directional transport of photogenerated electrons and holes results in a transmembrane potential, which is the basis of the light-driven ion transport phenomenon. As a proof of concept, we also show that this system can be used for enhanced osmotic energy generation. The artificial light-driven ion transport system proposed here offers a further step forward on the roadmap for development of ionic photoelectric conversion and integration into other applications, for example water desalination.     

选择性反向工程与自主创新整合

在传统意义反向工程的基础上将反向工程的应用拓展到管理领域,进一步分析并提出反向工程是一种学习手段和方法,在此理论上结合当前我国科技创新体系存在的问题,提出根据不同领域、行业、企业特点和技术水平的实际情况,将正向工程与反向工程有机结合起来的选择性反向工程科技创新战略。     

科研经历、差错管理氛围与科研创造力提升

提升研究生科研创造力是研究生教育体制改革的核心目标之一,已有研究重点从个性特征、导师因素探讨研究生科研创造力的影响因素,鲜见后天因素与团队氛围因素的考察。基于社会认知理论,旨在探讨个体科研经历,师门差错管理氛围对科研创造力的影响及其作用机制。以来自山东、北京、天津、上海四省/市部分科研院校的61个师门311名全日制研究生为被试。研究发现：科研经历对科研自我效能、科研创造力有显著正向影响;科研自我效能感对科研创造力有显著正向影响,并且在科研经历与科研创造力关系中具有部分中介作用;师门差错管理氛围对科研自我效能感、科研创造力的跨层正向影响显著;科研自我效能感在师门差错管理氛围与科研创造力关系中具有完全中介作用。     

A hybrid stochastic fractal search and local unimodal sampling based multistage PDF plus (1 + PI) controller for automatic generation control of power systems

This paper proposes to use a hybrid Stochastic Fractal Search (SFS) and Local Unimodal Sampling (LUS) based multistage Proportional Integral Derivative (PID) controller consisting of Proportional Derivative controller with derivative Filter (PDF) plus (1 + Proportional Integral) for Automatic Generation Control (AGC) of power systems. Initially, a single area multi-source power system consisting of thermal hydro and gas power plants is considered and parameters of Integral (I) controller is optimized by Stochastic Fractal Search (SFS) algorithm. The superiority of SFS algorithm over some recently proposed approaches such as optimal control, Differential Evolution (DE) and Teaching Learning Based Optimization (TLBO) is demonstrated. To improve the system performance further, LUS is subsequently employed. The study is further extended for different controllers like PID, and proposed multistage PID controller and the superiority of multistage PID controller over conventional PID controller structure is demonstrated. The study is further extended to a two-area six unit multi-source interconnected power system and the superiority of proposed approach over, TLBO and optimal control is demonstrated. Finally the study is extended to a three unequal area system power system with appropriate nonlinearities such as Generation Rate Constraint (GRC), Governor Dead Band (GDB) and time delay. From the analysis, it is found that hybrid SFS–LUS algorithm is superior to the original SFS algorithm and substantial improvement in system performance are realized with proposed multistage PID controller over conventional PID controller structure.     

The ability of European regions to diversify in renewable energies: The role of technological relatedness

Despite the global consensus about the growing significance of renewables, the regional drivers of innovation in these unique and novel technologies have been widely neglected in the literature. In this paper, we show that renewable energy (RE) inventions differ from other green inventions in the knowledge recombination processes leading to their generation as well as in their impact on subsequent inventions. The evidence on these specificities of RE technologies allows us hypothesizing that regional branching in renewables may rely on relatedness differently than other non-RE green technologies. In checking this hypothesis, we use a data set spanning the period 1981-2015 covering 277 European NUTS2 regions in the EU28 countries plus Norway. We obtain that relatedness is highly relevant in explaining regional specialization in RE, and more relevant than for other green technologies, which we associate to the lower generality in their impact and the narrower scope of the knowledge from which they nurture. This conclusion is maintained when considering separately regions with high and low development levels. However, the impact of relatedness increases for RE as the regional economic development decreases, signalling that a low endowment of resources and capabilities does not allow the region to break from its past technological specialization, depending more on relatedness. This would not be the case for other green technologies, probably due to their higher level of generality and wider scope.     

基于H.264的嵌入式无线视频监控系统设计

设计了一种基于H.264视频压缩标准的嵌入式无线视频监控系统,详细给出了该系统硬件和相应的软件实现方法,并针对RTP网络数据传输出现的问题给出了解决方案。实践证明,本系统设计合理,运行可靠。