2024-04-20 2024, Volume 5 Issue 4

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  • REVIEW
    Xuehua Ding , Chuanxin Wei , Lizhi Wang , Jing Yang , Wenxin Huang , Yongzheng Chang , Changjin Ou , Jinyi Lin , Wei Huang

    Flexible organic crystals are emerging as a potential candidate for smart materials and have aroused great interest over the past decade. In view of multicomponent supramolecular synthesis with a distinct advantage over single-component approach on the control of molecular arrangements and physicochemical properties, we take note of various multicomponent flexible organic crystals in the range from organic co-crystals, supramolecular salts, solvates, doping organic crystals to solid solution crystals, showing a great diversity of supramolecular architectures such as one-dimensional columns, two-dimensional layer packing, and three-dimensional interlocked structures. Some of them serve as promising multifunctional materials with both flexibility and photoelectric properties such as fluorescence, optical waveguide, and ferroelectricity. In this review, we focus on the packing structures of multicomponent flexible organic crystals and their related mechanical properties, highlight typical research works, and point out the main possible directions that remain to be developed in this field. From the perspectives of crystal engineering and supramolecular chemistry, the flexible crystals outlined here should offer helpful information for further design and investigation on the elusive class of mechanically compliant crystalline compounds.

  • RESEARCH ARTICLE
    Xingyi Liu , Xiaowen Gao , Lin Xiong , Shuoxue Li , Yu Zhang , Qi Li , Hong Jiang , Dongsheng Xu

    Low-dimensional hybrid halide perovskites represent a promising class of materials in optoelectronic applications because of strong broad self-trapped exciton (STE) emissions. However, there exists a limitation in designing the ideal A-site cation that makes the material satisfy the structure tolerance and exhibit STE emission raised by the appropriate electron–phonon coupling effect. To overcome this dilemma, we developed an inorganic metal-organic dimethyl sulfoxide (DMSO) coordinating strategy to synthesize a series of zero-dimensional (0D) Sb-based halide perovskites including Na3SbBr6·DMSO6 (1), AlSbBr6·DMSO6 (2), AlSbCl6·DMSO6 (3), GaSbCl6·DMSO6 (4), Mn2Sb2Br10·DMSO13 (5) and MgSbBr5·DMSO7 (6), in which the distinctive coordinating A-site cation [Am-DMSO6]n+ efficiently separate the [SbXz] polyhedrons. Advantageously, these materials all exhibit broadband-emissions with full widths at half maxima (FWHM) of 95–184 nm, and the highest photoluminescent quantum yield (PLQY) of 3 reaches 92%. Notably, compounds 2–4 are able to remain stable after storage of more than 120 d. First-principles calculations indicate that the origin of the efficient STE emission can be attributed to the localized distortion in [SbXz] polyhedron upon optical excitation. Experimental and calculational results demonstrate that the proposed coordinating strategy provides a way to efficiently expand the variety of novel high-performance STE emitters and continuously regulate their emission behaviors.

  • RESEARCH ARTICLE
    He Shao , Yueqing Li , Jiefeng Chen , Wei Yang , Le Wang , Jingwei Fu , Yiru Wang , Haifeng Ling , Linghai Xie , Wei Huang

    Retinal-inspired synaptic phototransistors, which integrate light signal detection, preprocessing, and memory functions, show promising applications in artificial vision sensors. In recent years, it has been reported to construct heterojunction in phototransistors to realize positive photoconductance (PPC) and negative photoconductance (NPC) modulations, thereby achieving visible and infrared wavelength discrimination and various visual functions. However, relatively little attention has been paid to wavelength-dependent switching and reconfigurability between two states (PPC and NPC), limiting further applications for complex simulations of biological visual functions. Here, a mixed organic–inorganic heterojunction synaptic phototransistor was constructed by integrating CsPbBr3 nanoplates (NPLs) with strong blue-light absorption and poly(3-hexylthiophene-2,5-diyl) (P3HT) with strong red-light absorption. Compared with the three-dimensional (3D) structure CsPbBr3 nanocubes (NCs), the two-dimensional (2D) CsPbBr3 NPLs exhibited more efficient charge transfer with P3HT. Based on the individual optical absorption properties in organic–inorganic heterojunction, the device exhibited wavelength-selective and reconfigurable behavior between PPC and NPC. A low power consumption of 0.053 fJ per synaptic event was achieved, which is comparable to a biological synapse. Finally, Drosophila’s evasive behavior to food under red and blue light can be successfully demonstrated. This work demonstrates the future potential of synaptic phototransistors for visuomorphic computing.

  • PERSPECTIVE
    Xiangyu Hou , Tengyu Jin , Yue Zheng , Wei Chen

    Two-dimensional (2D) materials with free of dangling bonds have the potential to serve as ideal channel materials for the next generation of field-effect transistors (FETs) due to their atomic-thin and excellent electronic properties. However, the performance of 2D materials-based FETs is still dictated by the interface between electrodes/dielectrics and 2D materials. Several technical challenges such as improving device stability, reducing contact resistance, and advancing mobility need to be overcome. Herein, we focus on the effects of atomic-scale interface engineering on the contact resistance and dielectric layer for 2D FETs. Universal strategies we consider to achieve ohmic contact and develop high-quality, defect-free dielectric layers are provided. Furthermore, advancing the performance of 2D materials-based FETs and binding to silicon substrates are briefly analyzed.

  • COMMENT
    Li Li , Zhicheng Zhang
  • REVIEW
    Yuewei Zhang , Yunlong Jia , Shoujun Zhu

    The near-infrared (NIR)-II bioimaging technique is highly important for both diagnosing and treating life-threatening diseases due to its exceptional imaging capabilities. However, the lack of suitable NIR-II fluorescent probes has hindered their widespread clinical application. To address this issue, the binding of albumin to cyanine dyes has emerged as a practical and efficient method for developing high-performance NIR-II probes. Cyanine dyes can bind with exogenous and endogenous albumin through either covalent or noncovalent interactions, serving various purposes. The resulting cyanine@albumin (or albumin@cyanine) fluorophores offer significant advantages, including strong brightness, excellent photostability, good biosafety, and a long-term, high-resolution imaging window. Cyanine dye in situ binding with endogenous albumin can also enhance the targeting imaging capability. This review provides a summary of the interaction mechanism, performance enhancement, tumor-targeting feature, and in vivo imaging applications of the cyanine@albumin fluorophores. These advancements not only highlight the unique characteristics of cyanine@albumin fluorophores in preclinical research but also emphasize their potential for clinical diagnosis.

  • RESEARCH ARTICLE
    Junyao Zhang , Ziyi Guo , Tongrui Sun , Pu Guo , Xu Liu , Huaiyu Gao , Shilei Dai , Lize Xiong , Jia Huang

    Photoelectric synaptic device is a promising candidate component in brain-inspired high-efficiency neuromorphic computing systems. Implementing neuromorphic computing with broad bandwidth is, however, challenging owing to the difficulty in realizing broadband characteristics with available photoelectric synaptic devices. Herein, taking advantage of the type-II heterostructure formed between environmentally friendly CuInSe2 quantum dots and organic semiconductor, broadband photoelectric synaptic transistors (BPSTs) that can convert light signals ranging from ultraviolet (UV) to near-infrared (NIR) into post-synaptic currents are demonstrated. Essential synaptic functions, such as pair-pulse facilitation, the modulation of memory level, long-term potentiation/depression transition, dynamic filtering, and learning-experience behavior, are well emulated. More significantly, benefitting from broadband responses, information processing functions, including arithmetic computing and pattern recognition can also be simulated in a broadband spectral range from UV to NIR. Furthermore, the BPSTs exhibit obvious synaptic responses even at an ultralow operating voltage of –0.1 mV with an ultralow energy consumption of 75 aJ per event, and show their potential in flexible electronics. This study presents a pathway toward the future construction of brain-inspired neural networks for high-bandwidth neuromorphic computing utilizing energy-efficient broadband photoelectric devices.

  • RESEARCH ARTICLE
    Yikun Liu , Yongju Gao , Beom Jin Kim , Meili Xia , Yunlong Zhou , Yongjing Zhang , Yang Li , Jianying Huang , Duxia Cao , Songfang Zhao , Jong-Hyun Ahn , Yuekun Lai

    Human–machine interactive platforms that can sense mechanical stimuli visually and digitally are highly desirable. However, most existing interactive devices cannot satisfy the demands of tactile feedback and extended integration. Inspired by the mechanoluminescence (ML) function of cephalopod skin and the sensitive perception of microcracked slit-organs, a bioinspired stretchable interactive platform is developed by designing a stretchable poly(styrene-block-butadiene-block-styrene)/fluorescent molecule (SFM) composite followed by the in situ polymerization of pyrrole (Py) and deposition of carbon nanotubes (CNTs), which possesses a simple multilayered structure and quantitatively senses the applied strains via the variations of digital electrical resistance and visual fluorescence intensity. Using the strain-dependent microstructures derived from the synergistic interactions of the rigid PPy/CNTs functional layer and SFM, the SFM/PPy/CNTs-based platforms exhibit excellent strain-sensing performance manifested by a high gauge factor (GF = 2.64 × 104), wide sensing range (∼270%), fast response/recovery time (∼155/195 ms), excellent stability (∼15,000 cycles at 40% strain), and sensitive ML characteristics under ultraviolet illumination. Benefiting from the novel fusion of digital data and visual images, important applications, including the detection of wrist pulses and human motions, and information dual-encryption, are demonstrated. This study demonstrates the superiority of advanced structures and materials for realizing superior applications in wearable electronics.

  • REVIEW
    Yifan Xie , Chenming Ding , Qingqing Jin , Lei Zheng , Yunqi Xu , Hongmei Xiao , Miao Cheng , Yanqin Zhang , Guanhua Yang , Mengmeng Li , Ling Li , Ming Liu

    With the rapid development of advanced technologies in the Internet of Things era, higher requirements are needed for next-generation electronic devices. Fortunately, organic thin film transistors (OTFTs) provide an effective solution for electronic skin and flexible wearable devices due to their intrinsic features of mechanical flexibility, lightweight, simple fabrication process, and good biocompatibility. So far considerable efforts have been devoted to this research field. This article reviews recent advances in various promising and state-of-the-art OTFTs as well as related integrated circuits with the main focuses on: (I) material categories of high-mobility organic semiconductors for both individual transistors and integrated circuits; (II) effective device architectures and processing techniques for large-area fabrication; (III) important performance metrics of organic integrated circuits and realization of digital and analog devices for future smart life; (IV) applicable analytical models and design flow to accelerate the circuit design. In addition, the emerging challenges of OTFT-based integrated circuits, such as transistor uniformity and stability are also discussed, and the possible methods to solve these problems at both transistor and circuit levels are summarized.

  • RESEARCH ARTICLE
    Xin Kong , Bin Liu , Zhongqiu Tong , Rui Bao , Jianhong Yi , Shuyu Bu , Yunpeng Liu , Pengfei Wang , Chun-Sing Lee , Wenjun Zhang

    Metallic phthalocyanines are promising electrocatalysts for CO2 reduction reaction (CO2RR). However, their catalytic activity and stability (especially under high potential) are still unsatisfactory. Herein, we synthesized a covalent organic polymer (COP-CoPc) by introducing charge-switchable viologen ligands into cobalt phthalocyanine (CoPc). The COP-CoPc exhibits great activity for CO2RR, including a high Faradaic efficiency over a wide potential window and the highest CO partial current density among all ligand-tuned phthalocyanine catalysts reported in the H-type cell. Particularly, COP-CoPc also shows great potential for practical applications, for example, a FECO of >95% is realized at a large current density of 150 mA/cm2 in a two-electrode membrane electrode assembly reactor. Ex situ and in situ X-ray absorption fine structure spectroscopy measurements and theory calculations reveal that when the charge-switchable viologen ligands switch to neutral-state ones, they can act as electron donors to enrich the electron density of Co centers in COP-CoPc and enhance the desorption of *CO, thus improving the CO selectivity. Moreover, the excellent reversible redox capability of viologen ligands and the increased Co–N bonding strength in the Co–N4 sites enable COP-CoPc to possess outstanding stability under elevated potentials and currents, enriching the knowledge of charge-switchable ligands tailored CO2RR performance.

  • RESEARCH ARTICLE
    Chuang Yuan , Qicai Xiao , Qiaohui Chen , Qiong Huang , Kelong Ai , Xinyu Yang

    Sepsis is a leading cause of death worldwide. This syndrome is commonly accompanied by overactivation of coagulation, excessive reactive oxygen species (ROS), and inflammatory cytokine storm. Notably, disseminated intravascular coagulation (DIC) accounts for around 40% of sepsis-associated deaths. However, anticoagulant therapy is still difficult for sepsis treatment because of the lethal bleeding side effects. Although the relationship between ROS and inflammatory cytokine storm has been described clearly, the pathogenic role of ROS in DIC, however, is still unclear, which renders novel therapeutic approaches hard to achieve bedside for inhibiting DIC. Herein, our new finding reveals that ROS greatly facilitates the entry of lipopolysaccharide (LPS) into the macrophage cytoplasm, which subsequently activates the caspase-11/gasdermin D pathway, and finally induces DIC through phosphatidylserine exposure. Based on this finding, novel gallic acid-modified Mo-based polyoxometalate dots (M-dots) with outstanding antioxidant activity are developed to provide ideal and efficient inhibition of DIC. As expected, M-dots are capable of markedly inhibiting sepsis-caused coagulation, organ injury, and death in sepsis. This therapeutic strategy, blocking the upstream pathway of coagulation rather than coagulation itself, can avoid the side effects of extensive bleeding caused by conventional anticoagulation therapy, and will provide a new avenue for the efficient treatment of sepsis.

  • RESEARCH ARTICLE
    Zhaoyu Ma , Zhiduo Sun , Zhichao Ye , Kai Cai , Wenbin Zhong , Wei Yuan , Weiyun Zhang , Jin Zhang , Kai Zhang , Huageng Liang , Heyou Han , Yanli Zhao

    Frequent intravesical chemotherapy is still the adopted clinical option after bladder cancer surgery with low adhesion, poor selectivity, low permeability, and drug resistance. Herein, we develop an ingenious bladder cancer dissociation method to enhance intravesical chemotherapy and tumor self-exclusion with urine. Ethylene diamine tetraacetic acid (EDTA), a common Ca2+ chelator, is loaded with the typical clinical bladder instillation drug doxorubicin (Dox) in chitosan-modified hollow gold nanorods and subsequently coated with cancer cell membranes. After bladder perfusion, the nanoplatform exhibits high affinity toward bladder tumors under homologous targeting, assisting in long-term retention. Under NIR-II laser irradiation, the photothermal effect accelerates the unloading of cargo, and the released EDTA then disrupts intratumoral junctions by depriving and chelating Ca2+ from the intercellular calcium-dependent connexin. The consequential intertumoral dissociation gives access to the deeper penetration of Dox and allows the exclusion of the shed small tumor masses from the body with the urine. This distinctive tumor dissociation concept holds great promise for modern clinical intravesical chemotherapy and perhaps for other gastrointestinal malignancies.

  • RESEARCH ARTICLE
    Xueyan Zhao , Yan Yan , Min Tan , Surong Zhang , Xiaona Xu , Zhibin Zhao , Maoning Wang , Xubin Zhang , Adila Adijiang , Zongliang Li , Elke Scheer , Dong Xiang

    Thanks to their excellent bond strength, phenyl-based molecules with thiol anchoring groups are extensively employed to form stable single-molecule junctions. However, two critical questions are still not answered which seriously hinder high-yield establishing reliable molecular functional devices: (1) Whether molecular dimer junctions will be formed, and if this is the case, whether the dimerization is caused by intermolecular disulfide bonds or π–π stacking of phenyl rings; (2) Upon a mechanical-compression force, is it possible that both anchoring groups of the molecule bond to the same electrode instead of bridging two opposite electrodes, which would drastically reduce the yield of the molecular junctions. Here, combining UV-Vis/Raman spectroscopy of bulk molecules and conductance/flicker-noise measurements of single molecules, we give compelling evidence that molecular dimers naturally form under ambient conditions, primarily via disulfide bonds rather than by π–π stacking. We further proposed a technique, named electrode-compression-hold-on (ECHO), and reveal that the two thiol groups of phenyl-backboned molecules will bond to the same electrode upon a compression force with a prolongated ECHO time. In contrast, the compression-time-dependent phenomenon is not observed for alkyl-backboned molecules. The underlying mechanism for these unprecedented observations is elucidated, shedding light on the yield of molecular junctions.