bluuebunny/crossref_metadata_2025 huggingface dataset:
Green Space Morphology and School Myopia in China
Authors: Yang Yahan , Liao Huipeng , Zhao Lanqin , Wang Xun , Yang XiaoWei , Ding Xiaohu , Li Xuelong , Jiang Zhiyu , Zhang Xingying , Zhang Qingling , He Huagui , Guo Liang , Lin Hualiang , Dong Guanghui , Spencer Bryan , He Mingguang , Congdon Nathan , Morgan Ian George , Lin Haotian
Published: January 2024

Importance

China has experienced both rapid urbanization and major increases in myopia prevalence. Previous studies suggest that green space exposure reduces the risk of myopia, but the association between myopia risk and specific geometry and distribution characteristics of green space has yet to be explored. These must be understood to craft effective interventions to reduce myopia.

Objective

To evaluate the associations between myopia and specific green space morphology using novel quantitative data from high-resolution satellite imaging.

Design, Setting, and Participants

This prospective cohort study included students grades 1 to 4 (aged 6 to 9 years) in Shenzhen, China. Baseline data were collected in 2016-2017, and students were followed up in 2018-2019. Data were analyzed from September 2020 to January 2022.

Exposures

Eight landscape metrics were calculated using land cover data from high-resolution Gaofen-2 satellite images to measure area, aggregation, and shape of green space.

Main Outcome and Measures

The 2-year cumulative change in myopia prevalence at each school and incidence of myopia at the student level after 2 years were calculated as main outcomes. The associations between landscape metrics and school myopia were assessed, controlling for geographical, demographic, and socioeconomic factors. Principal component analyses were performed to further assess the joint effect of landscape metrics at the school and individual level.

Results

A total of 138 735 students were assessed at baseline. Higher proportion, aggregation, and better connectivity of green space were correlated with slower increases in myopia prevalence. In the principal component regression, a 1-unit increase in the myopia-related green space morphology index (the first principal component) was negatively associated with a 1.7% (95% CI, −2.7 to −0.6) decrease in myopia prevalence change at the school level (P = .002). At the individual level, a 1-unit increase in myopia-related green space morphology index was associated with a 9.8% (95% CI, 4.1 to 15.1) reduction in the risk of incident myopia (P < .001), and the association remained after further adjustment for outdoor time, screen time, reading time, and parental myopia (adjusted odds ratio, 0.88; 95% CI, 0.80 to 0.97; P = .009).

Conclusions and Relevance

Structure of green space was associated with a decreased relative risk of myopia, which may provide guidance for construction and renovation of schools. Since risk estimates only indicate correlations rather than causation, further interventional studies are needed to assess the effect on school myopia of urban planning and environmental designs, especially size and aggregation metrics of green space, on school myopia.
Self‐Micropatterned Wood Hydrophone for Underwater Detection
Authors: Meng Qingyu , Ye Zewei , Wang Yuanyuan , Liu Chencong , Sun Qingfeng , Shamshina Julia L. , Shen Xiaoping
Published: January 2024

A hydrophone is a core component of sonar and plays a significant role in underwater detection. High sensitivity and wide‐frequency responsiveness are crucial parameters for underwater mechanosensors. This study introduces an innovative wood‐based hydrophone for precise detection of water wave spectra and a wide range of underwater sounds. The wood hydrophone consists of a conductive wood electrode with deposited polypyrrole (PPy) microbranches (polypyrrole wood (PW)) and a cellulosic micropatterned anti‐swelling hydrogel (MPASH) serving as the dielectric layer. As pressure increases within the range of 6.4 Pa to 1.2 kPa, the densely distributed PPy microbranches within the wood fiber cell lumina contact with more tips of the self‐wrinkled micropatterns of MPASH. This interaction results in a four‐order‐of‐magnitude increase in capacitance, leading to an unprecedented sensitivity of 1153 kPa−1 toward microstresses. Due to the presence of multisized configurations in both PW and MPASH, the sensitivity of the wood hydrophone decreases gradually (268 kPa−1 up to 37 kPa). The receiving sensitivity of the wood hydrophone for acoustic waves is greater than ‐174 dB within the frequency range of 250–2300 Hz. This work presents a promising avenue for the development of underwater detection devices utilizing graded wood channels and micropatterned cellulosic hydrogels.
Multivalent‐Ion Electrochromic Energy Saving and Storage Devices
Authors: Tong Zhongqiu , Zhu Xing , Xu Hongbo , Li Zhishan , Li Shaoyuan , Xi Fengshuo , Kang Tianxing , Ma Wenhui , Lee Chun‐Sing
Published: January 2024

Electrochromic devices (ECDs) show promising applications in various fields including energy‐saving smart windows, energy‐recycling batteries/supercapacitors, displays, thermal management, etc. Compared to monovalent cations (H+, Li+, Na+, and K+), multivalent‐ion carriers (Mg2+, Ca2+, Zn2+, and Al3+) can enable the ECDs with high optical contrast, high energy‐recycling capability, and attractive long‐term stability because of the multiple‐electron transfer redox. Additionally, Mg2+, Zn2+, and Al3+‐based ECDs assembled with metal anodes are exploited for applications in EC electronics, EC mirrors, flexible devices, etc. Attempts to develop multivalent‐ion ECDs can be traced to 2013. However, since 2017, the research activity in this field has surged in the world. Despite the fascinating achievements, there is still a long way from their maturity due to challenges related to the limited electrode materials and electrolytes, as well as the obscure multivalent‐ion redox mechanisms. This review aims to discuss 1) the EC mechanisms of electrode materials with multivalent ions, 2) the advantageous functionalities of multivalent‐ion ECDs, and 3) strategies developed for exploring electrode materials, electrolytes, and ECD structures. Additionally, future perspectives for remaining challenges and corresponding strategies for developing multivalent‐ion ECDs with designed functionalities are discussed.
Tilt‐Engineered Molecular‐Scale Selector for Enhanced Learning in Artificial Neural Networks
Authors: Eo Jung Sun , Shin Jaeho , Jeon Takgyeong , Jang Jingon , Wang Gunuk
Published: January 2024

Miniaturization of individual selectors in crossbar‐array‐based artificial neural networks is essential for the advancement of the underlying neuromorphic electronics, as it improves learning, recognition, and prediction accuracies. This study proposes a tilt‐engineered molecular‐scale selector comprising a heterostructure of biphenyl‐4‐thiol (OPT2) or 1‐octanethiol (C8) molecular layers and an n‐type two‐dimensional MoS2 monolayer (1L‐MoS2) at an approximate contact radius of 3 nm, which is evaluated via conductive atomic force microscopy under various tip‐loading forces. The molecular tilt configuration controlled by the tip‐loading force is used as a rectifying engineer for the OPT2/1L‐MoS2 and C8/1L‐MoS2 heterojunction accuracies. Rectification ratios and conductance levels are significantly influenced by the molecular backbones and tilt angle. The proposed tilt‐engineered selector can aid in controlling undesired neural signals affecting vector–matrix multiplications and adjusting the switching range compatibility of an integrated synaptic device cell, significantly influencing the pattern recognition accuracy. By controlling the tilt angle, the recognition accuracy on the MNIST dataset increases from 78.65% to 86.45% and from 7.74% to 86.09% when using the OPT2/1L‐MoS2 and C8/1L‐MoS2 selector, respectively. The proposed molecular tilt configuration can be used for developing customized molecular‐scale selectors for crossbar‐array‐based artificial neural networks to improve learning while suppressing undesired neural signals.
Shear Stress‐Triggered Theranostic Nanoparticles for Piezoelectric‐Fenton‐Photodynamic Thrombolysis and Endogenous Thrombus Imaging
Authors: Cao Wenxiong , Xie Shuang , Liu Yuan , Ran Pan , Zhang Zhanlin , Fang Qibo , Li Xiaohong
Published: January 2024

Thrombus therapy is challenged by potential bleeding risk of thrombolytic agents, and external irradiation is usually needed in thrombus imaging. Herein, highly efficient theranostic platforms are designed for piezoelectric‐Fenton‐photodynamic thrombolysis and endogenous thrombus imaging in response to the elevated shear stress at the thrombus site. Piezoelectric tetragonal barium titanate (tBT) nanoparticles (NPs) are coated with Fe3+‐coordinated metal‐organic frameworks (MOFs), followed by inoculation of chlorin e6‐luminol conjugates and heparin absorption to obtain theranostic tBT@MOFCL/Hep NPs. Shear stress‐induced piezopotential on NPs accelerates Fe3+/Fe2+ transformation to deplete MOF layers, activates Fenton reaction and produces reactive oxidative species (ROS) for non‐pharmacological thrombolysis. In the meantime, the site‐specific ROS generation oxidizes luminol and the chemiluminescent resonance energy transfer with chlorin e6 generates red fluorescence for thrombus imaging without using external light irradiation. After intravenous injection into a carotid artery thrombosis model, the heparin‐mediated thrombus targeting yields 6.5‐fold higher luminescent intensity at the thrombus site. Thrombi in the carotid arteries are almost completely dissolved with integration of piezoelectric dynamic therapy, piezopotential‐enhanced Fenton reaction, and chemiluminescence‐excited photodynamic therapy, while causing no haematologic and histopathologic abnormality. This study demonstrates a concise strategy to generate shear stress‐responsive built‐in piezoelectric potentials, site‐specific non‐pharmacological thrombolysis, self‐illuminating, and stenosis degree‐adaptable thrombus imaging.
Triboelectric Insoles with Normal‐Shear Plantar Stress Perception
Authors: Hu Songtao , Li Haoran , Lu Wenhui , Han Tianyu , Xu Youzhong , Shi Xi , Peng Zhike , Cao Xiaobao
Published: January 2024

Plantar stress perception is highly desired in sports science and medical research, with the constraint of external power supply to impede the portability and flexibility in daily life. Triboelectric nanogenerator (TENG) opens a new avenue for self‐power sensing; however, a comprehensive sensing of normal and shear plantar stress remains elusive, let alone the further exploration from a mapping perspective. Here, a TENG‐based self‐powered sensing insole is developed for a comprehensive normal‐shear plantar stress mapping among four critical positions. At each position, four TENG units with single‐electrode‐mode triboelectrification are incorporated to decouple the normal and shear stress based on asymmetrical outputs. The insole exhibits excellent static characteristics for plantar stress measurement. Also, it can dynamically capture plantar stress variations to distinguish between different states during a standing long jump, enabling sports performance evaluation and rectification. Moreover, with the assistance of artificial intelligence in signal processing, different abnormal gaits can be precisely identified by the insole, highlighting the potential for disease diagnosis and rehabilitation. To the best of the knowledge, this work is the first demonstration of a self‐powered TENG insole with a comprehensive perception of normal and shear plantar stress perception, holding promise for applications in sports science and medical research.
Proton Turnover Dominated Cascade Route for CO2 Photoreduction
Authors: Xie Zhongkai , Luo Hongyun , Xu Shengjie , Li Longhua , Shi Weidong
Published: January 2024

Photoreduction carbon dioxide (CO2) and water (H2O) into valuable chemicals is a huge potential to mitigate immoderate CO2 emissions and energy crisis. To date, tremendous attention is concentrated on the improvement of independent CO2 reduction or H2O oxidation behaviors. However, the simultaneous control of efficient electron and hole utilization is still a huge challenge due to the complex cascade redox reactions. Here, a proton turnover exists in the whole CO2 photoreduction process is discovered, which is defined as the pivot to concatenate the hole and electron behaviors. As a demonstration of the concept, the efficient activated hydrogen (*H) production centers of copper (Cu) and rapid hydrogenation centers of nickel (Ni) are coupled by an alloying strategy, and the proton turnover behaviors could be directly determined by adjustment of the molar ratios of CuxNiy. Moreover, Cu3Ni1–TiO2 exhibits the highest electron selectivity of 93.7% for methane (CH4) production with a rate of 175.9 µmol g−1 h−1, while Cu1Ni5–TiO2 reaches up to the highest carbon monoxide (CO) electron selectivity and generation rate at 84.4% and 164.6 µmol g−1 h−1, respectively. Consequently, the experimental and theoretical analysis all clarify the predominate proton turnover effect during the overall CO2 photoreduction process, which directly determines the categories and generated efficiency of C‐based products by regulating variable reaction pathways. Therefore, the revelation of the proton turnover pivot could broaden the new sights by bidirectional optimization of dynamics during the overall CO2 photoreduction system, which favors the efficient, selective, and stable photocatalytic CO2 reduction with H2O.
Ionogels: Preparation, Properties and Applications
Authors: Yan Chang‐Cun , Li Weizheng , Liu Ziyang , Zheng Sijie , Hu Yin , Zhou Yingjie , Guo Jiangna , Ou Xu , Li Qingning , Yu Jiangtao , Li Legeng , Yang Mingchen , Liu Qinbo , Yan Feng
Published: January 2024

Ionogels, composed of ionic liquids and supporting networks, possess a plethora of exceptional properties, including nonvolatility, remarkable thermal and electrochemical stability, elevated mechanical strength, as well as outstanding ionic conductivity. Based on these extraordinary characteristics, ionogels have found extensive applications in diverse fields encompassing functional materials, sensors, soft electronics, solid electrolytes, and biomedicine. In recent years, ionogels have witnessed significant advancements and emerged as a highly popular subject matter. Consequently, this review provides a comprehensive overview of the latest progress made in the realm of ionogels. The preparation methods of ionogels are initially introduced following a concise introduction. Subsequently, the properties of ionogels, encompassing mechanical properties, high and low temperature resistance, ionic conductivity, stimuli‐response properties, self‐healing properties, recyclability and their structure‐property relationships, are comprehensively discussed. Moreover, recent advancements in the utilization of ionogels in solid electrolytes, ionic skins, soft electronics, adhesions and other domains are also elaborated upon extensively. Finally, after a succinct summary, challenges and prospects regarding the future development of ionogels are thoroughly deliberated.
Moist‐Defined Polymers with Tunable Multisteady Mechano‐Responsiveness Enabled by Imine‐Coordinated Boroxine
Authors: Chen Wenbo , Zhang Kai
Published: January 2024

The mechanical properties with balanced plasticity and elasticity in hygroscopic materials offer unusual opportunities for their real‐world applications. However, current approaches for tuning their mechanical properties are severely limited by the intrinsic tie between their reversible hydroplasticity and the geometric shapes. Herein, moist‐defined biopolymers with tunable multisteady mechano‐responsiveness, thiolated cellulose 10‐undecenoyl esters cross‐linked with imine‐coordinated boroxine (TCUE‐IBs), are reported. The viscoelastic nature of polymer networks plays the key role in maintaining the geometry of materials with moist‐triggered stress adjustment under various relative humidity. Resulting hydroplasticity enabled by the dual dynamic bonds of boroxine and Schiff base allows shape‐changing on demand after binding sufficient water. Such an unusual equilibrium of plasticity and viscoelasticity within one single biobased polymer system permits unprecedented tunable multisteady mechano‐responsiveness and shape‐changing. At the same time, these mechanical features offer great prospects where water is present for geometric manipulation, such as multifunctional devices in biomedicine and environment.
Traditional Scraping (Gua Sha) Combined with Copper‐Curcumin Nanoparticle Oleogel for Accurate and Multi‐Effective Therapy of Androgenic Alopecia
Authors: Gao Jie , Weng Zhenzhen , Zhang Ze , Liu Yuanyuan , Liu Zikang , Pu Xinyue , Yu Simin , Zhong Yanhua , Bai Danmeng , Xin Hongbo , Wang Xiaolei
Published: January 2024

Androgenetic alopecia (AGA) is a prevalent systemic disease caused by diverse factors, for which effective treatments are currently limited. Herein, the oleogel (OG) containing copper‐curcumin (CuR) nanoparticles is developed, designated as CuRG, which is also combined with traditional naturopathic scraping (Gua Sha, SCR) as a multifunctional therapy for AGA. With the assistance of lipophilic OG and SCR, CuR can efficaciously penetrate the epidermal and dermal regions where most hair follicles (HFs) reside, thereby releasing curcumin (CR) and copper ions (Cu2+) subcutaneously to facilitate hair regeneration. Concomitantly, the mechanical stimulation induced by SCR promotes the formation of new blood vessels, which is conducive to reshaping the microenvironment of HFs. This study validates that the combination of CuRG and SCR is capable of systematically interfering with different pathological processes, ranging from improvement of perifollicular microenvironment (oxidative stress and insufficient vascularization), regulation of inflammatory responses to degradation of androgen receptor, thus potentiating hair growth. Compared with minoxidil, a widely used clinical drug for AGA therapy, the designed synergistic system displays augmented hair regeneration in the AGA mouse model.
A Novel Conductive Polypyrrole‐Chitosan Hydrogel Containing Human Endometrial Mesenchymal Stem Cell‐Derived Exosomes Facilitated Sustained Release for Cardiac Repair
Authors: Yan Changping , Wang Xinzhu , Wang Qi , Li Haiyan , Song Huifang , Zhou Jingli , Peng Zexu , Yin Wenjuan , Fan Xuemei , Yang Kun , Zhou Bingrui , Liang Yuxiang , Jiang Zengyu , Shi Yuwei , Zhang Sanyuan , He Sheng , Li Ren‐Ke , Xie Jun
Published: January 2024

Myocardial infarction (MI) results in cardiomyocyte necrosis and conductive system damage, leading to sudden cardiac death and heart failure. Studies have shown that conductive biomaterials can restore cardiac conduction, but cannot facilitate tissue regeneration. This study aims to add regenerative capabilities to the conductive biomaterial by incorporating human endometrial mesenchymal stem cell (hEMSC)‐derived exosomes (hEMSC‐Exo) into poly‐pyrrole‐chitosan (PPY‐CHI), to yield an injectable hydrogel that can effectively treat MI. In vitro, PPY‐CHI/hEMSC‐Exo, compared to untreated controls, PPY‐CHI, or hEMSC‐Exo alone, alleviates H2O2‐induced apoptosis and promotes tubule formation, while in vivo, PPY‐CHI/hEMSC‐Exo improves post‐MI cardiac functioning, along with counteracting against ventricular remodeling and fibrosis. All these activities are facilitated via increased epidermal growth factor (EGF)/phosphoinositide 3‐kinase (PI3K)/AKT signaling. Furthermore, the conductive properties of PPY‐CHI/hEMSC‐Exo are able to resynchronize cardiac electrical transmission to alleviate arrythmia. Overall, PPY‐CHI/hEMSC‐Exo synergistically combines the cardiac regenerative capabilities of hEMSC‐Exo with the conductive properties of PPY‐CHI to improve cardiac functioning, via promoting angiogenesis and inhibiting apoptosis, as well as resynchronizing electrical conduction, to ultimately enable more effective MI treatment. Therefore, incorporating exosomes into a conductive hydrogel provides dual benefits in terms of maintaining conductivity, along with facilitating long‐term exosome release and sustained application of their beneficial effects.
Air‐Stable Li2S Cathodes Enabled by an In Situ‐Formed Li+ Conductor for Graphite‐Li2S Pouch Cells
Authors: Qi Xiaoqun , Jin Xiaoyu , Xu Henghui , Pan Yujun , Yang Fengyi , Zhu Zhenglu , Ji Jie , Jiang Ruining , Du Haoran , Ji Yongsheng , Yang Dan , Qie Long , Huang Yunhui
Published: January 2024

Using Li2S cathodes instead of S cathodes presents an opportunity to pair them with Li‐free anodes (e.g., graphite), thereby circumventing anode‐related issues, such as poor reversibility and safety, encountered in Li‐S batteries. However, the moisture‐sensitive nature of Li2S causes the release of hazardous H2S and the formation of insulative by‐products, increasing the manufacturing difficulty and adversely affecting cathode performance. Here, Li4SnS4, a Li+ conductor that is air‐stable according to the hard–soft acid–base principle, is formed in situ and uniformly on Li2S particles because Li2S itself participates in Li4SnS4 formation. When exposed to air (20% relative humidity), the protective Li4SnS4 layer maintains its components and structure, thus contributing to the enhanced stability of the Li2S@Li4SnS4 composite. In addition, the Li4SnS4 layer can accelerate the sluggish conversion of Li2S because of its favorable interfacial charge transfer, and continuously confine lithium polysulfides owing to its integrity during electrochemical processes. A graphite‐Li2S pouch cell containing a Li2S@Li4SnS4 cathode is constructed, which shows stable cyclability with 97% capacity retention after 100 cycles. Hence, combining a desirable air‐stable Li2S cathode and a highly reversible Li‐free configuration offers potential practical applications of graphite‐Li2S full cells.
Strategies for the Nuclear Delivery of Metal Complexes to Cancer Cells
Authors: Huynh Marie , Vinck Robin , Gibert Benjamin , Gasser Gilles
Published: January 2024

The nucleus is an essential organelle for the function of cells. It holds most of the genetic material and plays a crucial role in the regulation of cell growth and proliferation. Since many antitumoral therapies target nucleic acids to induce cell death, tumor‐specific nuclear drug delivery could potentiate therapeutic effects and prevent potential off‐target side effects on healthy tissue. Due to their great structural variety, good biocompatibility, and unique physico‐chemical properties, organometallic complexes and other metal‐based compounds have sparked great interest as promising anticancer agents. In this review, strategies for specific nuclear delivery of metal complexes are summarized and discussed to highlight crucial parameters to consider for the design of new metal complexes as anticancer drug candidates. Moreover, the existing opportunities and challenges of tumor‐specific, nucleus‐targeting metal complexes are emphasized to outline some new perspectives and help in the design of new cancer treatments.
Broken Inversion Symmetry in Van Der Waals Topological Ferromagnetic Metal Iron Germanium Telluride
Authors: Zhang Kai‐Xuan , Ju Hwiin , Kim Hyuncheol , Cui Jingyuan , Keum Jihoon , Park Je‐Geun , Lee Jong Seok
Published: January 2024

Inversion symmetry breaking is critical for many quantum effects and fundamental for spin‐orbit torque, which is crucial for next‐generation spintronics. Recently, a novel type of gigantic intrinsic spin‐orbit torque is established in the topological van der Waals (vdW) magnet iron germanium telluride. However, it remains a puzzle because no clear evidence exists for interlayer inversion symmetry breaking. Here, the definitive evidence of broken inversion symmetry in iron germanium telluride directly measured by the second harmonic generation (SHG) technique is reported. The data show that the crystal symmetry reduces from centrosymmetric P63/mmc to noncentrosymmetric polar P3m1 space group, giving the threefold SHG pattern with dominant out‐of‐plane polarization. Additionally, the SHG response evolves from an isotropic pattern to a sharp threefold symmetry upon increasing Fe deficiency, mainly due to the transition from random defects to ordered Fe vacancies. Such SHG response is robust against temperature, ensuring unaltered crystalline symmetries above and below the ferromagnetic transition temperature. These findings add crucial new information to the understanding of this interesting vdW metal, iron germanium telluride: band topology, intrinsic spin‐orbit torque, and topological vdW polar metal states.
Breaking the Built‐In Electric Field Barrier in p–n Heterojunction for Self‐Powered, Wavelength Distinguishable Photoelectrochemical Photodetectors: Toward Low Power Consumption and Secure Underwater Wireless Sensor Network
Authors: Fathabadi Milad , Yin Yangyuan , Li Shichen , Zhao Songrui
Published: January 2024

Self‐powered, light wavelength distinguishable photodetectors (PDs) are appealing components to build a robust, secure, and low energy consumption underwater wireless sensor network (UWSN). However, achieving such devices is extremely difficult even today. In this context, the first self‐powered, light wavelength distinguishable PDs with photoelectrochemical (PEC) principles and using tunnel junction (TJ) to overcome the technical hurdles for self‐powered, light wavelength distinguishable PEC‐PDs with p–n junction working electrode is reported. For such devices, a single photoelectrode is used, that is, one photoelectrode is able to distinguish different light wavelengths without using any external electrical power, and they are able to distinguish light wavelengths in both the ultraviolet (UV) and blue wavelength ranges. High responsivities reaching mA/W range and ultrafast response time with less than 10 ms are achieved in self‐powered operation mode. Moreover, such devices are able to operate not only in acidic but also in NaCl electrolyte, making them potentially attractive for applications in ocean environment. In the end, it is demonstrated that leveraging such PEC‐PDs, excellent data security can be achieved in the data communication mimicking that in an UWSN in ocean environment. This study not only represents a breakthrough in PDs, but also significantly advances the development of UWSNs, especially for ocean environment.
Ultra‐Broadband Organic THz Generators: Influence of Substituents on THz Phonon Vibrations in Phenolic Parallel‐Type Cation–Anion Assembly
Authors: Lee Chae‐Won , Puc Uros , Kim Jongtaek , Jazbinsek Mojca , Kwon O‐Pil
Published: January 2024

Organic terahertz (THz) crystals consist of polar molecules with various functional substituents, resulting in numerous molecular phonon vibrations in the THz frequency range. However, the effect of incorporating substituents into organic THz crystals on the resulting THz absorption is rather an unexplored area. In this work, by choosing an appropriate model system consisting of two benchmark organic nonlinear optical crystals, exhibiting an identical type of phenolic cation–anion assembly but different substituents, their ultra‐broadband THz wave generation characteristics are demonstrated and investigated. Compared to the unsubstituted crystals, the substituted crystals possess one more methoxy substituent on highly polar cationic chromophores. Their vibrational modes and THz absorption characteristics are investigated theoretically by periodic density functional theory and experimentally by ultra‐broadband THz spectroscopy up to 12 THz. In phenolic parallel‐type cation–anion assembled organic THz crystals, the existence of a methoxy substituent differently influences the molecular vibrations in low and high THz frequency ranges. In the lower THz frequency range, the unsubstituted crystals exhibit additional strong entire molecular vibrations, the so‐called cation‐on‐cation slipping vibrations, which do not exist in the substituted crystals. In contrast, the methoxy substituent leads to additional strong intramolecular vibrations in the higher THz frequency range.
A Review on Reconfigurable Metalenses Revolutionizing Flat Optics
Authors: Khonina Svetlana Nikolaevna , Butt Muhammad Ali , Kazanskiy Nikolay Lvovich
Published: January 2024

Metalenses (MLs), representing a groundbreaking paradigm shift within the realm of optics, have ushered in a transformative era in the ability to manipulate and harness the power of light. Diverging from the conventional approach reliant on curved surfaces to bend light, MLs harness intricate arrays of minuscule nanostructures to exert precise control over the phase and amplitude of incident light waves. This revolutionary technology bestows a plethora of advantages, including the creation of ultra‐compact optical systems, the enhancement of focusing capabilities to unprecedented levels, and the capability to rectify optical aberrations in a significantly thinner and more lightweight form factor. MLs have discovered a multitude of applications spanning diverse fields, from imaging and photography to augmenting reality and refining medical devices. They stand as a beacon of hope for reshaping the landscape of optical systems, courtesy of their remarkable adaptability and exceptional performance. As the evolution of MLs forges ahead, they hold immense potential to transcend the boundaries of what can be accomplished in the domain of light‐based technologies. This review presents the recent advances in reconfigurable MLs and their applicability to imaging systems.
Observation of Magnetic Quadrupole Endowed Helical Dichroism in Artificial Propeller Meta‐Molecules
Authors: Ji Chang‐Yin , Xu Shibo , Liang Qinghua , Zhang Xiaochen , Hong Xiaorong , Wang Yang , Li Xiaowei , Jiang Lan , Wang Yeliang , Ni Jincheng , Wu Dong , Li Jiafang
Published: January 2024

This study demonstrates that the magnetic quadrupole (MQ) can make an indispensable contribution to helical dichroism (HD), which is distinct from HD caused by electric quadrupole (EQ). Specifically, the established multipole expansion theory of the light–matter interaction reveals that EQ‐induced HD belongs to the pure electric dipole–quadrupole (E1‐E2) excitation, while newly discovered MQ‐induced HD belongs to the pure magnetic dipole‐quadrupole (M1‐M2) excitation. Metallic propeller meta‐molecules are used to elaborate on this novel physical mechanism and demonstrate that HD can be significantly enhanced and flexibly tuned by increasing stereo twist of propeller meta‐molecules or slightly focusing the linearly polarized vortex beam to improve the orbital angular momentum number. Importantly, the aforementioned intriguing phenomena are validated by fabricating stereo twisted propeller meta‐molecules via nano‐kirigami method. The findings reveal a paradigm‐shift approach to manipulate the chiroptical response of a single metallic nanostructure via photonic orbital angular moment, opening prospects for optical encryption, communication, next‐generation chiroptical spectroscopy, and chiral vortex optical devices.
A Paramagnetic Metal‐Organic Framework Enhances Mild Magnetic Hyperthermia Therapy by Downregulating Heat Shock Proteins and Promoting Ferroptosis via Aggravation of Two‐Way Regulated Redox Dyshomeostasis
Authors: Wang Yi , Chen Zelong , Li Jiahui , Wen Yafei , Li Jiaxuan , Lv Yinghua , Pei Zhichao , Pei Yuxin
Published: January 2024

Mild magnetic hyperthermia therapy (MMHT) holds great potential in treating deep‐seated tumors, but its efficacy is impaired by the upregulation of heat shock proteins (HSPs) during the treatment process. Herein, Lac‐FcMOF, a lactose derivative (Lac‐NH2) modified paramagnetic metal‐organic framework (FcMOF) with magnetic hyperthermia property and thermal stability, has been developed to enhance MMHT therapeutic efficacy. In vitro studies showed that Lac‐FcMOF aggravates two‐way regulated redox dyshomeostasis (RDH) via magnetothermal‐accelerated ferricenium ions‐mediated consumption of glutathione and ferrocene‐catalyzed generation of ∙OH to induce oxidative damage and inhibit heat shock protein 70 (HSP70) synthesis, thus significantly enhancing the anti‐cancer efficacy of MMHT. Aggravated RDH promotes glutathione peroxidase 4 inactivation and lipid peroxidation to promote ferroptosis, which further synergizes with MMHT. H22‐tumor‐bearing mice treated with Lac‐FcMOF under alternating magnetic field (AMF) demonstrated a 90.4% inhibition of tumor growth. This work therefore provides a new strategy for the simple construction of a magnetic hyperthermia agent that enables efficient MMHT by downregulating HSPs and promoting ferroptosis through the aggravation of two‐way regulated RDH.
A Silver‐Induced Absorption Red‐Shifted Dual‐Targeted Nanodiagnosis‐Treatment Agent for NIR‐II Photoacoustic Imaging‐Guided Photothermal and ROS Simultaneously Enhanced Immune Checkpoint Blockade Antitumor Therapy
Authors: Bai Yulong , Hua Jing , Zhao Jingjin , Wang Shulong , Huang Mengjiao , Wang Yang , Luo Yanni , Zhao Shulin , Liang Hong
Published: January 2024

Tumor metastasis remains a leading factor in the failure of cancer treatments and patient mortality. To address this, a silver‐induced absorption red‐shifted core‐shell nano‐particle is developed, and surface‐modified with triphenylphosphonium bromide (TPP) and hyaluronic acid (HA) to obtain a novel nanodiagnosis‐treatment agent (Ag@CuS‐TPP@HA). This diagnosis‐treatment agent can dual‐targets cancer cells and mitochondria, and exhibits maximal light absorption at 1064 nm, thereby enhancing nesr‐infrared II (NIR‐II) photoacoustic (PA) signal and photothermal effects under 1064 nm laser irradiation. Additionally, the silver in Ag@CuS‐TPP@HA can catalyze the Fenton‐like reactions with H2O2 in the tumor tissue, yielding reactive oxygen species (ROS). The ROS production, coupled with enhanced photothermal effects, instigates immunogenic cell death (ICD), leading to a substantial release of tumor‐associated antigens (TAAs) and damage‐associated molecular patterns, which have improved the tumor immune suppression microenvironment and boosting immune checkpoint blockade therapy, thus stimulating a systemic antitumor immune response. Hence, Ag@CuS‐TPP@HA, as a cancer diagnostic‐treatment agent, not only accomplishes targeted the NIR‐II PA imaging of tumor tissue and addresses the challenge of accurate diagnosis of deep cancer tissue in vivo, but it also leverages ROS/photothermal therapy to enhance immune checkpoint blockade, thereby eliminating primary tumors and effectively inhibiting distant tumor growth.
One Dianionic Luminophore with Three Coordination Modes Binding Four Different Metals: Toward Unexpectedly Phosphorescent Transition Metal Complexes
Authors: Kirse Thomas M. , Maisuls Iván , Spierling Leander , Hepp Alexander , Kösters Jutta , Strassert Cristian A.
Published: January 2024

This work reports on a battery of coordination compounds featuring a versatile dianionic luminophore adopting three different coordination modes (mono, bi, and tridentate) while chelating Pd(II), Pt(II), Au(III), and Hg(II) centers. An in‐depth structural characterization of the ligand precursor (H2L) and six transition metal complexes ([HLPdCNtBu], [LPtCl], [LPtCNtBu], [LPtCNPhen], [HLHgCl], and [LAuCl]) is presented. The influence of the cations and coordination modes of the luminophore and co‐ligands on the photophysical properties (including photoluminescence quantum yields (ΦL), excited state lifetimes (τ), and average (non‐)radiative rate constants) are evaluated at various temperatures in different phases. Five complexes show interesting photophysical properties at room temperature (RT) in solution. Embedment in frozen glassy matrices at 77 K significantly boosts their luminescence by suppressing radiationless deactivation paths. Thus, the Pt(II)‐based compounds provide the highest efficiencies, with slight variations upon exchange of the ancillary ligand. In the case of [HLPdCNtBu], both ΦL and τ increase over 30‐fold as compared to RT. Furthermore, the Hg(II) complex achieves, for the first time in its class, a ΦL exceeding 60% and millisecond‐range lifetimes. This demonstrates that a judicious ligand design can pave the way toward versatile coordination compounds with tunable excited state properties.
Unraveling Ros Conversion Through Enhanced Enzyme‐Like Activity with Copper‐Doped Cerium Oxide for Tumor Nanocatalytic Therapy
Authors: Gu Zhengxiang , Zhong Dan , Hou Xingyu , Wei Xuelian , Liu Caikun , Zhang Yechuan , Duan Zhenyu , Gu Zhongwei , Gong Qiyong , Luo Kui
Published: January 2024

Nanozyme catalytic therapy for cancer treatments has become one of the heated topics, and the therapeutic efficacy is highly correlated with their catalytic efficiency. In this work, three copper‐doped CeO2 supports with various structures as well as crystal facets are developed to realize dual enzyme‐mimic catalytic activities, that is superoxide dismutase (SOD) to reduce superoxide radicals to H2O2 and peroxidase (POD) to transform H2O2 to ∙OH. The wire‐shaped CeO2/Cu‐W has the richest surface oxygen vacancies, and a low level of oxygen vacancy (Vo) formation energy, which allows for the elimination of intracellular reactive oxygen spieces (ROS) and continuous transformation to ∙OH with cascade reaction. Moreover, the wire‐shaped CeO2/Cu‐W displays the highest toxic ∙OH production capacity in an acidic intracellular environment, inducing breast cancer cell death and pro‐apoptotic autophagy. Therefore, wire‐shaped CeO2/Cu nanoparticles as an artificial enzyme system can have great potential in the intervention of intracellular ROS in cancer cells, achieving efficacious nanocatalytic therapy.
An Ideal Molecular Construction Strategy for Ultra‐Narrow‐Band Deep‐Blue Emitters: Balancing Bathochromic‐Shift Emission, Spectral Narrowing, and Aggregation Suppression
Authors: Luo Xiaofeng , Jin Qian , Du Mingxu , Wang Dong , Duan Lian , Zhang Yuewei
Published: January 2024

Narrowband emissive multiple resonance (MR) emitters promise high efficiency and stability in deep‐blue organic light‐emitting diodes (OLEDs). However, the construction of ideal ultra‐narrow‐band deep‐blue MR emitters still faces formidable challenges, especially in balancing bathochromic‐shift emission, spectral narrowing, and aggregation suppression. Here, DICz is chosen, which possesses the smallest full‐width‐at‐half‐maximum (FWHM) in MR structures, as the core and solved the above issue by tuning its peripheral substitution sites. The 1‐substituted molecule Cz‐DICz is able to show a bright deep‐blue emission with a peak at 457 nm, an extremely small FWHM of 14 nm, and a CIE coordinate of (0.14, 0.08) in solution. The corresponding OLEDs exhibit high maximum external quantum efficiencies of 22.1%–25.6% and identical small FWHMs of 18 nm over the practical mass‐production concentration range (1–4 wt.%). To the best of the knowledge, 14 and 18 nm are currently the smallest FWHM values for deep‐blue MR emitters with similar emission maxima under photoluminescence and electroluminescence conditions, respectively. These discoveries will help drive the development of high‐performance narrowband deep‐blue emitters and bring about a revolution in OLED industry.
Scalable High‐Permittivity Polyimide Copolymer with Ultrahigh High‐Temperature Capacitive Performance Enabled by Molecular Engineering
Authors: Dong Jiufeng , Li Li , Niu Yujuan , Pan Zizhao , Pan Yupeng , Sun Liang , Tan Li , Liu Yuqi , Xu Xinwei , Guo Xugang , Wang Qing , Wang Hong
Published: January 2024

Polymer capacitors are essential components of advanced electronic and power systems. However, the deficient high‐temperature capacitive performance of polymer dielectrics fails to meet the demand for harsh condition applications, due to the mutually restrictive relationships in permittivity (εr), glass transition temperature (Tg), and bandgap (Eg). Here, a modularized molecular engineering strategy is reported to enhance the high‐temperature capacitive performance of polymer dielectrics. First, the potential influences of multiple structural units on εr, Tg, and Eg of polymers are elucidated by comparing a set of polyimides (PIs). After screening out an excellent sulfonated PI with concurrently high εr (4.2), Eg (3.4 eV), and Tg (311.2 °C), a semi‐alicyclic sulfonyl‐containing PI copolymer is further synthesized that exhibits a superior discharged energy density of 4.3 J cm−3 above 90% efficiency at 200 °C and 485 MV m−1. Density functional theory calculations demonstrate that the combination of polar sulfonyl group, ether linkage, and alicyclic group in the backbones of the copolymer decouples the dipole orientation and the segmental motion of backbones, and reduces conjugation effects of aromatic groups, thereby minimizing the polarization relaxation loss and the conduction loss while retaining excellent thermal stability and high permittivity.
Boosting the Charge Density of Triboelectric Nanogenerator by Suppressing Air Breakdown and Dielectric Charge Leakage
Authors: Wang Jing , Zhang Baofeng , Zhao Zhihao , Gao Yikui , Liu Di , Liu Xiaoru , Yang Peiyuan , Guo Ziting , Wang Zhong Lin , Wang Jie
Published: January 2024

Charge generation and charge decay are two essential factors that determine the surface charge density of a triboelectric nanogenerator (TENG). However, research mainly focuses on boosting charge generation, and little attention is paid to suppressing charge decay. Here, a strategy of suppressing charge decay, including the air breakdown and dielectric charge leakage, of TENG with high surface charge density (HCD‐TENG) is proposed by utilizing a dual dielectric layer. A series of parameters of different dielectric materials are tested with the assistance of a charge excitation TENG (CE‐TENG) to reveal the relationships between charge generation, air breakdown, and dielectric charge leakage in the atmospheric environment. Further, the phenomenon of dielectric charge leakage limiting the maximum output of TENG prior to air breakdown is observed for the first time. With the simultaneous suppression of the air breakdown and dielectric charge leakage, the output of TENG is enhanced to 2.2 mC m−2. This work not only provides new insight into the performance optimization and material selection of TENG, but also provides significant guidance for obtaining high‐output TENG in the future.
F‐Doped Calcium Silicate Enabling Fast Ion Deposition Kinetics for Highly Reversible Zinc Metal Batteries
Authors: Du Hongxia , Wang Yuankun , Liu Xiaomeng , Wu Xianwen , Yan Zhenhua , Chen Jun
Published: January 2024

Aqueous zinc ion batteries (AZIBs) are subject to various unwanted side reactions, including dendrite growth, hydrogen evolution, and corrosion passivation, due to the highly active Zn anode. While constructing an artificial interface layer (AIL) can address these problems, the compromise in Zn deposition kinetics is considerable. Herein, F‐doped modified hydrated calcium silicate (F‐CSH) nanosheets are designed to enhance Zn2+ ion deposition kinetics. Combined with theoretical calculations, it is verified that the F‐doped contributes to higher interface adsorption energy with Zn metal and lower ion diffusion barrier, favoring faster charge transfer compared to non‐F‐doped counterparts. Additionally, the strong interaction between zincophilic F and Zn facilitates rapid desolvation of Zn2+ and promotes the deposition between the Zn metal and F‐CSH interphases. As a result, the F‐CSH layer maintains the stability on the Zn surface, enabling fast and reversible Zn deposition. The F‐CSH@Zn anode exhibits a long lifespan of over 2800 h at 5 mA cm−2, while running more than 2500 cycles at a ≈100% Coulombic efficiency. This work highlights the importance of constructing AIL with strong interaction with Zn2+/Zn in improving the interphase kinetics of zinc anode for realizing the stability of AZIBs.
The dynamics of PEG‐coated nanoparticles in concentrated protein solutions up to the molecular crowding range
Authors: Otto Ferdinand , Dallari Francesco , Westermeier Fabian , Wieland D. C. Florian , Parak Wolfgang J. , Lehmkühler Felix , Schulz Florian
Published: January 2024

Polymer‐coated nanoparticles are widely studied in the context of nanomedicine and it is therefore of utmost importance to understand not only how their structure but also how their colloidal dynamics are affected by physiologically relevant conditions. A characteristic feature of the cytosol of cells is the very high concentration of proteins among other matrix components, often termed macromolecular crowding. Here, the structure and colloidal dynamics of poly(ethylene glycol) (PEG)‐coated gold nanoparticles in the presence of bovine serum albumin (BSA) concentrations ranging from 0 to 265 mg/mL are studied with X‐ray photon correlation spectroscopy. For protein–nanoparticle mixtures with high BSA concentrations, comparable to intracellular levels, a significant deviation of the apparent viscosity from expectations for pure BSA solutions is found. The findings strongly indicate that the nanoscopic viscous properties of the dense protein solutions are significantly affected by the nanoparticles. At these high concentrations, the colloidal stability of the samples depends on the molecular weight of the coating PEG–ligand, whereas at lower concentrations no differences are observed.
A–D–A'–D–A type nonfused ring electron acceptors for efficient organic solar cells via synergistic molecular packing and orientation control
Authors: Wei Wenkui , Zhou Xia , Pang Shuting , Zhou Jiadong , Yuan Xiyue , Li Junyu , Chen Yuting , Pan Langheng , Xie Zengqi , Wu Hongbin , Huang Fei , Cao Yong , Duan Chunhui
Published: January 2024

Nonfused ring electron acceptors (NFREAs) are promising candidates for future commercialization of organic solar cells (OSCs) due to their simple synthesis. Still, the power conversion efficiencies (PCEs) of NFREA‐based OSCs have large room for improvement. In this work, by merging end group halogenation and side chain engineering, we developed four A–D–A'–D–A type NFREAs, which we refer to as EH‐4F, C4‐4F, EH‐4Cl, and C4‐4Cl. Single crystal X‐ray diffraction revealed that multiple intermolecular S···F interactions between cyclopentadithiophene and 5,6‐difluoro‐3‐(dicyanomethylene)indanone could cause an unfavorable dimer formation, leading to ineffective π–π stackings in EH‐4F and C4‐4F, whereas no such dimer was found in EH‐4Cl and C4‐4Cl after replacing with 5,6‐dichloro‐3‐(dicyanomethylene)indanone. Moreover, although the shorter n‐butyl side chain resulted in a closer molecular packing in C4‐4Cl, EH‐4Cl (2‐ethylhexyl substitution) with proper crystallinity exhibited enhanced face‐on orientation in thin film, which is favorable for vertical charge transport and further reducing charge recombination. As a result, a PCE of 13.0% is obtained for EH‐4Cl‐based OSC with a fill factor of 0.70. This work highlights the importance of molecular packing and orientation control toward future high‐performance A–D–A'–D–A type NFREAs.