Spatiotemporal Programmability of 3D Chiral Color Units Driven by Ink Spontaneous Diffusion toward Customized PrintingYang, Wenjie; Zheng, Chenglin; Sun, Li; Bie, Zhiying; Yue, Yuchen; Li, Xiuhong; Sun, Wentao; Ikeda, Tomiki; Wang, Jingxia; Jiang, Lei
doi: 10.1002/adma.202411988pmid: 39562166
Blue phase liquid crystals (BPLCs) have exhibited promising applications in 3D flexible displays due to their molecular‐level self‐assembled chiral structures, fast response, and tunable polarized colors. However, there remain challenges for spatiotemporal programming of 3D chiral color units for BPLC dynamic patterning. Herein, the programmable temporal evolution of micrometer‐scale color units and spatial configuration switch of chiral modes are achieved by spontaneous ink diffusion‐driven asymmetric lattice deformation in dual‐chiral polymer‐templated blue phases. Custom‐printed colorful patterns are designed by machine learning‐assisted parameter optimization, which displays programmable multidimensional encrypted information that incorporates temporal evolving colors (wavelength), spatial distribution (depth), chiral modes (L/R). The quantitative relationship between ink diffusion kinetics and blue‐phase dynamic 3D structural optics is established by in situ characterization, finite element analysis, and mathematical geometry modeling. This work provides insights into the microgeometric manipulation of 3D chiral color of BPLCs in the application of information security and self‐adaptive indicators.
Photoreceptor‐Like Signal Transduction Between Polymer‐Based ProtocellsHeuberger, Lukas; Korpidou, Maria; Guinart, Ainoa; Doellerer, Daniel; López, Diego Monserrat; Schoenenberger, Cora‐Ann; Milinkovic, Daela; Lörtscher, Emanuel; Feringa, Ben L.; Palivan, Cornelia G.
doi: 10.1002/adma.202413981pmid: 39491508
Deciphering inter‐ and intracellular signaling pathways is pivotal for understanding the intricate communication networks that orchestrate life's dynamics. Communication models involving bottom‐up construction of protocells are emerging but often lack specialized compartments sufficiently robust and hierarchically organized to perform spatiotemporally defined signaling. Here, the modular construction of communicating polymer‐based protocells designed to mimic the transduction of information in retinal photoreceptors is presented. Microfluidics is used to generate polymeric protocells subcompartmentalized by specialized artificial organelles. In one protocell population, light triggers artificial organelles with membrane‐embedded photoresponsive rotary molecular motors to set off a sequence of reactions starting with the release of encapsulated signaling molecules into the lumen. Intercellular communication is mediated by signal transfer across membranes to protocells containing catalytic artificial organelles as subcompartments, whose signal conversion can be modulated by environmental calcium. Signal propagation also requires selective permeability of the diverse compartments. By segregating artificial organelles in distinct protocells, a sequential chain of reactions mediating intercellular communication is created that is further modulated by adding extracellular messengers. This connective behavior offers the potential for a deeper understanding of signaling pathways and faster integration of proto‐ and living cells, with the unique advantage of controlling each step by bio‐relevant signals.
Atomic‐Level Electric Polarization in Entropy‐Driven Perovskites for Boosting Dielectric ResponseXiong, Xuhui; Liu, Zhengwang; Zhang, Ruixuan; Yang, Liting; Liang, Guisheng; Zhou, Xiaodi; Li, Bangxin; Zhang, Huibin; Lv, Hualiang; Che, Renchao
doi: 10.1002/adma.202415351pmid: 39610164
Dielectric oxides with robust relaxation responses are fundamental for electronic devices utilized in energy absorption, conversion, and storage. However, the structural origins governing the dielectric response remain elusive due to the involvement of atomically complex compositional and structural environments. Herein, configurational entropy is introduced as a regulatory factor to precisely control the structural heterogeneity in representative perovskite dielectric oxides. Through advanced structural and electric field visualization studies, a novel quantitative relationship is established between atomic‐level structural disorder‐induced electric field polarization and macroscopic dielectric properties. The results indicate that the degree of atomic delocalization in perovskite oxides exhibits a near‐parabolic trend with increasing entropy, reaching a maximum in medium‐entropy perovskite. Correspondingly, the atomic electric field vectors display significant asymmetrical distribution, thus greatly enhancing angstrom‐scale electric field polarization. Then, it is experimentally proven that entropy‐driven electric polarization can improve the dielectric relaxation behavior characterized by broader frequency and stronger intensity of electromagnetic energy absorption, with improvements of approximately 160% and 413% compared to structurally homogeneous control. This study unveils the quantitative correlation between angstrom‐scale electric field polarization and dielectric response in perovskite oxides, offering a novel perspective for exploring the structure–property relationship in dielectric materials.
Fabrication of Ultrahigh‐Loading Dual Copper Sites in Nitrogen‐Doped Porous Carbons Boosting Electroreduction of CO2 to C2H4 Under Neutral ConditionsHeng, Jin‐Meng; Zhu, Hao‐Lin; Zhao, Zhen‐Hua; Liao, Pei‐Qin; Chen, Xiao‐Ming
doi: 10.1002/adma.202415101pmid: 39548939
Synthesis of high‐loading atomic‐level dispersed catalysts for highly efficient electrochemical CO2 reduction reaction (eCO2RR) to ethylene (C2H4) in neutral electrolyte remain challenging tasks. To address common aggregation issues, a host‐guest strategy is employed, by using a metal‐azolate framework (MAF‐4) with nanocages as the host and a dinuclear Cu(I) complex as the guest, to form precursors for pyrolysis into a series of nitrogen‐doped porous carbons (NPCs) with varying loadings of dual copper sites, namely NPCMAF‐4‐Cu2‐21 (21.2 wt%), NPCMAF‐4‐Cu2‐11 (10.6 wt%), and NPCMAF‐4‐Cu2‐7 (6.9 wt%). Interestingly, as the loading of dual copper sites increased from 6.9 to 21.2 wt%, the partial current density for eCO2RR to yield C2H4 also gradually increased from 38.7 to 93.6 mA cm−2. In a 0.1 m KHCO3 electrolyte, at −1.4 V versus reversible hydrogen electrode (vs. RHE), NPCMAF‐4‐Cu2‐21 exhibits the excellent performance with a Faradaic efficiency of 52% and a current density of 180 mA cm−2. Such performance can be attributed to the presence of ultrahigh‐loading dual copper sites, which promotes C─C coupling and the formation of C2 products. The findings demonstrate the confinement effect of MAF‐4 with nanocages is conducive to the preparation of high‐loading atomic‐level catalysts.
NIR‐II AIE Liposomes for Boosting Type‐I Photodynamic and Mild‐Temperature Photothermal Therapy in Breast Cancer TreatmentZhen, Shijie; Xu, Zhe; Suo, Meng; Zhang, Teng; Lyu, Meng; Li, Tianwei; Zhang, Tianfu; Li, Meijing; Zhao, Zujin; Tang, Ben Zhong
doi: 10.1002/adma.202411133pmid: 39600034
Phototheranositcs has recently aroused extreme attention due to its exceptional advantages. However, the poor photothernostic efficiency, limited penetration depth, strong oxygen‐dependence, and inevitable damage to normal tissue of conventional photothernostic materials severely hindered their total theranostic efficacy. Herein, a series of near‐infrared second (NIR‐II) photosensitizers (PSs) featuring aggregation‐induced emission (AIE), NIR‐II fluorescence imaging (FLI), type I photodynamic therapy (PDT) and mild‐temperature photothermal therapy (PTT) are constructed through dual‐strategy methods combining donor group engineering and fluorination engineering. Profiting from sufficient molecular rotors and high electronegativity of fluorine, the developed 2‐(2‐((5‐(4‐((4‐(diphenylamino)phenyl)(phenyl)amino)phenyl)thiophen‐2‐yl)methylene)‐5,6‐difluoro‐3‐oxo‐2,3‐dihydro‐1H‐inden‐1‐ylidene)malononitrile (BTS‐2F) and 2‐(2‐((5‐(4‐(bis(4‐(diphenylamino)phenyl)amino)phenyl)thiophen‐2‐yl)methylene)‐5,6‐difluoro‐3‐oxo‐2,3‐dihydro‐1H‐inden‐1‐ylidene)malononitrile (TTS‐2F) are endowed with NIR‐II AIE property, high radical reactive oxygen species (ROS) generation ability and mild‐temperature photothermal conversion. Through thin film hydration method, the prepared BTS‐2F and TTS‐2F loaded liposomes exhibit significant NIR‐II FLI and improved type‐I PDT/mild‐temperature PTT therapy under laser irradiation both in vitro and orthotopic 4T1 mice models.
A Sucker‐Reactor Polyoxometalate Assembled Superstructures for Efficient Photocatalytic Nitrogen FixationGong, Xiangjiao; Teng, Wenkai; Liu, Wei; Xiao, Hang; Li, He; Ou, Honghui; Yang, Guidong
doi: 10.1002/adma.202412924pmid: 39533474
Designing a reaction system that integrates reactant capture and transformation in an artificial photosynthesis system to achieve high reaction efficiency remains challenging. Here, an ionic liquid (IL) ‐polyoxometalate (POM) superstructure photocatalyst (P2HPMo) is reported, where the anisotropy of the superstructure is allowed by adjusting the alkyl chain lengths of ILs. Experimental data and theoretical simulation show that ILs and POM serve as the “sucker” and “reactor” of the reaction system to capture and transform the reactants, respectively. In particular, the addition of quaternary phosphorous IL cations is not only conducive to the adsorption of N2 but also effectively promotes the activation of N2 by manipulating the energy band and electronic structure. Consequently, the synthesized P2HPMo exhibits an ammonia synthesis rate of 98 µmol·gcat−1·h−1, which is one of the highest values available in a sacrificial agent‐free system.
Achieving Significant Multilevel Modulation in Superior‐quality Organic Spin ValveZhang, Cheng; Ding, Shuaishuai; Tian, Yuan; Ke, Yunzhe; Wang, Jian‐Tao; Wang, Jing; Hu, Fengxia; Hu, Wenping; Shen, Baogen
doi: 10.1002/adma.202416629pmid: 39588899
Organic semiconductors, characterized by their exceptionally long spin relaxation times (≈ms) and unique spinterface effects, are considered game‐changers in spintronics. However, achieving high‐performance and wide‐range tunable magnetoresistance (MR) in organic spintronic devices remains challenging, severely limiting the development of organic spintronics. This work combines straintronic multiferroic heterostructures with organic spin valve (OSV) to develop a three‐terminal OSV device with a gate structure. The device exhibits a record‐high MR ratio of 281% which 10 times higher than the average in polymer systems. More importantly, this work can perform multilevel writing operations on the device using gate voltages and create at least 10 stable spin‐dependent working states within a single device. Both experiments and theoretical calculations confirm such an extraordinary tunability range originates from the synergistic effects of strain and charge accumulation that amplified by the spinterface. This study demonstrates the potential of OSV systems for efficient spin manipulation and highlights the spinterface as an ideal platform for amplifying spin effects for next‐generation spintronic devices.
An Ultra‐Miniaturized Fiber Humidity Sensor Based on Near‐Parallel Ion Pathways Induced Efficient Water−Electricity ConversionZhang, Qixiang; Ren, Ziqi; Jia, Peixue; Shi, Junjie; Yin, Jianyu; Lei, Dandan; Gao, Yihua; Liu, Nishuang
doi: 10.1002/adma.202411558pmid: 39558772
Humidity sensors are vital for ambient monitoring, but existing sensors focus on moisture absorption, overlooking the indispensable role of ion channels in the water‐electricity conversion process. Here, an ultra‐miniaturized fiber humidity (MFH) sensor based on near‐parallel ion pathways is presented. The well‐designed nanochannels significantly facilitate ion transport due to the stable charge distribution and the confined ions migration within near‐parallel nanostructure, which improves the water‐electricity conversion efficiency of moisture‐sensitive fibers. Optimized nanochannels enable the MFH sensor to improve the response/recovery speed by ≈5 times compared to the disordered nanochannels. Additionally, the MFH sensor can be woven for ultra‐miniaturization (0.50 mm2), which is much smaller than current sensors. Therefore, the integrated MFH sensor array demonstrated exceptionally high spatial resolution (sensor density of 1 mm−1), highlighting its potential in flexible wearables. This work provides new optimization strategies and assembly means for designing the high‐performance humidity sensors of the next generation.