List of Edited Articles
Recently published articles handled as primary editor:
Recently published articles handled as primary editor:
Yuan Zhong, Jiangwei Zhang, Tingting Li, Wenwu Xu, Qiaofeng Yao, Min Lu, Xue Bai, Zhennan Wu, Jianping Xie, Yu Zhang
Suppression of kernel vibrations by layer-by-layer ligand engineering boosts photoluminescence efficiency of gold nanoclusters (Journal Article)
In: Nature Communications, vol. 14, no. 658, 2023, (The photoluminescence of gold nanoclusters is affected by low-frequency acoustic vibrations. Here, the authors demonstrate that layer-by-layer ligand engineering can suppress such structural vibrations to achieve brighter emissions.).
The restriction of structural vibration has assumed great importance in attaining bright emission of luminescent metal nanoclusters (NCs), where tremendous efforts are devoted to manipulating the surface landscape yet remain challenges for modulation of the structural vibration of the metal kernel. Here, we report efficient suppression of kernel vibration achieving enhancement in emission intensity, by rigidifying the surface of metal NCs and propagating as-developed strains into the metal core. Specifically, a layer-by-layer triple-ligands surface engineering is deployed to allow the solution-phase Au NCs with strong metal core-dictated fluorescence, up to the high absolute quantum yields of 90.3 ± 3.5%. The as-rigidified surface imposed by synergistic supramolecular interactions greatly influences the low-frequency acoustic vibration of the metal kernel, resulting in a subtle change in vibration frequency but a reduction in amplitude of oscillation. This scenario therewith impedes the non-radiative relaxation of electron dynamics, rendering the Au NCs with strong emission. The presented study exemplifies the linkage between surface chemistry and core-state emission of metal NCs, and proposes a strategy for brighter emitting metal NCs by regulating their interior metal core-involved motion.
Yong Chen, Satoshi Takeya, Amadeu K. Sum
Topological dual and extended relations between networks of clathrate hydrates and Frank-Kasper phases (Journal Article)
In: Nature Communications, vol. 14, no. 596, 2023, (Topological dual and extended relations between networks of clathrate hydrates and Frank-Kasper phases Clathrate hydrates are topological duals of Frank-Kasper phases. Here, the authors employ MD simulations to provide an alternative way to explore the intrinsic structural relationships of H-bonded networks of clathrate hydrates and other unrelated ordered materials.).
Clathrate hydrates are a class of ordered structures that are stabilized via the delicate balance of hydrophobic interactions between water and guest molecules, of which the space-filling network of hydrogen-bonded (H-bonded) water molecules are closely related to tetrahedrally close-packed structures, known as Frank-Kasper (FK) phases. Here we report an alternative way to understand the intricate structures of clathrate hydrates, which unveils the diverse crystalline H-bonded networks that can be generated via assembly of one common building block. In addition to the intrinsic relations and pathways linking these crystals, we further illustrate the rich structural possibilities of clathrate hydrates. Given that the topological dual relations between networks of clathrate hydrates and tetrahedral close-packed structures, the descriptors presented for clathrate hydrates can be directly extended to other ordered materials for a more thorough understanding of their nucleation, phases transition, and co-existence mechanisms.
Ahmed A. Agiza, Kady Oakley, Jacob K. Rosenstein, Brenda M. Rubenstein, Eunsuk Kim, Marc Riedel, Sherief Reda
Digital circuits and neural networks based on acid-base chemistry implemented by robotic fluid handling (Journal Article)
In: Nature Communications, vol. 14, no. 496, 2023, (The complementarity of acids and bases is a fundamental chemical concept. Here, the authors use simple acid-base chemistry to encode binary information and perform information processing including digital circuits and neural networks using robotic fluid handling.).
Acid-base reactions are ubiquitous, easy to prepare, and execute without sophisticated equipment. Acids and bases are also inherently complementary and naturally map to a universal representation of “0” and “1.” Here, we propose how to leverage acids, bases, and their reactions to encode binary information and perform information processing based upon the majority and negation operations. These operations form a functionally complete set that we use to implement more complex computations such as digital circuits and neural networks. We present the building blocks needed to build complete digital circuits using acids and bases for dual-rail encoding data values as complementary pairs, including a set of primitive logic functions that are widely applicable to molecular computation. We demonstrate how to implement neural network classifiers and some classes of digital circuits with acid-base reactions orchestrated by a robotic fluid handling device. We validate the neural network experimentally on a number of images with different formats, resulting in a perfect match to the in-silico classifier. Additionally, the simulation of our acid-base classifier matches the results of the in-silico classifier with approximately 99% similarity.
Jeonghee Yeom, Ayoung Choe, Jiyun Lee, Jeeyoon Kim, Jinyoung Kimand Seung Hak Ohand Cheolhong Park, Sangyun Naand Young-Eun Shinand Youngoh Lee, Yun Goo Ro, Sang Kyu Kwak, Hyunhyub Ko
Photosensitive ion channels in layered MXene membranes modified with plasmonic gold nanostars and cellulose nanofibers (Journal Article)
In: Nature Communications, vol. 14, no. 359, 2023, (Artificial ion channels are in demand for ionotronic devices. Here, the authors use layered MXene membranes modified with plasmonic gold nanostars and cellulose nanofibers to convert a thermal gradient into an ion current for photosensitive ion channeling.).
Ion channels transduce external stimuli into ion-transport-mediated signaling, which has received considerable attention in diverse fields such as sensors, energy harvesting devices, and desalination membrane. In this work, we present a photosensitive ion channel based on plasmonic gold nanostars (AuNSs) and cellulose nanofibers (CNFs) embedded in layered MXene nanosheets. The MXene/AuNS/CNF (MAC) membrane provides subnanometer-sized ionic pathways for light-sensitive cationic flow. When the MAC nanochannel is exposed to NIR light, a photothermal gradient is formed, which induces directional photothermo-osmotic flow of nanoconfined electrolyte against the thermal gradient and produces a net ionic current. MAC membrane exhibits enhanced photothermal current compared with pristine MXene, which is attributed to the combined photothermal effects of plasmonic AuNSs and MXene and the widened interspacing of the MAC composite via the hydrophilic nanofibrils. The MAC composite membranes are envisioned to be applied in flexible ionic channels with ionogels and light-controlled ionic circuits.
Michael Moret, Irene Pachon Angona, Leandro Cotos, Shen Yan, Kenneth Atz, Cyrill Brunner, Martin Baumgartner, Francesca Grisoni, Gisbert Schneider
Leveraging molecular structure and bioactivity with chemical language models for de novo drug design (Journal Article)
In: Nature Communications, vol. 14, no. 114, 2023, (Generative Deep Learning holds promise for mining the unexplored "chemical universe" for new drugs. Here, the authors demonstrate the de novo design of phosphoinositide 3-kinase gamma (PI3Kγ) inhibitors for the PI3K/Akt pathway in human tumor cells.).
Generative chemical language models (CLMs) can be used for de novo molecular structure generation by learning from a textual representation of molecules. Here, we show that hybrid CLMs can additionally leverage the bioactivity information available for the training compounds. To computationally design ligands of phosphoinositide 3-kinase gamma (PI3Kγ), a collection of virtual molecules was created with a generative CLM. This virtual compound library was refined using a CLM-based classifier for bioactivity prediction. This second hybrid CLM was pretrained with patented molecular structures and fine-tuned with known PI3Kγ ligands. Several of the computer-generated molecular designs were commercially available, enabling fast prescreening and preliminary experimental validation. A new PI3Kγ ligand with sub-micromolar activity was identified, highlighting the method’s scaffold-hopping potential. Chemical synthesis and biochemical testing of two of the top-ranked de novo designed molecules and their derivatives corroborated the model’s ability to generate PI3Kγ ligands with medium to low nanomolar activity for hit-to-lead expansion. The most potent compounds led to pronounced inhibition of PI3K-dependent Akt phosphorylation in a medulloblastoma cell model, demonstrating efficacy of PI3Kγ ligands in PI3K/Akt pathway repression in human tumor cells. The results positively advocate hybrid CLMs for virtual compound screening and activity-focused molecular design.
Yingying Jiang, Martial Duchamp, Shi Jun Ang, Hongwei Yan, Teck Leong Tan, Utkur Mirsaidov
Dynamics of the fcc-to-bcc phase transition in single-crystalline PdCu alloy nanoparticles (Journal Article)
In: Nature Communications, vol. 14, no. 104, 2023, (Phase transitions in crystals are challenging to study with atomic resolution. Here, the authors reveal that the transition from fcc to bcc occurs across a coherent interface only a few atoms wide, which serves as a precursor phase for the nucleation of the bcc phase.).
Two most common crystal structures in metals and metal alloys are body-centered cubic (bcc) and face-centered cubic (fcc) structures. The phase transitions between these structures play an important role in the production of durable and functional metal alloys. Despite their technological significance, the details of such phase transitions are largely unknown because of the challenges associated with probing these processes. Here, we describe the nanoscopic details of an fcc-to-bcc phase transition in PdCu alloy nanoparticles (NPs) using in situ heating transmission electron microscopy. Our observations reveal that the bcc phase always nucleates from the edge of the fcc NP, and then propagates across the NP by forming a distinct few-atoms-wide coherent bcc–fcc interface. Notably, this interface acts as an intermediate precursor phase for the nucleation of a bcc phase. These insights into the fcc-to-bcc phase transition are important for understanding solid − solid phase transitions in general and can help to tailor the functional properties of metals and their alloys.
Tonghan Zhao, Dejing Meng, Zhijian Hu, Wenjing Sun, Yinglu Ji, Jianlei Han, Xue Jin, Xiaochun Wu, Pengfei Duan
Enhanced chiroptic properties of nanocomposites of achiral plasmonic nanoparticles decorated with chiral dye-loaded micelles (Journal Article)
In: Nature Communications, vol. 14, no. 81, 2023, (Circularly polarized luminescent materials with large dissymmetry and efficiency are in demand. Here, the authors investigate chirality-induced spin polarization in achiral gold nanorods decorated with chiral dye-loaded micelles to enhance chiroptic activity.).
The development of circularly polarized luminescence (CPL)-active materials with both large luminescence dissymmetry factor (glum) and high emission efficiency continues to be a major challenge. Here, we present an approach to improve the overall CPL performance by integrating triplet-triplet annihila- tion-based photon upconversion (TTA-UC) with localized surface plasmon resonance. Dye-loaded chiral micelles possessing TTA-UC ability are designed and attached on the surface of achiral gold nanorods (AuNRs). The long- itudinal and transversal resonance peaks of AuNRs overlap with the absorption and emission of dye-loaded chiral micelles, respectively. Typically, 43-fold amplification of glum value accompanied by 3-fold enhancement of upcon- version are obtained simultaneously when Au@Ag nanorods are employed in the composites. More importantly, transient absorption spectra reveal a fast accumulation of spin-polarized triplet excitons in the composites. Therefore, the enhancement of chirality-induced spin polarization should be in charge of the amplification of glum value. Our design strategy suggests that combining plasmonic nanomaterials with chiral organic materials could aid in the devel- opment of chiroptical nanomaterials.
Pengwei Xiao, Zhoufan Zhang, Junjun Ge, Yalei Deng, Xufeng Chen, Jian-Rong Zhang, Zhengtao Deng, Yu Kambe, Dmitri V. Talapin, Yuanyuan Wang
Surface passivation of intensely luminescent all-inorganic nanocrystals and their direct optical patterning (Journal Article)
In: Nature Communications, vol. 14, no. 49, 2023, (All-inorganic nanocrystals are of great importance for a variety of electronic applications. Here, the authors use metal salts to remove organic ligands to obtain passivated nanocrystals with improved fluorescence yield for direct optical patterning.).
All-inorganic nanocrystals (NCs) are of great importance in a range of electronic devices. However, current all-inorganic NCs suffer from limitations in their optical properties, such as low fluorescence efficiencies. Here, we develop a general surface treatment strategy to obtain intensely luminescent all-inorganic NCs (ILANs) by using designed metal salts with noncoordinating anions that play a dual role in the surface treatment process: (i) removing the original organic ligands and (ii) binding to unpassivated Lewis basic sites to preserve the photoluminescent (PL) properties of the NCs. The absolute photoluminescence quantum yields (PLQYs) of red-emitting CdSe/ZnS NCs, green-emitting CdSe/CdZnSeS/ZnS NCs and blue-emitting CdZnS/ZnS NCs in polar solvents are 97%, 80% and 72%, respectively. Further study reveals that the passivated Lewis basic sites of ILANs by metal cations boost the efficiency of radiative recombination of electron-hole pairs. While the passivation of Lewis basic sites leads to a high PLQY of ILANs, the exposed Lewis acidic sites provide the possibility for in situ tuning of the functions of NCs, creating opportunities for direct optical patterning of functional NCs with high resolution.
Yeongho Choi, Donghyo Hahm, Wan Ki Bae, Jaehoon Lim
Heteroepitaxial chemistry of zinc chalcogenides on InP nanocrystals for defect-free interfaces with atomic uniformity (Journal Article)
In: Nature Communications, vol. 14, no. 43, 2023, (Heteroepitaxy on colloidal nanocrystals often yields defective heterostructures due to intricate reaction pathways. Here, the authors decode the surface chemistry at the molecular level to realize defect-free interfaces with atomic uniformity.).
Heteroepitaxy on colloidal semiconductor nanocrystals is an essential strategy for manipulating their optoelectronic functionalities. However, their practical synthesis typically leads to scattered and unexpected outcomes due to the intervention of multiple reaction pathways associated with complicated side products of reactants. Here, the heteroepitaxy mechanism of zinc chalcogenide initiated on indium phosphide (InP) colloidal nanocrystals is elucidated using the precursors, zinc carboxylate and trialkylphosphine selenide. The high magnetic receptivity of 77Se and the characteristic longitudinal optical phonon mode of ZnSe allowed for monitoring the sequence of epilayer formation at the molecular level. The investigation revealed the sterically hindered acyloxytrialkylphosphonium and diacyloxytrialkylphosphorane to be main intermediates in the surface reaction, which retards the metal ion adsorption by a large steric hindrance. The transformation of adsorbates to the crystalline epilayer was disturbed by surface oxides. Raman scattering disclosed the pathway of secondary surface oxidation triggered by carboxylate ligands migrated from zinc carboxylate. The surface-initiated heteroepitaxy protocol is proposed to fabricate core/shell heterostructured nanocrystals with atomic-scale uniformity of epilayers. Despite the large lattice mismatch of ZnS to InP, we realised a uniform and interface defect-free ZnS epilayer (~0.3 nm thickness) on InP nanocrystals, as evidenced by a high photoluminescence quantum yield of 97.3%.
Yilong Zhou, Gaurav Arya
Discovery of two-dimensional binary nanoparticle superlattices using global Monte Carlo optimization (Journal Article)
In: Nature Communications, vol. 13, no. 7976, 2022, (Binary nanoparticle superlattices exhibit different collective optical, magnetic, and electronic properties. Here, the authors develop an efficient global optimization algorithm for the discovery of periodic 2D architectures forming at fluid interfaces.).
Binary nanoparticle (NP) superlattices exhibit distinct collective plasmonic, magnetic, optical, and electronic properties. Here, we computationally demonstrate how fluid-fluid interfaces could be used to self-assemble binary systems of NPs into 2D superlattices when the NP species exhibit different miscibility with the fluids forming the interface. We develop a basin-hopping Monte Carlo (BHMC) algorithm tailored for interface-trapped structures to rapidly determine the ground-state configuration of NPs, allowing us to explore the repertoire of binary NP architectures formed at the interface. By varying the NP size ratio, interparticle interaction strength, and difference in NP miscibility with the two fluids, we demonstrate the assembly of an array of exquisite 2D periodic architectures, including AB-, AB2-, and AB3-type monolayer superlattices as well as AB-, AB2-, A3B5-, and A4B6-type bilayer superlattices. Our results suggest that the interfacial assembly approach could be a versatile platform for fabricating 2D colloidal superlattices with tunable structure and properties.
Xueyan Chen, Qianqian Ding, Chao Bi, Jian Ruan, Shikuan Yang
Lossless enrichment of trace analytes in levitating droplets for multiphase and multiplex detection (Journal Article)
In: Nature Communications, vol. 13, no. 7807, 2022, (Efficient enrichment of molecules from liquids, solid objects, or the gas phase is critical for their detection at trace concentrations. Here, the authors report on the lossless enrichment of analytes in droplets using acoustic levitation for multiphase and multiplex SERS detection.).
Concentrating a trace amount of molecules from liquids, solid objects, or the gas phase and delivering them to a localized area are crucial for almost any trace analyte detection device. Analytes within a liquid droplet resting on micro/nanostructured surfaces with liquid-repellent coatings can be concentrated during solvent evaporation. However, these coatings suffer from complex manufacturing procedures, poor versatility, and limited analyte enrichment efficiency. Here, we report on the use of an acoustic levitation platform to losslessly concentrate the analyte molecules dissolved in any volatile liquid, attached to solid objects, or spread in air. Gold nanoparticles can be simultaneously concentrated with the analytes in different phases, realizing sensitive, surface-enhanced Raman scattering detection even at attomolar (10^−18 mol/L) concentration levels. The acoustic levitation platform-enabled, lossless analyte enrichment can significantly increase the analytical performance of many conventional microsensing techniques.
Xinquan Zhou, Lixin Ning, Jianwei Qiao, Yifei Zhao, Puxian Xiong, Zhiguo Xia
Interplay of defect levels and rare earth emission centers in multimode luminescent phosphors (Journal Article)
In: Nature Communications, vol. 13, no. 7589, 2022, (Information encryption technology calls for versatile multi-mode luminescent materials. Here, the authors develop phosphors with five integrated luminescence modes by exploiting the interplay of defect levels and rare-earth emission centers.).
Multimode luminescence generally involves tunable photon emissions in response to various excitation or stimuli channels, which demonstrates high coding capacity and confidentiality abilities for anti-counterfeiting and encryption technologies. Integrating multimode luminescence into a single stable material is a promising strategy but remains a challenge. Here, we realize distinct long persistent luminescence, short-lived down/upconversion emissions in NaGdTi2O6:Pr3+, Er3+ phosphor by emloying interplay of defect levels and rare earth emission centers. The materials show intense colorful luminescence statically and dynamically, which responds to a wide spectrum ranging from X-ray to sunlight, thermal disturbance, and mechanical force, further allowing the emission colors manipulable in space and time dimensions. Experimental and theoretical approaches reveal that the Pr3+ ↔ Pr4+ valence change, oxygen vacancies and anti-site TiGd defects in this disordered structure contributes to the multimode luminescence. We present a facile and nondestructive demo whose emission color and fade intensity can be controlled via external manipulation, indicating promise in high-capacity information encryption applications.
I-Ju Chen, Markus Aapro, Abraham Kipnis, Alexander Ilin, Peter Liljeroth, Adam S. Foster
Precise atom manipulation through deep reinforcement learning (Journal Article)
In: Nature Communications, vol. 13, no. 7499, 2022, (Engineering quantum states requires precise manipulations at the atomic level. Here, the authors use deep reinforcement learning to manipulate Ag adatoms on Ag surfaces, which combined with path planning algorithms enables autonomous atomic assembly.).
Atomic-scale manipulation in scanning tunneling microscopy has enabled the creation of quantum states of matter based on artificial structures and extreme miniaturization of computational circuitry based on individual atoms. The ability to autonomously arrange atomic structures with precision will enable the scaling up of nanoscale fabrication and expand the range of artificial structures hosting exotic quantum states. However, the a priori unknown manipulation parameters, the possibility of spontaneous tip apex changes, and the difficulty of modeling tip-atom interactions make it challenging to select manipulation parameters that can achieve atomic precision throughout extended operations. Here we use deep reinforcement learning (DRL) to control the real-world atom manipulation process. Several state-of-the-art reinforcement learning (RL) techniques are used jointly to boost data efficiency. The DRL agent learns to manipulate Ag adatoms on Ag(111) surfaces with optimal precision and is integrated with path planning algorithms to complete an autonomous atomic assembly system. The results demonstrate that state-of-the-art DRL can offer effective solutions to real-world challenges in nanofabrication and powerful approaches to increasingly complex scientific experiments at the atomic scale.
Shuzhen Yan, Kaiming Hu, Shuai Chen, Tiantian Li, Wenming Zhang, Jie Yin, Xuesong Jiang
Photo-induced stress relaxation in reconfigurable disulfide-crosslinked supramolecular films visualized by dynamic wrinkling (Journal Article)
In: Nature Communications, vol. 13, no. 7434, 2022, (The mechanics of reconfigurable supramolecular polymer networks are governed by their dynamic crosslinking chemistry and the resulting stress relaxations. Here, the authors use reversible wrinkling patterns to visualize localized stress relaxations, due to molecular network rearrangements.).
Stress relaxation in reconfigurable supramolecular polymer networks is strongly related to intermolecular behavior. However, the relationship between molecular motion and macroscopic mechanics is usually vague, and the visualization of internal stress reflecting precise regulation of molecules remains challenging. Here, we present a strategy for visualizing photo-driven stress relaxation induced by infinitesimal perturbations in the intermolecular exchange reaction via reprogrammable wrinkle patterns. The supramolecular films exhibit visible changes in microscopic wrinkle topography through ultraviolet (UV)-induced dynamic disulfide exchange reaction. In accordance with the trans-scale theoretical models, which quantitatively evaluate the chemical-dependent mechanical stresses in the supramolecular network, the unexposed disordered wrinkles evolved into highly oriented patterns and underwent subsequent mutations after thermal treatment. The stress-sensitive wrinkle macro-patterns can be repetitively written/erased through network topology rearrangement using different stimuli. This strategy provides an approach for visualizing and understanding the molecular behavior from dynamic chemistry to mechanical changes, and directly programming wrinkle patterns with regulated structures.
Bang Lin Li, Jun Jiang Luo, Hao Lin Zou, Qing-Meng Zhang, Liu-Bin Zhao, Hang Qian, Hong Qun Luo, David Tai Leong, Nian Bing Li
Chiral nanocrystals grown from MoS2 nanosheets enable photothermally modulated enantioselective release of antimicrobial drugs (Journal Article)
In: Nature Communications, vol. 13, no. 7289, 2022, (Chirality transfer from molecules to nanomaterials enables advanced optical functionalities. Here, the authors use exfoliated MoS2 nanosheets to seed the growth of chiral Au nanoparticles to form Au/MoS2 heterostructures for enantioselective drug release.).
The transfer of the concept of chirality from molecules to synthesized nanomaterials has attracted attention amongst multidisciplinary teams. Here we demonstrate heterogeneous nucleation and anisotropic accumulation of Au nanoparticles on multilayer MoS2 planes to form chiroptically functional nanomaterials. Thiol amino acids with chiral conformations modulate asymmetric growth of gold nanoarchitectures on seeds of highly faceted Au/MoS2 heterostructures. Consequently, dendritic plasmonic nanocrystals with partial chiral morphologies are synthesized. The chirality of dendritic nanocrystals inherited from cysteine molecules refers to the structural characteristics and includes specific recognition of enantiomeric molecules. With integration of the intrinsic photothermal properties and inherited enantioselective characteristics, dendritic Au/MoS2 heterostructures exhibit chirality-dependent release of antimicrobial drugs from hydrogel substrates when activated by exogenous infrared irradiation. A three-in-one strategy involving synthesis of chiral dendritic heterostructures, enantioselective recognition, and controlled drug release system is presented, which improves nanomaterial synthetic technology and enhances our understanding of crucial chirality information.
Siqi Yu, Yu Du, Xianghong Niu, Guangming Li, Da Zhu, Qian Yu, Guizheng Zou, Huangxian Ju
Arginine-modified black phosphorus quantum dots with dual excited states for enhanced electrochemiluminescence in bioanalysis (Journal Article)
In: Nature Communications, vol. 13, no. 7302, 2022, (Electrochemiluminescence is emitted via the radiative transition of a singlet or triplet excited state. Here, the authors propose an arginine modification of black phosphorus quantum dots that exhibits enhanced emission based on dual excited states.).
The electrochemiluminescence (ECL) is generally emitted via radiative transition of singlet or triplet excited state (S1 or T1). Herein, an ECL mechanism with the transitions of both S1 and T1 of black phosphorus quantum dots (BPQDs) is found, and an arginine (Arg) modification strategy is proposed to passivate the surface oxidation defects of BPQDs, which could modulate the excited states for enhancing the ECL efficiency of BPQDs. The Arg modification leads to greater spatial overlap of highest and lowest occupied molecular orbitals, and spectral shift of radiative transitions, and improves the stability of anion radical of BPQDs. To verify the application of the proposed mechanism, it is used to construct a sensitive method for conveniently evaluating the inhibiting efficiency of cyclo-arginine-glycine-aspartic acid-d-tyrosine-lysine to cell surface integrin by using Arg containing peptide modified BPQDs as signal tag. The dual excited states mediated ECL emitters provide a paradigm for adjustable ECL generation and extend the application of ECL analysis.
Qingyu Meng, Laura Abella, Yang-Rong Yao, Dumitru-Claudiu Sergentu, Wei Yang, Xinye Liu, Jiaxin Zhuang, Luis Echegoyen, Jochen Autschbach, Ning Chen
A charged diatomic triple-bonded U≡N species trapped in C82 fullerene cages (Journal Article)
In: Nature Communications, vol. 13, no. 7192, 2022, (Diatomic actinide molecules are ideal models for studying rare multiple-bond motifs. Here, the authors report host-guest structures of metastable charged U≡N diatoms confined in fullerene cages and stabilized by coordinative electron transfer.).
Actinide diatomic molecules are ideal models to study elusive actinide multiple bonds, but most of these diatomic molecules have so far only been studied in solid inert gas matrices. Herein, we report a charged U≡N diatomic species captured in fullerene cages and stabilized by the U-fullerene coordination interaction. Two diatomic clusterfullerenes, viz. UN@Cs(6)-C82 and UN@C2(5)-C82, were successfully synthesized and characterized. Crystallographic analysis reveals U-N bond lengths of 1.760(7) and 1.760(20) Å in UN@Cs(6)-C82 and UN@C2(5)-C82. Moreover, U≡N was found to be immobilized and coordinated to the fullerene cages at 100 K but it rotates inside the cage at 273 K. Quantum-chemical calculations show a (UN)2+@(C82)2− electronic structure with formal +5 oxidation state (f1) of U and unambiguously demonstrate the presence of a U≡N bond in the clusterfullerenes. This study constitutes an approach to stabilize fundamentally important actinide multiply bonded species.
Yuanzhi Xia, Semih Sevim, João Pedro Vale, Johannes Seibel, David Rodríguez-San-Miguel, Donghoon Kim, Salvador Pané, Tiago Sotto Mayor, Steven De Feyter, Josep Puigmartí-Luis
Covalent transfer of chemical gradients onto a graphenic surface with 2D and 3D control (Journal Article)
In: Nature Communications, vol. 13, no. 7006, 2022, (Covalent modification is an essential chemical method for altering the physicochemical properties of material interfaces. Here, the authors show that the no-slip conditions in microfluidic devices grant spatiotemporal control over molecular grafting.).
Control over the functionalization of graphenic materials is key to enable their full application in electronic and optical technologies. Covalent functionalization strategies have been proposed as an approach to tailor the interfaces’ structure and properties. However, to date, none of the proposed methods allow for a covalent functionalization with control over the grafting density, layer thickness and/or morphology, which are key aspects for fine-tuning the processability and performance of graphenic materials. Here, we show that the no-slip boundary condition at the walls of a continuous flow microfluidic device offers a way to generate controlled chemical gradients onto a graphenic material with 2D and 3D control, a possibility that will allow the sophisticated functionalization of these technologically-relevant materials.
Qianqian Fu, Wenyuan Yu, Guangyang Bao, Jianping Ge
Electrically responsive photonic crystals with bistable states for low-power electrophoretic color displays (Journal Article)
In: Nature Communications, vol. 13, no. 7007, 2022, (Conventional electrophoretic color displays require a permanent electric field, increasing power consumption. Here, the authors report an electrically responsive photonic crystal with switchable bistable states by particle rearrangement for low power consumption displays.).
Electrically responsive photonic crystals are promising materials for electrophoretic color displays with better brightness and color saturation. However, electric field must always be applied to maintain the specific colors, which brings concerns about the power consumption and signal stability and reversibility. Here, we show an electrically responsive photonic crystal with two stable states at 0 V, which are the colored state or the colorless state with ordered or disordered particle arrangement. The color state can be reversibly switched by applying a short-time electrical field, just like in the case of commercial electrophoretic ink. With optimized recipe and electric field, the photonic crystals encapsulated in the prototype display panel are proved to have potentials in high resolution, multi-color, and greyscale display, which lays down a firm basis for reflective displays with low power consumption and good visibility.
Ahyoung Kim, Thi Vo, Hyosung An, Progna Banerjee, Lehan Yao, Shan Zhou, Chansong Kim, Delia J. Milliron, Sharon C. Glotzer, Qian Chen
Symmetry-breaking in patch formation on triangular gold nanoparticles by asymmetric polymer grafting (Journal Article)
In: Nature Communications, vol. 13, no. 6774, 2022, (Patchy nanoparticles are desirable building blocks for the guided assembly of functional superstructures. Here, the authors demonstrate quantitative control over asymmetric polymer grafting on triangular Au nanoprisms based on polymer scaling theory.).
Synthesizing patchy particles with predictive control over patch size, shape, placement and number has been highly sought-after for nanoparticle assembly research, but is fraught with challenges. Here we show that polymers can be designed to selectively adsorb onto nanoparticle surfaces already partially coated by other chains to drive the formation of patchy nanoparticles with broken symmetry. In our model system of triangular gold nanoparticles and polystyrene-b-polyacrylic acid patch, single- and double-patch nanoparticles are produced at high yield. These asymmetric single-patch nanoparticles are shown to assemble into self-limited patch‒patch connected bowties exhibiting intriguing plasmonic properties. To unveil the mechanism of symmetry-breaking patch formation, we develop a theory that accurately predicts our experimental observations at all scales—from patch patterning on nanoparticles, to the size/shape of the patches, to the particle assemblies driven by patch‒patch interactions. Both the experimental strategy and theoretical prediction extend to nanoparticles of other shapes such as octahedra and bipyramids. Our work provides an approach to leverage polymer interactions with nanoscale curved surfaces for asymmetric grafting in nanomaterials engineering.
Pingping Zhang, Gaoling Yang, Fei Li, Jianbing Shi, Haizheng Zhong
Direct in situ photolithography of perovskite quantum dots based on photocatalysis of lead bromide complexes (Journal Article)
In: Nature Communications, vol. 13, no. 6713, 2022, (Perovskite nanomaterials may suffer degradation during conventional photolithography. Here, the authors report a non-destructive method for patterning perovskite quantum dots based on direct photopolymerization catalyzed by lead bromide complexes.).
Photolithography has shown great potential in patterning solution-processed nanomaterials for integration into advanced optoelectronic devices. However, photolithography of perovskite quantum dots (PQDs) has so far been hindered by the incompatibility of perovskite with traditional optical lithography processes where lots of solvents and high-energy ultraviolet (UV) light exposure are required. Herein, we report a direct in situ photolithography technique to pattern PQDs based on the photopolymerization catalyzed by lead bromide complexes. By combining direct photolithography with in situ fabrication of PQDs, this method allows to directly photolithograph perovskite precursors, avoiding the complicated lift-off processes and the destruction of PQDs by solvents or high-energy UV light, as PQDs are produced after lithography exposure. We further demonstrate that the thiol-ene free-radical photopolymerization is catalyzed by lead bromide complexes in the perovskite precursor solution, while no external initiators or catalysts are needed. Using direct in situ photolithography, PQD patterns with high resolution up to 2450 pixels per inch (PPI), excellent fluorescence uniformity, and good stability, are successfully demonstrated. This work opens an avenue for non-destructive direct photolithography of high-efficiency light-emitting PQDs, and potentially expands their application in various integrated optoelectronic devices.
Tolulope Michael Ajayi, Vijay Singh, Kyaw Zin Latt, Sanjoy Sarkar, Xinyue Cheng, Sineth Premarathna, Naveen K. Dandu, Shaoze Wang, Fahimeh Movahedifar, Sarah Wieghold, Nozomi Shirato, Volker Rose, Larry A. Curtiss, Anh T. Ngo, Eric Masson, Saw Wai Hla
Atomically precise control of rotational dynamics in charged rare-earth complexes on a metal surface (Journal Article)
In: Nature Communications, vol. 13, no. 6305, 2022, (Rare-earth elements are vital to advanced technological applications ranging from spintronic devices to quantum information science. Here, the authors formed charged rare-earth complexes on a material surface and demonstrated atomically precise control on their rotational dynamics.).
Complexes containing rare-earth ions attract great attention for their technological applications ranging from spintronic devices to quantum information science. While charged rare-earth coordination complexes are ubiquitous in solution, they are challenging to form on materials surfaces that would allow investigations for potential solid-state applications. Here we report formation and atomically precise manipulation of rare-earth complexes on a gold surface. Although they are composed of multiple units held together by electrostatic interactions, the entire complex rotates as a single unit when electrical energy is supplied from a scanning tunneling microscope tip. Despite the hexagonal symmetry of the gold surface, a counterion at the side of the complex guides precise three-fold rotations and 100% control of their rotational directions is achieved using a negative electric field from the scanning probe tip. This work demonstrates that counterions can be used to control dynamics of rare-earth complexes on materials surfaces for quantum and nanomechanical applications.
Yuzhu Ma, Hongjin Zhang, Runfeng Lin, Yan Ai, Kun Lan, Linlin Duan, Wenyao Chen, Xuezhi Duan, Bing Ma, Changyao Wang, Xiaomin Li, Dongyuan Zhao
Remodeling nanodroplets into hierarchical mesoporous silica nanoreactors with multiple chambers (Journal Article)
In: Nature Communications, vol. 13, no. 6136, 2022, (Multi-chambered structures have attracted great attention due to their ability to create multifunctional partitions in different chambers. Here, the authors prepared mesoporous silica nanoreactors with hierarchical chambers for catalytic cascades.).
Multi-chambered architectures have attracted much attention due to the ability to establish multifunctional partitions in different chambers, but manipulating the chamber numbers and coupling multi-functionality within the multi-chambered mesoporous nanoparticle remains a challenge. Herein, we propose a nanodroplet remodeling strategy for the synthesis of hierarchical multi-chambered mesoporous silica nanoparticles with tunable architectures. Typically, the dual-chambered nanoparticles with a high surface area of ~469 m2 g−1 present two interconnected cavities like a calabash. Furthermore, based on this nanodroplet remodeling strategy, multiple species (magnetic, catalytic, optic, etc.) can be separately anchored in different chamber without obvious mutual-crosstalk. We design a dual-chambered mesoporous nanoreactors with spatial isolation of Au and Pd active-sites for the cascade synthesis of 2-phenylindole from 1-nitro-2-(phenylethynyl)benzene. Due to the efficient mass transfer of reactants and intermediates in the dual-chambered structure, the selectivity of the target product reaches to ~76.5%, far exceeding that of single-chambered nanoreactors (~41.3%).
Yixuan Gao, Li Huang, Yun Cao, Marcus Richter, Jing Qi, Qi Zheng, Huan Yang, Ji Ma, Xiao Chang, Xiaoshuai Fu, Carlos-Andres Palma, Hongliang Lu, Yu-Yang Zhang, Zhihai Cheng, Xiao Lin, Min Ouyang, Xinliang Feng, Shixuan Du, Hong-Jun Gao
Selective activation of four quasi-equivalent C–H bonds yields N-doped graphene nanoribbons with partial corannulene motifs (Journal Article)
In: Nature Communications, vol. 13, no. 6146, 2022, (Selective activation of C–H bonds is a key challenge in organic reactions. Here, the authors achieve the selective activation of four quasi-equivalent C–H bonds, leading to the formation of N-doped graphene nanoribbons with partial corannulene motifs.).
Selective C–H bond activation is one of the most challenging topics for organic reactions. The difficulties arise not only from the high C–H bond dissociation enthalpies but also the existence of multiple equivalent/quasi-equivalent reaction sites in organic molecules. Here, we successfully achieve the selective activation of four quasi-equivalent C–H bonds in a specially designed nitrogen-containing polycyclic hydrocarbon (N-PH). Density functional theory calculations reveal that the adsorption of N-PH on Ag(100) differentiates the activity of the four ortho C(sp3) atoms in the N-heterocycles into two groups, suggesting a selective dehydrogenation, which is demonstrated by sequential-annealing experiments of N-PH/Ag(100). Further annealing leads to the formation of N-doped graphene nanoribbons with partial corannulene motifs, realized by the C–H bond activation process. Our work provides a route of designing precursor molecules with ortho C(sp3) atom in an N-heterocycle to realize surface-induced selective dehydrogenation in quasi-equivalent sites.
Chong Li, Qi Liu, Shengyang Tao
Coemissive luminescent nanoparticles combining aggregation-induced emission and quenching dyes prepared in continuous flow (Journal Article)
In: Nature Communications, vol. 13, no. 6034, 2022, (Developing efficient light harvesting systems at low cost is a challenge. Here, the authors synthesized coemissive dyes in a continuous flow microreactor featuring a controlled cascade FRET process combining aggregation-induced emission and quenching.).
Achieving an ideal light-harvesting system at a low cost remains a challenge. Herein, we report the synthesis of a hybrid dye system based on tetraphenylene (TPE) encapsulated organic dyes in a continuous flow microreactor. The composite dye nanoparticles (NPs) are synthesized based on supramolecular self-assembly to achieve the co-emission of aggregation-induced emission dyes and aggregation-caused quenching dyes (CEAA). Numerical simulations and molecular spectroscopy were used to investigate the synthesis mechanism of the CEAA dyes. Nanoparticles of CEAA dyes provide a platform for efficient cascade Förster resonance energy transfer (FRET). Composite dye nanoparticles of TPE and Nile red (NiR) are synthesized for an ideal light-harvesting system using coumarin 6 (C-6) as an energy intermediate. The light-harvesting system has a considerable red-shift distance (~126 nm), high energy-transfer efficiency (ΦET) of 99.37%, and an antenna effect of 26.23. Finally, the versatility of the preparation method and the diversity of CEAA dyes are demonstrated.
Jiří Doležal, Sofia Canola, Prokop Hapala, Rodrigo Cezar de Campos Ferreira, Pablo Merino, Martin Švec
Evidence of exciton-libron coupling in chirally adsorbed single molecules (Journal Article)
In: Nature Communications, vol. 13, no. 6008, 2022, (Vibronic coupling in molecules plays an essential role in photophysics. Here, the authors observe optical fingerprints of the coupling between librational states and charged excited states in a single phthalocyanine molecule chirally absorbed on a surface.).
Interplay between motion of nuclei and excitations has an important role in molecular photophysics of natural and artificial structures. Here we provide a detailed analysis of coupling between quantized librational modes (librons) and charged excited states (trions) on single phthalocyanine dyes adsorbed on a surface. By means of tip-induced electroluminescence performed with a scanning probe microscope, we identify libronic signatures in spectra of chirally adsorbed phthalocyanines and find that these signatures are absent from spectra of symmetrically adsorbed species. We create a model of the libronic coupling based on the Franck-Condon principle to simulate the spectral features. Experimentally measured librational spectra match very well the theoretically calculated librational eigenenergies and peak intensities (Franck-Condon factors). Moreover, the comparison reveals an unexpected depopulation channel for the zero libron of the excited state that can be effectively controlled by tuning the size of the nanocavity. Our results showcase the possibility of characterizing the dynamics of molecules by their low-energy molecular modes using µeV-resolved tip-enhanced spectroscopy.
Arrigo Calzolari, Corey Oses, Cormac Toher, Marco Esters, Xiomara Campilongo, Sergei P. Stepanoff, Douglas E. Wolfe, Stefano Curtarolo
Plasmonic high-entropy carbides (Journal Article)
In: Nature Communications, vol. 13, no. 5993, 2022, (Tunable plasmonic materials capable of surviving harsh environments are critical for advanced applications. Here, the authors report that some high-entropy transition-metal carbides can satisfy the requirements.).
Discovering multifunctional materials with tunable plasmonic properties, capable of surviving harsh environments is critical for advanced optical and telecommunication applications. We chose high-entropy transition-metal carbides because of their exceptional thermal, chemical stability, and mechanical properties. By integrating computational thermodynamic disorder modeling and time-dependent density functional theory characterization, we discovered a crossover energy in the infrared and visible range, corresponding to a metal-to-dielectric transition, exploitable for plasmonics. It was also found that the optical response of high-entropy carbides can be largely tuned from the near-IR to visible when changing the transition metal components and their concentration. By monitoring the electronic structures, we suggest rules for optimizing optical properties and designing tailored high-entropy ceramics. Experiments performed on the archetype carbide HfTa4C5 yielded plasmonic properties from room temperature to 1500K. Here we propose plasmonic transition-metal high-entropy carbides as a class of multifunctional materials. Their combination of plasmonic activity, high-hardness, and extraordinary thermal stability will result in yet unexplored applications.
Hyesung Jo, Dae Han Wi, Taegu Lee, Yongmin Kwon, Chaehwa Jeong, Juhyeok Lee, Hionsuck Baik, Alexander J. Pattison, Wolfgang Theis, Colin Ophus, Peter Ercius, Yea-Lee Lee, Seunghwa Ryu, Sang Woo Han, Yongsoo Yang
Direct strain correlations at the single-atom level in three-dimensional core-shell interface structures (Journal Article)
In: Nature Communications, vol. 13, no. 5957, 2022, (Understanding 3D interfacial strain at the atomic level has been a long-sought challenge in the field of core-shell nanomaterials. Here, the authors address this challenge by revealing the full 3D atomic structures of Pd@Pt core-shell nanoparticles.).
Nanomaterials with core-shell architectures are prominent examples of strain-engineered materials. The lattice mismatch between the core and shell materials can cause strong interface strain, which affects the surface structures. Therefore, surface functional properties such as catalytic activities can be designed by fine-tuning the misfit strain at the interface. To precisely control the core-shell effect, it is essential to understand how the surface and interface strains are related at the atomic scale. Here, we elucidate the surface-interface strain relations by determining the full 3D atomic structure of Pd@Pt core-shell nanoparticles at the single-atom level via atomic electron tomography. Full 3D displacement fields and strain profiles of core-shell nanoparticles were obtained, which revealed a direct correlation between the surface and interface strain. The strain distributions show a strong shape-dependent anisotropy, whose nature was further corroborated by molecular statics simulations. From the observed surface strains, the surface oxygen reduction reaction activities were predicted. These findings give a deep understanding of structure-property relationships in strain-engineerable core-shell systems, which can lead to direct control over the resulting catalytic properties.
Nan Xia, Jianpei Xing, Di Peng, Shiyu Ji, Jun Zha, Nan Yan, Yan Su, Xue Jiang, Zhi Zeng, Jijun Zhao, Zhikun Wu
Assembly-induced spin transfer and distance-dependent spin coupling in atomically precise AgCu nanoclusters (Journal Article)
In: Nature Communications, vol. 13, no. 5934, 2022, (The assembly of atomically precise clusters into ordered superstructures enables new functional material designs. Here, the authors propose a strategy for linear arrangements of AgCu clusters and explore the consequent transfer and coupling of magnetic spins.).
Nanoparticle assembly paves the way for unanticipated properties and applications from the nanoscale to the macroscopic world. However, the study of such material systems is greatly inhibited due to the obscure compositions and structures of nanoparticles (especially the surface structures). The assembly of atomically precise nanoparticles is challenging, and such an assembly of nanoparticles with metal core sizes strictly larger than 1 nm has not been achieved yet. Here, we introduced an on-site synthesis-and-assembly strategy, and successfully obtained a straight-chain assembly structure consisting of Ag77Cu22(CHT)48 (CHT: cyclohexanethiolate) nanoparticles with two nanoparticles separated by one S atom, as revealed by mass spectrometry and single crystal X-ray crystallography. Although Ag77Cu22(CHT)48 bears one unpaired shell-closing electron, the magnetic moment is found to be mainly localized at the S linker with magnetic isotropy, and the sulfur radicals were experimentally verified and found to be unstable after disassembly, demonstrating assembly-induced spin transfer. Besides, spin nanoparticles are found to couple and lose their paramagnetism at sufficiently short inter-nanoparticle distance, namely, the spin coupling depends on the inter-nanoparticle distance. However, it is not found that the spin coupling leads to the nanoparticle growth.
Zhiwei Yang, Yanze Wei, Jingjing Wei, Zhijie Yang
Chiral superstructures of inorganic nanorods by macroscopic mechanical grinding (Journal Article)
In: Nature Communications, vol. 13, no. 5844, 2022, (Chiroptic materials made of self-assembled nanomaterials are essential for advanced optical applications. Here, the authors show that macroscopic grinding can break the symmetry in achiral superlattices of inorganic nanorods, generating chiral superstructures.).
The development of mechanochemistry substantially expands the traditional synthetic realm at the molecular level. Here, we extend the concept of mechanochemistry from atomic/molecular solids to the nanoparticle solids, and show how the macroscopic grinding is being capable of generating chirality in self-assembled nanorod (NR) assemblies. Specifically, the weak van der Waals interaction is dominated in self-assembled NR assemblies when their surface is coated with aliphatic chains, which can be overwhelmed by a press-and-rotate mechanic force macroscopically. The chiral sign of the NR assemblies can be well-controlled by the rotating directions, where the clockwise and counter-clockwise rotation leads to the positive and negative Cotton effect in circular dichroism and circularly polarized luminescence spectra, respectively. Importantly, we show that the present approach can be applied to NRs of diverse inorganic materials, including CdSe, CdSe/CdS, and TiO2. Equally important, the as-prepared chiral NR assemblies could be served as porous yet robust chiral substrates, which enable to host other molecular materials and induce the chirality transfer from substrate to the molecular system.
Zhen-Yu Yi, Xue-Qing Yang, Jun-Jie Duan, Xiong Zhou, Ting Chen, Dong Wang, Li-Jun Wan
Evolution of Br⋯Br contacts in enantioselective molecular recognition during chiral 2D crystallization (Journal Article)
In: Nature Communications, vol. 13, no. 5850, 2022, (Halogen-mediated interactions control molecular recognition in many chemical and biological systems. Here, the authors demonstrate two types of Br⋯Br contacts and their importance in chiral on-surface crystallization.).
Halogen-mediated interactions play an important role in molecular recognition and crystallization in many chemical and biological systems, whereas their effect on homochiral versus heterochiral recognition and crystallization has rarely been explored. Here we demonstrate the evolution of Br⋯Br contacts in chiral recognition during 2D crystallization. On Ag(100), type I contacts prevail at low coverage and lead to homochiral recognition and the formation of 2D conglomerates; whereas type II contacts mediating heterochiral recognition are suppressed at medium coverage and appear in the racemates induced by structural transitions at high coverage. On Ag(111), type I contacts dominate the 2D crystallization and generate 2D conglomerates exclusively. DFT calculations suggest that the energy difference between type I and type II contacts is reversed upon adsorption due to the substrate induced mismatch energy penalty. This result provides fundamental understanding of halogen-mediated interactions in molecular recognition and crystallization on surface.
Maryam Arabi, Abbas Ostovan, Yunqing Wang, Rongchao Mei, Longwen Fu, Jinhua Li, Xiaoyan Wang, Lingxin Chen
Chiral molecular imprinting-based SERS detection strategy for absolute enantiomeric discrimination (Journal Article)
In: Nature Communications, vol. 13, no. 5757, 2022, (Absolute chiral discrimination in chiral imprinted systems is complicated by the nonspecific binding of enantiomers. Here, the authors report a SERS “inspector” recognition mechanism to distinguish between specifically and nonspecifically bound enantiomers, even in seawater and urine.).
Chiral discrimination is critical in environmental and life sciences. However, an ideal chiral discrimination strategy has not yet been developed because of the inevitable nonspecific binding entity of wrong enantiomers or insufficient intrinsic optical activities of chiral molecules. Here, we propose an “inspector” recognition mechanism (IRM), which is implemented on a chiral imprinted polydopamine (PDA) layer coated on surface-enhanced Raman scattering (SERS) tag layer. The IRM works based on the permeability change of the imprinted PDA after the chiral recognition and scrutiny of the permeability by an inspector molecule. Good enantiomer can specifically recognize and fully fill the chiral imprinted cavities, whereas the wrong cannot. Then a linear shape aminothiol molecule, as an inspector of the recognition status is introduced, which can only percolate through the vacant and nonspecifically occupied cavities, inducing the SERS signal to decrease. Accordingly, chirality information exclusively stems from good enantiomer specific binding, while nonspecific recognition of wrong enantiomer is curbed. The IRM benefits from sensitivity and versatility, enabling absolute discrimination of a wide variety of chiral molecules regardless of size, functional groups, polarities, optical activities, Raman scattering, and the number of chiral centers.
Lei Lei, Yubin Wang, Weixin Xu, Renguang Ye, Youjie Hua, Degang Deng, Liang Chen, Paras N. Prasad, Shiqing Xu
Manipulation of time-dependent multicolour evolution of X-ray excited afterglow in lanthanide-doped fluoride nanoparticlesamplification of time dependent multicolour evolution of X-ray excited afterglow in lanthanide doped fluoride nanoparticles (Journal Article)
In: Nature Communications, vol. 13, no. 5739, 2022, (X-ray activated afterglow nanomaterials are desirable components for advanced optoelectronic applications. Here, the authors present pathways to modulate the stimulus-responsive color emissions in lanthanide-doped fluoride core-shell nanoparticles.).
External manipulation of emission colour is of significance for scientific research and applications, however, the general stimulus-responsive colour modulation method requires both stringent control of microstructures and continously adjustment of particular stimuli conditions. Here, we introduce pathways to manipulate the kinetics of time evolution of both intensity and spectral characteristics of X-ray excited afterglow (XEA) by regioselective doping of lanthanide activators in core-shell nanostructures. Our work reported here reveals the following phenomena: 1. The XEA intensities of multiple lanthanide activators are significantly enhanced via incorporating interstitial Na+ ions inside the nanocrystal structure. 2. The XEA intensities of activators exhibit diverse decay rates in the core and the shell and can largely be tuned separately, which enables us to realize a series of core@shell NPs featuring distinct time-dependent afterglow colour evolution. 3. A core/multi-shell NP structure can be designed to simultaneously generate afterglow, upconversion and downshifting to realize multimode time-dependent multicolour evolutions. These findings can promote the development of superior XEA and plentiful spectral manipulation, opening up a broad range of applications ranging from multiplexed biosensing, to high-capacity information encryption, to multidimensional displays and to multifunctional optoelectronic devices.
Jing Ai, Xueliang Zhang, Te Bai, Qing Shen, Peter Oleynikov, Yingying Duan, Osamu Terasaki, Shunai Che, Lu Han
Synchronous quantitative analysis of chiral mesostructured inorganic crystals by 3D electron diffraction tomography (Journal Article)
In: Nature Communications, vol. 13, no. 5718, 2022, (Chiral mesostructured inorganic crystals exhibit distinctive twisting and helical hierarchical stacking. Here, the authors report a general approach for the synchronous quantitative analysis of rotation axis, torsion angle, pitch length, and arrangement modes.).
Chiral mesostructures exhibit distinctive twisting and helical hierarchical stacking ranging from atomic to micrometre scales with fascinating structural-chiral anisotropy properties. However, the detailed determination of their multilevel chirality remains challenging due to the limited information from spectroscopy, diffraction techniques, scanning electron microscopy and the two-dimensional projections in transmission electron microscopy. Herein, we report a general approach to determine chiral hierarchical mesostructures based on three-dimensional electron diffraction tomography (3D EDT), by which the structure can be solved synchronously according to the quantitative measurement of diffraction spot deformations and their arrangement in reciprocal space. This method was verified on two samples—chiral mesostructured nickel molybdate and chiral mesostructured tin dioxide—revealing hierarchical chiral structures that cannot be determined by conventional techniques. This approach provides more precise and comprehensive identification of the hierarchical mesostructures, which is expected to advance our understanding of structural–chiral anisotropy at the fundamental level.
Corentin Dabard, Victor Guilloux, Charlie Gréboval, Hong Po, Lina Makke, Ningyuan Fu, Xiang Zhen Xu, Mathieu G. Silly, Gilles Patriarche, Emmanuel Lhuillier, Thierry Barisien, Juan I. Climente, Benjamin T. Diroll, Sandrine Ithurria
Double-crowned 2D semiconductor nanoplatelets with bicolor power-tunable emission (Journal Article)
In: Nature Communications, vol. 13, no. 5094, 2022, (Nanocrystals are desirable light sources for advanced display technologies. Here, the authors report on double-crowned 2D semiconductor nanoplatelets as light downconverters that offer both green and red emissions to achieve a wide color gamut.).
Nanocrystals (NCs) are now established building blocks for optoelectronics and their use as down converters for large gamut displays has been their first mass market. NC integration relies on a combination of green and red NCs into a blend, which rises post-growth formulation issues. A careful engineering of the NCs may enable dual emissions from a single NC population which violates Kasha’s rule, which stipulates that emission should occur at the band edge. Thus, in addition to an attentive control of band alignment to obtain green and red signals, non-radiative decay paths also have to be carefully slowed down to enable emission away from the ground state. Here, we demonstrate that core/crown/crown 2D nanoplatelets (NPLs), made of CdSe/CdTe/CdSe, can combine a large volume and a type-II band alignment enabling simultaneously red and narrow green emissions. Moreover, we demonstrate that the ratio of the two emissions can be tuned by the incident power, which results in a saturation of the red emission due to non-radiative Auger recombination that affects this emission much stronger than the green one. Finally, we also show that dual-color, power tunable, emission can be obtained through an electrical excitation.
Lukas Grote, Martin Seyrich, Ralph Döhrmann, Sani Harouna-Mayer, Federica Mancini, Emilis Kaziukenas, Irene Fernandez-Cuesta, Cecilia Zito, Olga Vasylieva, Felix Wittwer, Michal Odstrcil, Natnael Mogos, Mirko Landmann, Christian Schroer, Dorota Koziej
Imaging Cu2O nanocube hollowing in solution by quantitative in-situ X-ray ptychography (Journal Article)
In: Nature Communications, vol. 13, no. 4971, 2022, (Observing morphological changes of nanoparticles in solution requires advanced in-situ imaging methods. Here, the authors use X-ray ptychography to image the growth and hollowing of Cu2O nanocubes in 3D.).
Understanding morphological changes of nanoparticles in solution is essential to tailor the functionality of devices used in energy generation and storage. However, we lack experimental methods that can visualize these processes in solution, or in electrolyte, and provide three-dimensional information. Here, we show how X-ray ptychography enables in situ nano-imaging of the formation and hollowing of nanoparticles in solution at 155°C. We simultaneously image the growth of about 100 nanocubes with a spatial resolution of 66 nm. The quantitative phase images give access to the third dimension, allowing to additionally study particle thickness. We reveal that the substrate hinders their out-of-plane growth, thus the nanocubes are in fact nanocuboids. Moreover, we observe that the reduction of Cu2O to Cu triggers the hollowing of the nanocuboids. We critically assess the interaction of X-rays with the liquid sample. Our method enables detailed in-solution imaging for a wide range of reaction conditions.
Hajir Hilal, Qiang Zhao, Jeongwon Kim, Sungwoo Lee, MohammadNavid Haddadnezhad, Sungjae Yoo, Soohyun Lee, Woongkyu Park, Woocheol Park, Jaewon Lee, Joong Wook Lee, Insub Jung, Sungho Park
Three-dimensional nanoframes with dual rims as nanoprobes for biosensing (Journal Article)
In: Nature Communications, vol. 13, no. 4813, 2022, ( Most SERS-active nanostructures suffer from low robustness against misalignment to field polarization. Here, the authors demonstrate three-dimensional nanoframes of octahedral geometry, with two rims engraved on each facet, as polarization-independent SERS nanoprobes.).
Three-dimensional (3D) nanoframe structures are very appealing because their inner voids and ridges interact efficiently with light and analytes, allowing for effective optical-based sensing. However, the realization of complex nanoframe architecture with high yield is challenging because the systematic design of such a complicated nanostructure lacks an appropriate synthesis protocol. Here, we show the synthesis method for complex 3D nanoframes wherein two-dimensional (2D) dual-rim nanostructures are engraved on each facet of octahedral nanoframes. The synthetic scheme proceeds through multiple executable on-demand steps. With Au octahedral nanoparticles as a sacrificial template, sequential processes of edge-selective Pt deposition and inner Au etching lead to Pt octahedral mono-rim nanoframes. Then, adlayers of Au are grown on Pt skeletons via the Frank-van der Merwe mode, forming sharp and well-developed edges. Next, Pt selective deposition on both the inner and outer boundaries leads to tunable geometric patterning on Au. Finally, after the selective etching of Au, Pt octahedral dual-rim nanoframes with highly homogeneous size and shape are achieved. In order to endow plasmonic features, Au is coated around Pt frames while retaining their geometric shape. The resultant plasmonic dual-rim engraved nanoframes possess strong light entrapping capability verified by single-particle surface-enhanced Raman scattering (SERS) and show the potential of nanoprobes for biosensing through SERS-based immunoassay.
Lei Zhang, Chen Yang, Chenxi Lu, Xingxing Li, Yilin Guo, Jianning Zhang, Jinglong Lin, Zhizhou Li, Chuancheng Jia, Jinlong Yang, K. N. Houk, Fanyang Mo, Xuefeng Guo
Precise electrical gating of the single-molecule Mizoroki-Heck reaction (Journal Article)
In: Nature Communications, vol. 13, no. 4552 , 2022, (Guiding chemical reactions in a predictable and controllable manner is an ultimate goal of chemistry. Here, the authors show tuning of the single-molecule Mizoroki-Heck catalytic cycle through electrical gating and direct in-situ detection.).
Precise tuning of chemical reactions with predictable and controllable manners, an ultimate goal chemists desire to achieve, is valuable in the scientific community. This tunability is necessary to understand and regulate chemical transformations at both macroscopic and single-molecule levels to meet demands in potential application scenarios. Herein, we realise accurate tuning of a single-molecule Mizoroki-Heck reaction via applying gate voltages as well as complete deciphering of its detailed intrinsic mechanism by employing an in-situ electrical single-molecule detection, which possesses the capability of single-event tracking. The Mizoroki-Heck reaction can be regulated in different dimensions with a constant catalyst molecule, including the molecular orbital gating of Pd(0) catalyst, the on/off switching of the Mizoroki-Heck reaction, the promotion of its turnover frequency, and the regulation of each elementary reaction within the Mizoroki-Heck catalytic cycle. These results extend the tuning scope of chemical reactions from the macroscopic view to the single-molecule approach, inspiring new insights into designing different strategies or devices to unveil reaction mechanisms and discover novel phenomena.
Sungjae Yoo, Jaewon Lee, Hajir Hilal, Insub Jung, Woongkyu Park, Joong Wook Lee, Soobong Choi, Sungho Park
Nesting of multiple polyhedral plasmonic nanoframes into a single entity (Journal Article)
In: Nature Communications, vol. 13, no. 4544 , 2022, (The spatial configuration of nanostructure building blocks determines the physical and optical properties of their superstructures. Here, the authors report on complex nanoparticles in which different geometric forms of nanoframes are nested into a single entity by multistep chemical reactions.).
The development of plasmonic nanostructures with intricate nanoframe morphologies has attracted considerable interest for improving catalytic and optical properties. However, arranging multiple nanoframes in one nanostructure especially, in a solution phase remains a great challenge. Herein, we show complex nanoparticles by embedding various shapes of three-dimensional polyhedral nanoframes within a single entity through rationally designed synthetic pathways. This synthetic strategy is based on the selective deposition of platinum atoms on high surface energy facets and subsequent growth into solid platonic nanoparticles, followed by the etching of inner Au domains, leaving complex nanoframes. Our synthetic routes are rationally designed and executable on-demand with a high structural controllability. Diverse Au solid nanostructures (octahedra, truncated octahedra, cuboctahedra, and cubes) evolved into complex multi-layered nanoframes with different numbers/shapes/sizes of internal nanoframes. After coating the surface of the nanoframes with plasmonically active metal (like Ag), the materials exhibited highly enhanced electromagnetic near-field focusing embedded within the internal complicated rim architecture.
Mingu Kang, Hyun Woo Kim, Elham Oleiki, Yeonjeong Koo, Hyeongwoo Lee, Huitae Joo, Jinseong Choi, Taeyong Eom, Geunsik Lee, Yung Doug Suh, Kyoung-Duck Park
Conformational heterogeneity of molecules physisorbed on a gold surface at room temperature (Journal Article)
In: Nature Communications, vol. 13, no. 4133, 2022, (Tip-enhanced vibrational spectroscopy at room temperature is complicated by molecular conformational dynamics, photobleaching, contaminations, and chemical reactions in air. This study demonstrates that a sub-nm protective layer of Al2O3 provides robust conditions for probing single-molecule conformations.).
A quantitative single-molecule tip-enhanced Raman spectroscopy (TERS) study at room temperature remained a challenge due to the rapid structural dynamics of molecules exposed to air. Here, we demonstrate the hyperspectral TERS imaging of single or a few brilliant cresyl blue (BCB) molecules at room temperature, along with quantitative spectral analyses. Robust chemical imaging is enabled by the freeze-frame approach using a thin Al2O3 capping layer, which suppresses spectral diffusions and inhibits chemical reactions and contamination in air. For the molecules resolved spatially in the TERS image, a clear Raman peak variation up to 7.5 cm−1 is observed, which cannot be found in molecular ensembles. From density functional theory-based quantitative analyses of the varied TERS peaks, we reveal the conformational heterogeneity at the single-molecule level. This work provides a facile way to investigate the single-molecule properties in interacting media, expanding the scope of single-molecule vibrational spectroscopy studies.
Nam Heon Cho, Young Bi Kim, Yoon Young Lee, Sang Won Im, Ryeong Myeong Kim, Jeong Won Kim, Seok Daniel Namgung, Hye-Eun Lee, Hyeohn Kim, Jeong Hyun Han, Hye Won Chung, Yoon Ho Lee, Jeong Woo Han, Ki Tae Nam
Adenine oligomer directed synthesis of chiral gold nanoparticles (Journal Article)
In: Nature Communications, vol. 13, no. 3831, 2022, (Chiral plasmonic nanoparticles are of great interest in nanotechnology. Here, the authors demonstrate chiral shape guidance by single-stranded oligonucleotides during particle growth based on sequence-specific hydrogen bonding within the strand.).
Precise control of morphology and optical response of 3-dimensional chiral nanoparticles remain as a significant challenge. This work demonstrates chiral gold nanoparticle synthesis using single-stranded oligonucleotide as a chiral shape modifier. The homo-oligonucleotide composed of Adenine nucleobase specifically show a distinct chirality development with a dissymmetric factor up to g ~ 0.04 at visible wavelength, whereas other nucleobases show no development of chirality. The synthesized nanoparticle shows a counter-clockwise rotation of generated chiral arms with approximately 200 nm edge length. The molecular dynamics and density functional theory simulations reveal that Adenine shows the highest enantioselective interaction with Au(321)R/S facet in terms of binding orientation and affinity. This is attributed to the formation of sequence-specific intra-strand hydrogen bonding between nucleobases. We also found that different sequence programming of Adenine-and Cytosine-based oligomers result in chiral gold nanoparticles’ morphological and optical change. These results extend our understanding of the biomolecule-directed synthesis of chiral gold nanoparticles to sequence programmable deoxyribonucleic acid and provides a foundation for programmable synthesis of chiral gold nanoparticles.
Li-Zhe Feng, Jing-Jing Wang, Tao Ma, Yi-Chen Yin, Kuang-Hui Song, Zi-Du Li, Man-Man Zhou, Shan Jin, Taotao Zhuang, Fengjia Fan, Manzhou Zhu, Hong-Bin Yao
Biomimetic non-classical crystallization drives hierarchical structuring of efficient circularly polarized phosphors (Journal Article)
In: Nature Communications, vol. 13, no. 3339, 2022, (Chiral emitters with high photoluminescence quantum yield are desirable for use in circularly polarized LEDs. The authors demonstrate the transfer of chirality from nanoscale copper iodide clusters to microscale chiral luminescent polycrystals by non-classical crystallization.).
Hierarchically structured chiral luminescent materials hold promise for achieving efficient circularly polarized luminescence. However, a feasible chemical route to fabricate hierarchically structured chiral luminescent polycrystals is still elusive because of their complex structures and complicated formation process. We here report a biomimetic non-classical crystallization (BNCC) strategy for preparing efficient hierarchically structured chiral luminescent polycrystals using well-designed highly luminescent homochiral copper(I)-iodide hybrid clusters as basic units for non-classical crystallization. By monitoring the crystallization process, we unravel the BNCC mechanism, which involves crystal nucleation, nanoparticles aggregation, oriented attachment, and mesoscopic transformation processes. We finally obtain the circularly polarized phosphors with both high luminescent efficiency of 32% and high luminescent dissymmetry factor of 1.5 × 10^−2, achieving the demonstration of a circularly polarized phosphor converted light emitting diode with a polarization degree of 1.84% at room temperature. Our designed BNCC strategy provides a simple, reliable, and large-scale synthetic route for preparing bright circularly polarized phosphors.