Search

This study employs aberration-corrected transmission electron microscopy to provide definitive evidence of cation ordering within the superstructure of LiNi 0.5 Co 0.2 Mn 0.3 O 2 (NCM523), a prominent Ni-rich ternary cathode material, characterized by wave vector q = 1/3(2 a * - b *). We show that this ordering can be enhanced through controlled heating. Comparative analysis of LiNi x Co y Mn z O 2 samples with different compositions revealed that Mn ions are crucial for superstructure formation. The battery performance test shows that the superstructure has no obvious effect on the voltage platform during the charge-discharge cycle, but has a negative effect on the cycle performance and structural stability. This study elucidates the origin and detrimental effects of superstructures, advancing the understanding of their impact on battery performance, which is vital for the future development of ternary cathode materials.

The branched metal-organic frameworks (MOFs) are the first superstructures of this kind, and the growth mechanism may explain crystal shapes of other materials. The mechanism of the formation of fascinating structures having a hedrite, sheaf or spherulite appearance are detailed. The branching can be controlled, resulting in crystals that either exhibit multiple generations of branching or a single generation. These structures might result from an increasing number of defects on fast-grown rods. As the basal facets become less reactive, material is added to the prism facets, leading to secondary nucleation and triangular branches. These triangular structures are connected to the rod surface, growing longer than the central rod. Electron diffraction analyses show that the sheafs are polycrystalline structures with their fantails consisting of single-crystalline nanorods deviating gradually from each other in their orientation. The crystallographic structure consists of channels with opposite handedness. The accessibility of the nanochannels and the porosity of the superstructures are demonstrated by chromophore diffusion into the channels. The confinement and alignment of the chromophores inside the channels resulted in polarized-light dependent coloration of the crystals; the polycrystallinity generated areas having different optical properties., (© 2024 The Author(s). Chemistry - A European Journal published by Wiley-VCH GmbH.)

To endow non-antibacterial molecules with highly efficient bactericide activity is an important but challenging issue. Herein, a kind of cell-penetrating peptide octa-arginine (R8) is found to be effective in activating antibacterial ability when assembling with anionic surfactant sodium dodecyl sulfate (SDS), while individual R8 or SDS shows poor or no antibacterial ability. By combined electrostatic, hydrogen bond, and hydrophobic interactions, R8 and SDS associate into wormlike micelle and lamellar structure by forming supramolecular self-assembling units, depending on their charge ratio (CR). The lamellar aggregates show particularly high antibacterial activities against both Gram-negative Escherichia coli (E. coli) and Gram-positive Staphylococcus aureus (S. aureus). Interestingly, E. coli and S. aureus are killed by membrane-disrupting and membrane-penetrating mechanisms, respectively. Furthermore, in vivo experiments evidence that the R8/SDS lamellar aggregates accelerate the recovery of bacteria-infected wounds, wherein the reduced inflammation and promoted angiogenesis are clearly presented. This study proves that highly efficient bactericidal activity is triggered by the synergistic action of penetrating peptide and anionic amphiphiles, thus providing a new strategy to realize highly efficient and targetable antibacterial application., (© 2024 Wiley‐VCH GmbH.)

The self-assembly of inorganic nanocrystals offers an efficient way for the fabrication of functional materials. However, it is still challenging for the construction of multidimensional nanostructures with controllable shapes, compositions and functions. Here, a series of heterostructures in different dimensions by surface modification of polyoxometalate (POM) clusters is developed. Three kinds of POM clusters (phosphomolybdic acid (PMA), phosphotungstic acid (PTA) and silicotungstic acid (STA) and five kinds of metal oxides (TiO 2 , VO x , La 2 O 3 , In 2 O 3 and Gd 2 O 3 ) can be used as building blocks, and a class of 1D, 2D and 3D heterostructures can be achieved by the control of surface ligand coverage. Compared with individual building blocks and other cluster-based superstructures, TiO 2 -PMA superstructures exhibit enhanced catalytic activity toward thioether oxidations, which is attributed to the electron transfer between TiO 2 and POM clusters., (© 2024 Wiley‐VCH GmbH.)

Superstructures with complex hierarchical spatial configurations exhibit broader structural depth than single hierarchical structures and the associated broader application prospects. However, current preparation methods are greatly constrained by cumbersome steps and harsh conditions. Here, for the first time, a concise and efficient thermally responsive dynamic synthesis strategy for the preparation of multidimensional complex superstructures within soluble covalent organic networks (SCONs) with tunable morphology from 0D hollow supraparticles to 2D films is presented. Mechanism study reveals the thermally responsive dynamic "cleavage-remodeling" characteristics of SCONs, synthesized based on the unique bilayer structure of (2.2)paracyclophane, and the temperature control facilitates the process from reversible solubility to reorganization and construction of superstructures. Specifically, during the process, the oil-water-emulsion two-phase interface can be generated through droplet jetting, leading to the preparation of 0D hollow supraparticles and other bowl-like complex superstructures with high yield. Additionally, by modulating the volatility and solubility of exogenous solvents, defect-free 2D films are prepared relying on an air-liquid interface. Expanded experiments further confirm the generalizability and scalability of the proposed dynamic "cleavage-remodeling" strategy. Research on the enrichment mechanism of guest iodine highlights the superior kinetic mass transfer performance of superstructural products compared to single-hierarchical materials., (© 2024 Wiley‐VCH GmbH.)

Photoreceptor cells of vertebrates feature ultrastructural membranes interspersed with abundant photosensitive ion pumps to boost signal generation and realize high gain in dim light. In light of this, superstructured optoionic heterojunctions (SSOHs) with cation-selective nanochannels are developed for manipulating photo-driven ion pumping. A template-directed bottom-up strategy is adopted to sequentially assemble graphene oxide (GO) and PEDOT:PSS into heterogeneous membranes with sculptured superstructures, which feature programmable variation in membrane topography and contain a donor-acceptor interface capable of maintaining electron-hole separation upon photoillumination. Such elaborate design endows SSOHs with a much higher magnitude of photo-driven ion flux against a concentration gradient in contrast to conventional optoionic membranes with planar configuration. This can be ascribed to the buildup of an enhanced transmembrane potential owing to the effective separation of photogenerated carriers at the heterojunction interface and the increase of energy input from photoillumination due to a synergistic effect of reflection reduction, broad-angle absorption, and wide-waveband absorption. This work unlocks the significance of membrane topographies in photo-driven transmembrane transportation and proposes such a universal prototype that could be extended to other optoionic membranes to develop high-performance artificial ion pumps for energy conversion and sensing.

The coupling electrosynthesis involving CO 2 upgrade conversion is of great significance for the sustainable development of the environment and energy but is challenging. Herein, we exquisitely constructed the self-supported bimetallic array superstructures from the Cu(OH) 2 array architecture precursor, which can enable high-performance coupling electrosynthesis of formate and adipate at the anode and the cathode, respectively. Concretely, the faradaic efficiencies (FEs) of CO 2 -to-formate and cyclohexanone-to-adipate conversion simultaneously exceed 90% at both electrodes with excellent stabilities. Such high-performance coupling electrosynthesis is highly correlated with the porous nanosheet array superstructure of CuBi alloy as the cathode and the nanosheet-on-nanowire array superstructure of CuNi hydroxide as the anode. Moreover, compared to the conventional electrolysis process, the cell voltage is substantially reduced while maintaining the electrocatalytic performance for coupling electrosynthesis in the two-electrode electrolyzer with the maximal FE formate and FE adipate up to 94.2% and 93.1%, respectively. The experimental results further demonstrate that the bimetal composition modulates the local electronic structures, promoting the reactions toward the target products. Prospectively, our work proposes an instructive strategy for constructing adaptive self-supported superstructures to achieve efficient coupling electrosynthesis., Competing Interests: The authors declare no conflicts of interest., (© 2023 The Authors. Exploration published by Henan University and John Wiley & Sons Australia, Ltd.)

The helical twisting tendency of liquid crystals (LCs) is generally governed by the inherent configuration of the chiral emitter. Here, we introduce the multistage inversion of supramolecular chirality as well as circularly polarized luminescence (CPL) by manipulating the ratio of single enantiomeric emitters (R-PCP) to LC monomers (5CB). Increasing the content of R-PCP from 1 wt % to 3 wt % inverted the helix of LCs from left-handed to right-handed, accompanying a CPL sign changed from positive to negative. The biaxiality of chiral emitters, as well as the steric effect of chiral-chiral and chiral-achiral interaction, were identified as the reasons for helical sense inversion. Due to the strong helical twisting power, 4 wt % R-PCP drove the photonic band gap (PBG) of chiral LCs to match up with their emission range, leading to an inversion of the CPL again with a high dissymmetry factor (≈1.2). Directly adjusting the PBG using chiral emitters is seldom achieved in cholesteric LCs. On this basis, an achiral sensitizer PtTPBP was assembled into the helical superstructure. The generation of triplet-triplet annihilation-induced upconverted CPL from R-PCP and the downshifting CPL from PtTPBP with opposite rotation was achieved in a single chiral LC system by tuning the position of the PBG., (© 2023 Wiley-VCH GmbH.)

Self-assembled superstructures composed of nanocrystals (NCs) have shown immense potential for enhancing the performance in electrocatalytic applications. However, there has been limited research on the self-assembly of platinum (Pt) into low-dimensional superstructures as efficient electrocatalysts for oxygen reduction reaction (ORR). In this study, we designed a unique tubular superstructure composed of monolayer or sub-monolayer carbon-armored platinum nanocrystals (Pt NCs) using a template-assisted epitaxial assembly approach. The organic ligands on the surface of Pt NCs were in situ carbonized, resulting in few-layer graphitic carbon shells that encapsulate Pt NCs. Due to their monolayer assembly and tubular geometry, the Pt utilization of the supertubes was 1.5 times higher than that of conventional carbon-supported Pt NCs. As a result, such Pt supertubes exhibit remarkable electrocatalytic performance for the ORR in acidic media, with a high half-wave potential of 0.918 V and a high mass activity of 181 A g -1 at 0.9 V, which are comparable to commercial carbon-supported Pt (Pt/C) catalysts. Furthermore, the Pt supertubes demonstrate robust catalytic stability, as confirmed by long-term accelerated durability tests and identical-location transmission electron microscopy. This study presents a new approach to designing Pt superstructures for highly efficient and stable electrocatalysis.Pt at 0.9 V, which are comparable to commercial carbon-supported Pt (Pt/C) catalysts. Furthermore, the Pt supertubes demonstrate robust catalytic stability, as confirmed by long-term accelerated durability tests and identical-location transmission electron microscopy. This study presents a new approach to designing Pt superstructures for highly efficient and stable electrocatalysis., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Inc. All rights reserved.)

Developing an inexpensive bifunctional electrocatalyst for overall water splitting is critical for acquiring scalable green hydrogen and thereby realizing carbon neutralization. Herein, an "all-in-one" method is developed for the fabrication of highly N-doped binary FeCo-phosphides (N-FeCoP) with hierarchical superstructure, this delicately designed synthesis route allows the following merits for benefiting water splitting electrocatalysis in alkaline, including high N/defect-doping for mediating the surface property of the as-made N-FeCoP, binary Fe and Co components exhibiting strong coupling interaction, and 3D hierarchical superstructure for shortening diffusion length and thereby improving reaction kinetics. Electrochemical measurements reveal that the N-FeCoP sample exhibits very low overpotentials for initiating the hydrogen and oxygen evolution reactions. Remarkably, overall water splitting can be promoted on N-FeCoP using a commercial primary Zn-MnO 2 battery. The developed synthesis strategy may potentially inspire the preparation of other N-doped metal-based nanostructures for broad electrocatalysis., (© 2023 Wiley-VCH GmbH.)

The electrocatalytic nitrogen reduction reaction (NRR) to synthesize NH 3 under ambient conditions is a promising alternative route to the conventional Haber-Bosch process, but it is still a great challenge to develop electrocatalysts' high Faraday efficiency and ammonia yield. Herein, a facile and efficient exfoliation strategy to synthesize ultrathin 2D boron and nitrogen co-doped porous carbon nanosheets (B/NC NS) via a metal-organic framework (MOF)-derived van der Waals superstructure, is reported. The results of experiments and theoretical calculations show that the doping of boron and nitrogen can modulate the electronic structure of the adjacent carbon atoms; which thus, promotes the competitive adsorption of nitrogen and reduces the energy required for ammonia synthesis. The B/NC NS exhibits excellent catalytic performance and stability in electrocatalytic NRR, with a yield rate of 153.4 µg·h -1 ·mg -1 cat and a Faraday efficiency of 33.1%, which is better than most of the reported NRR electrocatalysts. The ammonia yield of B/NC NS can maintain 92.7% of the initial NRR activity after 48 h stability test. The authors' controllable exfoliation strategy using MOF-derived van der Waals superstructure can provide a new insight for the synthesis of other 2D materials., (© 2023 Wiley-VCH GmbH.)

Intricate superstructures possess unusual structural features and promising applications. The preparation of superstructures with single-crystalline nature are conducive to understanding the structure-property relationship, however, remains an intriguing challenge. Herein we put forward a new hierarchical assembly strategy towards rational and precise construction of intricate single-crystal superstructures. Firstly, two unprecedented superclusters in Rubik's cube's form with a size of ≈2×2×2 nm 3 are constructed by aggregation of eight {Pr 4 Sb 12 } oxohalide clusters as secondary building units (SBUs). Then, the Rubik's cubes further act as isolable tertiary building units (TBUs) to assemble diversified single-crystal superstructures. Importantly, intermediate assembly states are captured, which helps illustrate the evolution of TBU-based superstructures and thus provides a profound understanding of the assembly process of superstructures at the atomic level., (© 2023 Wiley-VCH GmbH.)

All inorganic CsPbBr 3 superstructures (SSs) have attracted much research interest due to their unique photophysical properties, such as their large emission red-shifts and super-radiant burst emissions. These properties are of particular interest in displays, lasers and photodetectors. Currently, the best-performing perovskite optoelectronic devices incorporate organic cations (methylammonium (MA), formamidinium (FA)), however, hybrid organic-inorganic perovskite SSs have not yet been investigated. This work is the first to report on the synthesis and photophysical characterization of APbBr 3 (A = MA, FA, Cs) perovskite SSs using a facile ligand-assisted reprecipitation method. At higher concentrations, the hybrid organic-inorganic MA/FAPbBr 3 nanocrystals self-assemble into SSs and produce red-shifted ultrapure green emissions, meeting the requirement of Rec. 2020 displays. We hope that this work will be seminal in advancing the exploration of perovskite SSs using mixed cation groups to further improve their optoelectronic applications.

Inducing protein aggregation in vitro under various formulation and stress conditions may lead to an increased understanding of the different association routes a protein can undergo. However, a range of factors can affect the aggregation process, often leading to heterogenous samples and experimental irreproducibility between labs. Here, we present detailed methods to reproducibly form homogenous samples of superstructures: amyloid-like fibrils, spherulites, and particulates from human insulin. We discuss pitfalls and good practice in the lab, with the aim of creating awareness on the potential sources of artefacts for protein stability and aggregation studies., (© 2023. Springer Science+Business Media, LLC, part of Springer Nature.)

The exploration of electrocatalysts with high catalytic activity and long-term stability for electrochemical energy conversion is significant yet remains challenging. Zeolitic imidazolate framework (ZIF)-derived superstructures are a source of atomic-site-containing electrocatalysts. These atomic sites anchor the guest encapsulation and self-assembly of aspheric polyhedral particles produced using microreactor fabrication. This review provides an overview of ZIF-derived superstructures by highlighting some of the key structural types, such as open carbon cages, 1D superstructures, hollow structures, and the interconversion of superstructures. The fundamentals and representative structures are outlined to demonstrate the role of superstructures in the construction of materials with atomic sites, such as single- and dual-atom materials. Then, the roles of ZIF-derived single-atom sites for the electroreduction of CO 2 and electrochemical synthesis of H 2 O 2 are discussed, and their electrochemical performance for energy conversion is outlined. Finally, the perspective on advancing single- and dual-atom electrode-based electrochemical processes with enhanced redox activity and a low-impedance charge-transfer pathway for cathodes is provided. The challenges associated with ZIF-derived superstructures for electrochemical energy conversion are discussed., (© 2022 The Authors. Small published by Wiley-VCH GmbH.)

In this work, we propose a novel strategy to fabricate nickel silicate nanoflakes inside hollow mesoporous carbon spheres (Ni 3 Si 2 O 5 (OH) 4 /C). Hollow mesoporous carbon spheres (HMCSs) can well regulate and limit the growth of Ni 3 Si 2 O 5 (OH) 4 nanosheets, which obviously enhance the structural stability and conductivity of the composites. The core-shell Ni 3 Si 2 O 5 (OH) 4 /C superstructure has been proven to possess an extremely excellent electrosorption capacity of 28.7 mg g -1 at 1.2 V under a NaCl concentration of 584 mg L -1 for capacitive deionization (CDI). This outstanding property can be attributed to the core-shell superstructure with ultrathin Ni 3 Si 2 O 5 (OH) 4 nanosheets as the stable core and mesoporous carbon as the conductive shell. This work will provide a direction for the application of core-shell superstructure carbon-based nanomaterials as high-performance electrode materials for CDI., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Inc. All rights reserved.)

Background: There is currently a lack of guidelines for clinicians regarding titanium hypersensitivity in implant dentistry. Diagnostic tests such as the epicutaneous test or the lymphocyte transformation test showed inconsistent results regarding reliability and validity and thus, evidence-based consensus recommendations regarding diagnostic and therapeutic options may be helpful in clinical decision-making. Therefore, the German S3 guideline on titanium hypersensitivity in implant dentistry was developed., Findings: In the objectives, procedure, voting method and venue were defined and the consensus participants were invited. A systematic literature research was performed, and the overall quality of the evidence was rated according to the GRADE working group. Eight recommendations were formulated within the framework of a structured consensus conference under independent moderation and could be voted on with strong consensus (> 95% agreement). The formulated statements and recommendations were developed in small groups according to the guidelines of the Association of the Scientific Medical Societies in Germany (AWMF) and were discussed and agreed upon in the plenum., Conclusions: For reasonable decision-making, a patient's clinical symptoms should be regarded as leading parameters, which are usually expressed by a local inflammatory reaction with subsequent disturbed osseous integration. Allergy tests, such as the epicutaneous test or the lymphocyte transformation test are not helpful in titanium intolerance assessments, since these tests indicate T cell-mediated allergies, which are not observed in titanium intolerance reactions. Other metals and impurities that might be present in superstructures or alloys also need to be considered as the cause of an intolerance reaction and a trigger for contact sensitization. In the case of a suspected titanium particle-related, local immunologically induced inflammatory reaction with subsequent impaired osseous integration, dental ceramic implants can be considered as a therapeutic option., (© 2022. The Author(s).)

Modulating intermolecular charge-transfer (ICT) interactions between specific donor and acceptor species in host-guest systems is a big challenge and full of research value in supramolecular chemistry and materials science. In this work, a strategy to modulate the supramolecular ICT interactions in the solid state is developed by compressing the binding cavity of a macrocyclic host named perethylated leaning pillar[6]arene (p-EtLP6). The solid-state ICT affinities of p-EtLP6 toward multi-types of electron-deficient planar guests could be significantly enhanced by transforming the macrocyclic backbone from the original para-bridged mode into a hybrid para- and meta-bridged isomeric form (m-EtLP6). X-ray single-crystal structural analyses incorporating theoretical calculation demonstrate that the improved ICT affinities are mainly attributed to the superior host-guest size fit arising from the compressed binding cavity in m-EtLP6 as compared with p-EtLP6., (© 2022 Wiley-VCH GmbH.)

Colloids with surface patches (or patchy particles) can bind and assemble with directionality. However, the bonding between the usually high-symmetry, dome-shaped patches is not precise, as it cannot lock the exact position and orientation of the relevant particles. This issue prevents the assembly of well-defined colloidal superstructures by design. Herein, we introduce low-symmetry, metal-organic framework (MOF)-based patchy colloids, which feature a polyhedral matrix and flat hexagonal patches, along with anisotropic surfaces and compositions. Guided by the encoded shape/chemical information and mediated by a site-selective liquid-bridging interaction, the distinct patchy particles self-assemble into supra-colloidal (or supra-framework) structures with unprecedented precision. In this case, the valence, position, and orientation of the particles within assemblies are fully coordinated and precisely aligned. The dynamic nature of the liquid bridges also allows us to investigate the unique assembly kinetics. Our strategy not only defines new modes of colloidal bonding, but also provides a powerful means toward creating hierarchical and multi-component MOF materials., (© 2021 Wiley-VCH GmbH.)

Molybdenum-based carbides and nitrides have been considered as catalysts for the hydrogen evolution reaction (HER). One of the challenges in using Mo-based HER electrocatalysts is establishing well-defined precursors which can be transformed into Mo-based carbides/nitrides with controllable structure and porosity. We report the synthesis of a series of superstructures consisting of organic-polyoxometalate co-crystals (O-POCs) as a new type of metal-organic precursor to synthesize Mo-based carbides/nitrides in a controlled fashion and to use them for efficient catalytic hydrogen production. This protocol enables to create electrocatalysts composed of abundant nanocrystallites and heterojunctions with tunable micro- and nanostructure and mesoporosity. The best performing electrocatalyst shows high HER activity and stability with a low overpotential of 162 mV at 100 mA cm -2 (in comparison to Pt/C with 263 mV), which makes it one of the best non-noble metal HER catalysts in alkaline media and seawater., (© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Synthesis of anisotropic carbonaceous nano- and micro-materials with well-ordered mesoporous structures has attracted increasing attention for a broad scope of applications. Although hard-templating method has been widely employed, overcoming the viscous forces to prepare anisotropic mesoporous materials is particularly challenging via the universal soft-templating method, especially from sustainable biomass as a carbon resource. Herein, the synthesis of biomass-derived nanowire-arrays based mesoporous nanorods and teeth-like superstructures is reported, through a simple and straightforward polyelectrolyte assisted soft-templating hydrothermal carbonization (HTC) approach. A surface energy induced interfacial assembly mechanism with the synergetic interactions between micelles, nanowire, nanorods, and polyelectrolyte is proposed. The polyelectrolyte acts not only as a stabilizer to decrease the surface energy of cylindrical micelles, nanowires and nanorods, but also as a structure-directing agent to regulate the oriented attachment and anisotropic assembly of micelles, nanowires, and nanorods. After a calcination treatment, the carbon nanorod and teeth-like superstructure are successfully coupled with Ru to directly produce supported catalysts for the hydrogen evolution reaction, exhibiting much better performance than the isotropic nanospheres based catalyst. This HTC approach will open up new avenues for the synthesis of anisotropic materials with various morphologies and dimensions, expanding the palette of materials selection for many applications., (© 2021 Wiley-VCH GmbH.)

Electrocatalytic CO 2 reduction reaction (CO 2 RR) toward formate production can be operated under mild conditions with high energy conversion efficiency while migrating the greenhouse effect. Herein, an integrated 3D open network of interconnected bismuthene arrays (3D Bi-ene-A/CM) is fabricated via in situ electrochemically topotactic transformation from BiOCOOH nanosheet arrays supported on the copper mesh. The resulted 3D Bi-ene-A/CM consists of 2D atomically thin metallic bismuthene (Bi-ene) in the form of an integrated array superstructure with a 3D interconnected and open network, which harvests the multiple structural advantages of both metallenes and self-supported electrodes for electrocatalysis. Such distinctive superstructure affords the maximized quantity and availability of the active sites with high intrinsic activity and superior charge and mass transfer capability, endowing the catalyst with good CO 2 RR performance for stable formate production with high Faradaic efficiency (≈90%) and current density (>300 mA cm -2 ). Theoretical calculation verifies the superior intermediate stabilization of the dominant Bi plane during CO 2 RR. Moreover, by further coupling anodic methanol oxidation reaction, an exotic electrolytic system enables highly energy-efficient and value-added pair-electrosynthesis for concurrent formate production at both electrodes, achieving substantially improved electrochemical and economic efficiency and revealing the feasibility for practical implementation., (© 2021 Wiley-VCH GmbH.)

Rationally designed carbon materials with superstructures are promising candidates in applications such as electrocatalysis. However, the synthesis of highly porous carbon superstructures with macropores and carbon defects from a simple crystalline solid remains challenging. In this work, superstructured macroporous carbon rods composed of defective graphitic nanosheets are synthesized by direct carbonization of crystalline poly tannic acid (PTA) rods as precursors. During carbonization, PTA rods with a highly ordered lamellar structure induce a spatially confined two-step localized contraction that takes place in different dimensions and directions in each step. The unexpected contraction behavior results in the sponge-like macroporous carbon superstructure with large surface area, high porosity, and abundant defects, thus showing a superior electrocatalytic performance with high activity and selectivity for oxygen reduction reaction. The study provides new understandings in the design of functional carbon materials with distinctive structures and applications., (© 2021 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Depletion of architectural factors globally alters chromatin structure but only modestly affects gene expression. We revisit the structure-function relationship using the inactive X chromosome (Xi) as a model. We investigate cohesin imbalances by forcing its depletion or retention using degron-tagged RAD21 (cohesin subunit) or WAPL (cohesin release factor). Cohesin loss disrupts the Xi superstructure, unveiling superloops between escapee genes with minimal effect on gene repression. By contrast, forced cohesin retention markedly affects Xi superstructure, compromises spreading of Xist RNA-Polycomb complexes, and attenuates Xi silencing. Effects are greatest at distal chromosomal ends, where looping contacts with the Xist locus are weakened. Surprisingly, cohesin loss creates an Xi superloop, and cohesin retention creates Xi megadomains on the active X chromosome. Across the genome, a proper cohesin balance protects against aberrant inter-chromosomal interactions and tempers Polycomb-mediated repression. We conclude that a balance of cohesin eviction and retention regulates X inactivation and inter-chromosomal interactions across the genome., Competing Interests: Declaration of interests J.T.L. is a cofounder of Translate Bio and Fulcrum Therapeutics and is an advisor to Skyhawk Therapeutics. B.N. is an inventor on patent applications related to the dTAG system (WO/2017/024318, WO/2017/024319, WO/2018/148440, and WO/2018/148443)., (Copyright © 2021 Elsevier Inc. All rights reserved.)

An electrocatalytic carbon dioxide reduction reaction (CO 2 RR) is an appealing route to obtain the value-added feedstocks and alleviate the energy crisis. However, how to achieve high-performance electrocatalysts for CO 2 reduction to formate is challenging owing to the poor intrinsic activity, insufficient conductivity, and low surface density of active sites. Herein, we fabricated an extremely active and selective hydrangea-like superstructured micro/nanoreactor of ultrathin bismuth nanosheets through an in situ electrochemical topotactic transformation of hierarchical bismuth oxide formate (BiOCOOH). The resulted bismuth nanosheet superstructure is in the form of three-dimensional intercrossed networks of ultrathin nanosheets, forming an ordered open porous structure through self-assembly, which can be used as a micro/nanoreactor to enable a large electrochemically active surface area as well as high atomic utilization. Such a distinctive nanostructure endows the material with high electrocatalytic performances for CO 2 reduction to formate with near-unity Faradaic selectivity (>95%) in a wide potential window from -0.78 to -1.18 V. Furthermore, this micro/nanoreactor can give the high current densities over 300 mA cm -2 at low applied potentials without compromising selectivity in a flow cell reactor. Density functional theory (DFT) and in situ attenuated total reflection-infrared spectroscopy ( in situ ATR-IR) were further conducted to interpret the CO 2 RR mechanisms.

Despite progress on DNA-assembled nanoparticle (NP) superstructures, their complicated synthesis procedures hamper their potential biomedical applications. Here, we present an exceptionally simple strategy for the synthesis of single-stranded DNA (ssDNA) assembled Fe 3 O 4 supraparticles (DFe-SPs) as magnetic resonance contrast agents. Unlike traditional approaches that assemble DNA-conjugated NPs via Watson-Crick hybridization, our DFe-SPs are formed with a high yield through one-step synthesis and assembly of ultrasmall Fe 3 O 4 NPs via ssDNA-metal coordination bridges. We demonstrate that the DFe-SPs can efficiently accumulate into tumors for sensitive MR imaging. By virtue of reversible DNA-metal coordination bridges, the DFe-SPs could be disassembled into isolated small NPs in vivo, facilitating their elimination from the body. This work opens a new avenue for the ssDNA-mediated synthesis of superstructures, which expands the repertoire of DNA-directed NP assembly for biomedical applications.

This contribution describes the synthesis of colloidal di-patch particles functionalized with DNA on the patches and their assembly into colloidal superstructures via cooperative depletion and DNA-mediated interactions. The assembly into flower-like Kagome, brick-wall like monolayer, orthogonal packed single or double layers, wrinkled monolayer, and colloidal honeycomb superstructures can be controlled by tuning the particles' patch sizes and assembly conditions. Based on these experimental results, we generate an empirical phase diagram. The principles revealed by the phase diagram provide guidance in the design of two-dimensional (2D) materials with desired superstructures. Our strategy might be translatable to the assembly of three-dimensional (3D) colloidal structures., (© 2020 Wiley-VCH GmbH.)

The electrochemical hydrogen evolution reaction (HER) is an attractive technology for the mass production of hydrogen. Ru-based materials are promising electrocatalysts owing to the similar bonding strength with hydrogen but much lower cost than Pt catalysts. Herein, an ordered macroporous superstructure of N-doped nanoporous carbon anchored with the ultrafine Ru nanoclusters as electrocatalytic micro/nanoreactors is developed via the thermal pyrolysis of ordered macroporous single crystals of ZIF-8 accommodating Ru(III) ions. Benefiting from the highly interconnected reticular macro-nanospaces, this superstrucure affords unparalleled performance for pH-universal HER, with order of magnitude higher mass activity compared to the benchmark Pt/C. Notably, an exceptionally low overpotential of only 13 mV@10 mA cm -2 is required for HER in alkaline solution, with a low Tafel slope of 40.41 mV dec -1 and an ultrahigh turnover frequency value of 1.6 H 2 s -1 at 25 mV, greatly outperforming Pt/C. Furthermore, the hydrogen generation rates are almost twice those of Pt/C during practical overall alkaline water splitting. A solar-to-hydrogen system is also demonstrated to further promote the application. This research may open a new avenue for the development of advanced electrocatalytic micro/nanoreactors with controlled morphology and excellent performance for future energy applications., (© 2021 Wiley-VCH GmbH.)

Deep understanding of structure-property relationship between packing of chiral building units and their chiroptical behaviors would significantly facilitate the rational design and fabrication of the emerging chiroptical materials such as circularly polarized luminescence (CPL) emissive materials. In this paper, we unveil the universal existence of supramolecular tilt helical superstructures in self-assembled π-conjugated amino acid derivatives. A series of coded amino acid methyl esters were conjugated to anthracene segments at N-terminus, which afforded 2 1 and 3 1 symmetry supramolecular tilt chirality in solid-states. Helical assemblies enabled diversified Cotton effects and CPL performances, which were in accordance with the tilted chirality between anthracene segments. Such correlation shows fine universality, whereby the chiroptical prediction could be realized. Furthermore, on top of charge-transfer complexation, manipulation of CPL emission colors and handedness were realized., (© 2020 Wiley-VCH GmbH.)

Silica materials attract an increasing amount of interest in (fundamental) research, and find applications in, for example, sensing, catalysis, and drug delivery. As the properties of these (nano)materials not only depend on their chemistry but also their size, shape, and surface area, the controllable synthesis of silica is essential for tailoring the materials to specific applications. Advantageously, bioinspired routes for silica production are environmentally friendly and straightforward since the formation process is spontaneous and proceeds under mild conditions. These strategies mostly employ amine-bearing phosphorylated (bio)polymers. In this work, we expand this principle to supramolecular polymers based on the water-soluble cationic cyanine dye Pinacyanol acetate. Upon assembly in water, these dye molecules form large, polyaminated, supramolecular fibers. The surfaces of these fibers can be used as a scaffold for the condensation of silicic acid. Control over the ionic strength, dye concentration, and silicic acid saturation yielded silica fibers with a diameter of 25 nm and a single, 4 nm pore. Unexpectedly, other unusual superstructures, namely, nummulites and spherulites, are also observed depending on the ionic strength and dye concentration. Transmission and scanning electron microscopy (TEM and SEM) showed that these superstructures are formed by aligned silica fibers. Close examination of the dye scaffold prior silicification using small-angle X-ray scattering (SAXS), and UV/Vis spectroscopy revealed minor influence of the ionic strength and dye concentration on the morphology of the supramolecular scaffold. Total internal reflection fluorescence (TIRF) during silicification unraveled that if the reaction is kept under static conditions, only silica fibers are obtained. Experiments performed on the dye scaffold and silica superstructures evidenced that the marked structural diversity originates from the arrangement of silica/dye fibers. Under these mild conditions, external force fields can profoundly influence the morphology of the produced silica., (© 2020 The Authors. Published by Wiley-VCH GmbH.)

Disulfide bonds prevent aggregation of globular proteins by stabilizing the native state. However, a disulfide bond within a disordered state may accelerate amyloidogenic nucleation by navigating fluctuating polypeptide chains towards an orderly assembly of β-sheets. Here, the self-assembly behavior of Glu-Cys-(Glu) 4 -Cys-Glu peptide (E 6 C 2 ), in which an intrachain disulfide bond is engineered into an amyloidogenic homopolypeptide motif, is investigated. To this end, the Thioflavin T (ThT) fluorescence kinetic assay is combined with infrared spectroscopy, circular dichroism (CD), atomic force microscopy (AFM) and Raman scattering measurements. Regardless of whether the disulfide bond is intact or reduced, E 6 C 2 monomers remain disordered within a broad range of pH. On the other hand, only reduced E 6 C 2 self-assembles into amyloid fibrils with the unique infrared traits indicative of three-center hydrogen bonds involving main-chain carbonyl as a bifurcating acceptor and main-chain NH and side-chain -COOH groups as hydrogen donors: the bonding pattern observed in so-called β 2 -fibrils. AFM analysis of β 2 -E 6 C 2 reveals tightly packed rectangular superstructures whose presence coincides with strong chiroptical properties. Our findings suggest that formation of chiral amyloid superstructures may be a generic process accessible to various substrates, and that the fully extended conformation of a poly-Glu chain is a condition sine qua non for self-assembly of β 2 -fibrils., Competing Interests: Declaration of competing interest The authors declare no conflict of interests., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Superstructures have attracted extensive attention because of their potential applications in materials science and biology. Herein, we fabricate the first centimeter-sized porous superstructure of carbon nanosheets (SCNS) by using metal-organic framework nanoparticles as a template and polyvinylpyrrolidone as an additional carbon source. The SCNS shows a honeycomb-like morphology with wall-sharing carbon cages, in each cavity of which a porous carbon sphere is encapsulated. A single piece of SCNS is directly used as the electrode for a two-electrode symmetrical supercapacitor cell without any binders and supports, benefiting from its advantage in ultra-large geometric size, and the Fe-immobilized SCNS exhibits excellent catalytic performances for oxygen reduction reaction and in a Zn-air battery. This synthetic strategy presents a facile approach for preparing functional SCNS at centimetric scale with controllable morphologies and compositions favoring the fabrication of energy devices., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Two-dimensional carbon architectures are attracting tremendous interests for various promising applications due to their outstanding electronic and mechanical properties, although it is a great challenge to rationally devise facile and operative methodologies to engineer their structural traits owing to complex synthetic processes. Herein, for the first time, we fabricate two-dimensional carbon nanoribbons via direct thermal exfoliation of one-dimensional Ni-based metal-organic framework (MOF) nanorods, in which interconnected graphitic carbon nanocages are self-assembled into a belt-like superstructure with carbon-encapsulated Ni nanoparticles immobilized on the surface. Due to the unparalleled structural superiority, the MOF-derived carbon nanobelts exhibit excellent catalytic performances in electrocatalytic hydrogen evolution. Importantly, the practical synthetic strategy may trigger the rapid development of carbon-based superstructures in many frontier fields.

Although linker-free Au nanoparticle superstructures (AuNPSTs) have demonstrated to have satisfactory photothermal conversion efficiency owing to their enhanced visible-near-infrared absorption caused by the interparticle coupling, they cannot be used directly for in vivo photothermal therapy (PTT) of cancer because of poor stability. To address this issue, we herein propose a polymer-coating strategy, dressing AuNPST on a poly(dopamine) (PDA) coat, and successfully investigate the in vivo PTT effect of AuNPSTs. By employing Triton X-100 as an emulsifier for the formation of AuNPSTs, dopamine was site-specifically polymerized around each AuNPST by the interaction between -OH of Triton X-100 and -NH 2 of dopamine. As-fabricated AuNPST/PDA has a sphere-like shape with an average diameter of ∼106 nm and the PDA shell is about 10 nm PDA thick. The AuNPST/PDA shows enhanced durability to heat, acid, and alkali compared with bare AuNPST. Also, under 808 nm laser irradiation, AuNPST/PDA shows photothermal conversion efficiency of ∼33%, higher than bare AuNPST (∼23%). Significantly, AuNPST/PDA can be used as in-vitro and in-vivo PTT agent and shows excellent therapeutic efficacy for tumor ablation thanks to its enhanced stability and biocompatibility, indicative of its potential practicability in clinical PTT., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Fiber-shaped energy storage devices areindispensableparts of wearable and portable electronics. Aqueous rechargeable Ni/Fe battery is a very appropriate energy storage device due to their good safety without organic electrolytes, high ionic conductivity, and low cost. Unfortunately, the low energy density, poor power density and cycling performance hinder its further practical applications. In this study, in order to obtain high performance negative iron-based material, we first synthesized α-iron oxide (α-Fe 2 O 3 ) nanorods (NRs) with superstructures on the surface of highly conductive carbon nanotube fibers (CNTFs), then electrically conductive polypyrrole (PPy) was coated to enhance the electron, ion diffusion and cycle stability. Theas-prepared α-Fe 2 O 3 @PPy NRs/CNTF electrode shows a high specific capacity of 0.62 Ah cm -3 at the current density of 1 A cm -3 . Furthermore, the Ni/Fe battery that was assembled by the above negative electrode shows a maximum volumetric energy density of 15.47 mWh cm -3 with 228.2 mW cm -3 at a current density of 1 A cm -3 . The cycling durability and mechanical flexibility of the Ni/Fe battery were tested, which show good prospect for practical application. In summary, these merits make it possible for our Ni/Fe battery to have practical applications in next generation flexible energy storage devices., (Copyright © 2020 Science China Press. Published by Elsevier B.V. All rights reserved.)

Monolayer thiol-protected noble metal nanoclusters are attractive nanoscale building blocks for well-defined colloidal superstructures. However, achieving facile reversible self-assembly of nanoclusters using external stimuli is still in its infancy. Herein, we report the synthesis and photon-assisted reversible self-assembly of thiolated azobenzene-stapled Au 25 nanoclusters. Photoactivation of functionalized nanoclusters in dichloromethane by irradiating ultraviolet light at 345 nm results in a visual change and formation of disc-like colloidal superstructures ( d ∼ 100-1000 nm). The superstructures readily disassemble into individual nanoclusters upon irradiating with visible light at 435 nm. Systematic changes in both the electronic absorption bands and nuclear magnetic resonance spectra of chromophores in solution suggest that the photoisomerization of surface ligands drives the self-assembly. High-resolution transmission electron microscopy, electron tomographic reconstruction, dynamic light scattering, and small-angle X-ray powder diffraction show that the disc-like superstructures contain densely packed nanoclusters. Long-range self-assembly and disassembly under ultraviolet and visible light, respectively, demonstrate reversible photoswitching in nanoclusters.

The structure of sodium saccharinate 1.875-hydrate is presented in three- and (3+1)-dimensional space. The present model is more accurate than previously published superstructures, due to an excellent data set collected up to a high resolution of 0.89 Å -1 . The present study confirms the unusual complexity of the structure comprising a very large primitive unit cell with Z' = 16. A much smaller degree of correlated disorder of parts of the unit cell is found than is present in the previously published models. As a result of pseudo-symmetry, the structure can be described in a higher-dimensional space. The X-ray diffraction data clearly indicate a (3+1)-dimensional periodic structure with stronger main reflections and weaker superstructure reflections. Furthermore, the structure is established as being commensurate. The structure description in superspace results in a four times smaller unit cell with an additional base centring of the lattice, resulting in an eightfold substructure (Z' = 2) of the 3D superstructure. Therefore, such a superspace approach is desirable to work out this high-Z' structure. The displacement and occupational modulation of the saccharinate anions have been studied, as well as their conformational variation along the fourth dimension., (open access.)

A facile one-step solvothermal approach to engineer a van der Waals integrated heteromaterial self-assembled superstructure composed of two structurally distinct species that is polyoxomolybdate and zirconia (POM-ZrO 2 ) is reported. Nonclassical aggregation-based self-assembly process grows the superstructure. The introduced POM not only behaves as a catalytically active component of the hybrid structure but also imparts flexibility to the developed POM-ZrO 2 superstructures. The material shows high performance toward oxygenation of thioethers as a result of its morphology, composition, and structure. This growing strategy may introduce a viable pathway to the rational design of Van der Waals integrated complex hybrid, catalytically active assemblies with potential applications in different fields., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Photothermal therapy triggered by near-infrared light in the second biowindow (NIR-II) has attracted extensive interest owing to its deeper penetration depth of biological tissue, lower photon scattering, and higher maximum permissible exposure. In spite of noble metals showing great potential as the photothermal agents due to the tunable localized surface plasmon resonance, the biological applications of platinum are rarely explored. Herein, a monocomponent hollow Pt nanoframe ("Pt Spirals"), whose superstructure is assembled with three levels (3D frame, 2D layered shells, and 1D nanowires), is reported. Pt Spirals exhibit outstanding photothermal conversion efficiency (52.5%) and molar extinction coefficients (228.7 m 2 mol -1 ) in NIR-II, which are much higher than those of solid Pt cubes. Simulations indicate that the unique superstructure can be a significant cause for improving both adsorption and the photothermal effect simultaneously in NIR-II. The excellent photothermal effect is achieved and subsequently verified in in vitro and in vivo experiments, along with superb heat-resistance properties, excellent photostability, and a prominent effect on computed tomography (CT) imaging, demonstrating that Pt Spirals are promising as effective theranostic platforms for CT imaging-guided photothermal therapy., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

2D mesoporous materials fabricated via the assembly of nanoparticles (NPs) not only possess the unique properties of nanoscale building blocks but also manifest additional collective properties due to the interactions between NPs. In this work, reported is a facile and designable way to prepare free-standing 2D mesoporous gold (Au) superstructures with a honeycomb-like configuration. During the fabrication process, Au NPs with an average diameter of 5.0 nm are assembled into a superlattice film on a diethylene glycol substrate. Then, a subsequent thermal treatment at 180 °C induces NP attachment, forming the honeycomb-like ordered mesoporous Au superstructures. Each individual NP connects with three neighboring NPs in the adjacent layer to form a tetrahedron-based framework. Mesopores confined in the superstructure have a uniform size of 3.5 nm and are arranged in an ordered hexagonal array. The metallic bonding between Au NPs increases the structural stability of architected superstructures, allowing them to be easily transferred to various substrates. In addition, electron energy-loss spectroscopy experiments and 3D finite-difference time-domain simulations reveal that electric field enhancement occurs at the confined mesopores when the superstructures are excited by light, showing their potential in nano-plasmonic applications., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The spontaneous self-assembly of chiral nanoparticles (NPs) into stationary fabrication has garnered great interest in technique investigation and science advancement due to its expected apparent properties via orderly collective behaviors. However, this kind of characterization of assembled nanoparticles superstructure (NPS) is rarely reported and is distinguished with monodispersed chiral NPs. In this work, we used l-cysteine (Cys) as the chiral molecule in the form of functional surfactant, which had capped CdS/CdTe NPs and was treated as a linkage bridge for constructing orderly assembled NPS. Among the circular dichrosim (CD) phenomenon, Cys ligands exhibit related changes in CD absorption, while whole-molecule solution was used for treatment in different pH-controlling procedures. Synthesized chiral NPs are organized into ordered rod-shaped NPS during the spontaneous self-assembly process, and the CD response of NPS is monitored in different cultivating times; it showed a persuasive response appears in sum frequency generation (SFG) spectroscopy. Both experimental works and theory calculation convey that the ordered stacking of chiral stabilizer and the chirality of NPS, which are identified from chiral molecular status and their collective optical activity, originated from ligand asymmetry.

Self-assembly is a critical process that can greatly expand the existing structures and lead to new functionality of nanoparticle systems. Multicomponent superstructures self-assembled from nanocrystals have shown promise as multifunctional materials for various applications. Despite recent progress in assembly of homogeneous nanocrystals, synthesis and self-assembly of Janus nanocrystals with contrasting surface chemistry remains a significant challenge. Herein, we designed a novel Janus nanocrystal platform to control the self-assembly of nanoparticles in aqueous solutions by balancing the hydrophobic and hydrophilic moieties. A series of superstructures have been assembled by systematically varying the Janus balance and assembly conditions. Janus Au-Fe 3 O 4 dumbbell nanocrystals (<20 nm) were synthesized with the hydrophobic ligands coated on the Au lobe and negatively charged hydrophilic ligands coated on the Fe 3 O 4 lobe. We systematically fine-tune the lobe size ratio, surface coating, external conditions, and even additional growth of Au nanocrystal domains on the Au lobe of dumbbell nanoparticles (Au-Au-Fe 3 O 4 ) to harvest self-assembly structures including clusters, chains, vesicles, and capsules. It was discovered that in all these assemblies the hydrophobic Au lobes preferred to stay together. In addition, these superstructures clearly demonstrated different levels of enhanced surface plasmon resonance that is directly correlated with the Au coupling in the assembly structure. The strong interparticle plasmonic coupling displayed a red-shift in surface plasmon resonance, with larger structures formed by Au-Au-Fe 3 O 4 assembly extending into the near-infrared region. Self-assembly of Janus dumbbell nanocrystals can also be reversible under different pH values. The biphasic Janus dumbbell nanocrystals offer a platform for studying the novel interparticle coupling and open up opportunities in applications including sensing, disease diagnoses, and therapy.

Herein, the assembly of 3D uniform gear-like architectures is demonstrated with a tobacco mosaic virus (TMV) disk as a building block. In this context, the intrinsic behavior of the TMV disk that promotes its assembly into nanotubes is altered by a synergistic effect of dual functional modifications at the 53rd arginine mutation and the introduction of lysine groups in the periphery at 1st and 158th positions of the TMV disk, which results in the formation of 3D gear-like superstructures. Therein, the 53rd arginine moiety significantly strengthens the linkage between TMV disks in the alkaline environment through hydrogen bond interactions. The charge of lysine-modified lateral surfaces is partially neutralized in the alkaline solution, which induces the TMV disk to form a gear-like architecture to maintain its structural stability by exploiting the electrostatic repulsion between neighboring TMV disks. This study not only provides explicit evidence regarding the molecular-level understanding of how the modification of site-specific amino acid affects the assembly of resultant superstructures but also encourages the fabrication of functional protein-based nanoarchitectures., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Peptide-mediated routes to the synthesis of plasmonic nanoparticles have been drawing increasing attention for the development of chiroptically active nanoscale architectures. However, designing a multifunctional peptide able to drive the formation of structurally defined nanomaterials endowed with specific functionalities is still challenging. In this work, iodination has been devised as a strategy to strengthen Au-reduction capability of the amyloidogenic peptide DFNKF and combine it with its distinctive self-assembly features. Thanks to the Au-mediated C-I activation on the phenylalanine iodobenzenes, the peptides yield efficient Au-reduction ability promoting the synthesis of Au nanoparticles, and simultaneously working as templates for their spontaneous self-assembly into spherical superstructures endowed with chiroptical activities. The reaction occurs in situ through a one-pot process in aqueous media. The generality of this approach has been demonstrated using an iodinated derivative of the peptide KLVFF, which also showed reducing and templating abilities forming chiroptically active helical superstructures decorated with Au nanoparticles.

Multiplexed detection of small noncoding RNAs responsible for posttranscriptional regulation of gene expression, known as miRNAs, is essential for understanding and controlling cell development. However, the lifetimes of miRNAs are short and their concentrations are low, which inhibits the development of miRNA-based methods, diagnostics, and treatment of many diseases. Here we show that DNA-bridged assemblies of gold nanorods with upconverting nanoparticles can simultaneously quantify two miRNA cancer markers, namely miR-21 and miR-200b. Energy upconversion in nanoparticles affords efficient excitation of fluorescent dyes via energy transfer in the superstructures with core-satellite geometry where gold nanorods are surrounded by upconverting nanoparticles. Spectral separation of the excitation beam and dye emission wavelengths enables drastic reduction of signal-to-noise ratio and the limit of detection to 3.2 zmol/ng RNA (0.11 amol or 6.5 × 10 4 copies) and 10.3 zmol/ng RNA (0.34 amol or 2.1 × 10 5 copies) for miR-21 and miR-200b, respectively. Zeptomolar sensitivity and analytical linearity with respect to miRNA concentration affords multiplexed detection and imaging of these markers, both in living cells and in vivo assays. These findings create a pathway for the creation of an miRNA toolbox for quantitative epigenetics and digital personalized medicine., Competing Interests: The authors declare no conflict of interest., (Copyright © 2019 the Author(s). Published by PNAS.)

Particle assembly and co-assembly have been research frontiers in chemistry and material science in the past few decades. To achieve a large variety of intricate structures and functional materials, remarkable progress has been made in particle assembly principles and strategies. Essentially, particle assembly is driven by intrinsic interparticle interactions or the external control. In this article, we focus on binary or ternary particle co-assembly and review the principles and feasible strategies. These advances have led to new disciplines of microfabrication technology and material engineering. Although significant achievement on particle-based structures has been made, it is still challenging to fully develop general and facile strategies to precisely control the one-dimensional (1D) co-assembly. This article reviews the recent development on multicomponent particle co-assembly, which significantly increases structural complexity and functional diversity. In particular, we highlight the advances in the particle co-assembly of well-ordered 1D binary superstructures by liquid soft confinement. Finally, prospective outlook for future trends in this field is proposed., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

High-quality (Pd cube)@(Pt helix) core@shell nanoparticles, with a novel spiral-structured shell and highly-ordered tangential channels are successfully fabricated through a facile wet chemistry method with the help of N,N-dimethyloctadecyl ammonium bromide acetate sodium (OTAB-Na). A bottom-up synthesis strategy provides accurate control of layers by simply changing the molar ratio of Pt/Pd with a uniform layer thickness of 2 nm maintained in all (1-3)-rounds samples. The irregular Pt superstructures of the shells, and sophisticated core@shell hybrid materials endow the as-produced samples with highly enhanced catalytic properties, when evaluated for hydrogenation of nitrobenzene as a probe reaction., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Helical structures at different scales endow functional materials with special optical, electrical, and magnetic properties. However, methods for constructing and regulating single-handed helicity, particularly complex 3D hierarchical structures, remain limited. In this study, co-self-assembly process combined with emulsion droplets is used to produce the various well-defined 3D hollow superstructures of conducting polyaniline (PANI) with single-handed helicity. The chirality of PANI is induced using enantiomeric r- or s-camphorsulfonic acid as a dopant; the chirality of the dopant is then transferred to the supramolecular chirality of PANI assemblies and consequently to the helicity of 3D superstructures by incorporating emulsion droplets to serve collectively as soft templates. The twisting and anisotropism of these superstructures vary with the enhancement of the supramolecular chirality and result in the transformation of their morphologies from seashell-like to spindle-like and their cavity becoming more slender than their original shape. Due to the supramolecular chirality and hierarchical characteristics of these superstructures, enhanced microwave absorption performance is observed under a filler content of as low as 20 wt%, suggesting their promising application as microwave absorbers., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Biconcave thin water layers represent a template to induce organization of supramolecular structures into ordered monolayers. Here we show how micelles form extensive micrometer-sized pseudo-2D superstructures that reveal size-sorting and geometric pattern formation, as shown by cryo-transmission electron microscopy (cryoTEM). Electron-rich gold particles inside the micelles facilitate direct visualization and determination of size, composition, and ordering of the micellar assemblies over multiple length scales. Some of the patterns observed show intriguing geometric patterns for superstructures, including Fibonacci-like, double-spiral domains that also appear in, for example, sunflower seed head patterns.