bluuebunny/crossref_metadata_2025_split huggingface dataset:
Stable Graphene Membranes for Selective Ion Transport and Emerging Contaminants Removal in Water
Authors: Sankar Siva Nemala , Fernandes João , dos Santos Marília Barreiros , Espiña Begoña , Alpuim Pedro , Díez Ander García , Lanceros‐Mendez Senentxu , Saini Lalita , Kaushik Suvigya , Kalon Gopinadhan , Capasso Andrea 
Published: March 2023

AbstractCarbon‐based materials, such as graphene oxide and reduced graphene oxide membranes have been recently used to fabricate ultrathin, high‐flux, and energy‐efficient membranes for ionic and molecular sieving in aqueous solution. However, these membranes appeared rather unstable during long‐term operation in water with a tendency to swell over time. Membranes produced from pristine, stable, layered graphene materials may overcome these limitations while providing high‐level performance. In this paper, an efficient and “green” strategy is proposed to fabricate µm‐thick, graphene‐based laminates by liquid phase exfoliation in Cyrene and vacuum filtration on a PVDF support. The membranes appear structurally robust and mechanically stable, even after 90 days of operation in water. In ion transport studies, the membranes show size selection (>3.3 Å) and anion‐selectivity via the positively charged nanochannels forming the graphene laminate. In antibiotic (tetracycline) diffusion studies under dynamic conditions, the membrane achieve rejection rates higher than 95%. Sizable antibacterial properties are demonstrated in contact method tests with Staphylococcus aureus and Escherichia coli bacteria. Overall, these “green” graphene‐based membranes represent a viable option for future water management applications.
Atomic Lattice Resolved Electron Tomography of a 3D Self‐Assembled Mesocrystal
Authors: Chu Xiaolei , Abelson Alex , Qian Caroline , Igouchkine Oleg , Field Ethan , Ma Kwan‐Liu , Law Matt , Moule Adam J. 
Published: March 2023

AbstractComplex 3D architectures of nanoscale building blocks can be created by self‐assembly, but characterization of the atomic to mesoscale structure of such materials is limited by the difficulty of visualizing atoms across multiple length scales. Here, scanning transmission electron microscopy (STEM) and full‐tilt tomographic reconstruction are used to image a single‐crystalline region of a 3D epitaxially‐fused PbSe quantum dot (QD) superlattice containing 633 QDs at a spatial resolution of 2.16 Å. The combined real‐space and reciprocal‐space analysis enables 3D mesoscale correlations of atomic lattice and superlattice order across hundreds of nanocrystals in 3D for the first time. Inhomogeneity in QD positional and orientational order reveals that the QD surface layers template the superlattice and that orientational entropy is higher in the interior layers than the surface layers. The measurement and analysis techniques presented here are applicable to a broad range of 3D nanostructured materials.
Tunable Mesoscopic Collagen Island Architectures Modulate Stem Cell Behavior
Authors: Nguyen Ryan Y. , Cabral Aidan T. , Rossello‐Martinez Alejandro , Zulli Alessandro , Gong Xiangyu , Zhang Qiuting , Yan Jing , Mak Michael 
Published: March 2023

AbstractThe extracellular matrix is the biophysical environment that scaffolds mammalian cells in the body. The main constituent is collagen. In physiological tissues, collagen network topology is diverse with complex mesoscopic features. While studies have explored the roles of collagen density and stiffness, the impact of complex architectures remains not well‐understood. Developing in vitro systems that recapitulate these diverse collagen architectures is critical for understanding physiologically relevant cell behaviors. Here, methods are developed to induce the formation of heterogeneous mesoscopic architectures, referred to as collagen islands, in collagen hydrogels. These island‐containing gels have highly tunable inclusions and mechanical properties. Although these gels are globally soft, there is regional enrichment in the collagen concentration at the cell‐scale. Collagen‐island architectures are utilized to study mesenchymal stem cell behavior, and it is demonstrated that cell migration and osteogenic differentiation are altered. Finally, induced pluripotent stem cells are cultured in island‐containing gels, and it is shown that the architecture is sufficient to induce mesodermal differentiation. Overall, this work highlights complex mesoscopic tissue architectures as bioactive cues in regulating cell behavior and presents a novel collagen‐based hydrogel that captures these features for tissue engineering applications.
Hierarchical Serpentine‐Helix Combination for 3D Stretchable Electronics
Authors: Yan Zhuocheng , Liu Yuting , Xiong Jian , Wang Bin , Dai Lingliang , Gao Min , Pan Taisong , Yang Weiqing , Lin Yuan 
Published: March 2023

Abstract3D stretchable electronics attract growing interest due to their new and more complex functionalities compared to 1D or 2D counterparts. Among all 3D configuration designs, a 3D helical structure is commonly used as it can be designed to achieve outstanding stretching ratios as well as highly robust mechanical performance. However, the stretching ratio that mainly focuses on the axis direction hinders its applications. Inspired by hierarchies in a tendon, a novel structural design of hierarchical 3D serpentine‐helix combination is proposed. The structural design constructed by a sequence with repeating small units winding in a helical manner around the axis can enable large mechanical forces transferred down to a smaller scale with the dissipation of potentially damaging stresses by microscale buckling, thereby endowing the electronic components made from high‐performance but hard‐to‐stretch materials with large stretchability (≥200%) in x‐, y‐, or z‐axis direction, high structural stability, and extraordinary electromechanical performance. Two applications including a wireless charging patch and an epidermal electronic system are demonstrated. The epidermal electronic system made of several hierarchical 3D serpentine‐helix combinations allows for high‐fidelity monitoring of electrophysiological signals, galvanic skin response, and finger‐movement‐induced electrical signals, which can achieve good tactile pattern recognition when combined with an artificial neural network.
Room‐Temperature Magnetism in 2D MnGa4‐H Induced by Hydrogen Insertion
Authors: Wei Nan , He Liangcheng , Wu Changwei , Lu Dabiao , Li Ruohan , Shi Haiwen , Lan Haihui , Wen Yao , He Jun , Long Youwen , Wang Xiao , Zeng Mengqi , Fu Lei 
Published: March 2023

Abstract2D room‐temperature magnetic materials are of great importance in future spintronic devices while only very few are reported. Herein, a plasma‐enhanced chemical vapor deposition approach is exploited to construct the 2D room‐temperature magnetic MnGa4‐H single crystal with a thickness down to 2.2 nm. The employment of H2 plasma makes hydrogen atoms can be easily inserted into the MnGa4 lattice to modulate the atomic distance and charge state, thereby ferrimagnetism can be achieved without destroying the structural configuration. The as‐obtained 2D MnGa4‐H crystal is high‐quality, air‐stable, and thermo‐stable, demonstrating robust and stable room‐temperature magnetism with a high Curie temperature above 620 K. This work enriches the 2D room‐temperature magnetic family and opens up the possibility for the development of spintronic devices based on 2D magnetic alloys.
Realizing Photoswitchable Mechanoluminescence in Organic Crystals Based on Photochromism
Authors: Xie Zongliang , Zhang Xiayu , Xiao Yuxin , Wang Hailan , Shen Mingyao , Zhang Simin , Sun Haodong , Huang Rongjuan , Yu Tao , Huang Wei 
Published: March 2023

AbstractOrganic mechanoluminescent (ML) materials possessing photophysical properties that are sensitive to multiple external stimuli have shown great potential in many fields, including optic and sensing. Particularly, the photoswitchable ML property for these materials is fundamental to their applications but remains a formidable challenge. Herein, photoswitchable ML is successfully realized by endowing reversible photochromic properties to an ML molecule, namely 2‐(1,2,2‐triphenylvinyl) fluoropyridine (o‐TPF). o‐TPF shows both high‐contrast photochromism with a distinct color change from white to purplish red, as well as bright blue ML (λML = 453 nm). The ML property can be repeatedly switched between ON and OFF states under alternate UV and visible light irradiation. Impressively, the photoswitchable ML is of high stability and repeatability. The ML can be reversibly switched on and off by conducting alternate UV and visible light irradiation in cycles under ambient conditions. Experimental results and theoretical calculations reveal that the change of dipole moment of o‐TPF during the photochromic process is responsible for the photoswitchable ML. These results outline a fundamental strategy to achieve for the control of organic ML and pave the way to the development of expanded smart luminescent materials and their applications.
An investigation of Solid‐State Emission of Halogenated Diphenyl Phosphanyl Anthracenes
Authors: Patten Tim , Graw Nico , Friedl Sebastian , Stalke Dietmar , Krawczuk Anna 
Published: March 2023

AbstractIn today's world, the development and research of optoelectronic materials and devices based on solid‐state luminescence is essential. Due to their versatile application possibilities, e.g. as light‐emitting diodes or lasers, they are already indispensable. This work presents three halogenated anthracene derivatives [9‐PPh2‐10‐X‐(C14H8)] and their respective photoluminescent behavior in solution and in the solid state. The formation of halogen–π interactions in the solid state leads to unanticipated luminescence properties for the chlorinated species, resulting in a strong bathochromic shift, green fluorescence and a longer lifetime. In contrast, the other two derivatives, which in turn form only weak π–π interactions due to a small overlap of the anthracene rings, barely change their luminescence behavior in the solid state. By employing additional charge density studies, the structure–property correlation is also investigated. In particular, focus is given to halogen bonding and halogen–π interactions and their influence on photophysical properties of the studied compounds. Through the new knowledge gained, this study will help in the future development and selective application of the photophysical properties of solid‐state luminescent materials.
Design and Polarization Control of the Modal Splitting in Hybrid Anisotropic Nanocavities
Authors: Patra Aniket , Pothuraju Renuka Devi , De Dhananjoy , Caligiuri Vincenzo , Vijaya R. , De Luca Antonio , Krahne Roman 
Published: March 2023

AbstractThe strong coupling of optical resonators results in a mode splitting proportional to the coupling strength, which can be achieved with metal‐dielectric‐metal (MDM) cavities that have similar thickness and refractive index. However, an active control of the mode coupling is challenging. Here, an alternative configuration of an MDM cavity coupled with a Guided‐Mode‐Resonator (GMR) is explored. The GMR grating is fabricated on top of the MDM cavity, such that the coupling can be tuned by the thickness of the central metal. The typical modal anti‐crossing (with a splitting of ≈50–65 meV) detected in the angular dispersion of the GMR‐MDM is observed. Excellent agreement of the experimental reflectance with simulations allows to report the angular dispersion from −50° to 50°. The anisotropy of the GMR modes enables to switch in and out of the strong coupling by changing the polarization of the incident light. Moreover, the asymmetry of the GMR‐MDM architecture induces a side‐dependent response. The MDM cavity is only transparent at its resonances, which leads to a suppression of all modes outside the resonance bands when impinging from the MDM side. These features are highly interesting for optoelectronic applications such as optical switches and multi‐level optical multiplexing.
Electronic Conductivity of Lithium Solid Electrolytes
Authors: Shao Bowen , Huang Yonglin , Han Fudong 
Published: March 2023

AbstractWhile significant efforts are being devoted to improving the ionic conductivity of lithium solid electrolytes (SEs), electronic transport, which has an important role in the calendar life, energy density, and cycling stability of solid‐state batteries (SSBs), is rarely studied. Here, the electronic conductivities of three representative SEs, including Li3PS4, Li7La3Zr2O12, and Li3YCl6, are reported. It is reported that the electronic conductivities of SEs are overestimated from the conventional measurements. By revisiting direct current polarizations using two‐blocking‐electrode cells and the Hebb‐Wagner approach, their sources of inaccuracy are provided and the anodic decomposition of SE is highlighted as the key source for the overestimated result. Modifications in the electrode selection and data interpretation are also proposed to approach the intrinsic electronic conductivity of SEs. A two‐step polarization method is also proposed to estimate the electronic conductivity of sulfides that decompose during measurement. Measured by the modified approach, the electronic conductivities of all SEs are one or two orders of magnitude lower than the reported value. Despite that, the electronic conductivity of sulfides seems to be still quite high to enable SSBs with a long calendar life of >10 years, highlighting the critical need for a more careful study of electronic transport in lithium SEs.
Organic amendments effects on soil aggregation and carbon sequestration in saline‐alkaline croplands in China
Authors: Zhang Yuexian , Li Fei , Lu Zhanyuan , Pei Zhifu , Zhao Huixin , Shen Qinguo , Hong Mei 
Published: March 2023

AbstractSaline‐alkaline soils are wide‐spread and approximately 6.5% of the world's land area is reported as being saline and sodic. Increasing soil organic carbon (SOC) concentration and aggregate stability in saline‐alkaline soils has been challenging due to the deleterious effects of soil salinity and sodicity. To address this issue, a 2‐year filed experiment was conducted to evaluate the effects of biochar (BC), farmyard manure (FM), corn straw (CS), and sheep manure (SM) in combination of chemical fertilizer (CK) on soil aggregation and C sequestration in mildly and moderately alkaline soils in Hetao Irrigation District, China. For mildly alkaline soil, the proportion of macroaggregates (>0.25 mm) was significantly higher under FM, CS, and SM (34.6%–51.2%) compared with CK (13.2%). The mean weight diameter (MWD) and geometric mean diameter (GMD) of water‐stable aggregates significantly increased under FM, CS, and SM by an average of 172.7% and 58.7% over CK. In addition, FM, CS, and SM enhanced the distribution of organic carbon (OC) in macroaggregates (>0.25 mm) and accelerated the accumulation of particulate organic matter within macroaggregates. Treatment BC enhanced OC distribution in microaggregates (0.053–0.25 mm) and exhibited a 7.40 g kg−1 SOC content, followed by SM and FM which exhibited SOC contents of 7.10 and 6.76 g kg−1. For moderately alkaline soil, data obtained in this study showed a slight influence from organic amendments on soil aggregates and C sequestration, suggesting that the moderately alkaline soil was not as sensitive to organic amendments as the mildly alkaline soil. Overall, the results of this study demonstrated that FM and SM combined with chemical fertilizer were the top organic amendments to improve soil aggregation and C sequestration in the mildly alkaline soil but not the moderately alkaline soil over the short term.
Nickel‐Catalyzed Sulfonylation of Aryl Bromides Enabled by Potassium Metabisulfite as a Uniquely Effective SO2 Surrogate
Authors: Hethcox J. Caleb , Johnson Heather C. , Kim Jungchul , Wang Xiao , Cheng Lili , Cao Yang , Tan Melissa , DiRocco Daniel A. , Ji Yining 
Published: March 2023

AbstractThe development and mechanistic investigation of a nickel‐catalyzed sulfonylation of aryl bromides is disclosed. The reaction proceeds in good yields for a variety of substrates and utilizes an inexpensive, stench‐free, inorganic sulfur salt (K2S2O5) as a uniquely effective SO2 surrogate. The active oxidative addition complex was synthesized, isolated, and fully characterized by a combination of NMR spectroscopy and X‐ray crystallography analysis. The use of the isolated oxidative addition complex in both stoichiometric and catalytic reactions revealed that SO2 insertion occurs via dissolved SO2, likely released upon thermal decomposition of K2S2O5. Key to the success of the reaction is the role of K2S2O5 as a reservoir of SO2 that is slowly released, thus preventing catalyst poisoning.
Metal‐Organic Framework Supported Copper Photoredox Catalysts for Iminyl Radical‐Mediated Reactions
Authors: Ma Ben , Xia Qi , Wang Deyang , Jin Ji‐Kang , Li Zekun , Liang Qiu‐Jiang , Sun Meng‐Ying , Liu Dongyi , Liu Li‐Juan , Shu Hui‐Xing , Yang Jun , Li Dan , He Jian 
Published: March 2023

AbstractVisible‐light copper photocatalysis has recently emerged as a viable technology for building sustainable synthetic processes. To broaden the applications of phosphine‐ligated copper(I) complexes, we describe herein an effective metal‐organic framework (MOF)‐supported copper(I) photocatalyst for multiple iminyl radical‐mediated reactions. Due to site isolation, the heterogenized copper photosensitizer has a significantly higher catalytic activity than its homogeneous counterpart. Using a hydroxamic acid linker to immobilize copper species on MOF supports affords the heterogeneous catalysts with high recyclability. The post‐synthetic modification sequence on MOF surfaces allows for the preparation of previously unavailable monomeric copper species. Our findings highlight the potential of using MOF‐based heterogeneous catalytic systems to address fundamental challenges in the development of synthetic methodologies and mechanistic investigations of transition‐metal photoredox catalysis.
Catalytic Chemo‐ and Regioselective Radical Carbocyanation of 2‐Azadienes for the Synthesis of α‐Amino Nitriles
Authors: Duan Shengzu , Du Ya , Wang Lingling , Tian Xun , Zi Yujin , Zhang Hongbin , Walsh Patrick J. , Yang Xiaodong 
Published: March 2023

Abstractα‐Amino nitriles are versatile structural motifs in a variety of biologically active compounds and pharmaceuticals and they serve as valuable building blocks in synthesis. The preparation of α‐ and β‐functionalized α‐amino nitriles from readily available scaffolds, however, remains challenging. Herein is reported a novel dual catalytic photoredox/copper‐catalyzed chemo‐ and regioselective radical carbocyanation of 2‐azadienes to access functionalized α‐amino nitriles by using redox‐active esters (RAEs) and trimethylsilyl cyanide. This cascade process employs a broad scope of RAEs and provides the corresponding α‐amino nitrile building blocks in 50–95 % yields (51 examples, regioselectivity >95 : 5). The products were transformed into prized α‐amino nitriles and α‐amino acids. Mechanistic studies suggest a radical cascade coupling process.
From Dinitrogen to N‐Containing Organic Compounds: Using Li2CN2 as a Synthon
Authors: Wu Li‐Jun , Wang Qianru , Guo Jianping , Wei Junnian , Chen Ping , Xi Zhenfeng 
Published: March 2023

AbstractThrough the synergies of a heterogeneous synthetic approach and a homogeneous synthetic methodology, N‐containing organic compounds can be synthesized via activated N‐containing species prepared from N2 gas and suitable carbon sources. From N2, carbon, and LiH, we have previously succeeded in the high‐yield preparation of Li2CN2 as the activated N‐containing species. In this work, we applied Li2CN2 as a novel synthetic synthon for constructing N‐containing organic compounds. A series of reaction models, including a substitution reaction, cycloaddition reaction, and transition metal‐catalyzed coupling reaction, were successfully performed using Li2CN2 under mild conditions. Various valuable cyanamides, carbodiimides, N‐aryl cyanamides and 1,2,4‐triazole derivatives were readily synthesized in moderate to excellent yields. With this method, the 15N‐labeled products, including oxazolidine derivatives with anti‐cancer activity, could also be facilely prepared from 15N2 gas.
Controlled Deformation of Soft Nanogel Particles Generates Artificial Biominerals with Ordered Internal Structure
Authors: Dong Yingxiang , Chi Jialin , Ren Zelun , Xiong Biao , Liu Ziqing , Zhang Wenjun , Wang Lijun , Fujii Syuji , Armes Steven P. , Ning Yin 
Published: March 2023

AbstractBiominerals can exhibit exceptional mechanical properties owing to their hierarchically‐ordered organic/inorganic nanocomposite structure. However, synthetic routes to oriented artificial biominerals of comparable complexity remain a formidable technical challenge. Herein we design a series of soft, deformable nanogels that are employed as particulate additives to prepare nanogel@calcite nanocomposite crystals. Remarkably, such nanogels undergo a significant morphological change—from spherical to pseudo‐hemispherical—depending on their degree of cross‐linking. This deformation occurs normal to the growth direction of the (104) face of the calcite and the underlying occlusion mechanism is revealed by in situ atomic force microscopy studies. This model system provides new mechanistic insights regarding the formation of oriented structures during biomineralization and offers new avenues for the design of synthetic nanocomposites comprising aligned anisotropic nanoparticles.
Chiral Supramolecular Multiblock Copolymerization Accompanying Chirality Transfer in Heterostructures via Living Chain Growth
Authors: Oh Jeong Sang , Kim Ka Young , Kim Minhye , Kim Sukyoung , Jung Sung Ho , Jung Jong Hwa 
Published: March 2023

AbstractWe report the unique synthesis of chiral supramolecular tri‐ and penta‐BCPs with controllable chirality using kinetically adjusted seeded supramolecular copolymerization in THF and DMSO (99 : 1, v/v). Tetraphenylethylene (d‐ and l‐TPE) derivatives bearing d‐ and l‐alanine side chains formed thermodynamically favored chiral products via a kinetically trapped in monomeric state with a long lag phase. In contrast, achiral TPE‐G containing glycine moieties did not form a supramolecular polymer owing to the energy barrier in its kinetically trapped state. We show that the copolymerization of the metastable states of TPE‐G not only enables the generation of supramolecular BCPs by the seeded living growth method, but also transfers chirality at the seed ends. This research demonstrates the generation of chiral supramolecular tri‐ and penta‐BCPs with B‐A‐B, A‐B‐A‐B‐A, and C‐B‐A‐B‐C block patterns accompanying chirality transfer via seeded living polymerization.
Reticular Chemistry‐Enabled Sonodynamic Activity of Covalent Organic Frameworks for Nanodynamic Cancer Therapy
Authors: Duan Yanqiu , Yu Yang , Liu Peilai , Gao Yao , Dai Xinyue , Zhang Liang , Chen Liang , Chen Yu 
Published: March 2023

AbstractThe development of covalent organic framework (COF) sonosensitizers with intrinsic sonodynamic effects is highly desirable. However, such COFs are generally constructed using small‐molecule photosensitizers. Herein, we report that the reticular chemistry‐based synthesis of COFs from two inert monomers yields a COF‐based sonosensitizer (TPE‐NN) with inherent sonodynamic activity. Subsequently, a nanoscale COF TPE‐NN is fabricated and embedded with copper (Cu)‐coordinated sites to obtain TPE‐NN‐Cu. Results show that Cu coordination can enhance the sonodynamic effect of TPE‐NN, whereas ultrasound (US) irradiation for sonodynamic therapy can augment the chemodynamic efficacy of TPE‐NN‐Cu. Consequently, TPE‐NN‐Cu upon US irradiation shows high‐performance anticancer effects based on mutually reinforced sono‐/chemo‐nanodynamic therapy. This study reveals the backbone‐originated sonodynamic activity of COFs and proposes a paradigm of intrinsic COF sonosensitizers for nanodynamic therapy.