24 research outputs found

    Discrete Miktoarm Star Block Copolymers with Tailored Molecular Architecture

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    Molecular architecture is a critical factor in regulating phase behaviors of the block copolymer and prompting the formation of unconventional nanostructures. This work meticulously designed a library of isomeric miktoarm star polymers with an architectural evolution from the linear-branched block copolymer to the miktoarm star block copolymer and to the star-like block copolymer (i.e., 3AB → 3(AB1)B2 → 3(AB)). All of the polymers have precise chemical composition and uniform chain length, eliminating inherent molecular uncertainties such as chain length distribution or architectural defects. The self-assembly behaviors were systematically studied and compared. Gradually increasing the relative length of the branched B1 block regulates the ratio between the bridge and loop configuration and effectively releases packing frustration in the formation of the spherical or cylindrical structures, leading to a substantial deflection of phase boundaries. Complex structures, such as Frank–Kasper phases, were captured at a surprisingly higher volume fraction. Rationally regulating the molecular architecture offers rich possibilities to tune the packing symmetry of block copolymers

    sj-docx-1-ejo-10.1177_11206721241240503 - Supplemental material for Novel compound heterozygous variants in <i>LTBP2</i> associated with relative anterior microphthalmos

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    Supplemental material, sj-docx-1-ejo-10.1177_11206721241240503 for Novel compound heterozygous variants in LTBP2 associated with relative anterior microphthalmos by Peimin Lin, Jie Xu, Ao Miao, Yi Lu, Yongxiang Jiang and Tianyu Zheng in European Journal of Ophthalmology</p

    A Single-Step Gold NanoparticleBlood Serum Interaction Assay Reveals Humoral Immunity Development and Immune Status of Animals from Neonates to Adults

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    A well-developed, functional immune system is paramount to combat harmful attacks from pathogenic organisms and prevent infectious diseases. Newborn animals and humans have only limited immunity upon birth, but their immune functions are expected to develop within weeks to months and eventually to reach a maturity that will provide full protection. Despite the importance of immune activity in animal and human health management, there is no convenient test available that allows for rapid assessment of the state of immune function in nonlaboratory settings. Here we report an extremely simple and rapid blood test that may be used in point-of-care clinics or field settings to evaluate the humoral immune status of animals. The test detects a cooperative interaction between a gold nanoparticle and arguably the three most important proteins involved in the immune system: immunoglobulin M (IgM), immunoglobulin G (IgG), and at least one complement protein, C3, in the blood serum. Such interactions cause the gold nanoparticles to form clusters and aggregates. The average particle size of the gold nanoparticle–serum mixture, measured by dynamic light scattering, corresponds positively to the immune status and activity of the subject. Our study demonstrates that the test may be used not only for monitoring the immune function development from neonates to adults, but also for detecting active immune responses during infection. Although data reported here are largely based on murine and bovine models, it is likely that this test will be applicable to humans as well

    Single Cobalt Ion-Immobilized Covalent Organic Framework for Lithium–Sulfur Batteries with Enhanced Rate Capabilities

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    Covalent organic frameworks (COFs) are notable for their remarkable structure, function designability, and tailorability, as well as stability, and the introduction of “open metal sites” ensures the efficient binding of small molecules and activation of substrates for heterogeneous catalysis and energy storage. Herein, we use the postsynthetic metal sites to catalyze polysulfide conversion and to boost the binding affinity to active matter for lithium–sulfur batteries (LSBs). A dual-pore COF, USTB-27, with hxl topology has been successfully assembled from the imine chemical reaction between 2,3,8,9,14,15-hexa(4-formylphenyl)diquinoxalino [2,3-a:2′,3′-c]phenazine and [2,2′-bipyridine]-5,5′-diamine. The chelating nitrogen sites of both modules are able to postsynthetically functionalize with single cobalt sites to generate USTB-27-Co. The discharge capacity of the sulfur-loaded S@USTB-27-Co composite in a LSB is 1063, 945, 836, 765, 696, and 644 mA h g–1 at current densities of 0.1, 0.2, 0.5, 1.0, 2.0, and 5.0 C, respectively, much superior to that of non-cobalt-functionalized species S@USTB-27. Following the increased current densities, the rate performance of S@USTB-27-Co is much better than that of S@USTB-27. In particular, the capacity retention at 5.0 C has a magnificent increase from 19% for the latter species to 61% for the former one. Moreover, S@USTB-27-Co exhibits a higher specific capacity of 543 mA h g–1 than that of S@USTB-27 (402 mA h g–1) at a current density of 1.0 C after electrochemical cycling for 500 runs. This work illustrates the “open metal sites” strategy to engineer the active chemical component conversion in COF channels as well as their binding strength for specific applications

    Constructing N‑Coordinated Co and Cu Single-Atomic-Pair Sites toward Boosted CO<sub>2</sub> Photoreduction

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    The visible-light-driven photocatalytic reduction reaction of carbon dioxide (CO2) (CO2RR) to value-added fuels presents a feasible approach to curb anthropogenic CO2 emissions and mitigate the increasing energy crisis. However, developing photocatalysts with excellent performance still remains a great challenge in this field. Herein Co,Cu,N-codoped carbon nanoparticles (Co1Cu1/NC) were fabricated through the pyrolysis of zeolitic imidazolate framework (ZIF-8) with Cu(NO3)2 adsorbed inside the cavities and CoTBPP decorated over the surface of ZIF. Spherical aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and electron energy loss spectroscopy measurements disclose the dual-metal single-atomic nature of Co1Cu1/NC consisting of atomically dispersed Co–Cu pair sites on a nitrogen-doped carbon support. Extended X-ray absorption fine-structure analysis reveals the tetra-N-coordinated nature of each metal in Co1Cu1/NC (N2–Co–N2–Cu–N2). For the purpose of comparative study, Co,N- and Cu,N-codoped carbon nanoparticles (Co1/NC and Cu1/NC) also with single atomic site nature have been fabricated following the same route. The as-prepared Co1Cu1/NC exhibits highly effective photocatalytic CO2-to-CO reduction with a considerably high CO-generating yield of 22.46 mmol g–1 and a CO selectivity of 83.4% after 2 h of visible-light irradiation. Experimental characterizations and in particular theoretical calculations disclose the close association of the remarkable CO2RR catalytic activity of Co1Cu1/NC with the synergetic effect of the Co–Cu atomic-pair sites, which facilitate the conversion of CO2 to CO via lowering the energy barrier for the formation of the *COOH intermediate. This work paves a new avenue for the rational design and construction of atomic-pair photocatalysts with boosted performance

    Discrete Linear–Branched Block Copolymer with Broken Architectural Symmetry

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    Rationally introducing chain length heterogeneity, such as binary blending, is a robust approach to regulate phase behavior of block copolymers. This work designed a library of discrete linear–branched block copolymers bearing two unequal branches. Diverse ordered nanostructures, including complex Frank–Kasper phases and quasicrystalline phase, were captured by tuning the compositional and architectural asymmetry. The precise chemistry rules out the interferences associated with statistical distribution, while the discrete feature decouples the intertwined variables. Compared with the symmetric counterparts, the synergies between the long and short chains effectively release the packing frustration during the formation of ordered structures, leading to a significant increase of lattice dimension and phase stability. The “built-in” chain length heterogeneity circumvents the shortcomings encountered by the conventional blending strategy, providing an excellent alternative for quantitatively assessing the effect of molecular symmetry on the self-assembly behaviors of block copolymers

    Cations Modulate Actin Bundle Mechanics, Assembly Dynamics, and Structure

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    Actin bundles are key factors in the mechanical support and dynamic reorganization of the cytoskeleton. High concentrations of multivalent counterions promote bundle formation through electrostatic attraction between actin filaments that are negatively charged polyelectrolytes. In this study, we evaluate how physiologically relevant divalent cations affect the mechanical, dynamic, and structural properties of actin bundles. Using a combination of total internal reflection fluorescence microscopy, transmission electron microscopy, and dynamic light scattering, we demonstrate that divalent cations modulate bundle stiffness, length distribution, and lateral growth. Molecular dynamics simulations of an all-atom model of the actin bundle reveal specific actin residues coordinate cation-binding sites that promote the bundle formation. Our work suggests that specific cation interactions may play a fundamental role in the assembly, structure, and mechanical properties of actin bundles

    Potential allelopathic azaphilones produced by the endophytic <i>Chaetomium globosum</i> TY1 inhabited in <i>Ginkgo biloba</i> using the one strain−many compounds method

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    <p>On the basis of the one strain−many compounds strategy, seven azaphilones, including Chaetomugilin A (<b>1</b>), D (<b>2</b>), S (<b>3</b>), I (<b>4</b>), J (<b>5</b>), Q (<b>6</b>) and O (<b>7</b>), were isolated from the endophytic <i>Chaetomium globosum</i> TY1. Their structures were identified by NMR and HRESIMS spectrometry data. All azaphilones were evaluated for plant growth regulation using eight species of herbaceous plant seeds seedling growth bioassay, which showed the plant growth influence of the seedling. Among these compounds tested, Chaetomugilin O (<b>7</b>) with tetrahydrofuran exhibited higher response index and lower IC<sub>50</sub> values than positive control glyphosate, a broad-spectrum systemic herbicide. <b>1</b>–<b>3</b> also showed better or similar inhibit activity to glyphosate. The structure−allelopathic activity relationship analysis of these isolated azaphilones indicates that both tetrahydrofuran and tetrahydrofuran combine with lactones ring groups give potent inhibition of seedling growth. Chaetomugilin O and Chaetomugilin A, D, S could be used to develop natural eco-friendly herbicides.</p

    Two-Dimensional Kagome Covalent Organic Frameworks with Single Atomic Co Sites for Superior Photocatalytic CO<sub>2</sub> Reduction

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    Covalent organic frameworks (COFs) have attracted great attention as pivotal photocatalysts for efficient CO2 photoreduction into value-added fuels, which hold great promise for simultaneously mitigating global warming and the energy crisis. However, the synthesis of COFs with a high crystalline state and hierarchically porous structure to boost CO2 photoreduction is still an enormous challenge and rarely reported, probably because of the great dependence upon monomers and rigorous preparation conditions. Herein, a series of functional kagome (kg m) topologic 2D COFs with high crystallinity and porosity were synthesized based on the condensation of 4,4′,4″,4‴-(ethene-1,1,2,2-tetrayl)­tetraaniline (ETTA) and 2,2′-bipyridyl-5,5′-dialdehyde (Bpy-CHO) building units combined with a postmodification strategy, named ETTA-Bpy-COF-M (M = H, Fe, Co, Ni, or Cu). Stimulated by the unique kg m topologized framework with well-ordered hierarchical micropores and mesopores, abundant exposed atomic Co sites, and remarkable photoelectrical performance, ETTA-Bpy-COF-Co is used as a photocatalyst for catalyzing the CO2-to-CO photoconversion and exhibits a high CO yield rate (9398.14 μmol g–1 h–1), a large CO selectivity (92.73%), and good durability. Experimental and theoretical analyses demonstrated that the superior performance for CO2 photoreduction catalyzed by ETTA-Bpy-COF-Co was attributed to the desirable cooperative contribution of kg m topological structure with hexagonal and triangular pores as well as atomic Co active sites, which can promote the photoexcited charge carrier kinetics, enhance the CO2 adsorption and activation, as well as reduce the energy barriers of *COOH generation and CO desorption. This work opens a new way to enhance COF photosynthesis for CO2 reduction and offers precious insights into related studies in the future
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