Advanced Science最新文献

The transformation of graphite into diamond (2-10 nm) at ordinary pressure by monodispersed Ta atoms was recently reported, while the effects of Ta concentration on the transition process remain obscure. Here, by regulating the Ta wire treatment time, as well as the annealing time and temperature, larger diamond grians (5-20 nm) are successfully synthesized, and the transition process of graphite to diamond is revealed to vary with Ta concentration. Specifically, short Ta wire treatments (5-10 min) induce graphite to form a "circle" structure and transforms into diamond directly after annealing. Long Ta wire treatments (15-25 min) produce larger and more "circle" structures, containing an increased number of graphite layers. After annealing at 1100 °C for 30-120 min, graphite first transforms into amorphous carbon, then to i-Carbon and n-Diamond, and finally to diamond. Notably, a large amount of n-Diamond and diamond are formed after 120 min annealing. By modulating the annealing temperature from 500 to 1200 °C for 30 min, diamond is already obtained at 500 °C, and hexagonal diamond up to 20 nm in size at 1200 °C. This provides a fresh insight into the graphite/diamond transition process and an approach for diamond synthesis.

Rheumatoid arthritis (RA) is a common chronic systemic autoimmune disease that often results in irreversible joint erosion and disability. Methotrexate (MTX) is the first-line drug against RA, but the significant side effects of long-term administration limit its use. Therefore, new therapeutic strategies are needed for treating RA. Here, dual-targeting biomimetic carrier-free nanomaterials (BSA-MTX-CyI nanosystem, BMC) is developed for synergistic photo-chemotherapy of RA. Bovine serum albumin (BSA), which has high affinity with SPARC (secreted protein acidic and rich in cysteine) in the RA joint microenvironment, is selected as the hydrophilic end and coupled with MTX and the phototherapeutic agent CyI to self-assemble into BMC. In vitro and in vivo experiments revealed that BMC accumulated significantly at the joint site in collagen antibody-induced arthritis mice and could be specifically recognized and taken up by folate receptors in proinflammatory M1 macrophages. Upon near-infrared laser irradiation, CyI exerted photodynamic and photothermal effects, whereas MTX not only inhibited cell proliferation but also increased cell sensitivity to reactive oxygen species, enhancing the apoptotic effect induced by CyI and achieving synergistic photo-chemotherapy. Moreover, BMC could induce macrophages to reprogram into anti-inflammatory M2 macrophages. This study provides innovative approaches for RA treatment via macrophage apoptosis and re-polarization.

The human visual nervous system excels at recognizing and processing external stimuli, essential for various physiological functions. Biomimetic visual systems leverage biological synapse properties to improve memory encoding and perception. Optoelectronic devices mimicking these synapses can enhance wearable electronics, with layered heterojunction materials being ideal materials for optoelectronic synapses due to their tunable properties and biocompatibility. However, conventional synthesis methods are complex and environmentally harmful, leading to issues such as poor stability and low charge transfer efficiency. Therefore, it is imperative to develop a more efficient, convenient, and eco-friendly method for preparing layered heterojunction materials. Here, a one-step ultrasonic method is employed to mix fullerene (C60) with graphene oxide (GO), yielding a homogeneous layered heterojunction composite film via self-assembly. The biomimetic optoelectronic synapse based on this film achieves 97.3% accuracy in dynamic visual recognition tasks and exhibits capabilities such as synaptic plasticity. Experiments utilizing X-ray photoelectron spectroscopy (XPS), X-ray diffraction spectroscopy (XRD), Fourier-transform infrared spectroscopy (FTIR), ultraviolet-visible spectroscopy (UV-vis), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) confirms stable π-π interactions between GO and C60, facilitating electron transfer and prolonging carrier recombination times. The novel approach leveraging high-density π electron materials advances artificial intelligence and neuromorphic systems.

Mn²⁺ ions doped CsPbCl₃ perovskite nanocrystals (NCs) exhibit superiority of spin-associated optical and electrical properties. However, precisely controlling the doping concentration, doping location, and the mono-distribution of Mn²⁺ ions in the large-micro-size CsPbCl₃ perovskite host is a formidable challenge. Here, the micro size CsPbCl₃ perovskite crystals (MCs) are reported with uniform Mn²⁺ ions doping by self-assembly of Mn²⁺ ions doped CsPbCl₃ perovskite NCs. The electron-phonon coupling strength is enhanced in the perovskite self-assembled CsPbCl₃ MCs, which remarkably accelerates the PL decay of Mn²⁺ ions in room temperature. Furthermore, the phonon-involved PL emission splits to two peaks at low temperature of 80 K, due to the phonon emission and absorption-induced energy exchange for exciton recombination in Mn²⁺ ions. These findings not only demonstrate a novel material system but also introduce a new theoretical framework for phonon-modulated PL manipulation in Mn²⁺-doped perovskite materials.

Bioinspired supramolecular architectonics is attracting increasing interest due to their flexible organization and multifunctionality. However, state-of-the-art bioinspired architectonics generally take place in solvent-based circumstance, thus leading to achieving precise control over the self-assembly remains challenging. Moreover, the intrinsic difficulty of ordering the bio-organic self-assemblies into stable large-scale arrays in the liquid environment for engineering devices severely restricts their extensive applications. Herein, a gaseous organization strategy is proposed with the physical vapor deposition (PVD) technology, allowing the bio-organic monomers not only self-assemble into architectures well-established from the solvent-based approaches but morphologies distinct from those delivered from the liquid cases. Specifically, 9-fluorenylmethyloxycarbonyl-phenylalanine-phenylalanine (Fmoc-FF) self-assembles into spheres with tailored dimensions in the gaseous environment rather than conventional nanofibers, due to the distinct organization mechanisms. Arraying of the spherical architectures can integrate their behaviors, thus endorsing the bio-organic film the ability of programmable optoelectronic properties, which can be employed to design P-N heterojunction-based bio-photocapacitors for non-invasive and nongenetic neurostimulations. The findings demonstrate that the gaseous strategy may offer an alternative approach to achieve unprecedented bio-organic superstructures, and allow ordering into large-scale arrays for behavior integration, potentially paving the avenue of developing supramolecular devices and promoting the practical applications of bio-organic architectonics.

Biomolecular condensates segregate nuclei into discrete regions, facilitating the execution of distinct biological functions. Here, it is identified that the WW domain containing adaptor with coiled-coil (WAC) is localized to nuclear speckles via its WW domain and plays a pivotal role in regulating alternative splicing through the formation of biomolecular condensates via its C-terminal coiled-coil (CC) domain. WAC acts as a scaffold protein and facilitates the integration of RNA-binding motif 12 (RBM12) into nuclear speckles, where RBM12 potentially interacts with the spliceosomal U5 small nuclear ribonucleoprotein (snRNP). Importantly, knockdown of RBM12, or deletion of the WAC CC domain led to altered splicing outcomes, resulting in an elevated level of BECN1-S, the short splice variant of BECN1 that is shown to upregulate mitophagy. Thus, the findings reveal a previously unrecognized mechanism for the nuclear regulation of mitochondrial function through liquid-liquid phase separation (LLPS) and provide insights into the pathogenesis of WAC-related disorders.

Black phosphorus (BP) has demonstrated potential as a drug carrier and photothermal agent in cancer therapy; however, its intrinsic functions in cancer treatment remain underexplored. This study investigates the immunomodulatory effects of polyethylene glycol-functionalized BP (BP-PEG) nanosheets in breast cancer models. Using immunocompetent mouse models-including 4T1 orthotopic BALB/c mice and MMTV-PyMT transgenic mice, it is found that BP-PEG significantly inhibits tumor growth and metastasis without directly inducing cytotoxicity in tumor cells. Mass cytometry analysis reveals that BP-PEG reshapes the tumor immune microenvironment by recruiting neutrophils. Neutrophil depletion experiments further demonstrate that the antitumor effects of BP-PEG are dependent on neutrophils. Moreover, bulk and single-cell RNA sequencing indicate that BP-PEG is mainly taken up by macrophages, leading to the release of inflammatory factors such as IL1A and CXCL2, which enhance neutrophil recruitment and activation, thereby amplifying the antitumor immune response. Finally, co-culture assays confirm that BP-PEG indeed enhances the antitumor activity of neutrophils and natural killer (NK) cells. These findings position BP-PEG as an immunomodulatory agent capable of reprogramming the tumor microenvironment to promote innate immunity against breast cancer. By stimulating neutrophil-mediated antitumor activity, BP-PEG offers a unique therapeutic approach that can potentially enhance the efficacy of existing cancer immunotherapies.

Immobilizing enzymes onto solid supports having enhanced catalytic activity and resistance to harsh external conditions is considered as a promising and critical method of broadening enzymatic applications in biosensing, biocatalysis, and biomedical devices; however, it is considerably hampered by limited strategies. Here, a core-shell strategy involving a soft-core hexahistidine metal assembly (HmA) is innovatively developed and characterized with encapsulated enzymes (catalase (CAT), horseradish peroxidase, glucose oxidase (GOx), and cascade enzymes (CAT+GOx)) and hard porous shells (zeolitic imidazolate framework (ZIF), ZIF-8, ZIF-67, ZIF-90, calcium carbonate, and hydroxyapatite). The enzyme-friendly environment provided by the embedded HmA proves beneficial for enhanced catalytic activity, which is particularly effective in preserving fragile enzymes that will have been deactivated without the HmA core during the mineralization of porous shells. The enzyme encapsulated within a core-shell particle exhibits noteworthy resilience against harsh external conditions, including heat, organic solvents, and proteinase K. Additionally, no significant alteration in the catalytic behavior of the enzyme is observed after multiple cycles of usage. This study offers a novel approach for immobilizing enzymes and rendering them resistant to harsh external conditions, with potential applications in diverse fields, including biocatalysis, bioremediation, and biomedical engineering.

Rice is highly sensitive to cold stress, particularly at the booting stage, which significantly threatens rice production. In this study, we cloned a gene, CTB6, encoding a lipid transfer protein involved in cold tolerance at the booting stage in rice, based on our previous fine-mapped quantitative trait locus (QTL) qCTB10-2. CTB6 is mainly expressed in the tapetum and young microspores of the anther. CTB6 interacts with catalases (CATs) to maintain their stability, thereby scavenging reactive oxygen species (ROS) accumulation in anthers and facilitating tapetum development under cold stress conditions. Additionally, CTB6 has lipid-binding ability and affects the lipid content in anthers to regulate cold tolerance at the booting stage. Haplotype analysis and promoter activity assay revealed a specific single nucleotide polymorphism (SNP)-489 variation in the promoter of CTB6, which enhances its expression and results in improved cold tolerance in Hap1-K varieties. The CTB6 near-isogenic line (NIL) exhibited enhanced cold tolerance at the booting stage, with no significant effects on other agronomic traits. Our findings uncover a natural variation of CTB6 for cold tolerance at the booting stage and provide new genetic resources for cold tolerance breeding in rice.

In this manuscript, an all-optical modulation photodetector based on a CdS/graphene/Ge sandwich structure is designed. In the presence of the modulation (near-infrared) light, the Fermi level of the graphene channel shifts, allowing for the tuning of the visible light response speed as well as achieving a broad responsivity range from negative (-3376 A/W) to positive (3584 A/W) response. Based on this, logical operations are performed by adjusting the power of the modulation light superimposed with the signal light. This facilitates more covert, all-optical, high-speed encrypted communication. The ultrahigh tunability and nearly symmetric positive and negative photoconductivity of all-optical modulation photodetectors significantly enhance the computational capacity of neuromorphic hardware. The proposed device exhibits substantial advantages in applications requiring high fault tolerance for integrated sensing-computing （ISC） and high-resolution motion object recognition, providing insights for the development of next-generation high-bandwidth, low-power-consumption ISC devices.