Search

Abstract Plasmonic materials can generate strong electromagnetic fields to boost the Raman scattering of surrounding molecules, known as surface-enhanced Raman scattering. However, these electromagnetic fields are heterogeneous, with only molecules located at the ‘hotspots’, which account for ≈ 1% of the surface area, experiencing efficient enhancement. Herein, we propose patterned plasmonic trimers, consisting of a pair of plasmonic dimers at the bilateral sides and a trap particle positioned in between, to address this challenge. The trimer configuration selectively directs probe molecules to the central traps where ‘hotspots’ are located through chemical affinity, ensuring a precise spatial overlap between the probes and the location of maximum field enhancement. We investigate the Raman enhancement of the Au@Al2O3-Au-Au@Al2O3 trimers, achieving a detection limit of 10−14 M of 4-methylbenzenethiol, 4-mercaptopyridine, and 4-aminothiophenol. Moreover, single-molecule SERS sensitivity is demonstrated by a bi-analyte method. Benefiting from this sensitivity, our approach is employed for the early detection of lung tumors using fresh tissues. Our findings suggest that this approach is sensitive to adenocarcinoma but not to squamous carcinoma or benign cases, offering insights into the differentiation between lung tumor subtypes.

ABSTRACTPurpose This study aimed to examine the impact of CA on DN and elucidate its underlying molecular mechanisms of inflammation.Methods We fed C57BL/6 mice injected with streptozotocin to induce diabetes. In addition, we stimulated NRK-52E cells with 20 mmol/L d-glucose to mimic the diabetic condition.Results Our findings demonstrated that CA effectively reduced blood glucose levels, and improved DN in mice models. Additionally, CA reduced kidney injury and inflammation in both mice models and in vitro models. CA decreased high glucose-induced ferroptosis of NRK-52E cells by inducing GSH/GPX4 axis. Conversely, the ferroptosis activator or the PI3K inhibitor reversed positive effects of CA on DN in both mice and in vitro models. CA suppressed PAQR3 expression in DN models to promote PI3K/AKT activity. The PAQR3 activator reduced the positive effects of CA on DN in vitro models. Moreover, CA directly targeted the PAQR3 protein to enhance the ubiquitination of the PAQR3 protein.Conclusion Overall, our study has uncovered that CA promotes the ubiquitination of PAQR3, leading to the attenuation of ferroptosis in DN. This effect is achieved through the activation of the PI3K/AKT signaling pathways by disrupting the interaction between PAQR3 and the P110α pathway. These findings highlight the potential of CA as a viable therapeutic option for the prevention of DN and other forms of diabetes.

Abstract SEMA6A is a multifunctional transmembrane semaphorin protein that participates in various cellular processes, including axon guidance, cell migration, and cancer progression. However, the role of SEMA6A in clear cell renal cell carcinoma (ccRCC) is unclear. Based on high-throughput sequencing data, here we report that SEMA6A is a novel target gene of the VHL-HIF-2α axis and overexpressed in ccRCC. Chromatin immunoprecipitation and reporter assays revealed that HIF-2α directly activated SEMA6A transcription in hypoxic ccRCC cells. Wnt/β-catenin pathway activation is correlated with the expression of SEMA6A in ccRCC; the latter physically interacted with SEC62 and promoted ccRCC progression through SEC62-dependent β-catenin stabilization and activation. Depletion of SEMA6A impaired HIF-2α-induced Wnt/β-catenin pathway activation and led to defective ccRCC cell proliferation both in vitro and in vivo. SEMA6A overexpression promoted the malignant phenotypes of ccRCC, which was reversed by SEC62 depletion. Collectively, this study revealed a potential role for VHL-HIF-2α-SEMA6A-SEC62 axis in the activation of Wnt/β-catenin pathway. Thus, SEMA6A may act as a potential therapeutic target, especially in VHL-deficient ccRCC.

The development of a dynamic network for commodity polymer systems via feasible methods has been explored in the context of a society-wide focus on the environment and sustainability. Herein, we demonstrate an adaptive post-curing method used to build a self-healable network of waterborne polyurethane–acrylate (WPUA) composite latex. The composite latex was synthesized via the miniemulsion polymerization of acrylates in the dispersion of waterborne polyurethane (PU), with commercial acetoacetoxyethyl methacrylate (AAEM) serving as the functional monomer. Then, a dynamic disulfide (S–S)-bearing diamine was applied as the crosslinking agent for the post-curing of the hybrid latex via keto-amine condensation, which occurred during the evaporation of water for film formation. It was revealed that the microphase separation in the hybrid films was suppressed by the post-curing network. The mechanical performance exhibited a high reliability as regards the contents of the crosslinking agents. The reversible exchange of S–S bonds meant that the film displayed associative covalent-adaptive networks in the range of medium temperature in stress relaxation tests, and ≥95% recovery in both the stress and the strain was achieved after the cut-off films were self-healed at 70 °C for 2 h. The rebuilding of the network was also illustrated by the >80% recovery in the elongation at break of the films after three crushing–hot pressing cycles. These findings offer valuable insights, not only endowing the traditional WPUA with self-healing and reprocessing properties, but broadening the field of study of dynamic networks to polymer hybrid latex.

Abstract SAD1/UNC84 domain protein-2 (SUN2) plays a tumor suppressor role in various types of cancer by inhibiting cancer cell proliferation, migration and promoting apoptosis. However, the post-translational regulation of SUN2 and the cellular mechanism responsible for its proteasomal degradation remains largely unknown. Here, we show that FBXO2, an E3 ubiquitin ligase of the F-box proteins (FBPs) family targets glycosylated SUN2 for ubiquitination and degradation via the ubiquitin-proteasome system (UPS). By integrating the Cancer Genome Atlas (TCGA), Gene Expression Omnibus (GEO), and the Encyclopedia of Cancer Cell Lines (CCLE) databases, we revealed that FBXO2 was selectively highly expressed in ovarian cancer (OV) tissues and cells. Patients with relatively high FBXO2 expression levels were associated with worse prognosis. Manipulation of the expression of FBXO2 affecting ovarian cancer cell proliferation, migration/invasion in vitro, and tumor growth in mice in vivo. The transcription factor SOX6 promoted FBXO2 expression by recognizing a putative response element localized on the promoter region of FBXO2. Abnormally highly expressed FBXO2 recognized and targeted glycosylated SUN2 protein for ubiquitination-depended degradation to prevent cell apoptosis, promote cell proliferation, and ultimately promote the progression of OV. Thus, we revealed a new SOX6-FBXO2-SUN2 axis that contributed to the development of OV, and targeting this axis may represent an effective OV treatment strategy.

Abstract Surface‐enhanced Raman scattering (SERS), a powerful analysis technique featuring ultrahigh sensitivity and the ability in chemically specific detection, has encountered intrinsic challenges in quantitative analysis due to the signal heterogeneity arising from sample preparation, molecular distribution, and experimental conditions. Herein, the plasmonic Janus nanoparticle, which is curved on one side and flat on the other, as a universal platform for quantitative analysis is proposed. The probe molecules are adsorbed on the curved side as internal standards to correct the signal fluctuation while the target molecules are adsorbed on the flat side for SERS measurement, and thus competitive adsorption between different molecules is prevented. Moreover, the Janus nanoparticles are partially embedded in a flexible and transparent membrane, enabling liquid‐state SERS measurement which is favorable to form a uniform self‐assembly molecular monolayer for quantitative SERS analysis. The quantitation of different biochemical molecules including Rhodamine 6G, crystal violet, and adenine are demonstrated, and an extension in linear response region for quantitative analysis is observed. The findings suggest a robust approach toward quantitative analysis.

Rolling microstructures have great potential among optics and micromechanics but on-demand construction with versatile materials remains challenging. Here Xu et al. precisely construct 3D rolling microstructures by liquid-triggered delamination in predictable manner and demonstrate their applications.

The comprehensive balance of the mechanical, interfacial, and environmental requirements of waterborne polyurethane (WPU) has proved challenging, but crucial in the specific application as the binder for high-performance polymer fiber composites. In this work, a multi-step chain extension (MCE) method was demonstrated using three kinds of small extenders and one kind of macro-chain extender (CE) for different chain extension steps. One dihydroxyl blocked small molecular urea (1,3-dimethylolurea, DMU) was applied as one of the CEs and, through the hybrid macrodiol/diamine systems of polyether, polyester, and polysiloxane, the WPU was developed by the step-by-step optimization on each chain extending reaction via the characterization on the H-bonding association, microphase separation, and mechanical properties. The best performance was achieved when the ratio of polyether/polyester was controlled at 6:4, while 2% of DMU and 1% of polysiloxane diamine was incorporated in the third and fourth chain extension steps, respectively. Under the condition, the WPU exhibited not only excellent tensile strength of 30 MPa, elongation of break of about 1300%, and hydrophobicity indicated by the water contact angle of 98°, but also effective interfacial adhesion to para-aramid fabrics. The peeling strength of the joint based on the polysiloxane incorporated WPU after four steps of chain extension was 430% higher than that prepared through only two steps of chain extension. Moreover, about 44% of the peeling strength was sustained after the joint had been boiling for 40 min in water, suggesting the potential application for high-performance fabric composites.

Summary: Development of highly sensitive, stable, and repeatable surface-enhanced Raman scattering (SERS) substrates is crucial for analytical detection, which is a challenge for traditional metallic structures. Here, by exploiting the high surface activity of the 1T′ transition metal telluride, we fabricate high-density gold nanoparticles (AuNPs) that are prepared spontaneously in situ on the 1T′ MoTe2 atomic layers, forming a plasmonic-2D material hybrid SERS substrate. This AuNP formation is unique to the 1T′ phase, which is repressed in 2H MoTe2 with lower surface activity. The hybrid structure generates coupling effects of electromagnetic and chemical enhancements, as well as excellent molecule adsorption, leading to ultrasensitive (4 × 10−17 M) and reproducible detection. Flexible SERS tapes are demonstrated in practical applications. Our approach facilitates ultrasensitive SERS detection by a facile method, as well as an enhanced mechanistic understanding of SERS beyond plasmonic effects.

Poly(p-phenylene terephthalamide) (PPTA) is one kind of lyotropic liquid crystal polymer. Kevlar fibers performed from PPTA are widely used in many fields due to their superior mechanical properties resulting from their highly oriented macromolecular structure. However, the “infusible and insoluble” characteristic of PPTA gives rise to its poor processability, which limits its scope of application. The strong interactions and orientation characteristic of aromatic amide segments make PPTA attractive in the field of self-assembly. Chemical derivation has proved an effective way to modify the molecular structure of PPTA to improve its solubility and amphiphilicity, which resulted in different liquid crystal behaviors or supramolecular aggregates, but the modification of PPTA is usually complex and difficult. Alternatively, higher-order all-PPTA structures have also been realized through the controllable hierarchical self-assembly of PPTA from the polymerization process to the formation of macroscopic products. This review briefly summarizes the self-assembly methods of PPTA-based materials in recent years, and focuses on the polymerization-induced PPTA nanofibers which can be further fabricated into different macroscopic architectures when other self-assembly methods are combined. This monomer-started hierarchical self-assembly strategy evokes the feasible processing of PPTA, and enriches the diversity of product, which is expected to be expanded to other liquid crystal polymers.

Clustering aims at discovering the natural groupings in a dataset, prevalent in many disciplines that involve multivariate data analysis. In this paper, we propose a physically inspired graph-theoretical clustering method, which first makes the data points organized into an attractive graph, called In-Tree, via a physically inspired rule, called Nearest Descent (ND). The rule of ND works to select the nearest node in the descending direction of potential as the parent node of each node, which is fundamentally different from the classical Gradient Descent. The constructed In-Tree proves a very good candidate for clustering due to its particular features and properties. In the In-Tree, the original clustering problem is reduced to a problem of removing the inter-cluster edges from this graph. Pleasingly, those inter-cluster edges are usually so distinguishable that they can be easily determined by different automatic edge-cutting methods. We also propose a visualized strategy to validate the effectiveness of the automatic edge-cutting methods. The experimental results reveal that the proposed method is superior to the related clustering methods. The results also reveal the characteristics of different automatic cutting methods and the meaningfulness of the visualized strategy in increasing the reliability of the clustering results in practice.

Abstract We mimic unique honeycomb structure as well as its functions of storing honey and pollen to assemble Au nanoparticle pattern on honeycomb-like Al nanobowl array by utilizing solid state dewetting process. Patterned Au nanoarrays of ‘one particle per bowl’ with tunable plasmonic bands ranging from the visible to the near-infrared region are fabricated by finely selecting the initial thickness of Au film, the geometry of Al nanobowl array and the thermal treatment parameters. This work presents a powerful approach to assemble Au nanoparticles into high density nanoarrays with superior spatial resolution, offering highly concentrated electromagnetic fields for plasmonic sensor applications.

Inspired by the growing demand for smart and environmentally friendly polymer materials, we employed 2,2′-disulfanediyldianiline (22DTDA) as a chain extender to synthesize a waterborne polyurethane (WPUR). Due to the ortho-substituted structure of the aromatic disulfide, the urea moieties formed a unique microphase structure in the WPUR, its mechanical strength was enhanced more 180 times relative to that of the material prepared without 22DTDA, and excellent self-healing abilities at body temperature in air or under ultrasound in water were obtained. If the self-healing process was carried out at 37 °C, 50 °C or under ultrasound, the ultimate tensile strength and elongation at break of the healed film could reach 13.8 MPa and 1150%, 15.4 MPa and 1215%, or 16 MPa and 1056%, respectively. Moreover, the WPUR films could be re-healed at the same fracture location over three cutting–healing cycles, and the recovery rates of the tensile strength and elongation at break remained almost constant throughout these cycles.