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Immunosuppressive tumor microenvironment and limited intratumoral permeation have largely constrained the outcome of tumor therapy. Herein, we report a tailored DNA structure-based nanoplatform with striking tumor-penetrating capability for targeted remodeling of immunosuppressive tumor microenvironment in vivo. In our design, chemo-immunomodulator (gemcitabine) can be precisely grafted in DNA sequences via a reactive oxygen species (ROS)-sensitive linker. After self-assembly, the gemcitabine-grafted DNA structure can site-specifically organize legumain-activatable melittin pro-peptide (promelittin) on each vertex for intratumoral delivery and further function as the template to load photosensitizers (methylene blue) for ROS production. The tailored DNA nanoplatform can achieve targeted accumulation, highly improved intratumoral permeation, and efficient immunogenic cell death of tumor cells by laser irradiation. Finally, the immunosuppressive tumor microenvironment can be successfully remodeled by reducing multi-type immunosuppressive cells and enhancing the infiltration of cytotoxic lymphocytes in the tumor. This rationally developed multifunctional DNA nanoplatform provides a new avenue for the development of tumor therapy.

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Biophotonic nanostructures in butterfly wing scales remain fascinating examples of biological functional materials, with intriguing open questions with regard to formation and evolutionary function. One particularly interesting butterfly species, Erora opisena (Lycaenidae: Theclinae), develops wing scales that contain three-dimensional photonic crystals that closely resemble a single gyroid geometry. Unlike most other gyroid-forming butterflies, E. opisena develops discrete gyroid crystallites with a pronounced size gradient hinting at a developmental sequence frozen in time. Here, we present a novel application of a hyperspectral (wavelength-resolved) microscopy technique to investigate the ultrastructural organization of these gyroid crystallites in dry, adult wing scales. We show that reflectance corresponds to crystallite size, where larger crystallites reflect green wavelengths more intensely; this relationship could be used to infer size from the optical signal. We further successfully resolve the red-shifted reflectance signal from wing scales immersed in refractive index liquids with varying refractive index, including values similar to water or cytosol. Such photonic crystals with lower refractive index contrast may be similar to the hypothesized nanostructural forms in the developing butterfly scales. The ability to resolve these fainter signals hints at the potential of this facile light microscopy method for in vivo analysis of nanostructure formation in developing butterflies.

Asunto(s)

Mariposas Diurnas , Microscopía , Alas de Animales , Animales , Alas de Animales/ultraestructura , Microscopía/métodos , Nanoestructuras , Fotones

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Chronic wound management is affected by three primary challenges: bacterial infection, oxidative stress and inflammation, and impaired regenerative capacity. Conventional treatment methods typically fail to deliver optimal outcomes, thus highlighting the urgency to develop innovative materials that can address these issues and improve efficacy. Recent advances in DNA nanotechnology have garnered significant interest, particularly in the field of functional nucleic acid (FNA) nanomaterials, owing to their exceptional biocompatibility, programmability, and therapeutic potential. Among them, FNAs with unique nanostructures have garnered considerable attention. First, they inherit the biological properties of FNAs, including biocompatibility, reactive oxygen species (ROS)-scavenging capabilities, and modulation of cellular functions. Second, based on a precise design, these nanostructures exhibit superior physical properties, stability, and cellular uptake. Third, by leveraging the programmability of DNA strands, FNA nanostructures can be customized to accommodate therapeutic nucleic acids, peptides, and small-molecule drugs, thereby enabling a stable and controlled drug delivery system. These unique characteristics enable the use of FNA nanostructures to effectively address the major challenges in chronic wound management. This review focuses on various FNA nanostructures, including tetrahedral framework nucleic acids (tFNAs), DNA hydrogels, DNA origami, and rolling-circle amplification (RCA) DNA assembly. Additionally, a summary of recent advancements in their design and application for chronic wound management as well as insights for future research in this field are provided.

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Pectobacterium carotovorum subsp. carotovorum (PCC) is a notorious plant pathogen responsible for severe soft rot in kimchi cabbage, which results in significant economic losses. To detect PCC rapidly and accurately in kimchi cabbage, we developed a surface-enhanced Raman scattering (SERS) substrate on which silver nanospheres (AgNSs), nanowires (AgNWs), and nanoseeds are combined on a polydimethylsiloxane (PDMS) platform. The incorporation of Ag nanoseeds creates a higher density of hotspots, which ensures a low detection limit of 1.001 CFU/mL. Electron microscopy and spectroscopic analyses confirmed the successful fabrication of the substrate and its enhanced sensitivity. The SERS substrate exhibits excellent selectivity by effectively distinguishing PCC from other bacteria commonly found in kimchi cabbage. The substrate gives rise to strong Raman signals across PCC concentrations ranging from 101 to 106 CFU/mL. Additionally, a predictive model was developed for accurately detecting PCC in real kimchi cabbage samples, and the results were validated by polymerase chain reaction measurements. A sensitive, selective, and rapid approach for PCC detection in kimchi cabbage that offers a promising improvement over existing methodologies is presented.

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Despite its effectiveness in eradicating cancer cells, current tumor radiotherapy often causes irreversible damage to the surrounding healthy tissues. To address this issue and enhance therapeutic outcomes, we developed a multifunctional injectable hydrogel that integrates electromagnetic shielding and magnetothermal effects. This innovation aims to improve the efficacy of brachytherapy while protecting adjacent normal tissues. Recognizing the limitations of existing hydrogel materials in terms of stretchability, durability, and single functionality, we engineered a composite hydrogel by self-assembling nickel nanoparticles on the surface of liquid metal particles and embedding them into an injectable hydrogel matrix. The resulting composite material demonstrates superior electromagnetic interference shielding performance (74.89 dB) and a rapid magnetothermal heating rate (10.9 °C/min), significantly enhancing its in vivo applicability. The experimental results confirm that this innovative nanocomposite hydrogel effectively attenuates electromagnetic waves during brachytherapy, thereby protecting normal tissues surrounding the tumor and enhancing radiotherapy efficacy through magnetothermal therapy. This study advances the safety and effectiveness of cancer treatments and provides new insights into the development of multifunctional biomedical materials, promoting the innovative application of nanotechnology in the medical field.

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The development and investigation of innovative nanomaterials stand poised to advance technological progress and meet the contemporary demand for efficient, environmentally friendly, and intelligent products. Hollow nanostructures (HNS), characterized by their hollow architecture, exhibit diverse properties such as expansive specific surface area, low density, high drug-carrying capacity, and customizable structures. These elaborated structures, encompass nanospheres, nanoboxes, rings, cubes, and nanowires, have wide-ranging applications in biomedicine, materials chemistry, food industry, and environmental science. Herein, HNS and their cutting-edge synthesis methods, including solvothermal methods, liquid-interface assembly methods, and the self-templating methods are discussed in-depth. Meanwhile, the potential applications of HNS in food and biomedicine such as food packing, biosensor, and drug delivery over the past three years are summarized, together with a prospective view of future research directions and challenges. This review will offer new insights into designing next generation of hollow nanomaterials for food and biomedicine applications.

Asunto(s)

Nanoestructuras , Nanoestructuras/química , Nanotecnología/métodos , Sistemas de Liberación de Medicamentos/instrumentación , Humanos , Tecnología de Alimentos/métodos , Técnicas Biosensibles/métodos , Técnicas Biosensibles/instrumentación

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Two-dimensional (2D) materials have emerged as a promising candidate in the chemoresistive gas sensor field to overcome the disadvantages of conventional metal-oxide semiconductors owing to their strong surface activities and high surface-to-volume ratio. This review summarizes the various approaches to enhance the 2D-material-based gas sensors and provides an overview of their progress. The distinctive attributes of semiconductor gas sensors employing 2D materials will be highlighted with their inherent advantages and associated challenges. The general operating principles of semiconductor gas sensors and the unique characteristics of 2D materials in gas-sensing mechanisms will be explored. The pros and cons of 2D materials in gas-sensing channels are discussed, and a route to overcome the current challenges will be delivered. Finally, the recent advancements to enhance the performance of 2D-material-based gas sensors including photo-activation, heteroatom doping, defect engineering, heterostructures, and nanostructures will be discussed. This review should offer a broad range of readers a new perspective toward the future development of 2D-material-based gas sensors.

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In cancer molecular imaging, selecting binders with high specificity and affinity for biomarkers is paramount for achieving high-contrast imaging within clinical time frames. Nanobodies have emerged as potent candidates, surpassing antibodies in pre-clinical imaging due to their convenient production, rapid renal clearance, and deeper tissue penetration. Multimerization of nanobodies is a popular strategy to enhance their affinity and pharmacokinetics; however, traditional methods are laborious and may yield heterogeneous products. In this study, we employ a Holliday junction (HJ)-like nucleic acid-based scaffold to create homogeneous nanostructures with precise multivalent and multiparatopic nanobody displays. The plug-and-play assembly allowed the screening of several nanobody multimer configurations for the detection of the breast cancer biomarker, human epidermal growth factor receptor 2 (HER2). In vitro studies demonstrated significant improvements in binding avidity, particularly with the biparatopic construct exhibiting high sensitivity, surpassing that of traditional antibody-based cell binding. Furthermore, our HJ platform allowed for adaptation from fluorescence-based to nuclear imaging, as demonstrated in xenografted mice, thereby allowing for future in vivo applications. This work highlights the potential of nucleic acid-mediated multimerization to markedly enhance nanobody binding, by exploring synergistic combinations and offering versatility for both in vitro diagnostics and cancer molecular imaging with prospects for future theranostic applications.

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Cascade-enzyme reaction systems have emerged as promising tools for treating malignant tumors by efficiently converting nutrients into toxic substances. However, the challenges of poor localized retention capacity and utilization of highly active enzymes often result in extratumoral toxicity and reduced therapeutic efficacy. In this study, we introduced a cell membrane-DNA nanoanchor (DNANA) with a spatially confined cascade enzyme for in vivo tumor therapy. The DNANAs are constructed using a polyvalent cholesterol-labeled DNA triangular prism, ensuring high stability in cell membrane attachment. Glucose oxidase (GOx) and horseradish peroxidase (HRP), both modified with streptavidin, are precisely confined to biotin-labeled DNANAs. Upon intratumoral injection, DNANA enzymes efficiently colonize the tumor site through cellular membrane engineering strategies, significantly reducing off-target enzyme leakage and the associated risks of extratumoral toxicity. Furthermore, DNANA enzymes demonstrated effective cancer therapy in vitro and in vivo by depleting glucose and producing highly cytotoxic hydroxyl radicals in the vicinity of tumor cells. This membrane-engineered cascade-enzyme reaction system presents a conceptual approach to tumor treatment.

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HYPOTHESIS: Predicting the exact nature of the self-assembly of amphiphilic molecules into supramolecular structures is of utmost importance for a variety of applications, but this is a challenge for nanotechnology. The amphiphilic drug delivery polymer-N-palmitoyl-N-monomethyl-N,N-dimethyl-N,N,N-trimethyl-6-O-glycolchitosan (GCPQ) self-assembles in aqueous media to form nanoparticles. EXPERIMENT: This work aimed to develop a systematic predictive mathematical model on the eventual nature of oil-loaded GCPQ-nanoparticles and to determine the main independent variables that affect their nanoarchitecture following self-assembly. GCPQ polymers were produced with varying degree of palmitoylation (DP, 5.7-23.8 mol%), degree of quaternization (DQ, 7.2-22.7 mol%), and molecular weight (MW, 11.2-44.2 kDa) and their critical hydrophilic-lipophilic balance (cHLB) optimized to produce oil-loaded nanocapsules. FINDINGS: Non-linear mathematical models (Particle size (nm) = 466.05 - 5.64DP - 6.52DQ + 0.13DQ2 - 0.03 MW2 - 14.48cHLB + 0.48cHLB2) were derived to predict the nanoparticle sizes (R2 = 0.998, R2adj = 0.995). Smaller nanoparticle sizes (148-157 nm) were obtained at high DP, DQ, and cHLB values, in which DP was the main independent variable responsible for nanoparticle size. Single or multiple-oil cores with small particles stabilizing polymer shells could be observed depending on the oil volume. Nanoparticle architectures, especially the nature of the oil-core(s), were driven by the DP, DQ, cHLB, and oil concentration. Here, we have developed a predictive model that may be applied to understand the nanoarchitecture of oil-loaded GCPQ-nanoparticles.

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Persistent luminescent nanoparticles (PLNPs) are promising for many bioapplications due to their unique afterglow luminescence following the stoppage of light excitation. However, PLNPs are prone to surface quenching that results in weak afterglow luminescence. Although some efforts have been made to reduce surface quenching through designing homogeneous core-shell PLNPs, the enhancement in afterglow luminescence was insignificant. We hypothesize that the independent absorption and emission of the shell caused less energy to reach the activator ions in the core. Hence, a heterogeneous core-shell PLNP where the shell has a higher band gap than the core would reduce the absorption and emission of the shell. In this work, ZnGa2O4 and Zn2GeO4 were coated on Zn1.2Ga1.6Ge0.2O4:Cr and Zn3Ga2Ge2O10:Eu nanocrystals, respectively, to form heterogeneous core-shell PLNPs and significant luminescence enhancement was achieved compared to their traditional homogeneous core-shell nanostructures.

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Supramolecular chemistry achieves higher-order molecular self-assembly through non-covalent interactions. Utilizing supramolecular methods to explore the polymorphism of proteins, the building blocks of life, from a "bottom-up" perspective is essential for constructing diverse and functional biomaterials. In recent years, significant progress has been achieved in the design strategies and functional applications of supramolecular protein self-assembly, becoming a focal point for researchers. This paper reviews classical supramolecular strategies driving protein self-assembly, including electrostatic interactions, metal coordination, hydrogen bonding, hydrophobic interactions, host-guest interactions, and other mechanisms. We discuss how these supramolecular interactions regulate protein assembly processes and highlight protein supramolecular assemblies' unique structural and functional advantages in constructing artificial photosynthetic systems, protein hydrogels, bio-delivery systems, and other functional materials. The enormous potential and significance of supramolecular protein materials are elucidated. Finally, the challenges in preparing and applying protein supramolecular assemblies are summarized, and future development directions are projected.

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Nucleation and growth of calcium carbonate on surfaces is of broad importance in nature and technology, being essential to the calcification of organisms, while negatively impacting energy conversion through crystallization fouling, also called scale formation. Previous work studied how confinements, surface energies, and functionalizations affect nucleation and polymorph formation, with surface-water interactions and ion mobility playing important roles. However, the influence of surface nanostructures with nanocurvature-through pit and bump morphologies-on scale formation is unknown, limiting the development of scalephobic surfaces. Here, it is shown that nanoengineered surfaces enhance the nucleation rate by orders of magnitude, despite expected inhibition through effects like induced lattice strain through surface nanocurvature. Interfacial and holographic microscopy is used to quantify crystallite growth and find that nanoengineered interfaces experience slower individual growth rates while collectively the surface has 18% more deposited mass. Reconstructions through nanoscale cross-section imaging of surfaces coupled with classical nucleation theory-utilizing local nanocurvature effects-show the collective enhancement of nano-pits.

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Achieving structural reconfiguration of supramolecular bottlebrush block copolymers toward topological engineering is of particular interest but challenging. Here, we address the creation of supramolecular architectures to discover how assembled topology influences the structured aggregates, combining hydrogen-bonded (H-bonded) bottlebrush block copolymers and electrostatic interaction induced polymer/inorganic eutectics. We first design H-bonding linear-brush block copolymer P(NBDAP-co-NBC)-b-P(NBPEO), bearing linear block P(NBDAP-co-NBC) (poly(norbornene-terminated diaminopyridine-co-norbornene-terminated hexane)) with pendant H-bonding DAP (diaminopyridine) motifs, and PEO (poly(ethylene oxide)) densely grafted P(NBPEO) brush block. Thanks to H-bonding association between DAP and thymine (Thy), incorporation of Thy-functionalized polystyrene (Thy-PS) enables solution self-assembly and formation of H-bonded bottlebrush block copolymers, generating augmented nanospheres with increasing Thy-PS amount. Noteworthy that integration of inorganic cluster silicotungstic acid (STA) to P(NBC-co-NBDAP)-b-P(NBPEO), endows the formation of PEO/STA eutectic core. Therefore, co-crystallization-assistant self-assembly at the interfaces of polymeric, inorganic and supramolecular chemistry is realized, reflecting multi-stage morphology transformation from hexagonal platelets, needle-like, curved rod-like micelles, finally to end-to-end closed rings, by gradually increasing Thy-PS while fixing STA content. Interestingly, such solution self-assembly to co-crystallization-assistant self-assembly strategy not only endows unique nanostructure transition, also induce in-to-out switch of PS domains. These findings clearly provide unique methodology towards programmable fabrication of geometrical objects promising in smart materials.

RESUMEN

Small-angle scattering (SAS) is a key experimental technique for analyzing nanoscale structures in various materials. In SAS data analysis, selecting an appropriate mathematical model for the scattering intensity is critical, as it generates a hypothesis of the structure of the experimental sample. Traditional model selection methods either rely on qualitative approaches or are prone to overfitting. This paper introduces an analytical method that applies Bayesian model selection to SAS measurement data, enabling a quantitative evaluation of the validity of mathematical models. The performance of the method is assessed through numerical experiments using artificial data for multicomponent spherical materials, demonstrating that this proposed analysis approach yields highly accurate and interpretable results. The ability of the method to analyze a range of mixing ratios and particle size ratios for mixed components is also discussed, along with its precision in model evaluation by the degree of fitting. The proposed method effectively facilitates quantitative analysis of nanoscale sample structures in SAS, which has traditionally been challenging, and is expected to contribute significantly to advancements in a wide range of fields.

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The particulate matter and soluble organic fraction emitted by diesel engine are hazardous to environment and human health. Exploring the effect mechanism of soluble organic fraction on soot oxidation is beneficial for reducing the emissions. In this study, the effects of four different types of soluble organic fractions on the soot oxidation activity and physicochemical properties are investigated. The results show that the attachment of oxygen-containing soluble organic fractions enhances the soot oxidation and reduces the peak characteristic temperature. However, the low volatility soluble organic fractions without oxygen element inhibit soot oxidation. Additionally, the high volatility soluble organic fractions without oxygen element elicit limited effects on soot oxidation. the contents of aliphatic C-H functional groups, carbonyl CO functional groups, and carboxylic acid O-CO functional groups significantly increase after adding oxygen-containing soluble organic fractions, while the limited increase in functional groups is observed in soluble organic fractions without oxygen element. Solid soluble organic fractions adhere to soot particles in the form of small particles, leading a reduction in the initial particle size distribution, while liquid soluble organic fractions exhibit block and chain shapes around the soot particles, which makes the initial particle size distribution increasing. Moreover, the attachment of all soluble organic fractions disrupts the surface order of soot particle, leading to a decrease in soot graphitization. This study is beneficial for revealing the interaction mechanism between soot and soluble organic fractions.

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The intrinsic limitation of low electrical conductivity of MoSe2 resulted in inferior dielectric properties, which restricts its electromagnetic wave absorption (EMWA) performances. Herein, a bimetallic selenide of MoSe2/CoSe2@N-doped carbon (NC) composites with hollow core-branch nanostructures are synthesized via the selenization treatment of MoO3 nanorods coated with ZIF-67. By adjusting the mass ratio of ZIF-67 to MoO3, the electromagnetic parameters and morphologies of composites are finely tuned, further ameliorating the impedance matching and EMWA performances. The involvement of NC improves the electronic conductivity of the composites. The synchronously formed heterostructure not only facilitates charge transfer but also leads to the accumulation and uneven distribution of charges, thus enhancing the conductive loss and polarization loss. The hollow core-branch nanostructure provides abundant conductive networks, heterointerfaces, and voids, significantly enhancing the EMWA property. Density functional theory implies that the heterostructures effectively boost charge transport and change charge distribution, which heightens the conductive loss and polarization loss. As a result, the composites demonstrate a minimum reflection loss value of -53.53 dB at 9.04 GHz, alongside a maximum effective absorption bandwidth of 6.32 GHz. This work offers invaluable insights into novel structural designs for future research and applications.

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The effective treatment of acute lung injury (ALI) remains a significant challenge. Patients with ALI demonstrate an abundance of proinflammatory mediators in both bronchoalveolar lavage fluid (BALF) and circulating plasma. Bardoxolone methyl (BM) is a semi-synthetic triterpenoid derived from oleanolic acid, a natural product known for its ability to inhibit proinflammatory signaling. GSDMD is a signaling protein involved in pyroptosis, a form of programmed cell death. It has been reported that its upstream proteins play a role in the pathogenesis of ALI. However, there is currently no research examining whether the effect of BM on the occurrence and development of ALI is associated with changes in GSDMD protein. In this study, we prepared nanostructured lipid carriers loaded with BM and conjugated with anti-PECAM-1 antibody (PECAM@BM NLCs). PECAM@BM NLCs were designed to specifically bind to pulmonary vascular endothelial cells that highly express the PECAM-1 receptors. We also aimed to investigate the protective effects of PECAM@BM NLCs on ALI and elucidate the underlying molecular mechanisms. The results demonstrated that PECAM@BM NLCs accumulated in the lung tissues and significantly alleviated the inflammatory injury of ALI. This was evidenced by the changes in the lung wet/dry ratio, the total protein concentration, proinflammatory cytokines in BALF, and the histopathological progress. Additionally, we elucidated that PECAM@BM NLCs had the ability to inhibit the assembly of NLRP3 inflammasome and pro-caspase-1 complex, thereby suppressing the induction of pyroptosis. This mechanism resulted in the inhibition of N-terminal GSDMD expression and effectively prevented the progression of ALI.

Asunto(s)

Lesión Pulmonar Aguda , Pulmón , Nanoestructuras , Ácido Oleanólico , Molécula-1 de Adhesión Celular Endotelial de Plaqueta , Ácido Oleanólico/farmacología , Ácido Oleanólico/análogos & derivados , Ácido Oleanólico/administración & dosificación , Ácido Oleanólico/química , Animales , Lesión Pulmonar Aguda/tratamiento farmacológico , Lesión Pulmonar Aguda/patología , Nanoestructuras/química , Molécula-1 de Adhesión Celular Endotelial de Plaqueta/metabolismo , Pulmón/efectos de los fármacos , Pulmón/metabolismo , Pulmón/patología , Portadores de Fármacos/química , Masculino , Ratones , Neumonía/tratamiento farmacológico , Neumonía/patología , Neumonía/metabolismo , Proteína con Dominio Pirina 3 de la Familia NLR/metabolismo , Ratones Endogámicos C57BL , Lípidos/química , Anticuerpos/farmacología , Líquido del Lavado Bronquioalveolar/química , Humanos , Sistemas de Liberación de Medicamentos/métodos , Inflamasomas/metabolismo , Inflamasomas/efectos de los fármacos

RESUMEN

The evolution of flexible sensors heavily relies on advances in soft-material design and sensing mechanisms. Supramolecular chemistry offers a powerful toolbox for manipulating nanoscale and molecular structures within soft materials, thus fostering recent advancements in flexible sensors and electronics. Supramolecular interactions have been utilized to nanoengineer functional sensing materials or construct chemical sensors with lower cost and broader targets. In this perspective, we will highlight the use of supramolecular interactions to regulate and optimize nanostructures within functional soft materials and illustrate their importance in expanding the nanocavities of bioreceptors for chemical sensing. Overall, a bridge between tissue-mimicking flexible sensors and cell-mimetic supramolecular chemistry has been built, which will further advance human healthcare innovation.