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Ubiquitous antibiotics threaten human health and ecosystem sustainability, and existing removal strategies, especially conventional multistep water treatments, are primarily limited by the antibiotic-specific removal capability. Here, we explore the natural biomass, plant polyphenols, in the capture of various antibiotics with a facile treatmentâpolyphenol-mediated antibiotic-independent supramolecular coagulation (PMAC). The PMAC shows a superior performance in removing five tetracyclines and quinolones (up to 98.54%), even under complex environmental parameters, including different pH, the presence of inorganic particles and ionic strength, and the presence of conventional colloid-associated contaminants. Our mechanistic studies suggested that PMAC is capable of exerting multiple molecular interactions with various antibiotics, and the coordination-driven self-assembly further destabilizes the phenolic-antibiotic nanocomplexes, enabling an antibiotic-independent coagulation. Collectively, the combination of efficient remediation with inexpensive biomass suggests a simple and scalable method for the sustainable removal of antibiotics. Our strategy shows great promise as a cost-effective, facile approach to eliminate antibiotics capable of being integrated into the currently existing water treatment systems.
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Albumin nanoparticles are widely used in biomedicine due to their safety, low immunogenicity, and prolonged circulation. However, incorporating therapeutic molecules into these carriers faces challenges due to limited binding sites, restricting drug conjugation efficiency. We introduce a universal nanocarrier platform (X-UNP) using polyphenol-based engineering to incorporate phenolic moieties into albumin nanoparticles. Integration of catechol or galloyl groups significantly enhances drug binding and broadens the drug conjugation possibilities. Our study presents a library of X-UNP nanoparticles with improved drug-loading efficiency, achieving up to 96% across 10 clinically used drugs, surpassing conventional methods. Notably, ibuprofen-UNP nanoparticles exhibit a 5-fold increase in half-life compared with free ibuprofen, enhancing in vivo analgesic and anti-inflammatory effectiveness. This research establishes a versatile platform for protein-based nanosized materials accommodating various therapeutic agents in biotechnological applications.
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Nanopartículas , Polifenóis , Polifenóis/química , Nanopartículas/química , Animais , Camundongos , Ibuprofeno/química , Portadores de Fármacos/química , Humanos , Albuminas/química , Soroalbumina Bovina/químicaRESUMO
Due to the presence of natural neoantigens, autologous tumor cells hold great promise as personalized therapeutic vaccines. Yet autologous tumor cell vaccines require multi-step production that frequently leads to the loss of immunoreactive antigens, causing insufficient immune activation and significantly hampering their clinical applications. Herein, we introduce a novel whole-cell cancer vaccine by cloaking cancer cells with lipopolysaccharide-decorated manganese(II)-phenolic networks (MnTA nanocloaks) to evoke tumor-specific immune response for highly efficacious synergistic cancer immunotherapy. The natural polyphenols coordinate with Mn2+ and immediately adhere to the surface of individual cancer cells, thereby forming a nanocloak and encapsulating tumor neoantigens. Subsequent decoration with lipopolysaccharide induces internalization by dendritic cells, where Mn2+ ions are released in the cytosol, further facilitating the activation of the stimulator of the interferon genes (STING) pathway. Highly effective tumor suppression was observed by combining the nanocloaked cancer cell treatment with anti-programmed cell death ligand 1 (anti-PD-L1) antibodies-mediated immune checkpoint blockade therapy. Our work demonstrates a universal yet simple strategy to engineer a cell-based nanobiohybrid system for enhanced cancer immunotherapy.
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Neoplasias , Vacinas , Humanos , Imunoterapia , Lipopolissacarídeos , Neoplasias/terapia , Microambiente Tumoral , Vacinas AnticâncerRESUMO
The creation of artificial high-performance photosynthetic assemblies with a tailorable antenna system to deliver absorbed solar energy to a photosynthetic reaction center, thereby mimicking biological photosynthesis, remains a major challenge. We report the construction of recyclable, high-performance photosynthetic nanofibers with a crystalline π-conjugated polyfluorene core as an antenna system that funnels absorbed solar energy to spatially defined sensitized Co(II) porphyrin photocatalysts for the hydrogen evolution reaction. Highly effective energy funneling was achieved by tuning the dimensions of the nanofibers to exploit the very long exciton diffusion lengths (>200 nm) associated with the highly crystalline polyfluorene core formed using the living crystallization-driven self-assembly seeded growth method. This enabled efficient solar light-driven hydrogen production from water with a turnover number of over 450 for 8 h of irradiation, an H2 production rate of ca. 65 mmol h-1 g-1, and an overall quantum yield of 0.4% in the wavelength region (<405 nm) beyond the absorption of the molecular photocatalyst. The strategy of using a tailored antenna system based on π-conjugated polymers and maximizing exciton transport to a reaction center reported in this work opens up future opportunities for potential applications in other fields such as solar overall water splitting, CO2 reduction, and photocatalytic small molecule synthesis.
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SO2 removal is critical to flue gas purification. However, based on performance and cost, materials under development are hardly adequate substitutes for active carbon-based materials. Here, we engineered biomass-derived nanostructured carbon nanofibers integrated with highly dispersed bimetallic Ti/CoOx nanoparticles through the thermal transition of metal-phenolic functionalized industrial leather wastes for synergistic SO2 adsorption and in situ catalytic conversion. The generation of surface-SO32- and peroxide species (O22-) by Ti/CoOx achieved catalytic conversion of adsorbed SO2 into value-added liquid H2SO4, which can be discharged from porous nanofibers. This approach can also avoid the accumulation of the adsorbed SO2, thereby achieving high desulfurization activity and a long operating life over 6000 min, preceding current state-of-the-art active carbon-based desulfurization materials. Combined with the techno-economic and carbon footprint analysis from 36 areas in China, we demonstrated an economically viable and scalable solution for real-world SO2 removal on the industrial scale.
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Carvão Vegetal , Dióxido de Enxofre , Adsorção , Biomassa , CarbonoRESUMO
Colloidal supraparticles integrated with multicomponent primary particles come with emerging or synergetic functionalities. However, achieving the functional customization of supraparticles remains a great challenge because of the limited options of building blocks with tailorability and functional extensibility. Herein, we developed a universal approach to construct customizable supraparticles with desired properties from molecular building blocks obtained by the covalent conjugation of catechol groups with a series of orthogonal functional groups. These catechol-terminated molecular building blocks can assemble into primary particles driven by various intermolecular interactions (i.e. metal-organic coordination, host-guest, and hydrophobic interactions), and then further assemble into supraparticles governed by catechol-mediated interfacial interactions. Our strategy enables the formation of supraparticles with diverse functionalities, such as dual-pH responsiveness, light-controllable permeability, and non-invasive fluorescence labeling of living cells. The ease with which these supraparticles can be fabricated, and the ability to tailor their chemical and physical properties through the choice of metals and orthogonal functional groups used, should enable a variety of applications.
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Fiber-like micelles based on biodegradable and biocompatible polymers exhibit considerable promise for applications in nanomedicine, but until recently no convenient methods were available to prepare samples with uniform and controllable dimensions and spatial control of functionality. "Living" crystallization-driven self-assembly (CDSA) is a seeded growth method of growing importance for the preparation of uniform 1D and 2D core-shell nanoparticles from a range of crystallizable polymeric amphiphiles. However, in the case of poly(l-lactide) (PLLA), arguably the most widely utilized biodegradable polymer as the crystallizable core-forming block, the controlled formation of uniform fiber-like structures over a substantial range of lengths by "living" CDSA has been a major challenge. Herein, we demonstrate that via simple modulation of the solvent conditions via the addition of trifluoroethanol (TFE), DMSO, DMF and acetone, uniform fiber-like nanoparticles from PLLA diblock copolymers with controlled lengths up to 1 µm can be prepared. The probable mechanism involves improved unimer solvation by a reduction of hydrogen bonding interactions among PLLA chains. We provide evidence that this minimizes undesirable unimer aggregation which otherwise favors self-nucleation that competes with epitaxial crystallization from seed termini. This approach has also allowed the formation of well-defined segmented block comicelles with PLLA cores via the sequential seeded-growth of PLLA block copolymers with different corona-forming blocks.
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Resinas Acrílicas/química , Micelas , Nanopartículas/química , Poliésteres/química , Cristalização , Ligação de Hidrogênio , Nanopartículas/ultraestrutura , Tamanho da Partícula , Solubilidade , SolventesRESUMO
Poly(l-lactide) (PLLA)-based nanoparticles have attracted much attention with respect to applications in drug delivery and nanomedicine as a result of their biocompatibility and biodegradability. Nevertheless, the ability to prepare PLLA assemblies with well-defined shape and dimensions is limited and represents a key challenge. Herein we report access to a series of monodisperse complex and hierarchical colloidally stable 2D structures based on PLLA cores using the seeded growth, "living-crystallization-driven self-assembly" method. Specifically, we describe the formation of diamond-shaped platelet micelles and concentric "patchy" block co-micelles by using seeds of the charge-terminated homopolymer PLLA24[PPh2Me]I to initiate the sequential growth of either additional PLLA24[PPh2Me]I or a crystallizable blend of the latter with the block copolymer PLLA42-b-P2VP240, respectively. The epitaxial nature of the growth processes used for the creation of the 2D block co-micelles was confirmed by selected area electron diffraction analysis. Cross-linking of the P2VP corona of the peripheral block in the 2D block co-micelles using Pt nanoparticles followed by dissolution of the interior region in good solvent for PLLA led to the formation of novel, hollow diamond-shaped assemblies. We also demonstrate that, in contrast to the aforementioned results, seeded growth of the unsymmetrical PLLA BCPs PLLA42-b-P2VP240 or PLLA20-b-PAGE80 alone from 2D platelets leads to the formation of diamond-fiber hybrid structures.
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Nanopartículas/química , Poliésteres/síntese química , Cristalização , Micelas , Conformação Molecular , Tamanho da Partícula , Poliésteres/química , Propriedades de SuperfícieRESUMO
Nature has exhibited a high degree of control over the structures and functions. Supramolecules have been utilized to mimic the subtle assembly in nature. However, sophisticated synthesis of molecular skeletons or programmable design of the driving forces raises great challenges in fabricating high-level superstructures in a controlled manner. Natural polyphenols show great promises as building blocks for a diverse of assemblies with controlled structures and functionalities. The intrinsically embedded phenolic groups (i. e., catechol and galloyl groups) are readily forming multiple molecular interactions, including coordination, hydrogen bonding, and π-π interactions with various materials of inorganic particles, organic compounds, synthetic polymers, and biomacromolecules, providing the self-assembled structures or nanocoating on surfaces. Subsequent assembly occurred by further bonding of polyphenols to construct supraparticles. To gain control over the self-assembly, the key lies in the interplay among the molecular interactions with one or two being dominant. In this Perspective, we introduce the representative polyphenol-based assemblies and their derived supraparticles to exhibit the effective harness of the controlled self-assembly by polyphenols.
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Rationale: Device implantation frequently triggers cardiac remodeling and fibrosis, with monocyte-driven inflammatory responses precipitating arrhythmias. This study investigates the role of m6A modification enzymes METTL3 and METTL14 in these responses and explores a novel therapeutic strategy targeting these modifications to mitigate cardiac remodeling and fibrosis. Methods: Peripheral blood mononuclear cells (PBMCs) were collected from patients with ventricular septal defects (VSD) who developed conduction blocks post-occluder implantation. The expression of METTL3 and METTL14 in PBMCs was measured. METTL3 and METTL14 deficiencies were induced to evaluate their effect on angiotensin II (Ang II)-induced myocardial inflammation and fibrosis. m6A modifications were analyzed using methylated RNA immunoprecipitation followed by quantitative PCR. NF-κB pathway activity and levels of monocyte migration and fibrogenesis markers (CXCR2 and TGF-ß1) were assessed. An erythrocyte microvesicle-based nanomedicine delivery system was developed to target activated monocytes, utilizing the METTL3 inhibitor STM2457. Cardiac function was evaluated via echocardiography. Results: Significant upregulation of METTL3 and METTL14 was observed in PBMCs from patients with VSD occluder implantation-associated persistent conduction block. Deficiencies in METTL3 and METTL14 significantly reduced Ang II-induced myocardial inflammation and fibrosis by decreasing m6A modification on MyD88 and TGF-ß1 mRNAs. This disruption reduced NF-κB pathway activation, lowered CXCR2 and TGF-ß1 levels, attenuated monocyte migration and fibrogenesis, and alleviated cardiac remodeling. The erythrocyte microvesicle-based nanomedicine delivery system effectively targeted inflamed cardiac tissue, reducing inflammation and fibrosis and improving cardiac function. Conclusion: Inhibiting METTL3 and METTL14 in monocytes disrupts the NF-κB feedback loop, decreases monocyte migration and fibrogenesis, and improves cardiac function. Targeting m6A modifications of monocytes with STM2457, delivered via erythrocyte microvesicles, reduces inflammation and fibrosis, offering a promising therapeutic strategy for cardiac remodeling associated with device implantation.
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Fibrose , Metiltransferases , Monócitos , NF-kappa B , Humanos , Metiltransferases/metabolismo , Metiltransferases/genética , Monócitos/metabolismo , Masculino , Animais , NF-kappa B/metabolismo , Eritrócitos/metabolismo , Adenosina/análogos & derivados , Adenosina/metabolismo , Feminino , Metilação , Camundongos , Fator de Crescimento Transformador beta1/metabolismo , Micropartículas Derivadas de Células/metabolismo , Leucócitos Mononucleares/metabolismo , Angiotensina II/metabolismo , Receptores de Interleucina-8B/metabolismo , Receptores de Interleucina-8B/genética , Remodelação Ventricular , Miocárdio/metabolismo , Miocárdio/patologia , Nanomedicina/métodosRESUMO
Extensive resection of the small intestine leads to the development of short bowel syndrome (SBS), which reduces the effective absorptive surface area of the intestine and predisposes patients to emaciation, malnutrition, and other severe symptoms. Herein, green tea catechin (-)-epigallocatechin gallate (EGCG) and ferrous ions (Fe2+ ) are utilized to construct a nutrient carrier platform that self-assembles with nutrients to form phenolic-based nutrient complexes (PNCs). PNCs effectively prolong the residence and absorption time of nutrients in the intestine. Further this platform is applied to integrate full nutrient formula, an enteral nutrition (EN) preparation containing a range of full nutrient components. In an SBS rat model, the prepared phenolic-based integrative nutrient complexes (PINCs) enhance nutritional status, improve anemia and immune function, as well as facilitate the growth of remaining intestinal villi and crypts, and maintain the integrity of the intestinal barrier. In addition, PINCs enable the modulation of gut microbial dysbiosis, enrich the abundance of beneficial bacteria, and have no toxic effects after the long-term ingestion. These results provide a proof of principle for the use of polyphenol-based nanocomplexes as EN preparation, offering a feasible strategy for both nutritional support and therapeutic perspectives for SBS treatment.
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Catequina , Síndrome do Intestino Curto , Animais , Ratos , Síndrome do Intestino Curto/terapia , Chá , Fenóis , NutrientesRESUMO
The growing global population necessitates substantial increases in food production. Hydroponic cultivation systems afford a critical alternative for food sustainability and enable stable annual production regardless of the climatic and geographical variations. However, the overgrowth of harmful algal blooms significantly threatens the crop yield by competing with nutrition in the solution and producing contaminants. The conventional practice of algaecides fails to control algal proliferation due to the limited efficiency and food safety concerns. Nanopesticides can deliver active ingredients responsively to suppress crop diseases and offer solutions to current practical challenges and difficulties. Inspired by prospects of nanotechnology for agricultural applications, we have utilized natural polyphenols and copper ions (Cu2+ ions) to develop self-assembled nanoalgaecides referred to as CuBes. The nanoalgaecide attached to algal cells via phenolic surface interactions, enabling localized Cu2+ ion release. This cell-targeted delivery suppressed Chlorella vulgaris for over 30 days (99% inhibition). Transcriptomics revealed that the nanoalgaecide disrupted algal metabolism by downregulating photosynthesis and chlorophyll pathways. In a solar-illuminated plant factory, the nanoalgaecide showed higher algal inhibition and lettuce biosafety versus the commercial Kocide 3000. Notably, the use of nanoalgaecide can enhance the nutrient value of lettuces, which meets the daily supply of Cu for adults. By integrating smart nanotechnology design with selective delivery mechanisms, this metal-phenolic nanoalgaecide provides a nanoenabled solution for controlling harmful algal blooms in hydroponics to advance food production.
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Chlorella vulgaris , Cobre , Adulto , Humanos , Hidroponia , Agricultura , Fenóis , Lactuca , ÍonsRESUMO
Drug-dependent design of hydrogels is currently required for engineering the controlled release of therapeutics, which is a major contributor to the technical challenges relating to the clinical translation of hydrogel-drug systems. Herein, by integrating supramolecular phenolic-based nanofillers (SPFs) into hydrogel microstructures we developed a facile strategy to endow a range of clinically relevant hydrogels with controlled release properties for diverse therapeutic agents. The assembly of multiscale SPF aggregates leads to tunable mesh size and multiple dynamic interactions between SPF aggregates and drugs, which relaxes the available choices of drugs and hydrogels. This simple approach allowed for the controlled release of 12 representative drugs evaluated with 8 commonly used hydrogels. Moreover, the anesthetic drug lidocaine was loaded into SPF-integrated alginate hydrogel and demonstrated sustained release for 14 days in vivo, validating the potential for long-term anesthesia in patients.
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Hidrogéis , Lidocaína , Humanos , Hidrogéis/química , Preparações de Ação Retardada , Sistemas de Liberação de MedicamentosRESUMO
Nano-/microplastics accumulate in aquatic bodies and raise increasing threats to ecosystems and human health. The limitation of existing water cleanup strategies, especially in the context of nano-/microplastics, primarily arises from their complexity (morphological, compositional, and dimensional). Here, highly efficient and bio-based flowthrough capturing materials (bioCap) are reported to remove a broad spectrum of nano-/microplastics from water: polyethylene terephthalate (anionic, irregular shape), polyethylene (net neutral, irregular shape), polystyrene (anionic and cationic, spherical shape), and other anionic and spherical shaped particles (polymethyl methacrylate, polypropylene, and polyvinyl chloride). Highly efficient bioCap systems that adsorb the ubiquitous particles released from beverage bags are demonstrated. As evidence of removal from drinking water, the in vivo biodistribution of nano-/microplastics is profiled, confirming a significant reduction of particle accumulation in main organs. The unique advantage of phenolic-mediated multi-molecular interactions is employed in sustainable, cost-effective, and facile strategies based on wood sawdust support for the removal of challenging nano-/microplastics pollutions.
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Microplásticos , Poluentes Químicos da Água , Humanos , Plásticos , Polifenóis , Ecossistema , Madeira/química , Distribuição Tecidual , Monitoramento Ambiental , ÁguaRESUMO
Rationale: Effective photothermal therapy (PTT) remains a great challenge due to the difficulties of delivering photothermal agents with both deep penetration and prolonged retention at tumor lesion spatiotemporally. Methods: Here, we report an intratumoral self-assembled nanostructured aggregate named FerH, composed of a natural polyphenol and a commercial iron supplement. FerH assemblies possess size-increasing dynamic kinetics as a pseudo-stepwise polymerization from discrete nanocomplexes to microscale aggregates. Results: The nanocomplex can penetrate deeply into solid tumors, followed by prolonged retention (> 6 days) due to the in vivo growth into nanoaggregates in the tumor microenvironment. FerH performs a targeting ablation of tumors with a high photothermal conversion efficiency (60.2%). Importantly, an enhanced immunotherapeutic effect on the distant tumor can be triggered when co-administrated with checkpoint-blockade PD-L1 antibody. Conclusions: Such a therapeutic approach by intratumoral synthesis of metal-phenolic nanoaggregates can be instructive to address the challenges associated with malignant tumors.
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Antígeno B7-H1 , Neoplasias , Linhagem Celular Tumoral , Humanos , Fatores Imunológicos , Imunoterapia , Ferro , Neoplasias/terapia , Fototerapia , Polifenóis , Microambiente TumoralRESUMO
Rationale: The combination of photosensitizers, oxygen supply agents, and adjuvant therapy drugs in a single nano-drug delivery system for photodynamic therapy (PDT) has been showing great promises to overcome the inherent challenges of PDT for tumor treatment. However, the complicated preparation of integrating multiple components hampers their further developments. Here, we describe a self-assembly nanomicelle with rationally designed building blocks, which shows a high efficiency of synergistic chemo-photodynamic therapy in the animal modal. Methods: The nanomicelle was prepared by a coordination-driven self-assembly based on a rationally designed ferrocene cyclopalladated compound coupled with photosensitizers and hyaluronic acid (referred to as FCP-Tph/HA). The morphology, targeting drug delivery, pharmacokinetics, hemolysis, and multimodal synergistic therapy of FCP-Tph/HA were investigated. Results: The formation of nanomicelles presents a low hemolysis rate and a prolonged blood circulation time. FCP-Tph/HA possesses an enhanced antitumor effect in vitro through the specific binding of HA to CD44 and combining chemotherapy with oxygen self-supplying PDT. Simultaneously, the nanomicelle facilitates a significantly improved antitumor efficacy (>90% tumor regression) on a breast cancer model in vivo. Conclusion: Our results present a modular self-assembled nanomicellar platform with synergistic chemo-photodynamic therapy for challenging PDT-based tumor treatment.
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Nanopartículas , Fotoquimioterapia , Animais , Linhagem Celular Tumoral , Hemólise , Nanopartículas/química , Oxigênio , Fotoquimioterapia/métodos , Fármacos Fotossensibilizantes/químicaRESUMO
Face masks are effective response to address this havoc pandemic caused by respiratory infection virus, but they are lack of reusable, antibacterial, and antiviral abilities due to their simple filtration mechanism, bringing to a supply shortage and severe plastic pollution globally. Herein, we designed reusable, antiviral, and antibacterial masks (referred to as R2A masks) that transformed from commonly-used standard masks and household fabrics based on the polyphenol-based surface functionalization. R2A nanocoatings are mainly composed of supramolecular complexation of natural polyphenols and metal ions, possessing a high performance of antibacterial property and comprehensive recyclability. Interfacial interaction of R2A nanocoating can effectively capture the spreading of particulate matters and aerosols containing virus-mimic nanoparticles even after 10 recycles. Moreover, R2A masks exist antibacteria and antivirus for severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2). Collectively, this simple functional enhancement of masks provides a sustainable and strategic preparation for combating the infectious respiratory diseases.
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COVID-19 , SARS-CoV-2 , Aerossóis , COVID-19/prevenção & controle , Filtração , Humanos , Pandemias/prevenção & controleRESUMO
The gut microbiota represents a large community of microorganisms that play an important role in immune regulation and maintenance of homeostasis. Living bacteria receive increasing interest as potential therapeutics for gut disorders, because they inhibit the colonization of pathogens and positively regulate the composition of bacteria in gut. However, these treatments are often accompanied by antibiotic administration targeting pathogens. In these cases, the efficacy of therapeutic bacteria is compromised by their susceptibility to antibiotics. Here, we demonstrate that a single-cell coating composed of tannic acids and ferric ions, referred to as 'nanoarmor', can protect bacteria from the action of antibiotics. The nanoarmor protects both Gram-positive and Gram-negative bacteria against six clinically relevant antibiotics. The multiple interactions between the nanoarmor and antibiotic molecules allow the antibiotics to be effectively absorbed onto the nanoarmor. Armored probiotics have shown the ability to colonize inside the gastrointestinal tracts of levofloxacin-treated rats, which significantly reduced antibiotic-associated diarrhea (AAD) resulting from the levofloxacin-treatment and improved some of the pre-inflammatory symptoms caused by AAD. This nanoarmor strategy represents a robust platform to enhance the potency of therapeutic bacteria in the gastrointestinal tracts of patients receiving antibiotics and to avoid the negative effects of antibiotics in the gastrointestinal tract.
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Antibacterianos , Probióticos , Animais , Antibacterianos/efeitos adversos , Bactérias , Diarreia/induzido quimicamente , Diarreia/tratamento farmacológico , Bactérias Gram-Negativas , Bactérias Gram-Positivas , Humanos , Levofloxacino/uso terapêutico , Probióticos/uso terapêutico , RatosRESUMO
Soft structures in nature, such as supercoiled DNA and proteins, can organize into complex hierarchical architectures through multiple noncovalent molecular interactions. Identifying new classes of natural building blocks capable of facilitating long-range hierarchical structuring has remained an elusive goal. We report the bottom-up synthesis of a hierarchical metal-phenolic mesocrystal where self-assembly proceeds on different length scales in a spatiotemporally controlled manner. Phenolic-based coordination complexes organize into supramolecular threads that assemble into tertiary nanoscale filaments, lastly packing into quaternary mesocrystals. The hierarchically ordered structures are preserved after thermal conversion into a metal-carbon hybrid framework and can impart outstanding performance to sodium ion batteries, which affords a capability of 72.5 milliampere hours per gram at an ultrahigh rate of 200 amperes per gram and a 90% capacity retention over 15,000 cycles at a current density of 5.0 amperes per gram. This hierarchical structuring of natural polyphenols is expected to find widespread applications.
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Polymer-based nanoparticles show substantial promise in the treatment and diagnosis of cancer and other diseases. Herein we report an exploration of the cellular uptake of tailored, low dispersity segmented 1D nanoparticles which were prepared from an amphiphilic block copolymer, poly(dihexylfluorene)-b-poly(ethyleneglycol) (PDHF13-b-PEG227), with a crystallizable PDHF core-forming block and a 'stealth' PEG corona-forming block with different end-group functionalities. Segmented C-B-A-B-C pentablock 1D nanofibers with varied spatially-defined coronal chemistries and a selected length (95 nm) were prepared using the living crystallization-driven self-assembly (CDSA) seeded-growth method. As the blue fluorescence of PDHF is often subject to environment-related quenching, a far-red BODIPY (BD) fluorophore was attached to the PEG end-group of the coronal B segments to provide additional tracking capability. Folic acid (FA) was also incorporated as a targeting group in the terminal C segments. These dual-emissive pentablock nanofibers exhibited uptake into >97% of folate receptor positive HeLa cells by flow cytometry. In the absence of FA, no significant uptake was detected and nanofibers with either FA or BD coronal groups showed no significant toxicity. Correlative light and electron microscopy (CLEM) studies revealed receptor-mediated endocytosis as an uptake pathway, with subsequent localization to the perinuclear region. A significant proportion of the nanofibers also appeared to interact with the cell membrane in an end-on fashion, which was coupled with fluorescence quenching of the PDHF core. These results provide new insights into the cellular uptake of polymer-based nanofibers and suggest their potential use in targeted therapies and diagnostics.