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Fighting aggregation-caused quenching and leakage of dyes in fluorescent polymer nanoparticles: universal role of counterion
摘要： Dye-loaded polymer nanoparticles (NPs) emerge as a powerful tool for bioimaging applications, owing to their exceptional brightness and controlled small size. However, aggregation-caused quenching (ACQ) and leakage of dyes at high loading remain important challenges of these nanomaterials. The use of bulky hydrophobic counterions has been recently proposed as an effective approach to minimize ACQ and dye leakage, but the role of counterion structure is still poorly understood. Here, a systematic study based on ten counterions, ranging from small hydrophilic perchlorate up to large hydrophobic tetraphenylborate derivatives, reveals how counterion nature can control encapsulation and emission of a cationic dye (rhodamine B octadecyl ester) in NPs prepared by nanoprecipitation of a biodegradable polymer, poly-lactide-co-glycolide (PLGA). We found that increase in counterion hydrophobicity enhances dye encapsulation efficiency and prevents dye adsorption at the particle surface. Cellular imaging studies revealed that ≥95% encapsulation efficiency, achieved with most hydrophobic counterions (fluorinated tetraphenylborates), is absolutely required, because non-encapsulated dye species at the NPs surface are the origin of dye leakage and strong background in cells. The size of counterions is found to be essential to prevent ACQ, where the largest species, serving as effective spacer between dyes, provide the highest fluorescence quantum yield. Moreover, we found that the most hydrophobic counterions favor dye-dye coupling inside NPs, leading to ON/OFF fluorescence switching of single particles. By contrast, less hydrophobic counterions tend to disperse dyes in the polymer matrix favoring stable emission of NPs. The obtained structure-property relationships validate the counterion-based approach as a mature concept to fight ACQ and dye leakage in the development of advanced polymeric nanomaterials with controlled optical properties.
关键词： dye-loaded polymer nanoparticles,fluorescent nanoparticles,bulky hydrophobic counterion,aggregation-caused quenching,bioimaging
更新于2025-09-23 15:23:52
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Luminescent switch of polysaccharide-peptide-quantum dot nanostructures for targeted-intracellular imaging of glioblastoma cells
摘要： Glioblastoma multiforme (or GBM) remains one of the deadliest types of brain cancers. Nanomedicine can offer new strategies for fighting against GBM by combining the earliest possible diagnosis with multiple options of therapy. Hence, in this work, cysteine (Cys) and Poly-L-Arginine (PA) moieties were grafted to carboxymethyl cellulose (CMC) to produce biofunctional hybridized macromolecules (CMC_Cys and CMC_PA). These polymer-peptide conjugates were used simultaneously as surface capping ligands and biofunctional modifiers for the synthesis of ternary Ag-In-S (AIS) quantum dots (AIS QDs) via a green chemical process in aqueous medium and room temperature. These core-shell supramolecular nanostructures (AIS@CMC, AIS@CMC_Cys, and AIS@CMC_PA) were tested as fluorescent nanoprobes (“OFF-ON”) for targeted bioimaging and in vitro intracellular tracking of glioblastoma cells (GBM, U-87 MG). The nanosystems were characterized for physicochemical, structural, and morphological properties by NMR, UV–Vis, PL, FTIR, TEM/EDX/SAED, zeta potential, and DLS. Cytocompatibility was evaluated by mitochondrial activity assay, and confocal laser scanning microscopy was performed for investigating the kinetics of cellular uptake. The grafting caused a noticeable reduction of surface charges, associated with a drastic photoluminescence quenching (i.e., “OFF-state”) of AIS@CMC_Cys and AIS@CMC_PA compared to unmodified AIS@CMC. This effect was smartly applied for bioimaging GBM cells and for monitoring the internalization process by intracellular tracking, which underwent strong “de-quenching” at very early incubation times (~5 min). Thus, these novel hybrid nanocolloids produced via eco-friendly scalable aqueous process show potential as responsive fluorescent bioprobes for bioimaging and tracking intracellular pathways and mechanisms as a powerful weapon for fighting against brain cancer cells.
关键词： nanoconjugates,nanomaterials,colloids,polymer-semiconductor nanoprobes,supramolecular nanoparticles,fluorescent nanoparticles
更新于2025-09-23 15:19:57
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Data on ultrabright fluorescent cellulose acetate nanoparticles for imaging tumors through systemic and topical applications
摘要： Characterization data of fluorescent nanoparticles made of cellulose acetate (CA-dots) are shown. The data in this article accompanies the research article “Data on ultrabright fluorescent cellulose acetate nanoparticles for imaging tumors through systemic and topical applications” [1]. The measurements and calculation of brightness of individual CA-dots are presented. The description of conjugation procedure Pluronic F127-Folic Acid copolymer and folic acid is shown. Identification of composition of CA dots using Raman and absorbance spectroscopy is demonstrated. The methods for image analysis of efficiency of CA-dot targeting of epithelial tumors xenografted in zebrafish is presented.
关键词： Materials Science,Cellulose acetate fluorescent nanoparticles
更新于2025-09-23 15:19:57
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Dual-functional supramolecular nanohybrids of quantum dot/biopolymer/chemotherapeutic drug for bioimaging and killing brain cancer cells in vitro
摘要： Glioblastoma (GBM) is the utmost aggressive and lethal primary brain cancer, which has a poor prognosis and remains virtually incurable. Nanomedicine with emerging disruptive nanotechnology alternatives, including designed supramolecular nanohybrids has excellent potential as multimodal tools against cancer by combining nanomaterials, biomacromolecules, and drugs. Thus, we developed and constructed for the first time quantum dot-biopolymer-drug nanohybrids based on host-guest chemistry for simultaneous bioimaging, targeting, and anti-cancer drug delivery against GBM cells in vitro. ZnS fluorescent quantum dots (ZnS-QDs) were produced using chemically modified polysaccharide, carboxymethylcellulose (CMC), as water-soluble capping ligand and biofunctional layer via a facile one-step eco-friendly aqueous colloidal process at room temperature and physiological pH. These hybrid inorganic-organic nanocolloids (ZnS@CMC) were electrostatically conjugated with doxorubicin (DOX) anti-cancer drug forming innovative supramolecular complexes (ZnS@CMC-DOX) for amalgamating bioimaging and killing cancer cells. These nanoconjugates were characterized regarding their optical and physicochemical properties combined with morphological and structural features. The cytocompatibility was evaluated by MTT assay using healthy and GBM cells. The results showed that ultra-small ZnS-QDs were expertly produced uniform nanocolloids (average size = 3.6 nm). They demonstrated photoluminescence emission within the visible range of spectra. The cell viability results in vitro showed no cytotoxicity of ZnS@CMC nanohybrids towards both cell types. In summary, the novelty of this research relies on using a nanotheranostic strategy for developing ZnS@CMC-DOX nanohybrids with supramolecular vesicle-like structures. They behaved simultaneously as active fluorescent nanoprobes and nanocarriers with modulated drug release for bioimaging and killing malignant glioma cells proving the high potential for applications in cancer nanomedicine.
关键词： Nanocarriers,Cancer nanotheranostic,Nanocolloids,Nanoconjugates,Fluorescent nanoparticles,Nanomedicine,Nanohybrids,Nanoparticles
更新于2025-09-12 10:27:22
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PEGylated Fluorescent Nanoparticles from One-Pot Atom Transfer Radical Polymerization and “Click Chemistry”
摘要： The preparation of PEGylated fluorescent nanoparticles (NPs) based on atom transfer radical polymerization (ATRP) and “click chemistry” in one-pot synthesis is presented. First, poly(p-chloromethyl styrene-alt-N-propargylmaleimide) (P(CMS-alt-NPM)) copolymer was prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization. Subsequently, the azido-containing fluorene-based polymer, poly[(9,9-dihexylfluorene)-alt-(9,9-bis-(6-azidohexyl)fluorene)] (PFC6N3), was synthesized via Suzuki coupling polymerization, followed by azidation. Finally, the PEGylated fluorescent NPs were prepared via simultaneous intermolecular “click” cross-linking between P(CMS-alt-NPM) and PFC6N3 and the ATRP of poly(ethylene glycol) methyl ether methacrylate (PEGMMA) using P(CMS-alt-NPM) as the macroinitiator. The low cytotoxicity of the PEGylated fluorescent NPs was revealed by incubation with KB cells, a cell line derived from carcinoma of the nasopharynx, in an in vitro experiment. The biocompatible PEGylated fluorescent NPs were further used as a labeling agent for KB cells.
关键词： ATRP,fluorescent nanoparticles,click chemistry,one-pot synthesis,PEGylated,cellular imaging
更新于2025-09-09 09:28:46