RESUMO
Stimuli-responsive antioxidant Pickering emulsions play crucial role in many industrial areas. This study demonstrated for the first time oil-in-water Pickering emulsions with outstanding antioxidation and responsive demulsification stabilized by functionalized cellulose nanocrystals (CNCs). Dialdehyde cellulose nanocrystals (DACs) were first prepared through the oxidation of CNCs with periodate, followed by the grafting of p-aminophenols (PAPs) onto their surfaces through Schiff base reaction, affording PAP grafted DACs (DAC-g-PAP) via dynamic covalent linkage. The degree of the oxidation (DO) of DACs had a significant effect on the yield of the targeting DAC-g-PAP nanoparticles. High DO (≥40 %) potentially led to the degradation of DACs during the grafting of PAP. The introduced PAP endowed DACs with excellent radical scavenging capability, thereby providing antioxidant properties while improving the hydrophobicity. DAC-g-PAP nanoparticles were then applied as Pickering emulsifiers to prepare oil-in-water Pickering emulsions. The resultant Pickering emulsions indicated exceptional antioxidant and pH-responsiveness together with good freezing-thaw stability. The structures of DAC-g-PAP nanoparticles were thoroughly characterized in this study.
Assuntos
Antioxidantes , Celulose , Emulsões , Nanopartículas , Emulsões/química , Nanopartículas/química , Celulose/química , Celulose/análogos & derivados , Antioxidantes/química , Concentração de Íons de Hidrogênio , Oxirredução , Interações Hidrofóbicas e Hidrofílicas , Água/químicaRESUMO
The implementation of light-sensitive Pickering emulsions with spatio-temporal responsiveness in advanced applications like drug-delivery, colloidal or reaction engineering would open new avenues. However, curiously, light-sensitive Pickering emulsions are barely studied in the literature and their biocompatibility and/or degradability scarcely addressed. Thus, their development remains a major challenge. As an original strategy, we synthesized light-sensitive nanoparticles based on biocompatible Poly(NitroBenzylAcrylate) grafted dextran (Dex-g-PNBA) to stabilize O/W Pickering emulsions. The produced emulsions were stable in time and could undergo time and space-controlled destabilization under light stimulus. Irradiation time and alkaline pH-control of the aqueous phase were proved to be the actual key drivers of destabilization. As the nanoparticles themselves were photolyzed under light stimulus, possible harmful effects linked to accumulation of nanomaterials should be avoided. In addition to UV light (365 nm), visible light (405 nm) was successfully used for the spatio-temporal destabilization of the emulsions, offering perspectives for life science applications.
Assuntos
Dextranos/química , Emulsões/química , Nanopartículas/química , Resinas Acrílicas/síntese química , Resinas Acrílicas/química , Resinas Acrílicas/efeitos da radiação , Alcanos/química , Dextranos/síntese química , Dextranos/efeitos da radiação , Emulsões/síntese química , Luz , Nanopartículas/efeitos da radiação , Fotólise , Estudo de Prova de Conceito , Água/químicaRESUMO
Stimuli-responsive surface-active microcrystalline cellulose (MCC) particles are obtained by interaction with conventional cationic surfactants such as cetyltrimethylammonium bromide (CTAB) in aqueous media, where MCC are in situ hydrophobized by adsorption of the cationic surfactant in water via electrostatic interaction and with the in situ hydrophobization removed by adding an equimolar amount of an anionic surfactant such as sodium dodecyl sulfate (SDS). The trigger is that the electrostatic interaction between the oppositely charged ionic surfactants is stronger than that between the cationic surfactant and the negative charges on particle surfaces, or the anionic surfactant prefers to form ion pairs with the cationic surfactants and thus making them desorbed from surface of MCC. Reversible O/W Pickering emulsions can then be obtained by using the MCC in combination with trace amount of a cationic surfactant and an anionic surfactant, and the anionic surfactant with a longer alkyl chain is more efficient for demulsification. With excellent biocompatibility, biodegradability, and renewability, as well as low toxicity, the biomass cellulose particles that can be made stimuli-responsive and able to reversibly self-assemble at fluid interface become ideal biocompatible particulate materials with extensive applications involving emulsions and foams.
RESUMO
Stimuli-responsive drug release and controlled delivery play crucial roles in enhancing the therapeutic efficacy and lowering over-dosage induced side effects. In this paper, we report magnetically-triggered drug release and in-vitro anti-colon cancer efficacy of Fe3O4@cellulose nanocrystal (MCNC)-stabilized Pickering emulsions containing curcumin (CUR). The loading efficiency of CUR in the micron-sized (≈7⯵m) MCNC-stabilized Pickering emulsions (MCNC-PE) template was found to be 99.35%. The drug release profiles showed that the exposure of MCNC-PE to external magnetic field (EMF) (0.7â¯T) stimulated the release of bioactive from MCNC-PE achieving 53.30⯱â¯5.08% of the initial loading over a 4-day period. The MTT assay demonstrated that the CUR-loaded MCNC-PE can effectively inhibits the human colon cancer cells growth down to 18% in the presence of EMF. The formulation also resulted in 2-fold reduction on the volume of the 3-D multicellular spheroids of HCT116 as compared to the control sample. The MCNC particle was found to be non-toxic to brine shrimp up to a concentration of 100⯵g/mL. Our findings suggested that the palm-based MCNC-PE could be a promising yet effective colloidal drug delivery system for magnetic-triggered release of bioactive and therapeutics.