Methylene Blue-Loaded Upconverting Hydrogel Nanocomposite: Potential Material for Near-Infrared Light-Triggered Photodynamic Therapy Application

The property of upconverting nanoparticles to convert the low-energy near-infrared (NIR) light into high-energy visible light has made them a potential candidate for various biomedical applications including photodynamic therapy (PDT). In this work, we show how a surface functionalization approach on the nanoparticle can be used to develop a nanocomposite hydrogel which can be of potential use for the PDT application. The upconverting hydrogel nanocomposite was synthesized by reacting 10-undecenoic acid-capped Yb3+/Er3+-doped NaYF4 nanoparticles with the thermosensitive N-isopropylacrylamide monomer. The formation of hydrogel was completed within 15 min and hydrogel nanocomposites showed strong enhancement in the visible light emission compared to the emission obtained from 10-undecenoic acid-capped Yb3+/Er3+-doped NaYF4 nanoparticles via the upconversion process (under 980 nm laser excitation). The upconverting hydrogel nanocomposites displayed high swelling behavior in water because of their porous nature. The porous structure ensured a higher loading of methylene blue dye (∼78% in 1 h) into the upconverting hydrogel, which was achieved via the swelling diffusion phenomenon. Upon excitation with the NIR light, the visible light emitted from the hydrogel activated the photosensitizer methylene blue which generated reactive oxygen species. Our results were able to show that the methylene blue-loaded composite hydrogel can be a potential platform for the future of NIR-triggered PDT in skin cancer treatment

The impact of cell culture media on the interaction of biopolymer-functionalized gold nanoparticles with cells: mechanical and toxicological properties

Understanding the nanoparticle-cell interactions in physiological media is vital in determining the biological fate of the nanoparticles (NPs). These interactions depend on the physicochemical properties of the NPs and their colloidal behavior in cell culture media (CCM). Furthermore, the impact of the bioconjugates made by nanoparticle with proteins from CCM on the mechanical properties of cells upon interaction is unknown. Here, we analyzed the time dependent stability of gold nanoparticles (AuNPs) functionalized with citrate, dextran-10, dextrin and chitosan polymers in protein poor- and protein rich CCM. Further, we implemented the high-throughput technology real-time deformability cytometry (RT-DC) to investigate the impact of AuNP-bioconjugates on the cell mechanics of HL60 suspension cells. We found that dextrin-AuNPs form stable bioconjugates in both CCM and have a little impact on cell mechanics, ROS production and cell viability. In contrast, positively charged chitosan-AuNPs were observed to form spherical and non-spherical aggregated conjugates in both CCM and to induce increased cytotoxicity. Citrate- and dextran-10-AuNPs formed spherical and non-spherical aggregated conjugates in protein rich- and protein poor CCM and induced at short incubation times cell stiffening. We anticipate based on our results that dextrin-AuNPs can be used for therapeutic purposes as they show lower cytotoxicity and insignificant changes in cell physiology

Methyl Oleate-Capped Upconverting Nanocrystals: A Simple and General Ligand Exchange Strategy To Render Nanocrystals Dispersible in Aqueous and Organic Medium

We report a simple and general ligand exchange strategy to functionalize the nanocrystals with both hydrophobic and hydrophilic ligands. This is achieved by first capping the Er/Yb-doped NaYF₄ nanocrystals with a weak ligand such as methyl oleate and subsequently ligand exchanged with various organic ligands which can strongly coordinate to the surface of the nanocrystals. The method involves only a simple stirring or sonication of the nanocrystals dispersion with the ligands of interest. Dicarboxylic acids such as sebacic acid, adipic acid, succinic acid, and malonic acid-functionalized nanocrystals which are difficult to achieve via thermal decomposition method were easily prepared by this ligand exchange strategy. In addition, low boiling point ligands like hexanoic acid can easily be coated over the surface of the Er/Yb-doped NaYF₄ nanocrystals. Both size and shape of the nanocrystals were preserved after the ligand exchange process. The methyl oleate-capped Er/Yb-doped NaYF₄ nanocrystals display strong upconversion emission after ligand exchanged with hydrophobic and hydrophilic molecules. The high stability of the nanocrystals after ligand exchange process is verified by performing time-dependent luminescent measurements at different pH, buffers, etc