Enhancement of enzyme activity by laser-induced energy propulsion of upconverting nanoparticles under near-infrared light: A comprehensive methodology for in vitro and in vivo applications.

If the appropriate immobilization method and carrier support are not selected, partial decreases in the activity of enzymes may occur after immobilization. Herein, to overcome this challenge, an excitation mechanism that enables energy transfer was proposed. Modified upconverting nanoparticles (UCNPs) were constructed and the important role of near-infrared (NIR) excitation in enhancing the catalytic activity of the enzyme was demonstrated. For this purpose, UCNPs were first synthesized via the hydrothermal method, functionalized with isocyanate groups, and then, PEG-L-ASNase was immobilized via covalent binding. UCNPs with and without PEG-L-ASNase were extensively characterized by different methods. These supports had immobilization yield and activity efficiency of >96 % and 78 %, respectively. Moreover, immobilized enzymes exhibited improved pH, thermal, and storage stability. In addition, they retained >65 % of their initial activity even after 20 catalytic cycles. Biochemical and histological findings did not indicate a trend of toxicity in rats due to UCNPs. Most importantly, PEG-L-ASNase activity was triggered approximately 5- and 2-fold under in vitro and in vivo conditions, respectively. Overall, it is anticipated that this pioneering work will shed new light on the realistic and promising usage of NIR-excited UCNPs for the immobilization of enzymes in expensive and extensive applications.

Selective photosensitization through an AND logic response: optimization of the pH and glutathione response of activatable photosensitizers.

A series of pH and GSH responsive photosensitizers were designed and synthesized. pKa values were optimized by adjusting the inductive contribution of substituents to reach a pH range (6.0-7.4) relevant to the tumour microenvironment. pH-Activatable behaviour and redox mediated release of the quencher from the PS by GSH allow the construction of an AND logic operator for selective photodynamic action in aqueous solutions.

Synthesis and characterization of Bodipy functionalized magnetic iron oxide nanoparticles for potential bioimaging applications.

Multifunctional magnetic nanoparticles were synthesized for potential bio-imaging applications. Uniform PEI coated magnetic Fe3O4 (PEI-Fe3O4) nanoparticles were prepared by a modified co-precipitation method and then covalently conjugated with a fluorophore molecule, Bodipy-5 by the DCC/DMAP coupling reaction. The covalent binding of Bodipy-5 to the PEI coated magnetic Fe3O4 nanoparticles were confirmed by means of FTIR and XPS measurements. The imaging ability of the Bodipy coated magnetic nanoparticles was determined on two human cancer cells, A549 (human lung adenocarcinoma epithelial) and Ishikawa (endometrial adenocarcinoma), for the first time. Cytotoxicity of BOD-MNPs was evaluated in both cancer cells and healthy human umbilical vein endothelial cell line (HUVEC) by standard MTT (3-(4,5-dimethythiazol-2-yl)-2,5-diphenyl tetrazolium bromide) assay. In vitro activities of the nanoparticles were also investigated.

Molecular insights into the selective action of a magnetically removable complexone-grafted adsorbent.

The binding and release of trivalent rare earth element (REE) cations (Dy(3+), Nd(3+) and La(3+)) from solutions by a new fully characterized magnetic nano adsorbent material, consisting of iminodiacetic acid ligand (H2IDA) grafted onto SiO2 covered γ-Fe2O3 nanoparticles, was investigated. The nano adsorbent revealed a slightly higher capacity towards heavier REE and appreciable selectivity, especially on desorption. It was found that the composition of the surface complex was RE(3+) : L = 1 : 1. The complexation of the molecular H2IDA with RE(3+) in this ratio under non-basic conditions was therefore investigated by X-ray crystallography to produce relevant molecular models. Unexpectedly big differences in coordination numbers and binding mode of IDA along with distinct analogies in packing of the ligand molecules in the obtained 2D-coordination polymer structures provided valuable insights into possible reasons for the observed selectivity.

Near IR excitation of heavy atom free Bodipy photosensitizers through the intermediacy of upconverting nanoparticles.

Orthogonal dimers of Bodipy were recently shown to be efficient generators of singlet oxygen. However, these dyes require green light for excitation, which would be very quickly attenuated inside the mammalian tissues. We now demonstrate that when these dyes are covalently attached to UCNPs, near IR irradiation results in very efficient generation of singlet oxygen.