Two Colors of Light Are Needed to Break Bonds and Release Small Molecules from the Surface of SiO₂–Au Core–Shell Nanoparticles

The photothermal effect is not able to break bonds and release small molecules from the surface of SiO₂–Au core–shell nanoparticles unless the nanosystem is first exposed to visible light. Only after this light triggers the ring-opening reaction of dithienylethene chromophores attached to the surface of the nanoparticles can the heat generated by the NIR light induce reverse Diels–Alder reactions

Fluorescent Quenching of Lanthanide-Doped Upconverting Nanoparticles by Photoresponsive Polymer Shells

A photoresponsive amphiphilic polymer was synthesized and used to encapsulate upconverting lanthanide-doped nanoparticles to produce a novel water-dispersible nanoassembly with a high loading of emission quenchers. The nanoassembly exhibits fluorescent emission in the visible region upon irradiation with 980 nm light, which can be reversibly modulated by toggling the isomeric state of photoresponsive chromophores attached to the polymer’s backbone using UV and visible light. Photon counting experiments show that the quenching mechanism for this new nanoassembly is a combination of Förster resonance energy transfer (FRET) and emission-reabsorption. Compared to the similar nanoassembly prepared from a reported “plug-and-play” method, this new nanoassembly has higher overall quenching efficiency due to the increased photoswitch loading (14 times compared to the existing nanoassembly)

Near-Infrared Light-Triggered Dissociation of Block Copolymer Micelles Using Upconverting Nanoparticles

We demonstrate a novel strategy enabling the use of a continuous-wave diode near-infrared (NIR) laser to disrupt block copolymer (BCP) micelles and trigger the release of their “payloads”. By encapsulating NaYF₄:TmYb upconverting nanoparticles (UCNPs) inside micelles of poly(ethylene oxide)-<i>block</i>-poly(4,5-dimethoxy-2-nitrobenzyl methacrylate) and exposing the micellar solution to 980 nm light, photons in the UV region are emitted by the UCNPs, which in turn are absorbed by <i>o</i>-nitrobenzyl groups on the micelle core-forming block, activating the photocleavage reaction and leading to the dissociation of BCP micelles and release of co-loaded hydrophobic species. Our strategy of using UCNPs as an internal UV or visible light source upon NIR light excitation represents a general and efficient method to circumvent the need for UV or visible light excitation that is a common drawback for light-responsive polymeric systems developed for potential biomedical applications

Controlling a Polymer Adhesive Using Light and a Molecular Switch

A thermally remendable polymer was synthesized by the Diels–Alder reaction between dithienylfuran and maleimide monomers to generate a photoresponsive diarylethene. UV light (312 nm) and visible light (>435 nm) “gate” the reversibility of the Diels–Alder reaction and turn the self-healing properties of the polymer “off” and “on”, respectively. After exposure to UV light, the strength of the polymer as an adhesive is enhanced. Visible light weakens the adhesive

Probing the Microenvironments in a Polymer-Wrapped Core–Shell Nanoassembly Using Pyrene Chromophores

The local environments within an amphiphilic polymer shell wrapped around lanthanide-doped upconverting nanoparticles were probed using steady-state and time-resolved fluorescence spectroscopy techniques. Emission lifetime measurements of pyrene chromophores trapped within the polymer shell reveal that there are at least two environments, where the organic pyrene molecules are encapsulated in hydrophobic environments that have lower polarity than in water. The migration of pyrene chromophores from their initial location to another location was also observed, demonstrating that the polymeric shell provides both hydrophobicity and mobility for entrapped molecules. These results offer insight into what outcomes can be expected when chemical reactions are carried out in these nanoassemblies, especially if they are to be used as nanoreactors for synthesis or delivery vehicles for therapeutics

Near Infrared Light Triggered Release of Biomacromolecules from Hydrogels Loaded with Upconversion Nanoparticles

Using a photosensitive hybrid hydrogel loaded with upconversion nanoparticles (UCNPs), we show that continuous-wave near-infrared (NIR) light (980 nm) can be used to induce the gel–sol transition and release large, inactive biomacromolecules (protein and enzyme) entrapped in the hydrogel into aqueous solution “on demand”, where their bioactivity is recovered. This study is a new demonstration and development in harnessing the unique multiphoton effect of UCNPs for photosensitive materials of biomedical interest

A “Plug-and-Play” Method to Prepare Water-Soluble Photoresponsive Encapsulated Upconverting Nanoparticles Containing Hydrophobic Molecular Switches

A convenient and versatile protocol to encapsulate lanthanide doped upconverting nanoparticles by an amphiphilic polymer shell containing photoresponsive diarylethene chromophores was developed. The assemblies are all water-soluble and fluoresce in the visible region of the spectrum when excited with 980 nm near-infrared light. The fluorescent emission can be selectively and reversibly modulated by alternatively irradiating the photoresponsive nanoparticles with UV light and visible light, which triggers ring-closing and ring-opening reactions of the chromophores, respectively. Fluorescence lifetime experiments suggest that the quenching mechanism is a combination of energy transfer and emission-reabsorption processes. These photoresponsive upconverting nanoparticles have the potential to advance bioimaging and other applications in nanophotonics

A Photoresponsive Biomimetic Dry Adhesive Based on Doped PDMS Microstructures

A Photoresponsive Biomimetic Dry Adhesive Based on Doped PDMS Microstructure