Nanoencapsulated Phase-Change Materials: Versatile and Air-Tolerant Platforms for Triplet-Triplet Annihilation Upconversion.

Efficient and long-term stable triplet-triplet annihilation upconversion (TTA-UC) can be achieved by effectively protecting the excited organic triplet ensembles from photoinduced oxygen quenching, and discovery of a new material platform that promotes TTA-UC in ambient conditions is of paramount importance for practical applications. In this study, we present the first demonstration of an organic nonparaffin phase-change material (PCM) as an air-tolerant medium for TTA-UC with a unique solid-liquid phase transition in response to temperature variation. For the proposed concept, 2,4-hexadien-1-ol is used and extensively characterized with several key features, including good solvation capacity, mild melting point (30.5 °C), and exclusive antioxidant property, enabling a high-efficiency, low-threshold, and photostable TTA-UC system without energy-intensive degassing processes. In-depth characterization reveals that the triplet diffusion among the transient species, i.e., 3sensitizer* and 3acceptor*, is efficient and well protected from oxygen quenching in both aerated liquid- and solid-phase 2,4-hexadien-1-ol. We also propose a new strategy for the nanoencapsulation of PCM by employing hollow mesoporous silica nanoparticles as vehicles. This scheme is applicable to both aqueous- and solid-phase TTA-UC systems as well as suitable for various applications, such as thermal energy storage and smart drug delivery.

Yolk-Shell-Type Gold Nanoaggregates for Chemo- and Photothermal Combination Therapy for Drug-Resistant Cancers.

Epithelial ovarian cancer is a gynecological cancer with the highest mortality rate, and it exhibits resistance to conventional drugs. Gold nanospheres have gained increasing attention over the years as photothermal therapeutic nanoparticles, owing to their excellent biocompatibility, chemical stability, and ease of synthesis; however, their practical application has been hampered by their low colloidal stability and photothermal effects. In the present study, we developed a yolk-shell-structured silica nanocapsule encapsulating aggregated gold nanospheres (aAuYSs) and examined the photothermal effects of aAuYSs on cell death in drug-resistant ovarian cancers both in vitro and in vivo. The aAuYSs were synthesized using stepwise silica seed synthesis, surface amino functionalization, gold nanosphere decoration, mesoporous organosilica coating, and selective etching of the silica template. Gold nanospheres were agglomerated in the confined silica interior of aAuYSs, resulting in the red-shifting of absorbance and enhancement of the photothermal effect under 808 nm laser irradiation. The efficiency of photothermal therapy was first evaluated by inducing aAuYS-mediated cell death in A2780 ovarian cancer cells, which were cultured in a two-dimensional culture and a three-dimensional spheroid culture. We observed that photothermal therapy using aAuYSs together with doxorubicin treatment synergistically induced the cell death of doxorubicin-resistant A2780 cancer cells in vitro. Furthermore, this type of combinatorial treatment with photothermal therapy and doxorubicin synergistically inhibited the in vivo tumor growth of doxorubicin-resistant A2780 cancer cells in a xenograft transplantation model. These results suggest that photothermal therapy using aAuYSs is highly effective in the treatment of drug-resistant cancers.

Versatile Yolk-Shell Encapsulation: Catalytic, Photothermal, and Sensing Demonstration.

Here, a novel, versatile synthetic strategy to fabricate a yolk-shell structured material that can encapsulate virtually any functional noble metal or metal oxide nanocatalysts of any morphology in a free suspension fashion is reported. This strategy also enables encapsulation of more than one type of nanoparticle inside a single shell, including paramagnetic iron oxide used for magnetic separation. The mesoporous organosilica shell provides efficient mass transfer of small target molecules, while serving as a size exclusion barrier for larger interfering molecules. Major structural and functional advantages of this material design are demonstrated by performing three proof-of-concept applications. First, effective encapsulation of plasmonic gold nanospheres for localized photothermal heating and heat-driven reaction inside the shell is shown. Second, hydrogenation catalysis is demonstrated under spatial confinement driven by palladium nanocubes. Finally, the surface-enhanced Raman spectroscopic detection of model pollutant by gold nanorods is presented for highly sensitive environmental sensing with size exclusion.

Upconverting Oil-Laden Hollow Mesoporous Silica Microcapsules for Anti-Stokes-Based Biophotonic Applications.

A recyclable, aqueous phase functioning and biocompatible photon upconverting system is developed. Hollow mesoporous silica microcapsules (HMSMs) with ordered radial mesochannels were employed, for the first time, as vehicles for the post-encapsulation of oil phase triplet-triplet annihilation upconversion (TTA-UC), with the capability of homogeneous suspension in water. In-depth characterization of such upconverting oil-laden HMSMs (UC-HMSMs) showed that the mesoporous silica shells reversibly stabilized the encapsulated UC oil in water to allow efficient upconverted emission, even under aerated conditions. In addition, the UC-HMSMs were found to actively bind to the surface of human mesenchymal stem cells without significant cytotoxicity and displayed upconverted bright blue emission under 640 nm excitation, indicating a potential of our new TTA-UC system in biophotonic applications. These findings reveal the great promise of UC-HMSMs to serve as ideal vehicles not only for ultralow-power in vivo imaging but also for stem cell labeling, to facilitate the tracking of tumor cells in animal models.

Flexible and Micropatternable Triplet-Triplet Annihilation Upconversion Thin Films for Photonic Device Integration and Anticounterfeiting Applications.

Triplet-triplet annihilation upconversion (TTA-UC) has recently drawn widespread interest for its capacity to harvest low-energy photons and to broaden the absorption spectra of photonic devices, such as solar cells. Although conceptually promising, effective integration of TTA-UC materials into practical devices has been difficult due to the diffusive and anoxic conditions required in TTA-UC host media. Of the solid-state host materials investigated, rubbery polymers facilitate the highest TTA-UC efficiency. To date, however, their need for long-term oxygen protection has limited rubbery polymers to rigid film architectures that forfeit their intrinsic flexibility. This study introduces a new multilayer thin-film architecture, in which scalable solution processing techniques are employed to fabricate flexible, photostable, and efficient TTA-UC thin films containing layers of oxygen barrier and host polymers. This breakthrough material design marks a crucial advance toward TTA-UC integration within rigid and flexible devices alike. Moreover, it introduces new opportunities in unexplored applications such as anticounterfeiting. Soft lithography is incorporated into the film fabrication process to pattern TTA-UC host layers with a broad range of high-resolution microscale designs, and superimposing host layers with customized absorption, emission, and patterning ultimately produces proof-of-concept anticounterfeiting labels with advanced excitation-dependent photoluminescent security features.