Efficient Visible-to-UV Photon Upconversion Systems Based on CdS Nanocrystals Modified with Triplet Energy Mediators

Developing high-performance visible-to-UV photon upconversion systems based on triplet–triplet annihilation photon upconversion (TTA-UC) is highly desired, as it provides a potential approach for UV light-induced photosynthesis and photocatalysis. However, the quantum yield and spectral range of visible-to-UV TTA-UC based on nanocrystals (NCs) are still far from satisfactory. Here, three different sized CdS NCs are systematically investigated with triplet energy transfer to four mediators and four annihilators, thus substantially expanding the available materials for visible-to-UV TTA-UC. By improving the quality of CdS NCs, introducing the mediator via a direct mixing fashion, and matching the energy levels, a high TTA-UC quantum yield of 10.4% (out of a 50% maximum) is achieved in one case, which represents a record performance in TTA-UC based on NCs without doping. In another case, TTA-UC photons approaching 4 eV are observed, which is on par with the highest energies observed in optimized organic systems. Importantly, the in-depth investigation reveals that the direct mixing approach to introduce the mediator is a key factor that leads to close to unity efficiencies of triplet energy transfer, which ultimately governs the performance of NC-based TTA-UC systems. These findings provide guidelines for the design of high-performance TTA-UC systems toward solar energy harvesting.     

Y4.67Si3O13-based phosphors: Structure,morphology and upconversion luminescence for optical thermometry

How to improve the sensitivity of the temperature-sensing luminescent materials is one of the most important objects currently. In this work, to obtain high sensitivity and learn the corresponding mechanism, the rare earth (RE) ions doped Y_4.67Si₃O₁₃ (YS) phosphors were developed by solid-state reaction. The phase purity, structure, morphology and luminescence characteristics were evaluated by XRD, TEM, emission spectra, etc. The change of the optical bandgaps between the host and RE-doped phosphors was found, agreeing with the calculation results based on density-functional theory. The temperature-dependence of the upconversion (UC) luminescence revealed that a linear relationship exists between the fluorescence intensity ratio of Ho³⁺ and temperature. The theoretical resolution was evaluated. High absolute (0.083 K⁻¹) and relative (3.53% K⁻¹ at 293 K) sensitivities have been gained in the YS:1%Ho³⁺, 10%Yb³⁺. The effect of the Yb³⁺ doping concentration and pump power on the sensitivities was discussed. The pump-power–dependence of the UC luminescence indicated the main mechanism for high sensitivities in the YS:1%Ho³⁺, 10%Yb³⁺. Moreover, the decay-lifetime based temperature sensing was also evaluated. The above results imply that the present phosphors could be promising candidates for temperature sensors, and the proposed strategies are instructive in exploring other new temperature sensing luminescent materials.     

Lighting the Path: Light Delivery Strategies to Activate Photoresponsive Biomaterials In Vivo

Photoresponsive biomaterials are experiencing a transition from in vitro models to in vivo demonstrations that point toward clinical translation. Dynamic hydrogels for cell encapsulation, light-responsive carriers for controlled drug delivery, and nanomaterials containing photosensitizers for photodynamic therapy are relevant examples. Nonetheless, the step to the clinic largely depends on their combination with technologies to bring light into the body. This review highlights the challenge of photoactivation in vivo, and presents strategies for light management that can be adopted for this purpose. The authors’ focus is on technologies that are materials-driven, particularly upconversion nanoparticles that assist in “direct path” light delivery through tissue, and optical waveguides that “clear the path” between external light source and in vivo target. The authors’ intention is to assist the photoresponsive biomaterials community transition toward medical technologies by presenting light delivery concepts that can be integrated with the photoresponsive targets. The authors also aim to stimulate further innovation in materials-based light delivery platforms by highlighting needs and opportunities for in vivo photoactivation of biomaterials.     

Ultralow-threshold wideband-tunable single-mode ultraviolet lasing from lanthanide-doped upconversion nanomaterials

Ultraviolet (UV) lasers with dynamic wavelength-tunability and high monochromaticity are crucial in a multitude of practical applications yet still remarkable challenges. Here, we show wide wavelength-tuning of single-mode UV lasing based on lanthanide-doped upconversion nanoparticles (UCNPs). The rationally designed Yb³⁺/Er³⁺/Tm³⁺/Gd³⁺/Ce³⁺ co-doped multilayer UCNPs, which exhibits a broad gain spectrum with the full width of half maximum of around 57 nm in the UV regime, are developed. More importantly, by taking advantages of a diffraction grating as the tuning component, stable single-mode emission can be achieved in the UCNPs-based external-cavity-extended Fabry–Pérot laser at room temperature. Specifically, the lasing threshold is around 137 µJ cm^–2, which is two orders of magnitude lower than that in the previously reported articles. Precise wavelength-tuning from 310 to 363 nm can be realized by adjusting the Littrow angle. This achievement highlights a portable alternative to continuously wideband-tunable UV lasers and opens up new opportunities for constructing compact solid-state UV photon sources.     

Designing Stimuli-Responsive Upconversion Nanoparticles that Exploit the Tumor Microenvironment

Tailoring personalized cancer nanomedicines demands detailed understanding of the tumor microenvironment. In recent years, smart upconversion nanoparticles with the ability to exploit the unique characteristics of the tumor microenvironment for precise targeting have been designed. To activate upconversion nanoparticles, various bio-physicochemical characteristics of the tumor microenvironment, namely, acidic pH, redox reactants, and hypoxia, are exploited. Stimuli-responsive upconversion nanoparticles also utilize the excessive presence of adenosine triphosphate (ATP), riboflavin, and Zn²⁺ in tumors. An overview of the design of stimulus-responsive upconversion nanoparticles that precisely target and respond to tumors via targeting the tumor microenvironment and intracellular signals is provided. Detailed understanding of the tumor microenvironment and the personalized design of upconversion nanoparticles will result in more effective clinical translation.     

A Flexi-PEGDA Upconversion Implant for Wireless Brain Photodynamic Therapy

Near-infrared (NIR) activatable upconversion nanoparticles (UCNPs) enable wireless-based phototherapies by converting deep-tissue-penetrating NIR to visible light. UCNPs are therefore ideal as wireless transducers for photodynamic therapy (PDT) of deep-sited tumors. However, the retention of unsequestered UCNPs in tissue with minimal options for removal limits their clinical translation. To address this shortcoming, biocompatible UCNPs implants are developed to deliver upconversion photonic properties in a flexible, optical guide design. To enhance its translatability, the UCNPs implant is constructed with an FDA-approved poly(ethylene glycol) diacrylate (PEGDA) core clad with fluorinated ethylene propylene (FEP). The emission spectrum of the UCNPs implant can be tuned to overlap with the absorption spectra of the clinically relevant photosensitizer, 5-aminolevulinic acid (5-ALA). The UCNPs implant can wirelessly transmit upconverted visible light till 8 cm in length and in a bendable manner even when implanted underneath the skin or scalp. With this system, it is demonstrated that NIR-based chronic PDT is achievable in an untethered and noninvasive manner in a mouse xenograft glioblastoma multiforme (GBM) model. It is postulated that such encapsulated UCNPs implants represent a translational shift for wireless deep-tissue phototherapy by enabling sequestration of UCNPs without compromising wireless deep-tissue light delivery.     

Photon Upconversion Hydrogels for 3D Optogenetics

The ability to optically induce biological responses in 3D has been dwarfed by the physical limitations of visible light penetration to trigger photochemical processes. However, many biological systems are relatively transparent to low-energy light, which does not provide sufficient energy to induce photochemistry in 3D. To overcome this challenge, hydrogels that are capable of converting red or near-IR (NIR) light into blue light within the cell-laden 3D scaffolds are developed. The upconverted light can then excite optically active proteins in cells to trigger a photochemical response. The hydrogels operate by triplet–triplet annihilation upconversion. As proof-of-principle, it is found that the hydrogels trigger an optogenetic response by red/NIR irradiation of HeLa cells that have been engineered to express the blue-light sensitive protein Cry2olig. While it is remarkable to photoinduce the clustering of Cry2olig with blanket NIR irradiation in 3D, it is also demonstrated how the hydrogels trigger clustering within a single cell with great specificity and spatiotemporal control. In principle, these hydrogels may allow for photochemical control of cell function within 3D scaffolds, which can lead to a wealth of fundamental studies and biochemical applications.     

Inorganic Protection of Polymer Nanocapsules: A Strategy to Improve the Efficiency of Encapsulated Optically Active Molecules

We demonstrate that the efficiency under ambient conditions of optically active molecules encapsulated in polymer nanocapsules can be significantly improved by depositing an inorganic layer onto the polymeric shell. A triplet-triplet annihilation upconversion (TTA-UC) system consisting of a porphyrin derivative and perylene is used as a representative case. Different inorganic materials are deposited on the surface of functionalized polymer nanocapsules synthesized by free-radical polymerization in miniemulsion. First, a silicate clay with formula [Si₈(Mg_5.45Li_0.4)O₂₀(OH)₄]Na_0.7 is deposited on the surface of positively charged polystyrene nanocapsules via layer-by-layer deposition. Second, controlled in situ mineralization of hydroxyapatite and cerium(IV) oxide are carried out on the surface of negatively charged polystyrene nanocapsules. In both cases the inorganic materials on the nanocapsule surface act as a scavenger and avoid the entry of oxygen from the external environment. By avoiding the entry of oxygen, the photo-oxidation process of perylene molecules is avoided within the system, and an increase in the TTA-UC properties occurs.     

BiLaWO6: Er3+/Tm3+/Yb3+ phosphor: Study of multiple fluorescence intensity ratiometric thermometry at cryogenic temperatures

Highly thermally stable Er³⁺/Tm³⁺/Yb³⁺ tri-doped bismuth lanthanum tungstate phosphors were prepared by high temperature solid-state reaction method. The structural and morphological properties of the prepared phosphors were analysed by X-ray diffraction (XRD), Raman spectroscopy and Scanning electron microscopy (SEM) coupled with energy dispersion spectrum (EDS). Visible upconversion (UC) luminescence was measured by exciting the phosphors with 980 nm laser radiation. The dependence of the UC intensity of each emission band of Er³⁺ and Tm³⁺ ions as a function of temperature in the range from 30 to 300 K was monitored. Fluorescence intensity ratios (FIR) of thermally coupled levels (TCL) and non-thermally coupled levels (NTCL) were analysed and verified with appropriate theoretical validation. The absolute (S_A) and relative sensitivities (S_R) were estimated and compared with the reported systems. In the present case of BiLaWO₆: Er³⁺/Tm³⁺/Yb³⁺, S_R (0.43 % K^?1) related to TCL of Er³⁺ UC is found to have maximum sensitivity compared to any of the NTCL combinations at 300 K. From this study we inferred that the S_R values estimated from NTCL are smaller than that of TCL involved in BLW: Er³⁺/Tm³⁺/Yb³⁺ phosphor. The temperature dependent CIE color coordinates were also evaluated in the cryogenic temperature region.     

柠檬酸凝胶法制备Er,Tm∶Yb3Al5O12纳米粉体及发光性能

以柠檬酸为燃烧剂,采用柠檬酸凝胶法制备了Er,Tm∶Yb3Al5O12(Er,Tm:YbAG)纳米粉体,其最佳的制备工艺条件:Er3+和Tm3+掺杂的摩尔分数分别为2%和1%,柠檬酸与金属硝酸盐原子总数的摩尔比为1.7∶1,煅烧温度和时间分别为950℃和2h。制备的粉体颗粒为规则球形,粒径均匀、分散性好,平均粒径约为45nm。研究了样品的发光性能,结果表明:2%Er,1%Tm∶YbAG样品的发光性能最好,在1 587、1 658和1 711nm处有较强发射峰,分别对应Er3+的4 I13/2→4 I15/2跃迁和Tm3+的3 F4→3 H6跃迁。样品的上转换光谱表明,上转换荧光峰包括了蓝光、绿光和红光。