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.     

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.     

Shape-Controlled Synthesis and Upconversion Luminescence of Y2O3:Yb, Er Microstructures

The Y2O3: Yb3 , Er3 microstructures were fabricated by a hydrothermal method without surfactants.The microstructures structure was characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM,KYKY 1000B).The up-conversion luminescence spectra were studied under 978 nm laser diode excitation.In Yb3 and Er3 codoped Y2 O3 microcrystals, the relative intensity of green emission became stronger as the morphology of sample changed from wires to films.     

9-蒽甲酸/卟啉钯衍生物的pH响应上转换性能

以9-蒽甲酸(9-ACA)为发光剂,八乙基卟啉钯(Pd OEP)为光敏剂,在二者最佳配比〔n(9-ACA)∶n(Pd OEP)=80∶1〕下,构建了对溶液中氢离子和氢氧根离子具备灵敏响应性的上转换发光体系9-ACA/PdOEP。当pH处于4～8以及8～11时,上转换发光强度均与pH呈现良好的线性关系。参比实验中,单一组分9-ACA本身的荧光强度与pH没有呈现线性关系,证明了9-ACA/Pd OEP体系对于pH的宽范围响应来源于光敏剂与发光剂之间的三线态-三线态能量转移(TTET)过程。     

Gd2O3：Yb，Er纳米材料的制备及上转换发光研究

利用Triton X-100／正己醇／环己烷／正己烷／水制成W／O微乳反胶团体系制备Gd2O3：Yb，Er上转换材料。利用扫描电镜观察氧化物粉体的颗粒形貌均为球形；通过改变掺杂元素Yb和Er的比例，在980nm的红外光激发下，观察研究氧化物颗粒的发光性质。该粉体在波长为980nm的半导体激光器激发下发射出绿色和红色的上转换荧光，分别对应于Er^3＋离子的。^S3／2／^2H11／2→^4I15／2跃迁和。^F9／2→^I15／2跃迁。     

Enhancement of Upconverted Fluorescence by Interference Layers

Upconverting nanoparticles show potential applications in the field of photovoltaics and array‐based detection devices. While fluorescence enhancement using interference of incident radiation is well known in Stokes‐shift type systems such as fluorescent dyes; the effect of such interference geometry in nonlinear Anti‐Stokes type emission, such as in upconversion rare earth photophysics is demonstrated for the first time. This work describes in detail the influence of the interference modulation on both the excitation (interion energy transfer) and radiative decay with nonradiative decay processes active between emissive levels. These effects are illustrated in the thickness dependence of the decay rate and rise time. Single particle upconverted spectra and time‐resolved measurements show concurrent optimization of the infrared absorption and emission at 540 and 650 nm, with an average enhanced emission of 20 times at λ = 540 and 45 times at λ = 650 nm, dependent on the interference layer thickness and on the excitation intensity. The experimental results are correlated with finite element modeling. Both experiments and calculations show emission enhancement at an interference layer thickness of about 740 ± 20 nm, where such tolerance and the planar design, leads to ease in implementation in applications.