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.     

Red-shift and improved afterglow of Sr3Al2-xBxO5Cl2:Eu2+, Dy3+ phosphors via a cation substitution strategy

Sr₃Al_2-xB_xO₅Cl₂:Eu²⁺, Dy³⁺ (x = 0, 0.2, 0.4) long persistent phosphors were prepared via solid-state process. The pristine Sr₃Al₂O₅Cl₂:Eu²⁺, Dy³⁺ phosphor exhibits orange/red broad band emission around 609 nm, which can be attributed to the electric radiation transitions 4f⁶5 d¹→4f⁷ of Eu²⁺. Upon the same excitation, the B³⁺-doped Sr₃Al_2-xB_xO₅Cl₂:Eu²⁺, Dy³⁺ phosphors display red-shift from 609 nm to 625 nm with increasing B³⁺ concentrations. The XRD patterns show that Al³⁺ can be replaced by B³⁺ in the host lattice at the tetrahedral site, which causes lattice contraction and crystal field enhancement, and thereafter achieves the red-shift on the emission spectrum. The XPS investigation provides direct evidence of the dominant 2-valent europium in the phosphor, which can be ascribed for the broad band emission of the prepared phosphors. The afterglow of all phosphors show standard double exponential decay behavior, and the afterglow of Sr₃Al₂O₅Cl₂:Eu²⁺, Dy³⁺is rather weak, while the sample co-doped with B³⁺shows longer and stronger afterglow, as confirmed after the curve simulation. The analysis of thermally stimulated luminescence showed that, when B³⁺ is introduced, a much deeper trap is created, and the density of the electron trap is also significantly increased. As a result, B³⁺ ions caused redshift and enhanced afterglow for the Sr₃Al_2-xB_xO₅Cl₂:Eu²⁺, Dy³⁺ phosphor.     

Fabrication and characterizations of Cr3+-doped ZnGa2O4 transparent ceramics with persistent luminescence

0.5 at.% Cr:ZnGa₂O₄ precursor was synthesized by the co-precipitation method with nitrates as raw materials, using ammonium carbonate as the precipitant. Low-agglomerated Cr:ZnGa₂O₄ powders with an average particle size of 43 nm were obtained by calcining the precursor at 900℃ for 4 h. Using the powders as starting materials, 0.5 at.% Cr:ZnGa₂O₄ ceramics with an average grain size of about 515 nm were prepared by presintering at 1150℃ for 5 h in air and HIP post-treatment at 1100℃ for 3 h under 200 MPa Ar. The in-line transmittance of 0.5 at.% Cr:ZnGa₂O₄ ceramics with a thickness of 1.3 mm reaches 59.5% at the wavelength of 700 nm. The Cr:ZnGa₂O₄ ceramics can be effectively excited by visible light and produce persistent luminescence at 700 nm. For Cr:ZnGa₂O₄ transparent ceramics, the brightness of afterglow was larger than 0.32 mcd/m² after 30 min, which is far superior to that of Cr:ZnGa₂O₄ persistent luminescence powders.     

Luminescence and scintillation properties of rare-earth-doped LuF3 scintillation crystals

The Nd-doped and Er-doped LuF₃ single crystals were grown by the micro-pulling-down method to study their scintillation properties in the vacuum-ultraviolet (VUV) region. The doubly Nd–Er codoped single crystal was grown to study possibility of scintillation performance improvement by energy transfer from Er³⁺ to Nd³⁺ ions. The LiF flux was to avoid phase transition below melting temperature. The 1%Nd-doped sample showed the highest overall scintillation efficiency under X-ray excitation which was 7 times as high as that of the LaF₃:Nd 8% standard. The leading Nd³⁺ 5d–4f emission was situated at 176 nm, while the Er³⁺ 5d–4f emission for Er-doped samples was observed at 163 nm, which better matches the sensitivity of some VUV-sensitive photodetectors. The optimum Er concentration was determined to be around 1–3 mol%. No Er³⁺ 5d–4f emission was observed for the doubly Er,Nd-codoped sample due to energy transfer from the Er³⁺ to Nd³⁺ ions. Slight improvement of the light yield was observed in the doubly-doped sample with respect to the Nd-only doped one.     

Sparse non-convex Lp regularization for cone-beam X-ray luminescence computed tomography

Cone-beam X-ray luminescence computed tomography (CB-XLCT) is an attractive hybrid imaging modality, and it has the potential of monitoring the metabolic processes of nanophosphors-based drugs in vivo. However, the XLCT imaging suffers from a severe ill-posed problem. In this work, a sparse nonconvex L_p (0?p?L₁ regularization. Further, an iteratively reweighted split augmented lagrangian shrinkage algorithm (IRW_SALSA-L_p) was proposed to efficiently solve the non-convex L_p (0?p?p-values (1/16, 1/8, 1/4, 3/8, 1/2, 5/8, 3/4, 7/8) in both 3D digital mouse experiments and in vivo experiments. The results demonstrate that the proposed non-convex methods outperform L₂ and L₁ regularization in accurately recovering sparse targets in CB-XLCT. And among all the non-convex p-values, our L_p(1/4?p?相似文献   

Study on Luminescence Properties of High-Density Phosphors BiTaO4∶Pr3+ and BiTaO4

The photoluminescence properties of BiTaO4∶Pr3+ and BiTaO4 at room temperature were studied, and the infrared transmission and diffusion reflection spectra of BiTaO4 were measured. The photoluminescence spectrum of BiTaO4 peaks at about 420, 440 and 465 nm. There has an obvious excitation band from 330 to 370 nm. The photoluminescence spectrum of BiTaO4∶Pr3+ consists of the characteristic emission of Pr3+, and its main peak is at 606 nm from 3P0→3H6 transition of Pr3+. Its excitation spectrum consists of the wide band with maximum at 325 nm, the wide band in the range of 375～430 nm, and the characteristic excitation of Pr3+. The bands at 325 nm and 375～430 nm may be from the absorption of the charge transfer transition of the tantalate group and defect energy levels in its forbidden band, respectively. There is energy transfer from host to Pr3+. Because both the host density and photoluminescence peak intensity of BiTaO4∶Pr3+ are superior to PbWO4, BiTaO4∶Pr3+ may be a potential heavy scintillator.     

Colour Centres and Energy Transfer in BaF2-xClx:Eu2+ Phosphors

The optical absorption spectra of BaF2-xClx:Eu2 after ultraviolet (UV) light excitation were investigated.The differences between the absorption spectra after and before excitation (DAS) were observed.The DAS increase at both the high and the low energy side of F band in BaF2-xClx:Eu2 after 245 nm UV light excitation.The bleach effect of UV light and the absorption of electrons in the valence band may account for the former and the formation of Fa centres (association of F(Cl-) centres), whose absorption band matches the HeNe laser better, may explain the latter.In the write-in process, the transfer of electrons is via tunneling.In the readout process, the transfer of electrons captured in F(F-) and Fa centres is more likely via tunneling, and that of F(Cl-) centres is more likely via conduction band.     

台湾功能材料产业与研究概况

本文简要地介绍目前台湾功能材料产业与研究的情况，其中包括化合物半导体、电子构装材料、电子功能陶瓷材料、高温超导体、磁记录材料、稀土永磁材料、发光材料和传感器等。