Oxygen Activation of Apo‐obelin–Coelenterazine Complex

Ca²⁺‐regulated photoproteins use a noncovalently bound 2‐hydroperoxycoelenterazine ligand to emit light in response to Ca²⁺ binding. To better understand the mechanism of formation of active photoprotein from apoprotein, coelenterazine and molecular oxygen, we investigated the spectral properties of the anaerobic apo‐obelin–coelenterazine complex and the kinetics of its conversion into active photoprotein after exposure to air. Our studies suggest that coelenterazine bound within the anaerobic complex might be a mixture of N7‐protonated and C2(?) anionic forms, and that oxygen shifts the equilibrium in favor of the C2(?) anion as a result of peroxy anion formation. Proton removal from N7 and further protonation of peroxy anion and the resulting formation of 2‐hydroperoxycoelenterazine in obelin might occur with the assistance of His175. It is proposed that this conserved His residue might play a key role both in formation of active photoprotein and in Ca²⁺‐triggering of the bioluminescence reaction.     

Near-Infrared Bioluminescence Imaging with a through-Bond Energy Transfer Cassette

A coelenterazine (CTZ) analogue emitting near-infrared (NIR) bioluminescence was synthesized for through-bond energy transfer (TBET)-based imaging modalities. The analogue, named Cy5-CTZ, was prepared by conjugating cyanine-5 (Cy5) dye to CTZ through an acetylene linker. This novel derivative is intrinsically fluorescent and emits NIR-shifted luminescence upon reacting with an appropriate luciferase, the Renilla luciferase. This Cy5-CTZ substrate is optically stable in physiological samples and rapidly permeabilize through the plasma membrane into the cytosolic compartment of live cells.     

Structure,electrical and luminescent properties of the NBT:Er-0.3CT:Pr composite ceramics

A binary composite ceramic Na_0.5Bi_0.5TiO₃:0.002 Er-0.3CaTiO₃:0.003 Pr (NBT:Er-0.3CT:Pr) was fabricated by a conventional solid state reaction route. The effect of sintering temperature on the microstructure and phase structure of the ceramics has been investigated. And the basic electrical properties such as dielectric properties and ferroelectric performances of the ceramics were examined. Macro long-ranged ferroelectric order cannot be induced via electric field in the composite ceramics. And under local electric field using PFM, obvious ferroelectric switching is identified in the ceramics. Furthermore, the up-conversion luminescence, photochromic reaction, and luminescence modulation have been achieved in the ceramics. Additionally, photo-stimulated luminescence and thermal luminescence are obtained. The present study indicates that optical properties are tightly related to the sintering temperature. The prepared ceramic NBT:Er-0.3CT:Pr owns a piezoelectric performance and multi luminescence properties, which can widen the applications of ferroelectric ceramics.     

Effects of Reducing Atmosphere on the Luminescence of Eu3+-Doped Yttria-Stabilized Zirconia Sensor Layers in Thermal Barrier Coatings

The use of Eu³⁺-doped yttrium-stabilized zirconia (YSZ) as an embedded layer in thermal barrier coatings for luminescence temperature sensing has previously been demonstrated in air. In this work the effects of exposure to reducing atmospheres on the luminescence spectra and luminescence lifetime as a function of temperature are reported. No effect of reducing atmosphere, down to oxygen partial pressures(     ) of <10⁻¹¹ ppm, on either the Eu³⁺ luminescence spectrum or the luminescence lifetime up to 900°C are seen although the overall luminescence intensity is decreased. The insensitivity of the temperature dependence of the luminescence lifetime to oxygen partial pressure indicates that Eu³⁺-doped YSZ based temperature sensors can be used with confidence in reducing as well as in air atmospheres. The results also suggest that the charge transfer mechanism responsible for the temperature dependence of the luminescence lifetime is unaffected by the oxygen vacancies introduced by reduction.     

新型光化学反应器及二氧化碳光解反应研究

研究设计了可产生波长小于200 nm真空紫外光的光化学反应器,首次利用该波段的光在该反应器中进行了CO2光解反应的研究。用氮气为发光介质对其进行光强标定,实验表明主要产生120、149、174 nm波长的光(N原子谱线);实验条件下CO2光解后生成产物CO,结果表明光源电流一定时产生CO的量与光源工作气体的压力有关,在CO2和N2反应物系中,光源内发光介质N2的压力在2 500 Pa左右时CO的产率最大,而在该反应物系中加入甲烷后,CO的产率明显增大。     

Probing Tyrosine Nitration with a Small TbIII-Metallopeptide

Tyrosine nitration, a post-translational modification (PTM) that takes place under nitrosative stress conditions, occurs through a non-enzymatic peroxynitrite-mediated reaction. Although protein nitration has long been considered an irreversible PTM involved in nitrosative stress-associated diseases, it has also been suggested to be a regulatory mechanism of signal transduction. Therefore, the development of tools that help to understand this protein modification is of great interest. Herein, we explore a Tb^III-chelating metallopeptide to monitor tyrosine nitration. The luminescence of this probe decreases significantly between its non-nitrated and nitrated states, and this reduction in the luminescence intensity is directly related to the degree of tyrosine nitration after treatment with peroxynitrite. Remarkably, the luminescence intensity changes after nitration are not affected in the presence of complex biological media, which makes it a promising tool for understanding this protein modification.     

Reversible photoluminescence modulation in praseodymium-doped bismuth titanate ceramics for information storage based on photochromic reaction

Photoluminescence materials with reversible luminescence regulation properties have great potential for applications in photoswitches, optical sensing, and high-density optical data storage devices. In this work, a series of Pr³⁺-doped Bi₄Ti₃O₁₂ (BiT) ceramics were synthesized by a high-temperature solid-phase reaction method. It is well known that BiT is the most famous one within the Aurivillius ferroelectric (FE) system. Previous works routinely focused on the FE-related properties of BiT-based compounds, but little attention has been devoted to the luminescence, especially the luminescence modulation performance. Here, a large and reversible photoluminescence modulation by alternating visible light irradiation and thermal stimulus based on photochromic (PC) process was achieved. Meanwhile, the influence of sintering temperature on the luminescence modulation behavior was also illustrated. The luminescence regulation properties of the Pr³⁺-doped BiT ceramics prepared at optimized sintering temperature were investigated in detail. The mechanisms connected to the luminescence, luminescence manipulation, and PC effect were discussed. It is believed that Pr³⁺-doped BiT materials can be utilized as a kind of ideal optical medium for future information storage device.     

Effects of the Template Composition and Coating on the Photoluminescence Properties of ZnS:Mn Nanoparticles

Mn-doped ZnS nanocrystals based on low dopant concentrations (0–2%) and coated with a shell of Zn(OH)₂ have been prepared via soft template and precipitation reaction. The results indicate that the ZnS:Mn nanocrystal is cubic zinc blende structure and its diameter is 3.02 nm as demonstrated by XRD. Measured by TEM, the morphology of nanocrystals is a spherical shape, and their particle size (3–5 nm) is similar to that of XRD results. Photoluminescence spectra under ultraviolet region shows that the volume ratio of alcohol to water in the template has a great effect on the luminescence properties of ZnS:Mn particles. Compared with unpassivated ZnS:Mn nanocrystals, ZnS:Mn/Zn(OH)₂ core/shell nanocrystal exhibits much improved luminescence and higher absolute quantum efficiency. Meanwhile, we simply explore the formation mechanism of ZnS:Mn nanocrystals in alcohol and water system and analyze the reason why alcohol and water cluster structures can affect the luminescent properties of nanoparticle.     

Influence of charge compensation on the photoluminescence and temperature sensing of zinc titanate composites

Eu³⁺ activated zinc titanate red-emitting phosphors have been synthesized by a solid state reaction, and Li⁺ is added as the charge compensator to tune the optical performances of the phosphors. The structure of samples synthesized at different temperature reveals temperature dependence. The crystallization of particles is improved with increasing calcination temperature. The surface morphology and element distribution of the samples are observed by scanning electron microscope (SEM) and energy dispersive X-ray spectrometer (EDS). Various elements are evenly distributed in the matrix materials. The luminescence intensity of Eu³⁺ is effectively improved by co-doping Li⁺, and the luminescence intensity of the phosphor with Li⁺ content of 5 mol% and 7 mol% is twice than that of the phosphor without Li ⁺ when the annealing temperature is 600 °C. While the influence of Li ⁺ on the photoluminescence performance becomes weaker with the annealing temperature increasing. The highest relative sensitivity of 0.65%/K is obtained in the sample annealed at 1000 °C, which is not affected by the Li⁺ dopants.     

The upconversion luminescence modulation and its enhancement in Er3+‐doped Na0.5Bi0.5TiO3 based on photochromic reaction

A large and reversible upconversion (UC) luminescence modulation has been found in the Na_0.498Bi_0.498TiO₃:0.002Er (NBT:0.002Er) based on the photochromic reaction. The dependence of luminescence modulation of the ceramics on the wavelength of irradiation light and sintering temperature was investigated. It was found that the optimized sintering temperature and irradiation wavelength were 1130°C and 405 nm, respectively. The highest ΔR_t (defined as: ΔR_t = (R₀ – R_t)/R₀×100(%), where R₀ and R_t are the initial emission intensity and that after different irradiation time, respectively) value of 44.9% was obtained for the ceramics sintered at 1130°C after irradiation at 405 nm. More importantly, for the poled ceramics, ΔR_t value was promoted to a high value of 75.5%, which was 168% of that of the unpoled ones. The mechanism of luminescence modulation and its enhancement via electric field poling were discussed. This study demonstrated that electric field poling was an effective strategy to enhance the PC reaction in the NBT ceramics.     

Insight into the evolution mechanism of carbon film and Eu valence in carbon coated BaMgAl10O17: Eu2+ phosphor annealed in air

Performing carbon coating on the surface of phosphors has been proven to be an effective strategy to enhance the oxidation resistance, which is an important factor to achieve stable luminescent devices. Therefore, a good understanding of the protection mechanism favors a continuous improvement of oxidation resistance of phosphors. In present paper, the evolution of the carbon layer, Eu valence (Eu²⁺/Eu³⁺), and luminescent properties for the C coated BaMgAl₁₀O₁₇: Eu²⁺ phosphor when annealed at high temperature is investigated carefully. Decrease of carbon layer promotes the appearance color transition from black to white as the annealing temperature rises to 1000?°C in air. As expected, the decrease of carbon layer will enhance the luminescence intensity, but risk the possible oxidation of Eu²⁺ to Eu³⁺, which inhibits the blue emission ascribed to Eu²⁺. The results indicate that luminescence intensity of phosphor is dependent on the synergistic effect of carbon thickness and Eu²⁺/Eu³⁺ ratio. Additionally, a reduction reaction of Eu³⁺ to Eu²⁺ is observed in C coated BaMgAl₁₀O₁₇: Eu²⁺ phosphor when annealed at high temperature, which also contributes to the higher luminescence intensity.     

Enhanced near band edge luminescence of Ti/ZnO nanorod heterostructures due to the surface diffusion of Ti

Information on the mechanistic differences in the luminescence properties of Ti/ZnO nanorods (NRs) has been obtained through the preparation of heterostructures by (a) varying the thickness of Ti from 1 nm to 20 nm keeping the substrate temperature at 400 °C, (b) varying the substrate temperature from room temperature (RT) to 500 °C while keeping the metal thickness constant at 10 nm and (c) annealing the RT Ti sputtered NRs at temperatures of 400 °C and 500 °C. The photoluminescence (PL) spectra show that the near band edge luminescence of ZnO in the ultraviolet (UV) region is enhanced as the thickness of Ti increases up to 5 nm and, thereafter, it falls. Sputtering of Ti on ZnO NRs at RT does not cause any UV enhancement but when sputtered at and above 400 °C, the UV intensity is enhanced. Annealing of RT Ti sputtered NRs at and above 400 °C also results in the enhancement of the UV peak, although with a lesser magnitude. Analysis of the PL results, supported by X-ray diffraction, field emission scanning electron microscopy, elemental mapping, high resolution transmission electron microscopy, Fourier transform infrared spectroscopy and electrical I-V measurement results, show a clear indication that the surface diffusion of Ti causes a reduction in the surface defects.     

真空紫外光化学反应器的研究

设计了能产生波长小于200 nm的真空紫外光化学反应器,通过工作气体氮气进行光强标定表明,其主要产生109 nm,120 nm,149 nm,174 nm波长的光(N原子谱线)。首次在该光化学反应器中进行了CO2光解反应的研究,实验结果表明该实验条件下CO2光解后生成产物CO,当光源电流300 mA时,生成CO的相对量与光源内工作气体的真空度相关。提出了光化学反应器设计时存在的问题、影响因素及考虑因素,为光化学反应器设计放大和操作条件优化提供实验依据和理论思路。     

Low-temperature luminescence of lead silicate glass

The temperature quenching of intrinsic luminescence of a lead silicate glass of the 20PbO · 80SiO₂ composition has been investigated in the temperature range 7–200 K. It has been found that the temperature behavior of the intensity of intrinsic luminescence does not obey the well-known Mott’s law for intracenter quenching of luminescence but is adequately described by the empirical Street’s formula. It has been demonstrated that, with allowance made for the disorder of the atomic structure, the experimental temperature dependence of the luminescence intensity of the glass can be represented as a superposition of Mott’s dependences for an ensemble of local luminescence centers. The obtained distribution of luminescence centers over the activation energies of quenching has an asymmetric form with prevailing low-energy states. It has been assumed that this feature has a general character and, at low temperatures, determines the specificity of the processes of nonradiative relaxation of the electronic subsystem for many oxide glasses.     

Photoluminescence Probing of the Formation of Titanium Dioxide Sols from a Titanium Peroxide Solution

Photoluminescence spectroscopy was used to probe the formation of colloidal TiO₂ sols from a titanium peroxide solution, which were prepared by reaction of H₂O₂ and titanium hydrate gel that was precipitated from acidic TiOCl₂ solution neutralized by NH₄OH, during aging at 100°C for 0–64 h. Emission spectra revealed broad band luminescence which is interpreted as the superposition of a multiple photoluminescence process involving TiO₂ precursors. The maximum peak position of the luminescence band was shifted to a shorter wavelength by the generation of the dominant emission peak as aging time increased, and a peak at ∼390 nm, indicating the anatase phase, was observed after aging for >48 h. However, sols aged for 2 h already were of the anatase phase, according to X-ray diffraction analysis. It was deduced that the interfacial layers between the particles and the liquid in an aqueous solution caused luminescence quenching or accelerated sink.     

Novel Self‐Activated Zinc Gallogermanate Phosphor: The Origin of its Photoluminescence

Since 2012, zinc gallogermanate has drawn interests as an excellent host phosphor for a variety of dopants (e.g., Cr³⁺, Bi³⁺ and Mn²⁺). However, the origin of its self‐activated luminescence has been largely unknown. Here, zinc gallogermanate of the composition Zn_1+xGa_2?2xGe_xO₄ (0 ≤ x ≤ 1) is prepared by solid‐state reaction, and the evolution of the crystal structure with the composition is studied. The phosphors show a broad white‐bluish emission upon excitation by ultraviolet (UV) light, and the luminescence intensity greatly increases as Ga³⁺ are substituted by Ge⁴⁺. A full spectrum of the defects and trap centers responsible for the luminescence is given by a multiple characterization methods, such as low temperature electron spin resonance, positron annihilation lifetime and thermoluminescence spectra. The results show that the zinc gallogermanate is a promising self‐activated phosphor for a variety of applications.     

Influence of gamma radiation and action of neutrons on photoluminescence and the microhardness of barium silicate glass

The influence of nanocrystals on the optical centers of barium silicate glass has been studied experimentally. It is found that, when glass is irradiated in the thermal column of an atomic reactor or in a gammasource ⁶⁰Cо, the phase transformation of SiO₂ nanocrystals (crystoballite into tridymite) and BaO into BaO₂ and BaSiO₃ occurs, which creates a brown coloration, reduction in the microhardness, and weakening of the luminescence intensity.     

Ferric Iron Species in Alkali Aluminosilicate Glasses During Fusion

The luminescence spectra of Fe³⁺ in alkali aluminosilicate glasses indicate that several species of Fe³⁺ are present during early stages of melting. When the glass has been heat-treated for periods of time on the order of 20 h at 1400°C, the luminescence spectra simplify to that of a single species which is interpreted as due to Fe³⁺ in the glass-forming framework.     

Anomalous enhancement of photoluminescence intensity of sintered YAG:Ce particles‐embedded glasses

For high‐power white LED applications, YAG:Ce‐based yellow phosphors were embedded in a low‐T_g Bi₂O₃–B₂O₅–ZnO–Sb₂O₅ glass by sintering route. Effects of sintering temperature (325‐390°C) on the microstructure and photoluminescence properties were investigated. X‐ray diffraction was used to measure the retained fraction of YAG:Ce phase after sintering. Scanning electron microscope and transmission electron microscope, equipped with energy‐dispersive X‐ray spectrometry, were used to examine the microstructure, including the element distribution across the phosphor–glass interface. Photoluminescence properties of the samples before and after sintering were compared. With the increasing sintering temperature, the retained fraction of YAG:Ce decreased from 83.3% to 82%. This effect tends to reduce the luminescence intensity of the samples after sintering. The increasing sintering temperature also enhances the diffusion of cations (esp. Bi) from glass matrix to YAG:Ce. This effect tends to increase the luminescence intensity of the YAG:Ce particles after sintering. When the sintering temperature was lower (325°C), the effect of YAG:Ce loss was dominant, thus the luminescence intensity was reduced after sintering. When the sintering temperature was higher (350‐390°C), the effect of solute dissolution was dominant, resulting in luminescence intensity anomalously higher than that before sintering. Similar result has not been reported in literatures. The maximum luminescence intensity of the sintered samples is 1.57 times as high as that of the samples before sintering.     

Excitation density dependence of luminescence spectrum of electron-hole plasma in diamond

Time-resolved band edge luminescence spectrum in IIa diamond has been measured with the 5th harmonics of a pulsed YAG laser (5.82 eV) and an ICCD image intensifier of 5 ns gate width at 290 K. The time-resolved luminescence spectrum is decomposed into three components of free exciton (FE), excitonic complex (EC) and electron-hole plasma (EHP). The decay times of the FE and EC luminescence are 45 and 27 ns, respectively and that of the EHP luminescence has been seen to be shorter than the gate width, 5 ns. The low energy onset of the EHP luminescence spectrum has been observed to decrease with increasing excitation density and attains the onset of the electron-hole drop luminescence spectrum at the excitation density of 0.6 J/cm², at which the electron-hole pair density is 1.2 × 10²⁰ cm^? 3. Furthermore, the excitation density dependences of the FE, EC and EHP luminescence intensities are explained with the percolation theory.