多色长余辉材料的发光性质及动态防伪应用

发光防伪具有可视性强、设计简便的特点,是众多防伪技术中常用的方法。传统防伪材料存在发光颜色单一、防伪图案和颜色静态的缺点,易于模仿,亟需开发可实现动态、可靠防伪性能的发光材料。本工作采用水热法制备了铬掺杂镓锗酸锌多色长余辉材料,并对其余辉性能和动态防伪应用进行研究。实验结果表明:通过改变镓锗比,可以调节蓝绿光和红光区的发射强度,实现发光颜色的可调。该系列样品在波长为254和365nm的紫外光激发下分别呈现白色和红色,发光颜色具有多模态发光特征。此外该系列样品具有多色的余辉发光,不同颜色的衰减速率不同,可以实现余辉颜色随时间发生动态变化的效果。据此设计成的防伪图案,发光颜色在时间维度上具有动态变化特性,可显著提高防伪安全性,表明所制备的铬掺杂镓锗酸锌多色长余辉材料在动态防伪领域有重要的应用前景。     

Ultralong Phosphorescence of Water‐Soluble Organic Nanoparticles for In Vivo Afterglow Imaging

Afterglow or persistent luminescence eliminates the need for light excitation and thus circumvents the issue of autofluorescence, holding promise for molecular imaging. However, current persistent luminescence agents are rare and limited to inorganic nanoparticles. This study reports the design principle, synthesis, and proof‐of‐concept application of organic semiconducting nanoparticles (OSNs) with ultralong phosphorescence for in vivo afterglow imaging. The design principle leverages the formation of aggregates through a top‐down nanoparticle formulation to greatly stabilize the triplet excited states of a phosphorescent molecule. This prolongs the particle luminesce to the timescale that can be detected by the commercial whole‐animal imaging system after removal of external light source. Such ultralong phosphorescent of OSNs is inert to oxygen and can be repeatedly activated, permitting imaging of lymph nodes in living mice with a high signal‐to‐noise ratio. This study not only introduces the first category of water‐soluble ultralong phosphorescence organic nanoparticles but also reveals a universal design principle to prolong the lifetime of phosphorescent molecules to the level that can be effective for molecular imaging.     

烧成条件对长余辉蓄光玻璃光学性能的影响

以ＳｒＡｌ_２Ｏ_４：Ｅｕ,Ｄｙ长余辉发光粉体和低熔点硼硅酸盐玻璃为原料,在一定条件下合成了长余辉蓄光玻璃．研究结果表明,烧成温度和保温时间对该玻璃的发光效果影响较大．温度越高,保温时间越长,由于空气的氧化作用,蓄光玻璃的发光效果越差,本试验控制烧成温度在７５０～８００℃间,保温时间在 １０ｍｉｎ以内,能合成性能较好的蓄光玻璃．余辉衰减曲线表明蓄光玻璃的发光性能较之原始发光粉体有所下降．ＳＥＭ分析表明,低温合成的蓄光玻璃中,所含能继续保持发光性质的粉体料,明显比高温合成样要多．     

长余辉(寿命)发光材料研究的最新进展

综述了近几年来长余辉发光材料研究的最新进展,包括三方面:新材料研制,新应用领域的开拓和发光机理研究的模型.材料方面,主要介绍了红光、蓝光研究的进展与获得长余辉发光的关键因素-结构缺陷形成的陷阱态,以及稀土掺杂的作用.为促进新材料的研究着重概述了对长余辉发光机理研究的新进展,除了载流子传输与隧穿效应外,还介绍了两种最新观点;双光子吸收与V_K中心模型,并对其存在的问题作了评述.应用方面,除了已有的弱光照明与显示领域外,还在向光电信息功能,特别是二维图像存储,高能粒子射线探测方面发展.     

Room-Temperature Phosphorescence Resonance Energy Transfer for Construction of Near-Infrared Afterglow Imaging Agents

Afterglow imaging that detects photons after cessation of optical excitation avoids tissue autofluorescence and thus possesses higher sensitivity than traditional fluorescence imaging. Purely organic molecules with room-temperature phosphorescence (RTP) have emerged as a new library of benign afterglow agents. However, most RTP luminogens only emit visible light with shallow tissue penetration, constraining their in vivo applications. This study presents an organic RTP nanoprobe (mTPA-N) with emission in the NIR range for in vivo afterglow imaging. Such a probe is composed of RTP molecule (mTPA) as the phosphorescent generator and an NIR-fluorescent dye as the energy acceptor to enable room-temperature phosphorescence resonance energy transfer (RT-PRET), ultimately resulting in redshifted phosphorescent emission at 780 nm. Because of the elimination of background noise and redshifted afterglow luminescence in a biologically transparent window, mTPA-N permits imaging of lymph nodes in living mice with a high signal-to-noise ratio. This study thus opens up a universal approach to develop organic RTP luminogens into NIR afterglow imaging agents via construction of RT-PRET.     

In Vivo Repeatedly Activated Persistent Luminescence Nanoparticles by Radiopharmaceuticals for Long‐Lasting Tumor Optical Imaging

Persistent luminescence nanoparticles (PLNPs) with rechargeable near‐infrared afterglow properties attract much attention for tumor diagnosis in living animals since they can avoid tissue autofluorescence and greatly improve the signal‐to‐background ratio. Using UV, visible light, or X‐ray as excitation sources to power up persistent luminescence (PL) faces the challenges such as limited tissue penetration, inefficient charging capability, or tissue damage caused by irradiation. Here, it is proved that radiopharmaceuticals can efficiently excite ZnGa₂O₄:Cr³⁺ nanoparticles (ZGCs) for both fluorescence and afterglow luminescence via Cerenkov resonance energy transfer as well as ionizing radiation. ¹⁸F‐FDG, a clinically approved tumor‐imaging radiopharmaceutical with a short decay half‐life around 110 min, is successfully used as the internal light source to in vivo excite intravenously injected ZGCs for tumor luminescence imaging over 3 h. The luminescence with similar decay time can be re‐obtained for multiple times upon injection of ¹⁸F‐FDG at any time needed with no health concern. It is believed this strategy can not only provide tumor luminescence imaging with high sensitivity, high contrast, and long decay time at desired time, but also guarantee the patients much less radiation exposure, greatly benefiting image‐guided surgery in the future.     

Excited State Modulation for Organic Afterglow: Materials and Applications

Organic afterglow materials, developed recently by breaking through the difficulties in modulating ultrafast‐decayed excited states, exhibit ultralong‐lived emission for persistent luminescence with lifetimes of several orders of magnitude longer than traditional fluorescent and phosphorescent emissions at room temperature. Their exceptional properties, namely ultralong luminescent lifetime, large Stokes shifts, facile excited state transformation, and environmentally sensitive emission, have led to a diverse range of advanced optoelectronic applications. Here, the organic afterglow is reviewed from the perspective of fundamental concepts on both phenomenon and mechanism, examining the technical challenges in relation to excited state tuning and lifetime elongation. In particular, the advances in material design strategies that afford a large variety of organic afterglow materials for a broad utility in optoelectronics including lighting and displays, anti‐counterfeiting, optical recording, chemical sensors and bio‐imaging are highlighted.     

Polymeric Nanoparticles with Sequential and Multiple FRET Cascade Mechanisms for Multicolor and Multiplexed Imaging

The ability to map multiple biomarkers at the same time has far‐reaching biomedical and diagnostic applications. Here, a series of biocompatible poly(d,l ‐lactic‐co‐glycolic acid) and polyethylene glycol particles for multicolor and multiplexed imaging are reported. More than 30 particle formulations that exhibit distinct emission signatures (ranging from the visible to NIR wavelength region) are designed and synthesized. These particles are encapsulated with combinations of carbocyanine‐based fluorophores DiO, Dil, DiD, and DiR, and are characterized as <100 nm in size and brighter than commercial quantum dots. A particle formulation is identified that simultaneously emits fluorescence at three different wavelengths upon a single excitation at 485 nm via sequential and multiple FRET cascade events for multicolor imaging. Three other particles that display maximum fluorescence intensities at 570, 672, or 777 nm for multiplexed imaging are also identified. These particles are individually conjugated with specific (Herceptin or IgG2A11 antibody) or nonspecific (heptaarginine) ligands for targeting and, thus, could be applied to differentiate different cancer cells from a cell mixture according to the expressions of cell‐surface human epidermal growth factor receptor 2 and the receptor for advanced glycation endproducts. Using an animal model subcutaneously implanted with the particles, it is further demonstrated that the developed platform could be useful for in vivo multiplexed imaging.     

Molecular Imaging Using Nanoparticle Quenchers of Cerenkov Luminescence

Cerenkov luminescence (CL) imaging is an emerging technique that collects the visible photons produced by radioisotopes. Here, molecular imaging strategies are investigated that switch the CL signal off. The noninvasive molecularly specific detection of cancer is demonstrated utilizing a combination of clinically approved agents, and their analogues. CL is modulated in vitro in a dose dependent manner using approved small molecules (Lymphazurin), as well as the clinically approved Feraheme and other preclinical superparamagnetic iron oxide nanoparticles (SPIO). To evaluate the quenching of CL in vivo, two strategies are pursued. [¹⁸F]‐FDG is imaged by PET and CL in tumors prior to and following accumulation of nanoparticles. Initially, non‐targeted particles are administered to mice bearing tumors in order to attenuate CL. For targeted imaging, a dual tumor model (expressing the human somatostatin receptor subtype‐2 (hSSTr2) and a control negative cell line) is used. Targeting hSSTr2 with octreotate‐conjugated SPIO, quenched CL enabling non‐invasive distinction between tumors' molecular expression profiles is demonstrated. In this work, the quenching of Cerenkov emissions is demonstrated in several proof of principle models using a combination of approved agents and nanoparticle platforms to provide disease relevant information including tumor vascularity and specific antigen expression.     

Self‐Assembled Semiconducting Polymer Nanoparticles for Ultrasensitive Near‐Infrared Afterglow Imaging of Metastatic Tumors

Detection of metastatic tumor tissues is crucial for cancer therapy; however, fluorescence agents that allow to do share the disadvantage of low signal‐to‐background ratio due to tissue autofluorescence. The development of amphiphilic poly(p‐phenylenevinylene) derivatives that can self‐assemble into the nanoagent (SPPVN) in biological solutions and emit near‐infrared afterglow luminescence after cessation of light irradiation for ultrasensitive imaging of metastatic tumors in living mice is herein reported. As compared with the counterpart nanoparticle (PPVP) prepared from the hydrophobic PPV derivate, SPPVN has smaller size, higher energy transfer efficiency, and brighter afterglow luminescence. Moreover, due to the higher PEG density of SPPVN relative to PPVP poly(ethylene glycol), SPPVN has a better accumulation in tumor. Such a high sensitivity and ideal biodistribution allow SPPVN to rapidly detect xenograft tumors with the size as small as 1 mm³ and tiny peritoneal metastatic tumors that are almost invisible to naked eye, which is not possible for PPVP. Moreover, the oxygen‐sensitive afterglow makes SPPVN potentially useful for in vivo imaging of oxygen levels. By virtue of enzymatic biodegradability and ideal in vivo clearance, these organic agents can serve as a platform for the construction of advanced afterglow imaging tools.     

Combined Positron Emission Tomography and Cerenkov Luminescence Imaging of Sentinel Lymph Nodes Using PEGylated Radionuclide‐Embedded Gold Nanoparticles

New imaging probes with high sensitivity and stability are urgently needed to accurately detect sentinel lymph nodes (SLNs) for successful cancer diagnosis. Herein, the use of highly sensitive and stable PEGylated radionuclide‐embedded gold nanoparticles (PEG‐RIe‐AuNPs) is reported for the detection of SLNs by combined positron emission tomography and Cerenkov luminescence imaging (PET/CLI). PEG‐RIe‐AuNPs show high sensitivity and stability both in vitro and in vivo, and are not toxic to normal ovarian and immune cells. In vivo PET/CLI imaging clearly reveals SLNs as early as 1 h post PEG‐RIe‐AuNP‐injection, with peak signals achieved at 6 h postinjection, which is consistent with the biodistribution results. Taken together, the data provide strong evidence that PEG‐RIe‐AuNPs are promising as potential lymphatic tracers in biomedical imaging for pre and intraoperative surgical guidance.     

硼酸对蓝色铝酸锶长余辉材料的物相及发光特性的影响

采用高温固相法制备了xSrO·yAl2O3:Eu2+,Dy3++m%(摩尔分数)(H3BO3)(m=15,20,23,25,30,35)系列蓝色光致发光材料。X射线衍射(XRD)结果表明:m=15～20之间产品为SrAl2O4,Sr2Al6O11和Sr4Al14O25的混合物,m=23时产品主相为Sr2Al6O11,m=25～35之间产品主相为Sr4Al14O25。利用荧光分光光度计和亮度计研究了材料的发射光谱,衰减曲线,结果显示:随着硼酸量的增加,发射峰值先蓝移后红移,而余辉时间则逐渐变长。从而得到了制备蓝色铝酸锶发光材料Sr2Al6O11:Eu2+,Dy3+的最佳硼酸量,并且对硼酸在材料合成过程中的作用机理进行了探讨。     

Au@pNIPAM SERRS Tags for Multiplex Immunophenotyping Cellular Receptors and Imaging Tumor Cells

Detection technologies employing optically encoded particles have gained much interest toward clinical diagnostics and drug discovery, but the portfolio of available systems is still limited. The fabrication and characterization of highly stable surface‐enhanced resonance Raman scattering (SERRS)‐encoded colloids for the identification and imaging of proteins expressed in cells are reported. These plasmonic nanostructures are made of gold octahedra coated with poly(N‐isopropylacrylamide) microgels and can be readily encoded with Raman active dyes while retaining high colloidal stability in biofluids. A layer‐by‐layer polyelectrolyte coating is used to seal the outer surface of the encoded particles and to provide a reactive surface for covalent conjugation with antibodies. The targeted multiplexing capabilities of the SERRS tags are demonstrated by the simultaneous detection and imaging of three tumor‐associated surface biomarkers: epidermal growth factor receptor (EGFR), epithelial cell adhesion molecule (EpCAM), and homing cell adhesion molecule (CD44) by SERRS spectroscopy. The plasmonic microgels are able to discriminate tumor A431 (EGFR+/EpCAM+/CD44+) and nontumor 3T3 2.2 (EGFR?/EpCAM?/CD44+) cells while cocultured in vitro.     

铝酸盐长余辉发光材料的功能化表面改性研究进展

系统概括了铝酸盐长余辉发光材料在应用中存在的一些功能性缺失,归纳与评述了其相应的功能化表面改性研究现状与不足,对今后的进一步深入研究特别是在表面包覆改性方法、过程控制与功能化调控等方面进行了展望.     

热释发光-正电子湮灭法研究SrAl2O4基磷光体长余辉发光机制

利用传统陶瓷制备方法合成了长余辉SrAl2O4：Eu，Dy发光粉材料，并利用热释发光—正电子湮灭法对该材料的发光性能及机理进行了研究。研究结果表明，掺杂的Eu在基质材料中主要充当发光中心，而Dy离子主要充当陷阱能级。正电子湮灭试验结果表明，Sr0.94Al2O4：Eu0.02和Sr0.94Al2O4：Eu0.02，Dy0.04存在带负电中心的缺陷，共掺杂的Dy^3 进到Sr^2 位，同时产生一定量的Sr空位，热释发光谱结果表明，单掺杂Eu离子的磷光体中缺陷陷阱深度较深，约为0．95eV，随着Dy的共掺杂，热释发光强度相应增加，陷阱深度降为0．51eV，对于长余辉发光机制，认为陷阱能级捕获的空穴与介稳态(Eu^1 )^*的复合，导致了长余辉现象的发生，并且由于陷阱深度的变化，导致余辉性能出现较大的差异。     

ZnO纳米棒的水热合成及光学性能

以二水醋酸锌（ZnAc2·2H2O）和氢氧化钠（NaOH）为原料,采用水热法制备了ZnO纳米棒,用X射线衍射（XRD）、扫描电镜（SEM）、透射显微镜（TEM）和荧光仪（PL）对产物的物相、微观形貌、发光特性进行表征,结果表明,产物为六方纤锌矿结构ZnO,呈棒状,分散性较好,直径为100-200nm,平均长度约为4μm,光致发光光谱显示纳米棒在522nm显出绿色发光峰,分析认为O空位Zn填隙缔合缺陷（VoZni）至价带的跃迁可能是引起绿光发射的原因之一。     

Nanoparticles for Optical Molecular Imaging of Atherosclerosis

Molecular imaging contributes to future personalized medicine dedicated to the treatment of cardiovascular disease, the leading cause of mortality in industrialized countries. Endoscope‐compatible optical imaging techniques would offer a stand‐alone alternative and high spatial resolution validation technique to clinically accepted imaging techniques in the (intravascular) assessment of vulnerable atherosclerotic lesions, which are predisposed to initiate acute clinical events. Efficient optical visualization of molecular epitopes specific for vulnerable atherosclerotic lesions requires targeting of high‐quality optical‐contrast‐enhancing particles. In this review, we provide an overview of both current optical nanoparticles and targeting ligands for optical molecular imaging of atherosclerotic lesions and speculate on their applicability in the clinical setting.

     

Organic Long-Persistent Luminescence from a Thermally Activated Delayed Fluorescence Compound

Organic long-persistent luminescence (OLPL) is one of the most promising methods for long-lived-emission applications. However, present room-temperature OLPL emitters are mainly based on a bimolecular exciplex system which usually needs an expensive small molecule such as 2,8-bis(diphenyl-phosphoryl)dibenzo[b,d]thiophene (PPT) as the acceptor. In this study, a new thermally activated delayed fluorescence (TADF) compound, 3-(4-(9H-carbazol-9-yl)phenyl)acenaphtho[1,2-b]pyrazine-8,9-dicarbonitrile (CzPhAP), is designed, which also shows OLPL in many well-known hosts such as PPT, 2,2′,2″-(1,3,5-benzinetriyl)-tris(1-phenyl-1-H-benzimidazole) (TPBi), and poly(methyl methacrylate) (PMMA), without any exciplex formation, and its OLPL duration reaches more than 1 h at room temperature. Combining the low cost of PMMA manufacture and flexible designs of TADF molecules, pure organic, large-scale, color tunable, and low-cost room-temperature OLPL applications become possible. Moreover, it is found that the onset of the 77 K afterglow spectra from a TADF-emitter-doped film is not necessarily reliable for determining the lowest triplet state energy level. This is because in some TADF-emitter-doped films, optical excitation can generate charges (electron and holes) that can later recombine to form singlet excitons during the phosphorescence spectrum measurement. The spectrum taken in the phosphorescence time window at low temperature may consequently consist of both singlet and triplet emission.