Crystallization‐Induced Emission Enhancement of a Deep‐Blue Luminescence Material with Tunable Mechano‐ and Thermochromism

Organic luminescent materials with the ability to reversibly switch the luminescence when subjected to external stimuli have attracted considerable interest in recent years. However, the examples of luminescent materials that exhibit multiresponsive properties are rarely reported. In this work, a new stimuli‐responsive dye P1 is designed and synthesized with two identical chromophores of naphthalimide, one at each side of an amidoamine‐based spacer. This amide‐rich molecule offers many possibilities for forming intra‐ and intermolecular hydrogen bond interactions. Particularly, P1 has an intrinsic property of cocrystallizing with methanol. Compared with the pristine P1 sample, the as‐prepared two‐component cocrystalline material displays an exceptive deep‐blue emission, which is extremely rare among naphthalimide‐based molecules in the solid state. Furthermore, the target material exhibits an obvious mechanochromic fluorescent behavior and a large spectral shift under force stimuli. On the other hand, the cocrystalline material shows an unusual “turn off” thermochromic luminescence accompanied by solvent evaporation. Moreover, using external stimuli to reversibly manipulate fluorescent quantum yields is rarely reported to date. The results demonstrate the feasibility of a new design strategy for solid‐state luminescence switching materials: the incorporation of solvents into organic compounds by cocrystallization to obtain a crystalline state luminescence system.     

A Fluorescence–Phosphorescence–Phosphorescence Triple‐Channel Emission Strategy for Full‐Color Luminescence

Organic luminogens constitute promising prototypes for various optoelectronic applications. Since gaining distinct color emissions normally requires the alternation of the conjugated backbone, big issues remain in material synthetic cost and skeleton compatibility while pursuing full‐color luminescence. Upon a facile one‐step coupling, three simple but smart perchalcogenated (O, S, and Se) arenes are synthesized. They exhibit strong luminescent tricolor primaries (i.e., blue, green, and red, respectively) in the solid state with a superior quantum yield up to >40% (5–10 times higher than that in corresponding solutions). The properties originate from a fluorescence–phosphorescence–phosphorescence triple‐channel emission effect, which is regulated by S and Se heavy atoms–dependent intersystem crossing upon molecular packing, as well as Se–Se atom interaction–caused energy splittings. Consequently, full‐color luminescence, including a typical white‐light luminescence with a Commission Internationale de I'Eclairage coordinate of (0.30, 0.35), is realized by complementarily incorporating these tricolor luminescent materials in the film. Moreover, mechanochromic luminescent color conversions are also observed to achieve the fine‐tuning of the luminescent tints. This strategy can be smart to address full‐color luminescence on the same molecular skeleton, showing better material compatibility as an alternative to the traditional multiple‐luminophore engineering.     

Fluorescence of Nonaromatic Organic Systems and Room Temperature Phosphorescence of Organic Luminogens: The Intrinsic Principle and Recent Progress

Following the development of photoluminescence systems with various compositions, some nontraditional structures, including nonaromatic organic systems as fluorophores and organic luminogens as the source of phosphorescence emission at room temperature, have attracted considerable attention for their advantages in biological and medical applications, and for the updated photophysical understandings in science. In this Review, the recent progress in understanding these organic compounds or polymers for fluorescence and phosphorescence is briefly summarized, with the aim of exploring the intrinsic principle of these novel photoluminescence systems and providing reasonable constructs for molecular design. Finally, some prospects are suggested for further development of this continually expanding area of research, with the coined concept of Molecular Uniting Set Identified Characteristic (MUSIC).     

Nonconventional Luminescent Piperazine-Containing Hyperbranched Polysiloxanes with Pure n-electron

Nonconventional luminogens with high quantum yield (QY) possess very potential applications in various fields. However, the preparation of such luminogens remains a great challenge. Herein, the first example of piperazine-containing hyperbranched polysiloxane exhibiting blue and green fluorescence is reported under the irradiation of different excitation wavelength and a high QY of 20.9%. The density functional theory (DFT) calculations and experimental results revealed that the through-space conjugation (TSC) within the clusters of N and O atoms is produced via the induction of multiple intermolecular hydrogen bonds and flexible Si O units, which is accountable for the fluorescence. Meanwhile, the introduction of the rigid piperazine units not only rigidifies the conformation, but also enhances the TSC. In addition, the fluorescence of both P1 and P2 shows concentration-, excitation-, and solvent-dependent emission, especially exhibits significant pH-dependent emission and obtains an ultrahigh QY of 82.6% at pH 5. The synthetic luminogens show excellent applications in fluorescence detection for Fe³⁺ and Co²⁺, information encryption, and fluorescent film. This study provides a novel strategy to rationally design high-efficiency nonconventional luminogens.     

Hydrophilic Ultralong Organic Nanophosphors

Ultralong organic phosphorescence (UOP), enabling of persistent luminescence after removal of external excitation light, shows great promise in biological applications such as bioimaging in virtue of antibackground fluorescence interference. Despite of good biocompatibility and outstanding phosphorescent properties, most current organic phosphors are hydrophobic with poor water solubility in the form of bulk crystal with large size, limiting their potential in the biological field. Here, a facile and versatile approach is provided to obtain nanoscale hydrophilic phosphorescent phosphors (HPPs) by physically loading ultralong organic phosphors into hollow mesoporous silica nanoparticles. The as‐prepared HPPs can be well suspended in aqueous solution and effectively internalized by HeLa cells with very low cytotoxicity. Such HPPs are successfully applied for afterglow bioimaging in living nude mice with a very high signal‐to‐noise ratio up to 31. The current study not only provides a universal strategy to realize UOP in aqueous media but also demonstrates their great potential for biomedical purposes as an advanced imaging indicator with long‐lived emission lifetime.     

Upconversion luminescence Ca--Mg--Si bioactive glasses synthesized using the containerless processing technique

In this study, a series of Er³⁺/Yb³⁺ co-doped Ca--Mg--Si glasses were prepared via the containerless processing. Phase composition and luminescent properties of the prepared materials were investigated through XRD and spectrometry, and bioactivity, biocompatibility and cytotoxicity were evaluated. The XRD patterns indicated that akermanite (AKT) ceramic powders were completely transformed into the glassy phase (AKT-G, EYA) through the containerless processing, which exhibit upconversion luminescence, and the luminescence intensity increased with the increase of the doping amount of Er³⁺ and Yb³⁺. High amount of Yb³⁺ doping and existence of Ca²⁺ in glasses resulted in more intensive red-light emission. The SEM observation, combined with EDS analysis, and cell culture experiments showed that the as-prepared glasses were nontoxic, biocompatible and bioactive. All these results demonstrated that the contai-nerless processing is a facile method for preparing homogeneous luminescent bioactive glasses. Furthermore, this luminescent Ca--Mg--Si glasses may be used as bone implant materials to study the in vivo distribution of degradation products of bone implants, which may be of great significance for the development and clinical application of new bone grafting materials.     

Precise Molecular Design for High-Performance Luminogens with Aggregation-Induced Emission

Precise design of fluorescent molecules with desired properties has enabled the rapid development of many research fields. Among the different types of optically active materials, luminogens with aggregation-induced emission (AIEgens) have attracted significant interest over the past two decades. The negligible luminescence of AIEgens as a molecular species and high brightness in aggregate states distinguish them from conventional fluorescent dyes, which has galvanized efforts to bring AIEgens to a wide array of multidisciplinary applications. Herein, the useful principles and emerging structure–property relationships for precise molecular design toward AIEgens with desirable properties using concrete examples are revealed. The cutting-edge applications of AIEgens and their excellent performance in enabling new research directions in biomedical theranostics, optoelectronic devices, stimuli-responsive smart materials, and visualization of physical processes are also highlighted.     

Recent Advances of Carbon Dots with Afterglow Emission

Carbon dots (CDs) have gradually become a new generation of nano-luminescent materials, which have received extensive attention due to excellent optical properties, wide source of raw materials, low toxicity, and good biocompatibility. In recent years, there are many reports on the luminescent phenomenon of CDs, and great progress has been achieved. However,there are rarely systematic summaries on CDs with persistent luminescence. Here, a summary of the recent progress on persistent luminescent CDs, including luminous mechanism, synthetic strategies, property regulation, and potential applications, is given. First, a brief introduction is given to the development of CDs luminescent materials. Then, the luminous mechanism of afterglow CDs from room temperature phosphorescence (RTP), delayed fluorescence (DF), and long persistent luminescence (LPL) is discussed. Next, the constructed methods of luminescent CDs materials are summarized from two aspects, including matrix-free self-protected and matrix-protected CDs. Moreover, the regulation of afterglow properties from color, lifetime, and efficiency is presented. Afterwards, the potential applications of CDs, such as anti-counterfeiting, information encryption, sensing, bio-imaging, multicolor display, LED devices, etc., are reviewed. Finally, an outlook on the development of CDs materials and applications is proposed.     

稀土激活发光材料的研究进展

稀土发光材料是一种很有发展前途的新型功能材料.介绍了稀土发光材料的性质和应用,详细阐述了高温固相、共沉淀、燃烧、气体反应、水热和微波等稀土发光材料的制备方法,探讨了稀土离子对发光材料的激活机理,并展望了该领域的发展前景.作者利用燃烧法制备出以SrAl2O4为基质,稀土元素铈和铽为激活剂的光致黄色荧光发光材料,显示了其优越的发光性能.     

新型有机电致荧光材料研究进展

有机发光二极管因独特的优势被看作新一代的照明及平面显示技术,引起了研究人员的广泛关注。传统的荧光材料仅能利用单重态激子发光,因而效率并不理想。近年来,能够利用三重态激子能量发光的新型荧光材料的研究实现了新的突破。按照三重态激子到单重态激子的转化机理,荧光材料可以分为三重态-三重态湮灭、热致延迟荧光和局域电荷转移杂化激发态三种特殊类型。本文围绕着这几种类型的荧光材料展开了探讨,介绍了有机电致荧光器件的概况以及不同类型荧光材料的发光机理,并从分子设计的角度说明了高性能发光器件的设计思路。     

Facile Synthesis of Efficient Luminogens with AIE Features for Three-Photon Fluorescence Imaging of the Brain through the Intact Skull

Visualization of the brain in its native environment is important for understanding common brain diseases. Herein, bright luminogens with remarkable aggregation-induced emission (AIE) characteristics and high quantum yields of up to 42.6% in the solid state are synthesized through facile reaction routes. The synthesized molecule, namely BTF, shows ultrabright far-red/near-infrared emission and can be fabricated into AIE dots by a simple nanoprecipitation procedure. Due to their high brightness, large Stokes shift, good biocompatibility, satisfactory photostability, and large three-photon absorption cross section, the AIE dots can be utilized as efficient fluorescent nanoprobes for in vivo brain vascular imaging through the intact skull by a three-photon fluorescence microscopy imaging technique. This is the first example of using AIE dots for the visualization of the cerebral stroke process through the intact skull of a mouse with high penetration depth and good image contrast. Such good results are anticipated to open up a new venue in the development of efficient emitters with strong nonlinear optical effects for noninvasive bioimaging of living brain.     

长余辉蓄光玻璃的制备及其性能研究

利用传统陶瓷制备方法合成了SrAl2O4:Eu,Dy长余辉发光粉体,该磷光体主发射波长位于520nm,余辉时间长达8h以上。并以硼硅酸盐低熔点玻璃为底材,掺杂该发光粉体,在一定温度下烧成,结果制得长余辉蓄光玻璃。研究还表明,烧成温度对该玻璃的发光性能影响较大,随着温度的升高,发光强度及余辉时间明显下降。     

N-B-Al共掺荧光4H-SiC施主受主对发光性能研究

施主受主共掺杂的荧光4H-SiC可以通过复合发出可见光, 影响其发光性能的一个重要因素是施主-受主掺杂的浓度。本研究通过PVT生长方法制备了3英寸N-B-Al共掺的4H-SiC晶体, 采用Raman光谱、SIMS对晶体的结晶类型和掺杂浓度进行了表征; 采用PL发射谱和激发谱、荧光衰减曲线表征和内量子效率对晶体的发光波长、强度、施主-受主对复合发光性能进行了研究。结果发现, 低浓度Al掺杂样品在室温下发出黄绿色荧光。低浓度Al掺杂在晶体中提供较少的受主; 高浓度B、N掺杂形成施主, 从而贡献充足的电子-空穴对。这些电子-空穴的复合提高了施主-受主对复合的内量子效率, 进而增强光致发光强度, 增加平均发光寿命。     

AIE Nanoparticles with High Stimulated Emission Depletion Efficiency and Photobleaching Resistance for Long‐Term Super‐Resolution Bioimaging

Stimulated emission depletion (STED) nanoscopy is a typical super‐resolution imaging technique that has become a powerful tool for visualizing intracellular structures on the nanometer scale. Aggregation‐induced emission (AIE) luminogens are ideal fluorescent agents for bioimaging. Herein, long‐term super‐resolution fluorescence imaging of cancer cells, based on STED nanoscopy assisted by AIE nanoparticles (NPs) is realized. 2,3‐Bis(4‐(phenyl(4‐(1,2,2‐triphenylvinyl)phenyl)amino)phenyl) fumaronitrile (TTF), a typical AIE luminogen, is doped into colloidal mesoporous silica to form fluorescent NPs. TTF@SiO₂ NPs bear three significant features, which are all essential for STED nanoscopy. First, their STED efficiency can reach more than 60%. Second, they are highly resistant to photobleaching, even under long‐term and high‐power STED light irradiation. Third, they have a large Stokes' shift of ≈150 nm, which is beneficial for restraining the fluorescence background induced by the STED light irradiation. STED nanoscopy imaging of TTF@SiO₂‐NPs‐stained HeLa cells is performed, exhibiting a high lateral spatial resolution of 30 nm. More importantly, long‐term (more than half an hour) super‐resolution cell imaging is achieved with low fluorescence loss. Considering that AIE luminogens are widely used for organelle targeting, cellular mapping, and tracing, AIE‐NPs‐based STED nanoscopy holds great potential for many basic biomedical studies that require super‐resolution and long‐term imaging.     

发光波长可调的聚吡咯甲烷的制备及光学特性

聚合物发光材料因其拥有诸多优点,在有机发光二极管器件方面的应用前景广阔.然而,对于蓝光聚合物发光材料,由于其发光性能、使用寿命等方面仍然存在不足,难以满足全色显示的需要.以吡咯类单体和4-乙基苯甲醛单体为原料,采用溶液缩聚法制备了3种聚吡咯甲烷(聚{吡咯-[2,5-二(4-乙基苯甲烷)]}(PPE)、聚{N-甲基吡咯-...     

Aqueous synthesis and bio-imaging application of highly luminescent and low cytotoxicity Mn-doped ZnSe nanocrystals

In this paper, Mn²⁺-doped ZnSe quantum dots (Mn:ZnSe d-dots) are synthesized successfully by a nucleation-doping method in aqueous solution with 3-Mercaptopropionic acid as the stabilizer and sodium selenite as the Se source for the first time in contrast to the use of oxygen-sensitive NaHSe or H₂Se as Se source. The obtained quantum dots performed strong band-edge luminescence, narrow size distribution and weak trap emission without post-treatments. The results of transmission electron microscopy and X-ray diffraction demonstrated the small particle size (3-4 nm), good monodispersity and ZnSe(S) alloyed structure of as-prepared quantum dots. Finally, the biological application of luminescent Mn²⁺-doped ZnSe nanocrystals to PK 15 cell imaging was also illustrated, which showed excellent biocompatibility and low cytotoxicity, implying their potential as a new generation of fluorescent labels for biological assays, tissues, and even in vivo investigations.     

Full‐Color Tunable Circularly Polarized Luminescent Nanoassemblies of Achiral AIEgens in Confined Chiral Nanotubes

Circularly polarized luminescent (CPL) materials are currently attracting great interest. While a chiral building is usually necessary in order to obtain CPL materials, here, this study proposes a general approach for fabricating 1D circularly polarized luminescent nanoassemblies from achiral aromatic molecules or aggregation‐induced emissive compounds (AIEgens). It is found that a C₃ symmetric chiral gelator can individually form hexagonal nanotube structures and encapsulate the guest molecules. When achiral AIEgens are encapsulated into the confined nanotubes via organogelation, the AIEgens will emit circularly polarized luminescence. Further, the direction of the CPL could be controlled by the supramolecular chirality of the nanotube. Remarkably, the approach is universal and various kinds of the AIEgens can be doped to show such property, providing a full‐color‐tunable circularly polarized luminescence.     

Nanoparticle fluorescence based technology for biological applications

Fluorescence is widely used in biological detection and imaging. The emerging luminescent nanoparticles or quantum dots provide a new type of biological agents that can improve these applications. The advantages of luminescent nanoparticles for biological applications include their high quantum yield, color availability, good photo-stability, large surface-to-volume ratio, surface functionality, and small size. In this review article, we first introduce quantum size confinement, photoluminescence and upconversion luminescence of nanoparticles, then describe the preparation and conjugation of water soluble nanoparticles and introduce the applications of luminescence nanoparticles for in vitro and in vivo imaging, fluorescence resonance energy based detection, and the applications of luminescence nanoparticles for photodynamic activation.     

Label-free detection of single protein molecules using deep UV fluorescence lifetime microscopy

We present the detection of single beta-galactosidase molecules from Escherichia coli (Ecbeta Gal) using deep UV laser-based fluorescence lifetime microscopy. The native fluorescence from intrinsic tryptophan emission has been observed after one-photon excitation at 266 nm. Applying the time-resolved single-photon counting method, we investigated the fluorescence lifetime distribution and the bursts of autofluorescence photons from tryptophan residues in Ecbeta Gal protein as well as fluorescence correlation spectroscopy of Ecbeta Gal. The results demonstrate that deep UV laser-based fluorescence lifetime microscopy is useful for identification of biological macromolecules at the single-molecule level using intrinsic fluorescence.     

Ce-YAG微晶玻璃的制备及其发光性能

采用高温固相熔融法在弱还原气氛下制备了Ce3+离子掺杂的Y2O3-A12O3-SiO2(SAY)系基础玻璃,并在1250℃~1300℃热处理一定时间制备了晶相为YAG的黄色微晶玻璃。通过XRD、SEM研究了微晶玻璃的结构及相组成;激发和发射光谱分析了Ce3+离子在玻璃及微晶玻璃不同基质中的发光特性,以及Al2O3/Y2O3摩尔比对微晶玻璃样品发光性能的影响。结果表明:基础玻璃经热处理能得到Ce-YAG微晶玻璃,晶粒大小在80~120nm范围内,晶粒发育良好。该微晶玻璃样品能被450nm有效激发,并在530nm处有宽带发射峰,归属于Ce3+的5d-4f(2F2/7)。该微晶玻璃在LED照明领域中有很大的应用开发价值。Al2O3和Y2O3的摩尔含量变化对微晶玻璃发光性能有较大影响,在Al2O3/Y2O3的摩尔比为1.5时,样品的发光性能最佳。