Recent Advances of Persistent Luminescence Nanoparticles in Bioapplications

Persistent luminescence phosphors are a novel group of promising luminescent materials with afterglow properties after the stoppage of excitation.In the past decade,persistent luminescence nanoparticles(PLNPs)with intriguing optical properties have attracted a wide range of attention in various areas.Especially in recent years,the development and applications in biomedical fields have been widely explored.Owing to the efficient elimination of the autofluorescence interferences from biotissues and the ultra-long near-infrared afterglow emission,many researches have focused on the manipulation of PLNPs in biosensing,cell tracking,bioimaging and cancer therapy.These achievements stimulated the growing interest in designing new types of PLNPs with desired superior characteristics and multiple functions.In this review,we summarize the works on synthesis methods,bioapplications,biomembrane modification and biosafety of PLNPs and highlight the recent advances in biosensing,imaging and imaging-guided therapy.We further discuss the new types of PLNPs as a newly emerged class of functional biomaterials for multiple applications.Finally,the remaining problems and challenges are discussed with suggestions and prospects for potential future directions in the biomedical applications.

长余辉纳米粒子的合成及其生物成像应用

长余辉发光是一种在激发停止后产生持久余辉发光的特殊光学现象,这种现象在防伪、信息或数据存储、光催化、传感和生物成像等领域中呈现出巨大的前景。长余辉纳米粒子(PLNPs)无需原位激发,能够减少组织的自发荧光和光散射干扰,被广泛用于生物成像领域。此外,发光性能可调节,且具有X射线激发、近红外区域长寿命发光或多模式成像特征的长余辉纳米探针能够应用于深层组织生物成像,为细胞或组织提供更为丰富的成像信息。该综述总结了近年来PLNPs的合成方法及其在生物成像应用中的最新研究进展,重点介绍了PLNPs在指纹成像、细胞和活体成像等方面的应用,同时还讨论了PLNPs在生物成像领域面临的挑战和未来的发展趋势。

基于光诱导电子转移的比率型发光传感器定量检测生物样本中的多巴胺

长余辉发光材料是一种光致发光材料,在激发停止后以光的形式将储存的能量缓慢释放出来,因其优异的光学性能而在生物传感和生物成像领域得到广泛应用.本文将发光性能优异的双发射长余辉纳米粒子Sr_(2.992)Mg_(0.9)Si_(2)O_(8)∶0.008Eu^(2+),0.10Mn^(2+)(SEM)和酪氨酸酶(Tyrosinase,TYR)共价偶联,开发了一种比率型发光传感器(SEM-TYR),其可避免自发荧光干扰和外部干扰,可用于高灵敏、高选择性检测生物样本中的多巴胺(DA).当DA存在时,酪氨酸酶将其氧化生成多巴醌,依据光诱导电子转移(PET)原理,SEM-TYR光致激发的电子部分转移至电子受体多巴醌,导致SEM-TYR中680 nm红色余辉猝灭.在最优实验条件下,双发射余辉猝灭比值Δ(I680/I460)与DA浓度呈良好的线性关系,线性范围为0.2~10μmol/L(R^(2)=0.9965),检出限为40 nmol/L.将该方法用于生物样本血清、尿液及汗液中DA的检测,回收率分别为94.8%~104.0%,91.3%~101.6%和97.4%~105.2%,RSD<6.8%(n=10).所开发的比率型发光传感器用于生物样本中DA的检测具有潜在的应用前景.

纳米长余辉发光材料在生物医学检测、生物成像与肿瘤治疗中的研究进展

长余辉发光材料是一种能储存外界激发光能量、在激发光停止激发后仍能持续发光的材料。由于其长余辉寿命、无需原位激发、无组织背景信号干扰和高信噪比等优点,纳米长余辉发光材料广泛应用于生物医学检测、生物成像和肿瘤治疗领域。本文综述了近年来纳米长余辉发光材料在生物医学检测、生物成像和肿瘤治疗(化疗、光热治疗、光动力治疗和免疫治疗)方面的应用进展,并进一步探讨了其在生物医学应用中所面临的挑战,对其未来的发展趋势也进行了展望。

长余辉基适配体传感器在食品安全检测中的应用进展

食品工业的迅速发展离不开安全体系的构建。食品安全检测关系经济民生,是分析领域的研究热点。长余辉纳米粒子具有免原位激发和磷光可再生性,在激发光停止后持续发光,从而消除背景荧光干扰,是理想的光学传感元件。适配体是具有识别性能的寡核苷酸序列,兼具快速响应性、高特异性和灵敏度。二者通过基团键合可构建性能独特的探针,产生靶标刺激的信号变化,在食品安全检测领域享有壮阔前景。本文阐述了近年来长余辉基适配体传感器在食品安全检测中的研究进展。重点聚焦于实现传感器光学激活的设计策略,简要介绍了相应原理的研究应用,最后对于该技术面临的挑战和机遇进行讨论和展望,以推进食品安全检测的发展。

Recent advances in autofluorescence-free biosensing and bioimaging based on persistent luminescence nanoparticles

Persistent luminescence nanoparticles (PLNPs) are a series of emerging luminescent nanomaterials which can emit persistently after ceasing the external excitation. Due to the long decay time of persistent luminescence, the background autofluorescence in complex sample and tissues can be effectively eliminated, thus significantly improving the sensitivity of bioanalysis. Besides, such a long decay time of luminescence also makes PLNPs valuable for long-term bioimaging. Benefiting from these merits, PLNPs have been widely used for biomedical applications, especially biosensing and bioimaging. In this review,we conclude the progress in the application of PLNPs at biosensing and bioimaging in recent years, and also provide our understanding of the prospects.

Recent progress in synthesis of lanthanide-based persistent luminescence nanoparticles

Persistent luminescence nanoparticles(PLNPs)are a kind of phosphors that can remain luminescent for seconds to several days after the stoppage of excitation.Lanthanides show the special capability to largely broaden the emission range and enhance the luminescence intensity of PLNPs due to their dense energy structure and unique electronic configurations.In the past decades,various methods have been developed for the synthesis of lanthanide-based PLNPs with excellent pe rsistent luminescence propertie s,and the lanthanide-based PLNPs are widely studied in areas including biome dicine,energy,and information storage.In this review,we summarized the research progress in the synthe sis of lanthanidebased PLNPs and outline d several typical synthesis methods.We discussed the fundamental concepts of preparation methods as well as the advantages and drawbacks of the typical synthetic approache s.Moreove r,the current challenges and the potential solutions for the development of lanthanide-based PLNP s are also discussed in an attempt to provide strate gies to further improve the optical properties of lanthanide-based PLNPs.We hope this review can contribute to the design of lanthanide-based PLNPs with desired properties and further promote their applications in biomedicine,energy,and information science.

Near-infrared light activated persistent luminescence nanoparticles via upconversion

Persistent luminescence nanoparticles （PLNPs） and upconversion nanoparticles （UCNPs） are two special optical imaging nanoprobes. In this study, efficient upconverted persistent luminescence （UCPL） is realized by combining their unique features into polymethyl methacrylate, forming a film composed of both PLNPs and UCNPs. The red persistent luminescence （-640 nm） of the PLNPs （CaS：Eu,Tm, Ce） can be activated by upconverted green emission of UCNPs （-NaYF4：Yb, Er@NaYF4） excited by near-infrared light （NIR）. Using this strategy, both the unique optical properties of PLNPs and UCNPs can be optimally synergized, thus generating efficient upconversion, photoluminescence, and UCPL simultaneously. The UCPL system has potential applications in in vivo bioimaging by simply monitoring the biocompatible low power density of NIR-light-excited persistent luminescence. Due to its simplicity, we anticipate that this method for the preparation of UCPL composite can be easily adjusted using other available upconversion and persistent phosphor pairs for a number of biophotonic and photonic applications.

Red/NIR/SWIR multi-band persistent luminescent nanoparticles as ultrasensitive multi-channel tracers in water and crude oil/water emulsions

We report the use of CaTiO_(3):Pr^(3+)multiband persistent luminescent nanoparticles,which can simultaneously emit red(610 nm),near-infrared(893 nm),and short-wave infrared(1040 nm)photoluminescence and persistent luminescence,as the tracer nanoagents for water tracer sensing.By using a spectrofluorometer,an Si charge-coupled device(CCD)camera and an InGaAs array camera as the detection tools,we evaluated the sensing capabilities of the three emission bands of CaTiO_(3):Pr^(3+)nanoparticles in brine water solutions and crude oil/brine water emulsions in both photoluminescence mode and persistent luminescence mode.Among these different detection combinations,the persistent luminescence-based Si CCD camera imaging exhibits the best sensing performance with the detection limits being at a single-digit ppb level for the 610 and 893 nm bands and about 100–200 ppb for the 1040 nm band in both water solutions and crude oil/water emulsions,while the photoluminescencebased Si CCD camera imaging has a much higher detection limit of~10 ppm in water solutions and of~200 ppm in oil/water emulsions.The persistent luminescence-based InGaAs array camera imaging to the 1040 nm band has the worst performance with the detection limits higher than 200 ppm for both solutions.The sensing performances of the spectrofluorometer to photoluminescence signals and persistent luminescence signals in the two solutions are about the same,with the detection limits being around 100–200 ppm.

Room-Temperature Persistent Luminescence in Metal Halide Perovskite Nanocrystals for Solar-Driven CO_(2)Bioreduction

The rapid crystal growth of metal halide perovskite(MHP)nanocrystals inevitably leads to the generation of abundant crystal defects in the lattice.Here,defects-mediated long-lived charges and accompanying room-temperature persistent luminescence are demonstrated to be a general phenomenon in MHP nanocrystals.Density functional theory calculations suggest that the collaboration of Schottky and point defects enables upward cascading depletion for electron transfer in MHP nanocrystals,leading to the generation of long-lived photoexcited charges with lifetimes over 30 min.The excellent optical properties including the presence of long-lived charges,high charge separation efficiency,and broad absorption in the visible region make MHPs ideal candidates for both photocatalysis and photobiocatalysis.The MHPs were further integrated with enzymes to construct a light-driven biosynthetic system for the selective production of fine chemicals from CO_(2)with solar energy.The biosynthetic system can produce formate with a quantum yield of 3.24%,much higher than that of plants(∼0.2-1.6%).These findings will benefit the understanding of the optoelectronic properties of MHPs and further provide opportunities for the development of biosynthetic systems for solar-to-chemical synthesis.

稀土掺杂长余辉纳米材料研究简述

长余辉纳米粒子(persistent luminescence nanoparticles,PLNPs)是一种特殊的发光材料,具有很长的余辉时间。尤其是稀土元素(rare earth elements,REE)掺杂PLNPs(REE-PLNPs)具有独特的4f电子构型、优异的物理化学稳定性、高的发光强度和量子产率以及长的余辉时间。通过调节REE掺杂离子的种类和浓度,可以改变REE-PLNPs的发射波长范围。虽然发光中心相同,但由于不同材料所属的晶格不同,不同PLNPs基质材料的光学性质往往不同。因此,改变基质材料以及稀土共掺杂离子的种类,以提高REE-PLNPs的发光强度,进而可对余辉性能进行优化,故REE-PLNPs在室内装修、安全标志、仪表显示、生物检测和成像、诊疗一体化等领域受到了研究者的关注。以镧系元素和Sc与Y等掺杂REE-PLNPs为例,介绍了REE-PLNPs的组成和余辉发光性能及其在光学性质方面的研究进展。评述了REE在改善PLNPs的发射波长和余辉强度方面的优势,展望了REE-PLNPs研究未来的发展方向。

小尺寸长余辉纳米颗粒的制备及发光性能

尺寸小且光学性能良好的长余辉纳米颗粒(PLNPs)在生物医学领域中具有广泛的应用前景。目前,PLNPs一般需要通过高温煅烧获得,而高温煅烧会造成颗粒团聚、尺寸过大、不利于在生物医学领域应用。因此,发展尺寸小且余辉发光性能良好的PLNPs制备方法具有重要意义。采用溶剂热法,以油酸和十八烯为溶剂,甲醇(CH_(3)OH)为辅助溶剂制备了铬掺杂镓酸锌PLNPs(ZGC-CH_(3)OH),对ZGC-CH_(3)OH煅烧后进一步用乙二胺四乙酸二钠进行刻蚀获得ZGC-CH_(3)OH-EDTA。研究了CH_(3)OH和EDTA刻蚀效应对PLNPs尺寸大小、余辉发光性能以及晶体结构的影响。结果表明:该方法制备的PLNPs(ZGC-CH_(3)OH-EDTA)不仅尺寸小,而且具有很长的余辉时间,其平均粒径为11.12nm,最大余辉发射波长为696nm,NIR余辉时间超过120h。

Zn_(1.4)Ga_(2)O_(4)∶(0.03Cr^(3+),0.002In^(3+),xEr^(3+))近红外发光长余辉纳米颗粒的制备及其光学性质

利用一步水热法制备了Zn_(1.4)Ga_(2)O_(4)∶0.03Cr^(3+),0.002In^(3+),xEr^(3+)(x=0,0.005,0.01,0.015)PLNPs,研究Er^(3+)对ZnGa_(2)O_(4)体系纳米粒子余辉性能的影响,对其系列样品进行X射线粉末衍射(XRD)、透射电镜(TEM)、荧光光谱等表征,结果表明Er^(3+)的掺杂改善了材料的光学性质。当Er^(3+)掺杂量从0 mmol增加0.015 mmol时,样品发光强度先增强后降低,Er^(3+)掺杂量为0.01 mmol时NIR发射最强,尺寸为最小,材料的余辉时间可达5 d。XRD分析结果显示,Er^(3+)的掺杂对PLNPs晶体结构无明显影响,Zn_(1.4)Ga_(2)O_(4)∶0.03Cr^(3+),0.002In^(3+),xEr^(3+)(x=0,0.005,0.01,0.015)系列样品组织为纯相的尖晶石结构;TEM表征结果显示合成的系列样品尺寸小,掺杂Er后,平均粒径在10 nm左右。制备的小尺寸PLNPs在生物医学领域有着潜在的应用前景。

MgGa_(2)O_(4)∶Cr^(3+),Al^(3+)近红外发光长余辉纳米粒子的制备及发光性能研究

利用乙二醇辅助共沉淀法,制备了小尺寸近红外发光Al^(3+)共掺杂镓酸镁(MgGa_(2)O_(4))∶0.3%Cr^(3+)(MGO∶0.3%Cr^(3+),Al^(3+))长余辉发光纳米粒子(PLNP),考察了Al^(3+)掺杂对MGO∶0.3%Cr^(3+)晶体结构和光学性质的影响。研究结果表明,Al^(3+)掺杂对MGO∶0.3%Cr^(3+)的晶体结构无影响,但能提高MGO∶0.3%Cr^(3+)的发光强度。当Al^(3+)掺杂量为0.4%(摩尔分数)时,MGO∶0.3%Cr^(3+),0.4%Al^(3+)(Al^(3+)、Cr^(3+)相对于Ga^(3+)的物质的量比,摩尔分数)PLNP发光强度最强,余辉平均发光寿命从46.98s(MGO∶0.3%Cr^(3+))增大至78.75s(MGO∶0.3%Cr^(3+),0.4%Al^(3+)),平均粒径为(6.53±1.79)nm。本研究为制备小尺寸和高发光强度的PLNP提供了一种有效的方法。此外,高发光强度和长余辉寿命的MGO∶0.3%Cr^(3+),0.4%Al^(3+) PLNP为光学传感、成像和治疗等提供了材料支撑。

双波长发射长余辉纳米颗粒Zn_(2)SiO_(4)∶Ga的制备及动态防伪应用

双波长发射的长余辉纳米材料在信息加密与防伪方面有着重要的应用潜能。采用水热和煅烧结合的方法,制备了具有双波长发射的Zn_(2)Si_(x)O_(4)∶Ga_(0.01)(x=0.8~1.2)长余辉纳米颗粒。通过优化合成过程中前驱体溶液的pH值和硅离子含量,使Zn_(2)Si_(x)O_(4)∶Ga_(0.01)获得了较好的长余辉发光性能。研究结果表明,Ga^(3+)掺杂对Zn_(2)SiO_(4)的晶体结构没有影响,当前驱体溶液pH值为7时,Zn_(2)Si_(1.1)O_(4)∶Ga_(0.01)纳米颗粒分散性较好,平均粒径为(86.18±1.26)nm。在254 nm紫外光激发下,Zn_(2)Si_(1.1)O_(4)∶Ga_(0.01)在417和770 nm两个波长下发射,417 nm下的平均发光寿命(τav)为54.05 s,770 nm下的平均发光寿命为96.35 s,在近红外区可观察到216 h的余辉发光,并成功应用于多模动态防伪中。双波长发射的Zn_(2)Si_(x)O_(4)∶Ga_(0.01)还将在生物传感与成像等领域具有潜在应用价值。

新型长余辉纳米材料的制备及应用研究进展

长余辉材料是一种储能型发光材料,其可以将吸收的一部分能量储存在陷阱中,在外部刺激下以光的形式缓慢释放出来。近年来,新型的长余辉纳米材料在可控制备方法和独特的光学性能方面取得了的突破,在新型涂料、建筑节能、信息防伪及生物医学等领域中引起了广泛关注。综述了新型长余辉纳米材料的制备方法、光物理性质的调控策略及在不同领域中的应用研究进展,并对下一代长余辉纳米材料的未来研究方向和挑战进行了展望。

羟基氧化钴长余辉纳米探针用于食品中VC的检测

采用水热两相法结合高温短时煅烧,制备出一种具有超高亮度、单分散尺寸及光学稳定近红外发光的三掺杂镓锗酸锌长余辉纳米材料(ZGGO∶Cr^(3+),Yb^(3+),Er^(3+)persistent luminescence nanoparticles,ZGGO∶Cr^(3+),Yb^(3+),Er^(3+)PLNPs),在其表面修饰羟基氧化钴(Co OOH),并通过Co OOH与VC之间的特异性氧化还原反应构建出一种检测VC的纳米探针。该探针以ZGGO∶Cr^(3+),Yb^(3+),Er^(3+)PLNPs作为光学信号单元,Co OOH为猝灭剂,基于荧光内滤效应,实现对VC高选择性、高灵敏度的快速检测。结果表明,Co OOH可有效猝灭PLNPs的发光;VC可通过还原Co OOH使PLNPs的发光得到恢复,且荧光恢复与VC含量具有良好的线性相关性(R2=0.993 15),检出限为1.18 mg/kg。用于实际样品猕猴桃、柠檬、草莓中VC的检测,测定结果与高效液相色谱的检测结果具有较好的一致性。此外,合成的ZGGO∶Cr^(3+),Yb^(3+),Er^(3+)PLNPs在近红外区具有超长的余辉性能,测定时无需激发,可进一步用于细胞及活体内VC的监测与成像。

长余辉纳米颗粒改性研究进展

对长余辉纳米颗粒(PLNP)优异的余辉发光性能不断地进行优化,使其在信息储存和生物医学领域具有广阔的应用前景。归纳了近年来PLNP改性的几种方法,包括调整掺杂元素和基质材料的组成、加入共掺杂离子、制备方法的改性、表面修饰增强生物相容性以及控制反应条件等。介绍了通过上述方法改性后的PLNP表现出的优异发光性能相关的研究成果,评述了改性后的PLNP在生物成像、肿瘤成像及治疗、多功能纳米平台的构建等领域的应用研究进展。最终,对PLNP未来的制备工艺和应用发展进行了展望。

Defect Luminescence Based Persistent Phosphors—From Controlled Synthesis to Bioapplications

Persistent luminescence is an optical phenomenon where solid phosphors can store photoenergy in defects and release the energy by luminescence after stopping excitation.Due to the intriguing optical characteristics,the defect luminescence based persistent phosphors have attracted enormous attention in recent decades,especially in biomedical fields such as biosensing and bioimagin8.Persistent luminescence nanoparticles(PLNPs)can effectively avoid the autofluorescence interference from complex samples or tissues,leading to significantly improved sensitivity in biological analysis.In this review,we summarized the methods to control the optical performance of PLNPs from the perspectives of controlled synthesis and defect regulation,and emphasized the close relationship between their optical performance and applications.We further provided a summary about a series of PLNPs nanoprobes designed by our group for biosensing and bioimaging.Our efforts,summarized in this review,will not only open a window for manipulating luminescence in PLNPs,but also further promote the application of PLNPs in biomedicine.

Dy,Cr共掺杂ZnGa2O4长余辉纳米粒子的制备及发光性能研究

以乙二醇辅助水热法制备了Dy^(3+),Cr^(3+)共掺杂ZnGa_2O_4的小尺寸、近红外长余辉纳米粒子(PLNPs)。通过优化反应条件、锌的比例和共掺杂稀土离子Dy^(3+)等措施,不仅提高了PLNPs的余辉发光性能,而且有效控制了PLNPs的粒径。结果表明,当起始溶液p H为7、Ga:Zn的比例为2:1.2、Dy^(3+)的掺杂量为1%时,所合成的PLNPs的尺寸在6 nm左右,而且具有良好的余辉发光性能,其近红外余辉时间大于72 h,在高信噪比生物医学成像中具有潜在应用价值。