基于氧杂蒽结构可控官能化的荧光探针研究新进展

荧光分子探针技术在表达分子间识别行为及复杂生命和环境体系的内状态信息方面具有非常优异的性能,氧杂蒽及其衍生物螺连隐色体结构变化伴随的分子荧光变换模型,广泛且深入的应用于构建新型功能光敏探针分子.近年来此类探针的合成设计及功能化调控研究异常活跃,新的突破不断涌现.综述了新近基于氧杂蒽及其衍生物的荧光探针在金属阳离子、pH、阴离子识别检测方面的研究进展,并简要阐释了该类探针分子的构筑,识别检测机理以及探针在生物成像和环境监测等方面的应用.     

基于硅杂蒽类染料的荧光探针及其应用

近年来,荧光成像技术为人们研究活体细胞及组织内的化学生物学过程提供了有效的研究工具,可以无损、实时、原位地以高时空分辨率实现对目标物进行生物荧光成像与分析。荧光成像技术在生物学、环境监测、临床诊断和药物发现等诸多研究领域发挥着越来越重要的作用。生物荧光成像技术的最新进展对发展新型小分子荧光染料及探针提出了更高的要求。激发和发射波长位于近红外光区（600~900 nm）的荧光染料及探针由于具有光毒性低、生物分子自发荧光干扰小、光散射低、组织穿透能力强等优点,非常适合用于生物荧光成像领域。通过将罗丹明分子中O桥原子用Si代替,得到了一类新型的探针分子--硅杂蒽类荧光探针。这类染料分子在保留了氧杂蒽荧光染料优越的光学性质的同时,光谱发生明显红移,满足了近红外荧光检测的要求,具有良好的生物相容性。本文综述了近年来基于硅杂蒽及其衍生物荧光探针的合成及在金属离子、pH值、小分子、生物酶等检测方面的研究进展,并且简要阐述了基于硅杂蒽类探针分子的识别检测机理以及其在生物成像等方面的应用。     

动脉粥样硬化光学成像探针研究进展

心血管疾病(Cardiovascular disease, CVD)是全球疾病致死的主要原因之一. 动脉粥样硬化(Atherosclerosis, AS)是引发各种CVD的首要危险因素, 其发生发展通常经历持续的慢性炎症过程. 因此, 及时高效地检测AS, 对于早期评估、 诊断和治疗CVD具有重要临床意义. 光学探针成像拥有极高的灵敏度和空间分辨率以及超快的信号采集处理速度, 被广泛应用于生物医学检测与成像. 本文综合评述了6种常见用于AS成像的光学探针, 涉及小分子荧光探针、 聚集诱导发光(Aggregate-induced emission, AIE)纳米探针、 量子点探针、 上转换纳米探针、 光声探针和多模态探针等; 并对各种探针的优缺点进行了分析比较. 在此基础上, 展望了光学探针在AS成像领域的发展前景, 并提出了相应建议.     

活性氧检测荧光探针的设计、合成及应用研究进展

首先介绍了生物体氧化还原状态的动态平衡机理以及生物体氧化应激的产生原因及影响,然后总结、概括了目前流行的荧光分析法—荧光探针的设计构成及识别机理,并详细介绍了近几年各类活性氧自由基检测荧光探针的研究进展,为活性氧检测荧光探针的进一步发展提供了新思路。     

荧光/化学发光探针成像检测超氧阴离子自由基的研究进展

超氧阴离子自由基(O·-2)是细胞内氧气单电子还原后最先产生的一类含氧的高活性物种(活性氧,ROS),与生命过程息息相关.正常稳态浓度的O·-2起重要的信号调控作用,包括细胞的增殖、分化、自噬等.但O·-2浓度的异常,又与癌症、神经退行性疾病、糖尿病等多种疾病的发生发展密切相关.因此,监测O·-2浓度的变化对揭示相关疾病的机理具有至关重要作用.由于荧光成像检测方法具有诸多优势,发展高灵敏、高选择性检测O·-2的荧光探针成为揭示相关疾病发生发展分子机制的关键切入点.近年来,随着荧光显微技术的发展,研究者开发了多种荧光/化学发光探针,实现了对细胞及活体内O·-2水平的可视化监测.本文综述了近五年用于检测O·-2的分子探针、纳米探针、蛋白探针以及化学发光探针的研究进展,并对其发展前景进行了展望.     

三嗪类光学探针与标记分析

评述了以三聚氰氯作桥联剂或骨架而合成的三嗪类衍生物、特别是其光学标记探针的研究进展及分析应用。     

改性活性炭负载氯化铁催化氧杂蒽衍生物的合成

制备了一种新型改性活性炭负载FeCl₃催化剂(MAC-FeCl₃),并通过红外光谱及等离子体发射光谱等技术手段对其进行了表征。 在MAC-FeCl₃催化下,β-萘酚与醛在PEG200中,于120 ℃反应60~120 min,合成了一系列氧杂蒽类衍生物,收率为79%~93%。 该方法操作简单、产率高、环境友好。 制备的催化剂性能稳定,使用4次仍保持较高活性。     

检测活性氮物种的荧光探针

活性氮是一类具有高生物化学活性的含氮原子的化学物种。这类活性物种具有特殊的生理功能,并在生命体的生理和病理过程中起着至关重要的作用。因此,设计开发用于选择性识别和高灵敏检测生物体内的活性氮物种的技术具有十分重要的意义。荧光探针作为一种具有高灵敏度、高选择性、对生物样品损伤小的实时原位的可视化检测技术,为深入阐明活性氮物种在生理和病理过程中所起的作用提供了一个便利有效的检测手段,并已在检测活性氮物种领域中得到了广泛应用。活性氮物种荧光探针可以进一步阐述活性氮物种特殊的生理功能,提高人们对该类物种在细胞信号转导方面的认知。本文根据活性氮物种的种类对荧光探针进行了分类,详细介绍了近四年来用于检测活性氮物种的荧光探针的研究进展,主要探讨了探针的设计方法、荧光响应机制及其生物应用,并对探针的设计合成和应用前景进行了展望。     

一种罗丹明类次氯酸荧光探针的合成与分析应用

通过一步反应合成了一种次氯酸(HOCl)荧光探针罗丹明6G酰肼,利用核磁和质谱对探针结构进行表征,并研究了其检测HOCl的荧光性能。实验结果表明,探针对HOCl的荧光分析具有高的灵敏性和选择性。利用不可逆的氧化还原反应,探针在中性溶液中快速产生与HOCl浓度呈线性比例的荧光增强信号,检测的线性范围为2~400μmol/L,检出限为0.06μmol/L,其他常见活性氧物种对检测影响小。探针能检测自来水中HOCl的含量,并在HeLa活细胞中实现了HOCl的荧光成像。     

过氧化氢荧光探针的研究进展

过氧化氢(H2 O2)与生命系统中的许多生理和病理过程有关.但是,过量的H2 O2会导致一系列生理疾病,因此,有效地识别和检测H2 O2非常重要.近年来已经报道了许多用于检测生物体系中H2 O2的荧光探针,与传统的检测方法相比,其具有灵敏度高、无创检测及实时成像等优点.本文根据不同的荧光团,评述了近五年H2 O2荧光探...     

用于检测生物体系中线粒体活性氧的荧光探针

In addition to being the energy powerhouse of the cell, mitochondria are an important source of reactive oxygen species (ROS) during the process of molecular oxygen metabolism. Mitochondrial ROS are closely associated with normal physiological functions as well as human diseases, and participate in cell signaling, nucleic acid and protein damage, and oxidative stress induction. However, the complicated interplay between mitochondrial ROS and the cellular pathological state has not been fully elucidated. It is expected that research on the mitochondrial ROS undertaking in the molecular pathogenesis of human diseases would benefit from development of efficient tools for the detection of these ROS. In recent years, an increasing number of fluorescent probes for mitochondrial ROS with high sensitivity and selectivity have been developed. Here, we present a review of the recent advances in small molecular fluorescent probes for selective detection of ROS inside the mitochondria. In this review, the design, synthesis, characteristics, and applications of the published fluorescent probes for mitochondrial ROS are discussed in detail.     

In Vivo Electrochemical Biosensors for Reactive Oxygen Species Detection: A Mini-Review

Due to the significance of reactive oxygen species (ROS) in numerous physiological processes including pathogen response, apoptosis, and induction of defense genes, various methods have been developed for their quantitative analysis. However, the conventional methods using exogenous tracers lack the capability to conduct real-time in vivo measurements. The electrochemical biosensors have shown their potentials for in vivo applications with the rapid and reagentless detection processes. In this article, electrochemical biosensors that are capable of making in vivo ROS detections are reviewed. The different configurations of these biosensors with corresponding strategies to enhance sensitivity and selectivity are discussed in detail. With further studies to promote the biosensor performance, these devices promise to provide more facile ways for ROS research in life sciences.     

光致活性氧淬灭方法检测生物抗氧化剂动力学模型分析

以TiO2纳米颗粒光催化反应为模型,研究了反应过程中的活性氧( ROS)产生以及活性氧淬灭的反应动力学模型。对苯二甲酸分子与体系中的光催化反应产生的OH·反应,生成具有荧光性质的2-羟基对苯二甲酸( lex=315 nm,lem=425 nm),因此对苯二甲酸作为氧化探针分子与体系中的生物抗氧化剂( AOs)分子竞争与ROS的反应,根据体系的荧光、反应时间以及AOs的浓度建立了AOs淬灭ROS的反应动力学模型。根据此模型推导AOs清除ROS的动力学常数,发现常见的生物抗氧化剂的抗氧化活性大小顺序为：硫辛酸、没食子酸、谷胱甘肽、尿酸、维生素C、维生素E、水溶性维生素E和胆红素。     

A Multi-responsive Fluorescent Probe Reveals Mitochondrial Nucleoprotein Dynamics with Reactive Oxygen Species Regulation through Super-resolution Imaging

Understanding the biomolecular interactions in a specific organelle has been a long-standing challenge because it requires super-resolution imaging to resolve the spatial locations and dynamic interactions of multiple biomacromolecules. Two key difficulties are the scarcity of suitable probes for super-resolution nanoscopy and the complications that arise from the use of multiple probes. Herein, we report a quinolinium derivative probe that is selectively enriched in mitochondria and switches on in three different fluorescence modes in response to hydrogen peroxide (H₂O₂), proteins, and nucleic acids, enabling the visualization of mitochondrial nucleoprotein dynamics. STED nanoscopy reveals that the proteins localize at mitochondrial cristae and largely fuse with nucleic acids to form nucleoproteins, whereas increasing H₂O₂ level leads to disassociation of nucleic acid–protein complexes.     

Recent Progress in the Biological Applications of Reactive Oxygen Species-Responsive Polymers

Abstract

Responsive polymeric materials that are sensitive to biological stimuli including temperature, pH, enzymes, or redox conditions have attracted research interest in recent years. Among these, reactive oxygen species (ROS)-responsive polymers are particularly appealing because of the special role of ROS in living organisms. ROS are the indicator and cause of certain diseases, and they are also important signaling molecules. ROS-responsive polymers could possess the following functions: drug carriers, ROS probes, or medications for certain ROS-related diseases. In this review, we analyze the progress about ROS-responsive polymers made in recent years and predict the future trends of ROS-responsive polymers from the above mentioned perspectives. Due to the limited scope of this review, some older articles are not covered here and are left for more comprehensive reviews.     

SERS纳米探针对电刺激过程中细胞内产生活性氧的检测

电刺激是用于细胞内紊乱电活动引起疾病的一类重要治疗方式. 在电刺激过程中是否会诱导细胞内活性氧(ROS)水平的改变, 以及常规抗氧化抑制药物与电刺激治疗同时运用带来的影响, 目前尚未有相关研究. 本文设计了一种具有较好生物相容性的金/银核壳纳米棒表面增强拉曼(SERS)活性探针, 用于电刺激过程中细胞内产生ROS的检测. 将该探针与细胞共孵育, 使其内化入细胞, 对细胞进行不同时间的电刺激, 利用拉曼光谱对SERS探针的信号进行检测. 实验结果表明, 随着电刺激时间的延长, SERS信号减弱, 说明细胞内产生ROS的量明显增加. 该传感机制是利用ROS能刻蚀金/银核壳纳米棒的银壳, 从而使其变薄引起SERS信号减弱. 抗坏血酸(AA)和谷胱甘肽(GSH)两种抗氧化抑制剂类药物与电刺激同时运用时, 可观察到它们会对电刺激过程产生的ROS有清除作用. 该研究发展了一类用于细胞内ROS检测的光谱方法, 也为异常的氧化应激和肿瘤治疗过程中的组合用药提供了建议.     

Study on Sensitization from Reactive Oxygen Species for Electrochemiluminescence of Luminol in Neutral Medium

In this paper, the sensitization on electrochemiluminescent (ECL) reaction of luminol from reactive oxygen species (ROSs) in neutral medium was studied. The powerful sensitization from ROSs even related with organics and organisms were examined under selected conditions which were suitable for biochemical analysis. The results indicated that whether the enhancers were dissolved in solutions or immobilized on the surface of conventional electrodes, stronger ECL intensity of luminol could be obtained. Enhanced ECL helped to provide groundwork for the detection of biomolecules for which would further enhance or quench the ECL signals. The technique may provide new means in a variety of fields such as clinical diagnostics, immunological analysis and environmental monitoring due to its simplicity and high efficiency.     

A Multi‐responsive Fluorescent Probe Reveals Mitochondrial Nucleoprotein Dynamics with Reactive Oxygen Species Regulation through Super‐resolution Imaging

Understanding the biomolecular interactions in a specific organelle has been a long‐standing challenge because it requires super‐resolution imaging to resolve the spatial locations and dynamic interactions of multiple biomacromolecules. Two key difficulties are the scarcity of suitable probes for super‐resolution nanoscopy and the complications that arise from the use of multiple probes. Herein, we report a quinolinium derivative probe that is selectively enriched in mitochondria and switches on in three different fluorescence modes in response to hydrogen peroxide (H₂O₂), proteins, and nucleic acids, enabling the visualization of mitochondrial nucleoprotein dynamics. STED nanoscopy reveals that the proteins localize at mitochondrial cristae and largely fuse with nucleic acids to form nucleoproteins, whereas increasing H₂O₂ level leads to disassociation of nucleic acid–protein complexes.     

Fluorescence Evaluation of Scavenging Efficiency of Antioxidants Against Reactive Oxygen Species (ROS) in Cigarette Smoke

Cigarette smoke can cause cellular oxidative stress that contributes to various adverse health effects associated with smoke exposure, partially due to reactive oxygen species (ROS) present in cigarette smoke. Reduction of abundant ROS in the cigarette mainstream smoke (MSS) is of importance for human health. In this work, a simple, rapid, and reliable fluorescence evaluation of scavenging efficiency of antioxidants as potential filter additives against ROS in cigarette smoke is reported. This method was based on the combination of model glass reactor and a fluorescence assay of ROS in cigarette smoke using dihydrorhodamine 6 G (DHR-6 G). The antioxidant was added into a glass reactor attached to cigarette filter, which simplified the preparation of combined filter containing additives. The ROS scavenging efficiency of antioxidants was then determined using spectrofluorimetry by the change in fluorescence intensity of whole smoke-bubbled solutions before and after addition of antioxidants into the glass reactor. The proposed method was successfully applied to the determination of ROS scavenging efficiency of several potential additives, such as tert-butylhydroquinone (TBHQ), vitamin C, β-carotene, grape seed extract, and Ginkgo biloba extract. Moreover, the relationship between MSS ROS scavenging efficiency and antioxidant activities (DPPH radicals scavenging efficiency and Fe²⁺ reducing power) of these compounds was also investigated.