2019 Volume 30 Issue 10

Heteroatom-substituted rhodamine dyes: Structure and spectroscopic properties
Deng Fei , Xu Zhaochao
2019, 30(10): 1667-1681  doi: 10.1016/j.cclet.2018.12.012
[Abstract](1560) [FullText HTML] [PDF 4185KB](17)
Abstract:
Rhodamine is one class of most popular dyes used in fluorescence imaging due to the outstanding photoproperties including high brightness and photostability. In recent years, replacement the xanthene oxygen with other elements, especially silicon, has attracted great attentions in the development of new rhodamine derivatives. This review summarized the structures and photophysical properties of heteroatom-substituted rhodamines. We hope this review can help to understand the structure-property relationships of rhodamine dyes and then elucidate the way to create derivatives with improved photoproperties.
Synthesis and application of near-infrared substituted rhodamines
Li Min , Li Yuntao , Wang Xijing , Cui Xiaoyan , Wang Ting
2019, 30(10): 1682-1688  doi: 10.1016/j.cclet.2019.06.036
[Abstract](2117) [FullText HTML] [PDF 936KB](12)
Abstract:
Near infrared (NIR) fluorescent probes are highly attractive in the field of fluorescent imaging of living organisms for their outstanding signal-to-noise ratio, strong tissue penetration and low biotoxicity. Herein, we summarized some recent progress in the synthesis and application of NIR rhodamines by replacing the bridging oxygen atom with main group elements such as silicon and phosphorus.
Photodynamic therapy based on organic small molecular fluorescent dyes
Li Li , Chen Yisha , Chen Weijie , Tan Ying , Chen Haiyan , Yin Jun
2019, 30(10): 1689-1703  doi: 10.1016/j.cclet.2019.04.017
[Abstract](2500) [FullText HTML] [PDF 1462KB](46)
Abstract:
Photodynamic therapy (PDT) has shown promise as an effective treatment modality for cancer and other localized diseases due to its noninvasive properties and spatiotemporal selectivity. Near-infrared (NIR) fluorescent dyes based on organic small molecules are characterized with low cytotoxicity, good biocompatibility and excellent phototoxicity, which are widely used in PDT. In this review, we attempt to summarize the development of imaging-induced PDT based on organic small molecules and classify it according to the structures of dyes including cyanines, 4, 4-difluoro-4-bora-3a, 4a-diaza-s-indacene (BODIPY) analogues, phthalocyanine and other agents such as rhodamine analogues.
Small molecule fluorescent probes of protein vicinal dithiols
Hu Guodong , Jia Huiyi , Zhao Lanning , Cho Dong-Hyung , Fang Jianguo
2019, 30(10): 1704-1716  doi: 10.1016/j.cclet.2019.06.039
[Abstract](2100) [FullText HTML] [PDF 1325KB](9)
Abstract:
The vicinal dithiol motif is widely present in proteins, and is critical for proteins' structures and functions. In recent years, a variety of fluorescent probes with high specificity and outstanding optical properties for sensing protein vicinal dithiols have been developed. In this review, we summarized the fluorescent probes of protein vicinal dithiols in literature. These probes are classified into four types based on their acceptor sites, i.e., biarsenical probes, monoarsenical probes, dimaleimide probes and diacrylate probes. Through analyzing the properties of different probes, we expect that this review would help readers further understand the structural factors of these probes and provide the design strategy for novel fluorescent probes with improved properties.
Thermally activated delayed fluorescence molecules and their new applications aside from OLEDs
Chen Wenlong , Song Fengling
2019, 30(10): 1717-1730  doi: 10.1016/j.cclet.2019.08.032
[Abstract](1710) [FullText HTML] [PDF 1923KB](26)
Abstract:
Thermally activated delayed fluorescence (TADF) organic molecules feature with long-lived delayed fluorescence, because they can undergo not only efficient intersystem crossing (ISC), but also efficient reverse intersystem crossing (RISC) at room temperature. As a new type of luminescent molecules, they have exhibited successful applications in organic light emitting diodes (OLEDs). Aside from OLEDs, they are also found to have potential applications in time-resolved luminescence imaging based on long-lived fluorescence property. Meanwhile, due to their excited triplet characteristic originated from efficient ISC, they were found to be applied in triplet-triplet annihilation upconversion (TTA-UC), photodynamic therapy (PDT) and organic photocatalytic synthesis. This review briefly summarizes the characteristics and excellent photophysical properties of TADF organic compounds, then covers their applications to date aside from OLEDs based on their highly efficient ISC ability and RISC ability at room temperature.
Recent advances on small-molecule fluorophores with emission beyond 1000 nm for better molecular imaging in vivo
Tu Le , Xu Yuling , Ouyang Qingying , Li Xiangyang , Sun Yao
2019, 30(10): 1731-1737  doi: 10.1016/j.cclet.2019.05.022
[Abstract](1624) [FullText HTML] [PDF 1010KB](10)
Abstract:
In the second near-infrared channel (NIR-Ⅱ, 1000-1700 nm), organic and inorganic fluorophores are designed with superior chemical/optical properties to provide real-time information with deeper penetration depth and higher resolution owing to the innate lower light scattering and absorption of the NIR-Ⅱ imaging than conventional optical imaging. Among them, the small-molecule based fluorophores have been highlighted due to their desirable biocompatibility and favorable pharmacokinetics. In this review, we introduced the latest research progress of the rational design of small-molecule NIR-Ⅱ fluorophores and their impressively biological applications including the NIR-Ⅱ signal imaging, multimodal imaging and theranostic.
Recent progress in two-photon small molecule fluorescent probes for enzymes
Chen Ding , Qin Wenjing , Fang Haixiao , Wang Lan , Peng Bo , Li Lin , Huang Wei
2019, 30(10): 1738-1744  doi: 10.1016/j.cclet.2019.08.001
[Abstract](2151) [FullText HTML] [PDF 1112KB](5)
Abstract:
Enzymes are macromolecular biological catalysts which can accelerate chemical reactions in living organisms. Almost all the physiological metabolism activities in the cell need enzymes to sustain life via rapid catalysis. Currently, medical research has proved that abnormal enzyme activity is associated with numerous diseases, such as Parkinson's disease (PD), Alzheimer's disease (AD) and cancers. On the other hand, early diagnosis of those diseases is of great significance to improve the survival rate and cure rate. In the current diagnostic tools, two-photon fluorescent probes (TPFPs) are developing rapidly due to their unique advantages, such as higher spatial resolution, deeper imaging depth, and lower biotoxicity. Therefore, the design and synthesis of two-photon (TP) small molecule enzymatic probes have broad prospects for early diagnosis and treatment of diseases. As of now, scientists have developed many TP small molecule enzymatic probes. This review aims to summarize the TP small molecule enzymatic probes and expound the reaction mechanism.
Recent advances in the development of polydiacetylene-based biosensors
Zhang Zhijie , Wang Fang , Chen Xiaoqiang
2019, 30(10): 1745-1757  doi: 10.1016/j.cclet.2019.08.035
[Abstract](1806) [FullText HTML] [PDF 2282KB](8)
Abstract:
Biosensors that effectively and selectively detect biomolecules and monitor biological processes have become an important component of biological and medical studies. Because they possess several attractive features, polydiacetylenes (PDAs) have been employed as frameworks for fluorometric and colorimetric sensors. PDAs are formed in their non-fluorescent blue-colored state by UV light induced polymerization of head group functionalized diacetylene monomers (DAs) and they undergo a transition to form fluorescent red-colored PDAs in response to a variety of stimuli. Importantly, by properly choosing a headgroup in the DA, the formed PDA can be designed to undergo a fluorescence/colorimetric change in response to a specific biological stimulus. This review summarizes recent advances that have been made in the development of PDA biosensors with an emphasis being given to design strategies and applications.
Pillararene-based fluorescent sensors for the tracking of organic compounds
Cao Derong , Meier Herbert
2019, 30(10): 1758-1766  doi: 10.1016/j.cclet.2019.06.026
[Abstract](2107) [FullText HTML] [PDF 1320KB](6)
Abstract:
Fluorescent chemosensors based on pillararene complexes represent a new, promising branch in sensor technology. Because of CH …π interactions, aliphatic chains are well suited for the columnar cavities of pillararenes and bulky or sheet-like (sub)structures can be arranged on the portals. Thus, pillararenes form versatile receptors and an alteration of the fluorescence behavior upon complexation ensures the function of these chemosensors as the reporter. Although this field of research exists only since a few years, remarkable chemosensors were developed for substances as diverse as medical drugs, biochemicals, herbicides and explosives.
Our expedition in the construction of fluorescent supramolecular metallacycles
Zhu Junlong , Liu Xi , Huang Junhai , Xu Lin
2019, 30(10): 1767-1774  doi: 10.1016/j.cclet.2019.08.027
[Abstract](1663) [FullText HTML] [PDF 1490KB](8)
Abstract:
During the past few years, the construction of fluorescent supramolecular metallocycles has attracted extensive attention due to their diverse applications such as sensing, photoelectric devices, and mimicking complicated natural photo-processes. In this review, we will discuss how we entered the field of fluorescent supramolecular metallacycles and what we investigated in this field. The preparation of various fluorescent supramolecular metallacycles and their applications in monitoring the dynamics of coordination-driven self-assembly, sensing, catalysts, and supramolecular gels will be summarized.
Recent advances in molecular fluorescent probes for organic phosphate biomolecules recognition
Li Wei , Gong Xiangyang , Fan Xiaopeng , Yin Shulu , Su Dongdong , Zhang Xiaobing , Yuan Lin
2019, 30(10): 1775-1790  doi: 10.1016/j.cclet.2019.07.056
[Abstract](2180) [FullText HTML] [PDF 2030KB](9)
Abstract:
Organic phosphate biomolecules (OPBs) are indispensable components of eukaryotes and prokaryotes, such as acting as the fundamental components of cell membranes and important substrates for nucleic acids. They play pivotal roles in various biological processes, such as energy conservation, metabolism, and signal modulation. Due to the difficulty of detection caused by variety OPBs, investigation of their respective physiological effects in organisms has been restrained by the lack of efficient tools. Many small fluorescent probes have been employed for selective detection and monitoring of OPBs in vitro or in vivo due to the advantages of tailored properties, biodegradability and in situ high temporal and spatial resolution imaging. In this review, we summarize the recent advances in fluorescent probes for OPBs, such as nucleotides, NAD(P)H, FAD/FMN and PS. Importantly, we describe their identification mechanisms in detail and discuss the general strategies for these OPBs probe designs, which provide new insights and ideas for the future probe designs.
Fluorescent probes for detection of biothiols based on "aromatic nucleophilic substitution-rearrangement" mechanism
Kang Yan-Fei , Niu Li-Ya , Yang Qing-Zheng
2019, 30(10): 1791-1798  doi: 10.1016/j.cclet.2019.08.013
[Abstract](1608) [FullText HTML] [PDF 1119KB](5)
Abstract:
Biothiols, including cysteine (Cys), homocysteine (Hcy), and glutathione (GSH) play important roles in physiological processes, and the detection of thiol using fluorescent probes has attracted attention due to their high sensitivity and selectively and invasive on-time imaging. However, the similar structures and reactivity of these biothiols present great challenges for selective detection. This review focused on the the "aromatic nucleophilic substitution-rearrangement (SNAr-rearrangement) mechanism", which provided a powerful tool to design fluorescent probes for the discrimination between biothiols. We classify the fluorescent probes according to types of fluorophores, such as difluoroboron dipyrromethene (BODIPY), nitrobenzoxadiazole (NBD), cyanine, pyronin, naphthalimide, coumarin, and so on. We hope this review will inspire exploration of new fluorescent probes for biothiols and other relevant analytes.
New trends of molecular probes based on the fluorophore 4-amino-1, 8-naphthalimide
Zhou Lin , Xie Lijuan , Liu Chuanhao , Xiao Yi
2019, 30(10): 1799-1808  doi: 10.1016/j.cclet.2019.07.051
[Abstract](1588) [FullText HTML] [PDF 1880KB](6)
Abstract:
4-Amino-1, 8-naphthalimide (ANI) represents a valuable fluorophore from which a large number of probes have been derived in order to meet the requirements from the fields of biological sensing and imaging. In this review, the major progresses of ANI-based fluorescent probes in the past decade have been highlighted and categorized into three trends. The future development of ANI probes is also expected. This review provides a great deal of references and illuminating comments which will be helpful for the researchers designing and using fluorescent probes.
Recent progress on pure organic room temperature phosphorescence materials based on host-guest interactions
Qu Guojuan , Zhang Yaopeng , Ma Xiang
2019, 30(10): 1809-1814  doi: 10.1016/j.cclet.2019.07.042
[Abstract](1521) [FullText HTML] [PDF 1026KB](5)
Abstract:
Pure organic room temperature phosphorescence (RTP) has been attracting a lot interest recently. So far, many strategies have succeeded in achieving efficient organic RTP materials by increasing the rate of intersystem crossing (ISC) and suppressing non-radiative transitions. In supramolecular chemistry, the control and regulation of molecular recognition based on the role of the host and guest in supramolecular polymers matrix, has attracted much attention. Recently, researchers have successfully achieved room temperature phosphorescence of pure organic complexes through host-guest interactions. The host molecule specifically includes the phosphorescent guest to reduce non-radiative transitions and enhance room temperature phosphorescence emission. This review aims to describe the developments and achievements of pure organic room temperature phosphorescence systems through the mechanism of host-guest interactions in recent years, and demonstrates the exploration and pursuit of phosphorescent materials of researchers in different fields.
Structural modification of BODIPY: Improve its applicability
Liu Mengdi , Ma Siyue , She Mengyao , Chen Jiao , Wang Zhaohui , Liu Ping , Zhang Shengyong , Li Jianli
2019, 30(10): 1815-1824  doi: 10.1016/j.cclet.2019.08.028
[Abstract](1837) [FullText HTML] [PDF 1832KB](28)
Abstract:
BODIPY has been considered a potential scaffold because of their neutral total charge, sharp absorption, and emission with high fluorescence quantum yield. However, the drawback of emission wavelength at less than 600 nm and hydrophobicity limit its application. One of the extremely interesting properties of BODIPY is that small modifications to their structures could be able to tune their properties, mainly including the absorption/emission wavelength and the hydrophilicity. This review focuses on the modification at different positions of BODIPY to improve the water-solubility and emission wavelength that describe their spectral, photophysical properties and applicability, which is helpful for the researchers to rationally design BODIPY dyes to adapt a wide range of applications.
Toward the most versatile fluorophore: Direct functionalization of BODIPY dyes via regioselective C-H bond activation
Sheng Wanle , Lv Fan , Tang Bing , Hao Erhong , Jiao Lijuan
2019, 30(10): 1825-1833  doi: 10.1016/j.cclet.2019.08.004
[Abstract](1799) [FullText HTML] [PDF 1536KB](24)
Abstract:
Fluorescent dyes are heavily sought for their potentials applications in bioimaging, sensing, theranostic, and optoelectronic materials. Among them, BODIPY dyes are privileged fluorophores that are now widely used in highly diverse research fields. The increasing success of BODIPY dyes is closely associated with their excellent and tunable photophysical properties due to their rich functionalization chemistry. Recently, growing research efforts have been devoted to the direct functionalization of the BODIPY core, because it allows the facile installation of desired functional groups in a single atom economical step. The challenges of this direct C-H derivation come from the difficulties in finding suitable functionalization agents and proper control of the regioselectivity of the functionalization. The aim of this work is to provide an overview of BODIPY dyes and a summarization of the different synthetic methodologies reported for direct C-H functionalization of the BODIPY framework.
Organelle targetable fluorescent probes for hydrogen peroxide
Wen Ying , Huo Fangjun , Yin Caixia
2019, 30(10): 1834-1842  doi: 10.1016/j.cclet.2019.07.006
[Abstract](2219) [FullText HTML] [PDF 1321KB](7)
Abstract:
Hydrogen peroxide (H2O2), as important products of oxygen metabolism, plays an important role in many biological processes, such as immune responses and cellular signal transduction. However, abnormal production of H2O2 can damage cellular biomolecules, which was closely associated with many diseases. Thus, it is urgent to monitor the level change of H2O2 in living cells, particularly at subcellular levels. Toward this end, a wide variety of H2O2 fluorescent probes have been designed, developed and applied for imaging of H2O2 in subcellular levels. In this review, we highlight the representative cases of H2O2 fluorescent probes with mitochondria, nuclei and lysosomes-targetable ability. The review contains organelle target strategies, structures, fluorescence behavior and biological applications of these probes.
Nanocrystals for large Stokes shift-based optosensing
Zhou Ronghui , Lu Xiaomei , Yang Qin , Wu Peng
2019, 30(10): 1843-1848  doi: 10.1016/j.cclet.2019.07.062
[Abstract](2252) [FullText HTML] [PDF 1016KB](11)
Abstract:
Stokes shift is an important feature of fluorescence, which reveals the energy loss between the excitation and the emission. For most fluorescent materials (e.g., organic dyes and proteins), the large overlap between the absorption and emission spectra endow them a small Stokes shift that induced reabsorption by fluorophore itself. Although the self-absorption can be effectively reduced due to the emergence of fluorescent nanomaterials, fluorescence attenuation is still observed in aggregated or concentrated nanocrystals, causing reduced sensitivity of biosensors. Therefore, increasing the Stokes shift can effectively improve the performance of nano-agents based biosensing. In this critical review, through understanding the Stokes shift from the viewpoint of self-absorption, the influence of Stokes shift on fluorescence properties are discussed. Based on the principle of changing the Stokes shift of fluorescent nanomaterials, we described the methods for constructing various optically large Stokes shift-based nanomaterials, and the application of these nanocrystals in biosensing is especially concerned in this review.
Molecularly near-infrared fluorescent theranostics for in vivo tracking tumor-specific chemotherapy
Yan Chenxu , Shi Limin , Guo Zhiqian , Zhu Weihong
2019, 30(10): 1849-1855  doi: 10.1016/j.cclet.2019.08.038
[Abstract](1633) [FullText HTML] [PDF 1109KB](9)
Abstract:
Molecularly near-infrared (NIR) theranostics, combining in vivo sensing and tumor-specific therapeutic capability within one molecular system, have received considerable attention in recent years. Compared with the visible fluorescence imaging, NIR imaging (emission wavelength at 650-900 nm) possesses unique advantages including the minimum photodamage to biological samples, deep penetration, and low interference from auto-fluorescence. In over past decades, there has been an explosive development in the design of molecular imaging contrasts and imaging-guided therapeutics. In this review, we have sumarried the strategies of the NIR theranostics for imaging and tumor-specific chemotherapy applications in living systems. It is noted that the molecularly NIR theranostic design strategy could address current challenges of real-time in vivo sense-and-release for the intelligent biosensing and personalized treatment.
Near-infrared dyes, nanomaterials and proteins
Chang Zong , Liu Feng , Wang Liang , Deng Mengying , Zhou Chunhua , Sun Qinchao , Chu Jun
2019, 30(10): 1856-1882  doi: 10.1016/j.cclet.2019.08.034
[Abstract](2203) [FullText HTML] [PDF 3257KB](19)
Abstract:
Taking the advantage of reduced scattering and low autofluorescence background, the NIR fluorescence probes, such as fluorescence proteins, organic molecules and nanoparticles, not only hold the promise of in vivo imaging of biological processes in physiology and pathology with high signal-to-noise ratio, but also for clinical diagnosis. In this review, we provide an overview of the recent progress on NIR probes, focusing on fundamental mechanisms of NIR dyes and nanoparticles, and protein engineering strategies for NIR proteins.
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