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2017 Volume 34 Issue 12
2017, 34(12): 1343-1343
doi: 10.11944/j.issn.1000-0518.2017.12.170422
Abstract:
2017, 34(12): 1344-1354
doi: 10.11944/j.issn.1000-0518.2017.12.170301
Abstract:
A number of detection techniques have been developed for the early detection of environmental pollutants and health hazard substances, the prevention and treatment of diseases. Among them, fluorescent probe technique as a convenient, sensitive and visual method has been widely applied. Macrocyclic supramolecular fluorescent probes have gradually attracted the attention of the scientific community. Macrocyclic molecules possess cavities with certain size, which could complex with specific groups to form supramolecules. Therefore, in the design of supramolecular fluorescent probes, the cavity advantage of macrocyclic molecules can be taken into consideration and utilized. In addition, due to easy functionalization, a variety of functional macrocyclic molecules have been synthesized, providing more choices for the design of macrocyclic supramolecular fluorescent probes. This paper reviews the design strategies of macrocyclic supramolecular fluorescent probes with focuses on the chemical composition and detection mechanisms of the probe, which might provide a systematic theoretical guidance for the design of supramolecular fluorescent probes.
A number of detection techniques have been developed for the early detection of environmental pollutants and health hazard substances, the prevention and treatment of diseases. Among them, fluorescent probe technique as a convenient, sensitive and visual method has been widely applied. Macrocyclic supramolecular fluorescent probes have gradually attracted the attention of the scientific community. Macrocyclic molecules possess cavities with certain size, which could complex with specific groups to form supramolecules. Therefore, in the design of supramolecular fluorescent probes, the cavity advantage of macrocyclic molecules can be taken into consideration and utilized. In addition, due to easy functionalization, a variety of functional macrocyclic molecules have been synthesized, providing more choices for the design of macrocyclic supramolecular fluorescent probes. This paper reviews the design strategies of macrocyclic supramolecular fluorescent probes with focuses on the chemical composition and detection mechanisms of the probe, which might provide a systematic theoretical guidance for the design of supramolecular fluorescent probes.
2017, 34(12): 1355-1369
doi: 10.11944/j.issn.1000-0518.2017.12.170302
Abstract:
It is of great importance to selectively detect and effectively monitor zinc ion because of its wide distribution in human cells and vital roles in human metabolism. Fluorescent probes have been extensively applied in zinc sensing because of the advantages of simple-design, easy-operation, high sensitivity and cell imaging capability. Fluorescent zinc probes are generally constructed based on the mechanisms of photo-induced electron transfer, intra-molecular charge transfer, fluorescence resonance energy transfer, aggregation-induced emission and chelation-enhanced fluorescence. Among these mechanisms, zinc probes constructed on chelation-enhanced fluorescence have the advantages of easy design and synthesis because its fluorophore can simultaneously act as the receptor. In this review, fluorescent zinc probes based on the aforementioned mechanisms, especially, chelation-enhanced fluorescence, reported in recent years are briefly summarized.
It is of great importance to selectively detect and effectively monitor zinc ion because of its wide distribution in human cells and vital roles in human metabolism. Fluorescent probes have been extensively applied in zinc sensing because of the advantages of simple-design, easy-operation, high sensitivity and cell imaging capability. Fluorescent zinc probes are generally constructed based on the mechanisms of photo-induced electron transfer, intra-molecular charge transfer, fluorescence resonance energy transfer, aggregation-induced emission and chelation-enhanced fluorescence. Among these mechanisms, zinc probes constructed on chelation-enhanced fluorescence have the advantages of easy design and synthesis because its fluorophore can simultaneously act as the receptor. In this review, fluorescent zinc probes based on the aforementioned mechanisms, especially, chelation-enhanced fluorescence, reported in recent years are briefly summarized.
2017, 34(12): 1370-1378
doi: 10.11944/j.issn.1000-0518.2017.12.170303
Abstract:
Mitochondria, a cell organelle with a double membrane structure, plays significant roles in cell metabolism, including energy circulation and ions balance. Some small positively charged molecule fluorescent dyes/probes can label mitochondria due to the traction of the mitochondrial inner membrane negative potential, providing an important visual imaging tool for investigation of mitochondrial morphology and function. However, most mitochondrial dyes/probes are unsatisfactory as targeting marker of mitochondria, because the mitochondrial potential is constantly changing, when the potential reduced, the affinity of the dye accordingly decreases. Especially, the mitochondrial membrane potential will be significantly reduced when cell metabolism is blocked in pathological conditions(such as apoptosis), thus cationic dyes will spread away from mitochondria and result in non-specific fluorescence. Recently, the Kim team and our team proposed a new concept of fixed mitochondrial probe, with the active group of fluorescent molecular probe can be fixed in the mitochondria through the covalent bond, and developed a series of fluorescent probes that stably targeted mitochondria for the quantitative detection of microenvironment pH, viscosity, and membrane potential. We believe that the development of immobilized mitochondrial fluorescent molecular probes is an inevitable trend in tracking and detecting mitochondria with highly dynamic characteristics. Therefore, this paper reviews and prospects the fixable fluorescent dyes of mitochondria.
Mitochondria, a cell organelle with a double membrane structure, plays significant roles in cell metabolism, including energy circulation and ions balance. Some small positively charged molecule fluorescent dyes/probes can label mitochondria due to the traction of the mitochondrial inner membrane negative potential, providing an important visual imaging tool for investigation of mitochondrial morphology and function. However, most mitochondrial dyes/probes are unsatisfactory as targeting marker of mitochondria, because the mitochondrial potential is constantly changing, when the potential reduced, the affinity of the dye accordingly decreases. Especially, the mitochondrial membrane potential will be significantly reduced when cell metabolism is blocked in pathological conditions(such as apoptosis), thus cationic dyes will spread away from mitochondria and result in non-specific fluorescence. Recently, the Kim team and our team proposed a new concept of fixed mitochondrial probe, with the active group of fluorescent molecular probe can be fixed in the mitochondria through the covalent bond, and developed a series of fluorescent probes that stably targeted mitochondria for the quantitative detection of microenvironment pH, viscosity, and membrane potential. We believe that the development of immobilized mitochondrial fluorescent molecular probes is an inevitable trend in tracking and detecting mitochondria with highly dynamic characteristics. Therefore, this paper reviews and prospects the fixable fluorescent dyes of mitochondria.
2017, 34(12): 1379-1402
doi: 10.11944/j.issn.1000-0518.2017.12.170304
Abstract:
Photoswitchable fluorescent dithienylethene is one kind of the most typical diarylethene structures. Hydrophilization of photoswitchable fluorescent dithienylethene has become one of the key factors to come true its practical applications as a fluorescence photoswitching probes. Owing to its excellent fatigue resistance and unique thermal bistability, it has been widely studied and applied. This paper reviews the development history of photoswitchable fluorescent thienylethenes, summarizes the mechanism of fluorescence photoswitching mechanisms, describes some important achievements on the foundational research about novel structures and improved properties of photoswitchable fluorescent thienylethene in recent years. We also focus on the systemic overview of the applications of photoswitchable fluorescent dithienylethylene in optical memory, non-destructive read-out, single-molecule fluorescence imaging, bio-imaging, all-optical transistors. In the end, the challenges encountered during the study of diarylethenes are analyzed. It is believable that photoswithcable fluorescent polymers based on dithienylethene is the research direction in the future. Moreover, the promising application of diarylethenes in super-resolution imaging is prospected.
Photoswitchable fluorescent dithienylethene is one kind of the most typical diarylethene structures. Hydrophilization of photoswitchable fluorescent dithienylethene has become one of the key factors to come true its practical applications as a fluorescence photoswitching probes. Owing to its excellent fatigue resistance and unique thermal bistability, it has been widely studied and applied. This paper reviews the development history of photoswitchable fluorescent thienylethenes, summarizes the mechanism of fluorescence photoswitching mechanisms, describes some important achievements on the foundational research about novel structures and improved properties of photoswitchable fluorescent thienylethene in recent years. We also focus on the systemic overview of the applications of photoswitchable fluorescent dithienylethylene in optical memory, non-destructive read-out, single-molecule fluorescence imaging, bio-imaging, all-optical transistors. In the end, the challenges encountered during the study of diarylethenes are analyzed. It is believable that photoswithcable fluorescent polymers based on dithienylethene is the research direction in the future. Moreover, the promising application of diarylethenes in super-resolution imaging is prospected.
2017, 34(12): 1403-1412
doi: 10.11944/j.issn.1000-0518.2017.12.170308
Abstract:
Xanthene dyes are a series of brilliant fluorescent dyes exhibiting superior photophysical properties, which facilitate their applications in various field. Traditionally, they are prepared via acid-catalyzed condensations between electron-rich resorcinol(m-aminophenols) and phthalic anhydride. Recently, structurally complicated xanthenes are often in need for bioimaging applications and not readily accessed with the aforementioned methods. This has promoted the development of novel pathways for their synthesis, which are summarized in this review. The scope and limitations of each methods are briefly discussed.
Xanthene dyes are a series of brilliant fluorescent dyes exhibiting superior photophysical properties, which facilitate their applications in various field. Traditionally, they are prepared via acid-catalyzed condensations between electron-rich resorcinol(m-aminophenols) and phthalic anhydride. Recently, structurally complicated xanthenes are often in need for bioimaging applications and not readily accessed with the aforementioned methods. This has promoted the development of novel pathways for their synthesis, which are summarized in this review. The scope and limitations of each methods are briefly discussed.
2017, 34(12): 1413-1432
doi: 10.11944/j.issn.1000-0518.2017.12.170309
Abstract:
Highly toxic agents, such as phosgene and nerve agents, cause severe threats to public security and humankind. In contrast to traditional ways, the approaches to detect phosgene and nerve agents are expected to be effective detection in vivo. Fluorescent probes have been applied widely in various research fields due to their high selectivity and sensitivity, excellent cell permeability and so on. Herein, we review recent advances relating to fluorescent probes for phosgene and nerve agents and prospect their future developments.
Highly toxic agents, such as phosgene and nerve agents, cause severe threats to public security and humankind. In contrast to traditional ways, the approaches to detect phosgene and nerve agents are expected to be effective detection in vivo. Fluorescent probes have been applied widely in various research fields due to their high selectivity and sensitivity, excellent cell permeability and so on. Herein, we review recent advances relating to fluorescent probes for phosgene and nerve agents and prospect their future developments.
2017, 34(12): 1433-1449
doi: 10.11944/j.issn.1000-0518.2017.12.170327
Abstract:
Due to the unique D-A-D conjugate structure, squaraine dyes possess strong absorption and fluorescence emission in the visible and near infrared regions. As the fluorophore of near infrared fluorescent probes, it has been applied for detection of proteins, amino acids and small biological molecules in vivo, environmental pollutants and so on. In this paper, we reviewed the application of squaraine dyes in the detection of proteins, amino acids, small molecules, cations and other substances according to the work of our group in these years.
Due to the unique D-A-D conjugate structure, squaraine dyes possess strong absorption and fluorescence emission in the visible and near infrared regions. As the fluorophore of near infrared fluorescent probes, it has been applied for detection of proteins, amino acids and small biological molecules in vivo, environmental pollutants and so on. In this paper, we reviewed the application of squaraine dyes in the detection of proteins, amino acids, small molecules, cations and other substances according to the work of our group in these years.
2017, 34(12): 1450-1456
doi: 10.11944/j.issn.1000-0518.2017.12.170319
Abstract:
In the field of biological imaging, two-photon fluorescent dyes with stable optical properties under physiological conditions have broad application prospects. Herein, we designed and synthesized a two-photon fluorescent dye 2-[(1E)-2-[4-(dimethylamino)phenyl]ethenyl]-6-methyl-4(3H)-pyrimidinone(NHP). NHP was obtained by condensation between 2, 4-dismethyl-6-pyrimidinol and 4-dimethylaminobenzaldehyde. The chemical structure and optical properties of NHP was characterized by mass spectrometry(MS), nuclear magnetic resonance spectroscopy(NMR), ultraviolet-visible(UV-Vis) absorption spectra and fluorescence emission spectra method as well as the external environment change effect on the emission spectrum. The results show that the absorption peak of NHP is around 400 nm, and the emission peak of which is around 550 nm. The fluorescence emission of NHP is stable in various pH, ions and amino acids conditions. Furthermore, biological experimental results show that NHP is able to image HepG2/SH-SY5Y cells and Drosophila brains with negligible cytotoxicity. All of those indicate that NHP is an ideal two-photon fluorescence dye for bioimaging.
In the field of biological imaging, two-photon fluorescent dyes with stable optical properties under physiological conditions have broad application prospects. Herein, we designed and synthesized a two-photon fluorescent dye 2-[(1E)-2-[4-(dimethylamino)phenyl]ethenyl]-6-methyl-4(3H)-pyrimidinone(NHP). NHP was obtained by condensation between 2, 4-dismethyl-6-pyrimidinol and 4-dimethylaminobenzaldehyde. The chemical structure and optical properties of NHP was characterized by mass spectrometry(MS), nuclear magnetic resonance spectroscopy(NMR), ultraviolet-visible(UV-Vis) absorption spectra and fluorescence emission spectra method as well as the external environment change effect on the emission spectrum. The results show that the absorption peak of NHP is around 400 nm, and the emission peak of which is around 550 nm. The fluorescence emission of NHP is stable in various pH, ions and amino acids conditions. Furthermore, biological experimental results show that NHP is able to image HepG2/SH-SY5Y cells and Drosophila brains with negligible cytotoxicity. All of those indicate that NHP is an ideal two-photon fluorescence dye for bioimaging.
2017, 34(12): 1457-1461
doi: 10.11944/j.issn.1000-0518.2017.12.170311
Abstract:
Hypochlorous acid(HClO) is one of the biologically important reactive oxygen species(ROS), which plays important roles in the human immune defence system, and contributes to the destruction of invading bacteria and pathogens. Here, a novel ratiometric probe for detection of hypochlorite was designed and developed based on the coumarin. The sensor shows excellent selectivity, high sensitivity(12 nmol/L) and a rapid response(within 5 s) toward hypochlorite, accompanied with an obvious color change from colorless to yellow. Other anions and ROS all triggers very minor changes. Furthermore, the sensing mechanism was confirmed by electrospray ionization-mass spectrometry(ESI-MS) and spectrometry analysis, which was based on the strong oxidized by HClO/ClO-, then hydrolyzed to generate fluorescent compound.
Hypochlorous acid(HClO) is one of the biologically important reactive oxygen species(ROS), which plays important roles in the human immune defence system, and contributes to the destruction of invading bacteria and pathogens. Here, a novel ratiometric probe for detection of hypochlorite was designed and developed based on the coumarin. The sensor shows excellent selectivity, high sensitivity(12 nmol/L) and a rapid response(within 5 s) toward hypochlorite, accompanied with an obvious color change from colorless to yellow. Other anions and ROS all triggers very minor changes. Furthermore, the sensing mechanism was confirmed by electrospray ionization-mass spectrometry(ESI-MS) and spectrometry analysis, which was based on the strong oxidized by HClO/ClO-, then hydrolyzed to generate fluorescent compound.
2017, 34(12): 1462-1467
doi: 10.11944/j.issn.1000-0518.2017.12.170316
Abstract:
Hypochlorite(ClO-) displays essential roles in human immune system, the detection of which has aroused extensive attention. Herein, a hydrazone type fluorescent probe(HEMQ) that containing quinazolinone skeleton was designed and synthesized, and the structure of HEMQ was characterized by 1H NMR, 13C NMR, and HRMS analysis. In V(ethanol):V(water)=1:1(c(PBS)=0.02 mol/L, pH=8.7) solution, probe HEMQ exhibits rapid response and good selectivity toward ClO- through distinct fluorescence quenching. HEMQ displays good sensitivity to ClO- with a detection limit of 1.0×10-4 mol/L. In addition, ClO- can induce a color change from yellow to colorless of the probe solution, thus, probe HEMQ can act as a colorimetric and florescent dual-channel ClO- probe.
Hypochlorite(ClO-) displays essential roles in human immune system, the detection of which has aroused extensive attention. Herein, a hydrazone type fluorescent probe(HEMQ) that containing quinazolinone skeleton was designed and synthesized, and the structure of HEMQ was characterized by 1H NMR, 13C NMR, and HRMS analysis. In V(ethanol):V(water)=1:1(c(PBS)=0.02 mol/L, pH=8.7) solution, probe HEMQ exhibits rapid response and good selectivity toward ClO- through distinct fluorescence quenching. HEMQ displays good sensitivity to ClO- with a detection limit of 1.0×10-4 mol/L. In addition, ClO- can induce a color change from yellow to colorless of the probe solution, thus, probe HEMQ can act as a colorimetric and florescent dual-channel ClO- probe.
2017, 34(12): 1468-1473
doi: 10.11944/j.issn.1000-0518.2017.12.170294
Abstract:
Molecular spectroscopy has the advantages of high sensitivity and simple operation. Therefore, it is significant to develop a probe with high selectivity for nickel ions(Ni2+). In this paper, a novel molecular probe was designed and synthesized from rhodamine B, hydrazine hydrate and 2-acetylpyrazine for the detection of Ni2+ with excellent selectivity in aqueous media. Simultaneously, the probe rhodamine B amide derivative(RWZ) can achieve "naked eye" recognition of Ni2+ in aqueous solution. Furthermore, the probe shows high sensitivity to Ni2+ with low limit of detection(0.5 μmol/L), indicating that the probe can be used for detection of Ni2+ in aqueous solution.
Molecular spectroscopy has the advantages of high sensitivity and simple operation. Therefore, it is significant to develop a probe with high selectivity for nickel ions(Ni2+). In this paper, a novel molecular probe was designed and synthesized from rhodamine B, hydrazine hydrate and 2-acetylpyrazine for the detection of Ni2+ with excellent selectivity in aqueous media. Simultaneously, the probe rhodamine B amide derivative(RWZ) can achieve "naked eye" recognition of Ni2+ in aqueous solution. Furthermore, the probe shows high sensitivity to Ni2+ with low limit of detection(0.5 μmol/L), indicating that the probe can be used for detection of Ni2+ in aqueous solution.
2017, 34(12): 1474-1480
doi: 10.11944/j.issn.1000-0518.2017.12.170156
Abstract:
4-(Diethylamino)butyl substituted trimethylthiazole orange(DEAB-TO3) is essentially nonfluorescent in aqueous solution, which can be used to detect nucleic acids in cells. The spectroscopic properties of 4-(two ethyl amino) butyl substituted methyl thiazole orange(DEAB-TO1) and DEAB-TO3 were studied by density functional theory method. The geometry optimization of the ground state and the excited state reveal highly distorted configuration of the excited state. Spectral analysis and orbital analysis show that the first excited state is a dark state with twisted intermolecular charge transfer. The ground state and the excited state potential energy curves show that DEAB-TO1 and DEAB-TO3 have very low energy gap and rotational energy barrier. These results explain their low background fluorescence.
4-(Diethylamino)butyl substituted trimethylthiazole orange(DEAB-TO3) is essentially nonfluorescent in aqueous solution, which can be used to detect nucleic acids in cells. The spectroscopic properties of 4-(two ethyl amino) butyl substituted methyl thiazole orange(DEAB-TO1) and DEAB-TO3 were studied by density functional theory method. The geometry optimization of the ground state and the excited state reveal highly distorted configuration of the excited state. Spectral analysis and orbital analysis show that the first excited state is a dark state with twisted intermolecular charge transfer. The ground state and the excited state potential energy curves show that DEAB-TO1 and DEAB-TO3 have very low energy gap and rotational energy barrier. These results explain their low background fluorescence.
