Co-reporter:Zhichao Dai, Lu Tian, Yunna Xiao, Zhiqiang Ye, Run Zhang and Jingli Yuan
Journal of Materials Chemistry A 2013 vol. 1(Issue 7) pp:924-927
Publication Date(Web):08 Jan 2013
DOI:10.1039/C2TB00350C
A unique cell-membrane-permeable europium complex has been developed as a probe for time-gated luminescence detection of singlet oxygen (1O2). Combined with the time-gated luminescence imaging technique, the probe was successfully used for investigating the time-dependent generation and distribution of 1O2 induced by the clinical drugs of photodynamic therapy in cancer cells.
Co-reporter:Mingjing Liu, Zhiqiang Ye, Chenglong Xin, Jingli Yuan
Analytica Chimica Acta 2013 Volume 761() pp:149-156
Publication Date(Web):25 January 2013
DOI:10.1016/j.aca.2012.11.025
Time-resolved luminescence bioassay technique using lanthanide complexes as luminescent probes/sensors has shown great utilities in clinical diagnostics and biotechnology discoveries. In this work, a novel terpyridine polyacid derivative that can form highly stable complexes with lanthanide ions in aqueous media, (4′-hydroxy-2,2′:6′,2′′-terpyridine-6,6′′-diyl) bis(methylenenitrilo) tetrakis(acetic acid) (HTTA), was designed and synthesized for developing time-resolved luminescence pH sensors based on its Eu3+ and Tb3+ complexes. The luminescence characterization results reveal that the luminescence intensity of HTTA–Eu3+ is strongly dependent on the pH values in weakly acidic to neutral media (pKa = 5.8, pH 4.8–7.5), while that of HTTA–Tb3+ is pH-independent. This unique luminescence response allows the mixture of HTTA–Eu3+ and HTTA–Tb3+ (the HTTA–Eu3+/Tb3+ mixture) to be used as a ratiometric luminescence sensor for the time-resolved luminescence detection of pH with the intensity ratio of its Tb3+ emission at 540 nm to its Eu3+ emission at 610 nm, I540 nm/I610 nm, as a signal. Moreover, the UV absorption spectrum changes of the HTTA–Eu3+/Tb3+ mixture at different pHs (pH 4.0–7.0) also display a ratiometric response to the pH changes with the ratio of absorbance at 290 nm to that at 325 nm, A290 nm/A325 nm, as a signal. This feature enables the HTTA–Eu3+/Tb3+ mixture to have an additional function for the pH detection with the absorption spectrometry technique. For loading the complexes into the living cells, the acetoxymethyl ester of HTTA was synthesized and used for loading HTTA–Eu3+ and HTTA–Tb3+ into the cultured HeLa cells. The luminescence imaging results demonstrated the practical utility of the new sensor for the time-resolved luminescence cell imaging application.Graphical abstractHighlights► A lanthanide complex-based ratiometric luminescent pH sensor was developed. ► The sensor can luminously respond to pH in weakly acidic to neutral media. ► The sensor can be used for monitoring pH with time-resolved luminescence mode. ► The sensor can be also used for monitoring pH with absorbance mode. ► The utility of the sensor for the luminescent cell imaging was demonstrated.
Co-reporter:Xiaojing Yu;Run Zhang;Bo Song;Jingli Yuan
Journal of Fluorescence 2013 Volume 23( Issue 6) pp:1113-1120
Publication Date(Web):2013 November
DOI:10.1007/s10895-013-1240-8
Nitric oxide (NO) is one of the most important intercellular signaling molecules, and plays important roles in various biological systems. In this work, a unique RuII complex, tris[(5-(4-methylamino-3-aminobenzylamino)-1,10-phenanthroline)] ruthenium(II) hexafluorophosphate [Ru(MAA-phen)3][PF6]2, has been designed and synthesized as a luminescent probe for the detection of NO in aqueous media. The complex itself is almost non-luminescent, but can specifically react with NO under the aerobic conditions to afford its highly luminescent triazole derivative in aqueous media, [Ru(MTA-phen)3]2+ (MTA-phen: methyl-trazolebenzylamino-1,10-phenanthroline), accompanied by a 302-fold increase in luminescence intensity at 598 nm with a 130 nm Stokes shift. The luminescence response of [Ru(MAA-phen)3]2+ to NO is rapid, highly specific without interferences of other reactive oxygen/nitrogen species, and highly stable against the pH changes in the range of pH 4.5–9.5. These features enable [Ru(MAA-phen)3]2+ to be used as a probe for the highly selective and sensitive luminescence detection of NO in weakly acidic, neutral, and weakly basic media.
Co-reporter:Lin Zhang, Lu Tian, Zhiqiang Ye, Bo Song, Jingli Yuan
Talanta 2013 Volume 108() pp:143-149
Publication Date(Web):15 April 2013
DOI:10.1016/j.talanta.2013.02.065
By using a visible-light-excited ternary Eu3+ complex, BHHBCB-Eu3+-BPT (BHHBCB: 1,2-bis[4′-(1“,1“,1“,2“,2“,3“,3“-heptafluoro-4″,6″-hexanedion-6″-yl)-benzyl]-4-chlorosulfobenzene; BPT: 2-(N,N-diethylanilin-4-yl)-4,6-bis(pyrazol-1-yl)-1,3,5-triazine), as a luminophore, two kinds of novel visible-light-excited europium materials, the silica-encapsulated BHHBCB-Eu3+-BPT (Eu@SiO2) nanoparticles and BHHBCB-Eu3+-BPT-conjugated bovine serum albumin (BSA–BHHBCB-Eu3+-BPT), were prepared for biolabeling and time-resolved luminescence cell imaging applications. The Eu@SiO2 nanoparticles, prepared by the copolymerization of 3-aminopropyl(triethoxy)silane–BHHBCB-Eu3+-BPT conjugate, free 3-aminopropyl(triethoxy) silane and tetraethyl orthosilicate in a water-in-oil reverse microemulsion, are monodispersed, spherical and uniform in size, and strongly luminescent with an excitation peak at ∼400 nm and a long luminescence lifetime of 346 μs. The BSA–BHHBCB-Eu3+-BPT, prepared by covalent binding of BHHBCB-Eu3+-BPT to BSA, shows also strong visible-light-excited luminescence with a excitation peak at ∼400 nm and a long luminescence lifetime of 402 μs. The two materials were used for labeling transferrin and folic acid. Using the time-resolved luminescence imaging of living HeLa cells, the cell-surface receptors of transferrin and folic acid were successfully visualized by the prepared biolabels based on the ligand–receptor affinity binding interaction. The results demonstrated the feasibility of the new materials as visible-light-excited biolabels for the time-resolved luminescence cell imaging.Highlights► Two kinds of new visible-light-excited europium biolabels have been prepared. ► The labels are highly luminescent with long luminescence lifetimes. ► The labels were used for labeling transferrin and folic acid. ► Two labeled biomarkers were used for imaging HeLa cells with time-resolved mode. ► The cell-surface receptors of two biomarkers were successfully visualized.
Co-reporter:Run Zhang, Bo Song, Zhichao Dai, Zhiqiang Ye, Yunna Xiao, Yan Liu, Jingli Yuan
Biosensors and Bioelectronics 2013 50() pp: 1-7
Publication Date(Web):
DOI:10.1016/j.bios.2013.06.005
Co-reporter:Lu Tian, Zhichao Dai, Lin Zhang, Ruoyu Zhang, Zhiqiang Ye, Jing Wu, Dayong Jin and Jingli Yuan
Nanoscale 2012 vol. 4(Issue 11) pp:3551-3557
Publication Date(Web):18 Apr 2012
DOI:10.1039/C2NR30233K
Silica-encapsulated luminescent lanthanide nanoparticles have shown great potential as biolabels for various time-gated luminescence bio-detections in recent years. The main problem of these nano-biolabels is their short excitation wavelengths within the UV region. In this work, a new type of silica-encapsulated luminescent europium nanoparticle, with a wide excitation range from UV to visible light in aqueous solutions, has been prepared using a conjugate of (3-isocyanatopropyl)triethoxysilane bound to a visible light-excited Eu3+ complex, 2,6-bis(1′,1′,1′,2′,2′,3′,3′-heptafluoro-4′,6′-hexanedion-6′-yl)-dibenzothiophene–Eu3+-2-(N,N-diethylanilin-4-yl)-4,6-bis(pyrazol-1-yl)-1,3,5-triazine (IPTES–BHHD–Eu3+–BPT conjugate), as a functionalized precursor. The nanoparticles, which are prepared by the copolymerization of the IPTES–BHHD–Eu3+–BPT conjugate, tetraethyl orthosilicate and (3-aminopropyl)triethoxysilane in a water-in-oil reverse microemulsion consisting of Triton X-100, n-octanol, cyclohexane and water in the presence of aqueous ammonia, are monodisperse, spherical and uniform in size. Their diameter is 42 ± 3 nm and they are strongly luminescent with a wide excitation range from UV to ∼475 nm and a long luminescence lifetime of 346 μs. The nanoparticles were successfully used for streptavidin labeling and the time-gated luminescence imaging detection of two environmental pathogens, cryptosporidium muris and cryptosporidium parvium, in water samples. The results demonstrated the practical utility of the new nanoparticles as visible light-excited biolabels for time-gated luminescence bioassay applications.
Co-reporter:Yunna Xiao, Run Zhang, Zhiqiang Ye, Zhichao Dai, Huaying An, and Jingli Yuan
Analytical Chemistry 2012 Volume 84(Issue 24) pp:10785
Publication Date(Web):November 28, 2012
DOI:10.1021/ac3028189
Two novel lanthanide complex-based luminescent probes, ANMTTA-Eu3+ and ANMTTA-Tb3+ {ANMTTA, [4′-(4-amino-3-nitrophenoxy)methylene-2,2′:6′,2″-terpyridine-6,6″-diyl] bis(methylenenitrilo) tetrakis(acetic acid)}, have been designed and synthesized for the highly sensitive and selective time-gated luminescence detection of hypochlorous acid (HOCl) in aqueous media. The probes are almost nonluminescent due to the photoinduced electron transfer (PET) process from the 4-amino-3-nitrophenyl moiety to the terpyridine-Ln3+ moiety, which quenches the lanthanide luminescence effectively. Upon reaction with HOCl, the 4-amino-3-nitrophenyl moiety is rapidly cleaved from the probe complexes, which affords strongly luminescent lanthanide complexes HTTA-Eu3+ and HTTA-Tb3+ {HTTA, (4′-hydroxymethyl-2,2′:6′,2″-terpyridine-6,6″-diyl) bis(methylenenitrilo) tetrakis(acetic acid)}, accompanied by the remarkable luminescence enhancements. The dose-dependent luminescence enhancements show good linearity with detection limits of 1.3 nM and 0.64 nM for HOCl with ANMTTA-Eu3+ and ANMTTA-Tb3+, respectively. In addition, the luminescence responses of ANMTTA-Eu3+ and ANMTTA-Tb3+ to HOCl are pH-independent with excellent selectivity to distinguish HOCl from other reactive oxygen/nitrogen species (ROS/RNS). The ANMTTA-Ln3+-loaded HeLa and RAW 264.7 macrophage cells were prepared, and then the exogenous HOCl in HeLa cells and endogenous HOCl in macrophage cells were successfully imaged with time-gated luminescence mode. The results demonstrated the practical applicability of the probes for the cell imaging application.
Co-reporter:Yunna Xiao ; Zhiqiang Ye ; Guilan Wang ;Jingli Yuan
Inorganic Chemistry 2012 Volume 51(Issue 5) pp:2940-2946
Publication Date(Web):February 22, 2012
DOI:10.1021/ic202195a
Reactive oxygen species (ROS) are important mediators in a variety of pathological events, but the oxidative stress owing to excessive generation of ROS is implicated in many human diseases. In this work, we designed and synthesized a novel dual-functional chelating ligand, [4′-(p-aminophenoxy)methylene-2,2′:6′,2″-terpyridine-6,6″-diyl]bis(methylenenitrilo)tetrakis(acetic acid) (AMTTA), that can strongly coordinate with both Eu3+ and Tb3+ in aqueous solutions for the recognition and time-gated luminescence detection of highly ROS (hROS), hydroxyl radical (•OH), and hypochlorite (ClO–). The complexes AMTTA-Ln3+ (Ln = Eu and Tb) are almost nonluminescent because of the photoinduced electron transfer from the electron-rich aminophenyl group to the terpyridine-Ln3+ moiety but can rapidly react with hROS to afford highly luminescent complexes (4′-hydroxymethyl-2,2′:6′,2″-terpyridine-6,6″-diyl)bis(methylenenitrilo)tetrakis(acetate)-Ln3+ (HTTA-Ln3+). Interestingly, when the AMTTA-Eu3+/Tb3+ mixture (AMTTA/Eu3+/Tb3+ = 2/1/1) was reacted with hROS, the intensity ratio of its Tb3+ emission at 540 nm to its Eu3+ emission at 610 nm, I540/I610, showed a ratiometric response toward hROS, and the dose-dependent increase of the ratio displayed a double-exponential correlation to the concentration of hROS. This unique luminescence response allowed the AMTTA-Eu3+/Tb3+ mixture to be used as a ratiometric probe for the time-gated luminescence detection of hROS.
Co-reporter:Run Zhang, Zhiqiang Ye, Yuejiao Yin, Guilan Wang, Dayong Jin, Jingli Yuan, and James A. Piper
Bioconjugate Chemistry 2012 Volume 23(Issue 4) pp:725
Publication Date(Web):March 21, 2012
DOI:10.1021/bc200506w
Ruthenium(II) complexes have rich photophysical attributes, which enable novel design of responsive luminescence probes to selectively quantify biochemical analytes. In this work, we developed a systematic series of Ru(II)-bipyrindine complex derivatives, [Ru(bpy)3-n(DNP-bpy)n](PF6)2 (n = 1, 2, 3; bpy, 2,2′-bipyridine; DNP-bpy, 4-(4-(2,4-dinitrophenoxy)phenyl)-2,2′-bipyridine), as luminescent probes for highly selective and sensitive detection of thiophenol in aqueous solutions. The specific reaction between the probes and thiophenol triggers the cleavage of the electron acceptor group, 2,4-dinitrophenyl, eliminating the photoinduced electron transfer (PET) process, so that the luminescence of on-state complexes, [Ru(bpy)3-n(HP-bpy)n]2+ (n = 1, 2, 3; HP-bpy, 4-(4-hydroxyphenyl)-2,2′-bipyridine), is turned on. We found that the complex [Ru(bpy)(DNP-bpy)2]2+ remarkably enhanced the on-to-off contrast ratio compared to the other two (37.8 compared to 21 and 18.7). This reveals a new strategy to obtain the best Ru(II) complex luminescence probe via the most asymmetric structure. Moreover, we demonstrated the practical utility of the complex as a cell-membrane permeable probe for quantitative luminescence imaging of the dynamic intracellular process of thiophenol in living cells. The results suggest that the new probe could be a very useful tool for luminescence imaging analysis of the toxic thiophenol in intact cells.
Co-reporter:Lin Zhang, Yanjiao Wang, Zhiqiang Ye, Dayong Jin, and Jingli Yuan
Bioconjugate Chemistry 2012 Volume 23(Issue 6) pp:1244
Publication Date(Web):May 31, 2012
DOI:10.1021/bc300075t
Luminescent lanthanide complexes that can be covalently bound to proteins have shown great utility as biolabels for highly sensitive time-gated luminescence bioassays in clinical diagnostics and biotechnology discoveries. In this work, three new tetradentate β-diketonate–europium complexes that can be covalently bound to proteins to display strong and long-lived Eu3+ luminescence, 1,2-bis[4′-(1″,1″,1″,2″,2″,3″,3″-heptafluoro-4″,6″-hexanedion-6″-yl)-benzyl]-4-chlorosulfobenzene-Eu3+ (BHHBCB-Eu3+), 1,2-bis[4′-(1″,1″,1″,2″,2″-pentafluoro-3″,5″-pentanedion-5″-yl)-benzyl]-4-chlorosulfobenzene-Eu3+ (BPPBCB-Eu3+), and 1,2-bis[4′-(1″,1″,1″-trifluoro-2″,4″-butanedion-4″-yl)-benzyl]-4-chlorosulfobenzene-Eu3+ (BTBBCB-Eu3+), have been designed and synthesized as biolabels for time-gated luminescence bioassay applications. The luminescence spectroscopy characterizations of the aqueous solutions of three complex-bound bovine serum albumin reveal that BHHBCB-Eu3+ has the strongest luminescence with the largest quantum yield (40%) and longest luminescence lifetime (0.52 ms) among the complexes, which is superior to the other currently available europium biolabels. The BHHBCB-Eu3+-labeled streptavidin was prepared and used for both the time-gated luminescence immunoassay of human prostate specific antigen and the time-gated luminescence microscopy imaging of a pathogenic microorganism Cryptosporidium muris. The results demonstrated the practical utility of the new Eu3+ complex-based biolabel for time-gated luminescence bioassay applications.
Co-reporter:Hui Zhang, Lu Tian, Ruoyu Zhang, Zhiqiang Ye and Jingli Yuan
Analyst 2012 vol. 137(Issue 19) pp:4502-4508
Publication Date(Web):23 Jul 2012
DOI:10.1039/C2AN35719D
Dissociation enhanced lanthanide fluoroimmunoassay (DELFIA) technique based on EDTA-Eu3+ derivative biolabels is the most widely used time-resolved luminescence bioassay technique for clinical diagnosis, but its major drawback is that the conventional luminescence enhancement solution of EDTA-Eu3+ requires UV excitation (<360 nm). In this work, three new visible-light-excited luminescence enhancement solutions are developed and their luminescence response behaviors to EDTA-Eu3+ are systematically investigated. The new solutions were prepared by co-dissolving a newly synthesized tetradentate β-diketone, 1,2-bis[8′-(1′′,1′′,1′′,2′′,2′′,3′′,3′′-heptafluoro-4′′,6′′-hexanedion-6′′-yl)-naphth-2′-yl]-benzene (BHHNB), and one of three derivatives of triazine, 2-(N,N-diethylanilin-4-yl)-4,6-bis(3,5-dimethylpyrazol-1-yl)-1,3,5-triazine (DPBT), 2-(N,N-diethylanilin-4-yl)-4,6-bis(3-methylpyrazol-1-yl)-1,3,5-triazine (MPBT) or 2-(N,N-diethylanilin-4-yl)-4,6-bis(pyrazol-1-yl)-1,3,5-triazine (BPT), in a weakly acidic aqueous buffer at pH 3.2 containing 0.1% Triton X-100. These solutions showed sensitive and rapid luminescence responses to non-luminescent EDTA-Eu3+ by the formation of the ternary Eu3+ complexes, BHHNB-Eu3+–DPBT, BHHNB-Eu3+–MPBT and BHHNB-Eu3+–BPT. These complexes have long luminescence lifetimes (>500 μs) and a wide excitation wavelength range from UV to visible light with the excitation peaks at 390, 400 and 420 nm, respectively, which enabled the solutions to be used as visible-light-excited luminescence enhancement solutions for the highly sensitive time-resolved luminescence detection of EDTA-Eu3+.
Co-reporter:Mingjing Liu, Zhiqiang Ye, Guilan Wang, Jingli Yuan
Talanta 2012 Volume 91() pp:116-121
Publication Date(Web):15 March 2012
DOI:10.1016/j.talanta.2012.01.028
A new europium(III) complex with a borono-substituted terpyridine polyacid ligand, (4′-borono-2,2′:6′,2″-terpyridine-6,6″-diyl) bis(methylenenitrilo) tetrakis(acetate)-Eu3+ (BTTA-Eu3+), has been designed and synthesized as a luminescence probe for hydrogen peroxide (H2O2). The complex is highly luminescent in aqueous buffers to display a typical Eu3+ emission pattern with a sharp emission peak at 610 nm and a long luminescence lifetime of 1.34 ms. Upon reaction with H2O2, the deboronation derivative of BTTA-Eu3+, (4′-hydroxy-2,2′:6′,2″-terpyridine-6,6″-diyl) bis(methylenenitrilo) tetrakis(acetate)-Eu3+ (HTTA-Eu3+), can be generated. It was found that the luminescence of BTTA-Eu3+ was pH-insensitive, whereas that of HTTA-Eu3+ was pH-dependent and could be remarkably weakened in neutral and basic buffers, which allowed BTTA-Eu3+ to be a luminescence probe for the time-gated luminescence detection of H2O2 in neutral and basic buffers. The H2O2–BTTA-Eu3+ system was applied to monitor the kinetics of the palladium-catalyzed Suzuki cross-coupling reaction between BTTA-Eu3+ and bromobenzene, which suggested a useful strategy for the application of time-gated luminescence technique in catalysis reaction researches.Highlights► A new europium(III) complex has been synthesized as a luminescence probe for H2O2. ► The complex is highly luminescent in buffers with a long luminescence lifetime. ► Upon reaction with H2O2, the complex's luminescence can be selectively quenched. ► The probe was used to monitor the kinetics of the Suzuki cross-coupling reaction.
Co-reporter:Yonggang Chen, Weihua Guo, Zhiqiang Ye, Guilan Wang and Jingli Yuan
Chemical Communications 2011 vol. 47(Issue 22) pp:6266-6268
Publication Date(Web):06 May 2011
DOI:10.1039/C0CC05658H
The first Eu3+ chelate-based luminescent probe specific for nitric oxide (NO) has been designed and synthesized for highly sensitive and selective time-gated luminescence detection of NO. Based on the probe, a time-gated luminescence imaging technique was developed for imaging the endogenous NO production in living plant cells/tissues.
Co-reporter:Zhiqiang Ye, Jinxue Chen, Guilan Wang, and Jingli Yuan
Analytical Chemistry 2011 Volume 83(Issue 11) pp:4163
Publication Date(Web):May 6, 2011
DOI:10.1021/ac200438g
A highly sensitive Tb3+ complex-based luminescent probe, N,N,N1,N1-[2,6-(3′- aminomethyl-1′-pyrazolyl)-4-(3′′,4′′-diaminophenoxy)methylene-pyridine] tetrakis(acetate)-Tb3+ (BMTA-Tb3+), has been designed and synthesized for the recognition and detection of hydrogen peroxide (H2O2) in aqueous solutions. This probe is almost nonluminescent because the Tb3+ luminescence is effectively quenched by the electron-rich moiety, diaminophenyl, on the basis of the photoinduced electron transfer (PET) mechanism. In the presence of peroxidase, the probe can react with H2O2 to cause the cleavage of the diaminophenyl ether, which affords a highly luminescent Tb3+ complex, N,N,N1,N1-[2,6-bis(3′-aminomethyl-1′-pyrazolyl)-4-hydroxymethyl-pyridine] tetrakis(acetate)-Tb3+ (BHTA-Tb3+), accompanied by a 39-fold increase in luminescence quantum yield with the increase of luminescence lifetime from 1.95 to 2.76 ms. The dose-dependent luminescence enhancement of the probe shows a good linearity with a detection limit of 3.7 nM for H2O2, which is approximately 14-fold lower than those of the commonly used fluorescent probes. The probe was used for the time-resolved luminescence imaging detection of the oligosaccharide-induced H2O2 generation in tobacco leaf epidermal tissues. On the basis of the probe, a background-free time-resolved luminescence imaging method for detecting H2O2 in complicated biological systems was successfully established.
Co-reporter:Run Zhang, Xiaojing Yu, Yuejiao Yin, Zhiqiang Ye, Guilan Wang, Jingli Yuan
Analytica Chimica Acta 2011 Volume 691(1–2) pp:83-88
Publication Date(Web):8 April 2011
DOI:10.1016/j.aca.2011.02.051
A heterobimetallic ruthenium(II)–copper(II) complex-based luminescent chemosensor, [Ru(bpy)2(bpy-DPA)Cu]4+ (bpy: 2,2′-bipyridine; bpy-DAP: 4-methyl-4′-[N,N-bis(2-picolyl)amino-methylene]-2,2′-bipydine), has been designed and synthesized for the highly selective and sensitive recognition and detection of sulfide anions in 100% aqueous solutions. Owing to the high affinity of sulfide to Cu(II), the non-luminescent chemosensor can specifically and rapidly react with sulfide to yield the corresponding ruthenium(II) complex, [Ru(bpy)2(bpy-DPA)]2+, accompanied by the remarkable luminescence enhancement. The dose-dependent luminescence enhancement of the sensor shows a good linearity with a detection limit of 20.7 nM for sulfide anions. The novel luminescence sensor has a widely available pH range from 4.5 to 10 and an excellent response selectivity to sulfide only even in the presence of various other anions. Based on this chemosensor, a rapid, selective and sensitive luminescence method for the detection of sulfide anions in wastewater samples was established. The coefficient variations (CVs) of the method are less than 3.1%, and the recoveries are in the range of 90.9–108.5%.
Co-reporter:Guanfeng Cui, Zhiqiang Ye, Jinxue Chen, Guilan Wang, Jingli Yuan
Talanta 2011 Volume 84(Issue 3) pp:971-976
Publication Date(Web):15 May 2011
DOI:10.1016/j.talanta.2011.02.051
Time-resolved (or time-gated) luminescence detection technique using lanthanide chelates as luminescent probes is a widely used and highly sensitive method for the biological applications. The developments of various functional lanthanide probes that can selectively recognize the biological targets are the essential objective of the technique. In this work, a unique Tb3+ chelate-based luminescent probe, N,N,N1,N1-[2,6-bis(3′-aminomethyl-1′-pyrazolyl)-4-(p-aminophenoxy)methylene-pyridine] tetrakis(acetate)-Tb3+(BMPTA-Tb3+), has been designed and synthesized for highly selective and sensitive time-resolved luminescence detection of one highly reactive oxygen species (ROS), hydroxyl radical (OH). The probe is almost non-luminescent, and can selectively react with hydroxyl radical to afford a highly luminescent Tb3+ chelate, N,N,N1,N1-[2,6-bis(3′-aminomethyl-1′-pyrazolyl)-4-hydroxymethyl-pyridine] tetrakis(acetate)-Tb3+ (BHTA-Tb3+), accompanied by a 49-fold increase in luminescence quantum yield with a long luminescence lifetime (2.76 ms). The luminescence response of the probe to hydroxyl radical is highly selective and insensitive to pH in the physiological pH range. For loading the probe into the living cells, the acetoxymethyl ester of BMPTA-Tb3+ was synthesized and used for the HeLa cell loading. Based on this probe, a background-free time-resolved luminescence imaging method for detecting hydroxyl radical in living cells was successfully established.
Co-reporter:Lina Jiang, Jing Wu, Guilan Wang, Zhiqiang Ye, Wenzhu Zhang, Dayong Jin, Jingli Yuan and James Piper
Analytical Chemistry 2010 Volume 82(Issue 6) pp:2529
Publication Date(Web):February 12, 2010
DOI:10.1021/ac100021m
The time-resolved luminescence bioassay technique using luminescent lanthanide complexes as labels is a highly sensitive and widely used bioassay method for clinical diagnostics and biotechnology. A major drawback of the current technique is that the luminescent lanthanide labels require UV excitation (typically less than 360 nm), which can damage living biological systems and is holding back further development of time-resolved luminescence instruments. Herein we describe two approaches for preparing a visible-light-sensitized Eu3+ complex in aqueous media for time-resolved fluorometric applications: a dissociation enhancement aqueous solution that can be excited by visible light for ethylenediaminetetraacetate (EDTA)−Eu3+ detection and a visible-light-sensitized water-soluble Eu3+ complex conjugated bovine serum albumin (BSA) for biolabeling and time-resolved luminescence bioimaging. In the first approach, a weakly acidic aqueous solution consisting of 4,4′-bis(1′′,1′′,1′′,2′′,2′′,3′′,3′′-heptafluoro-4′′,6′′-hexanedion-6′′-yl)-o-terphenyl (BHHT), 2-(N,N-diethylanilin-4-yl)-4,6-bis(3,5-dimethylpyrazol-1-yl)-1,3,5-triazine (DPBT), and Triton X-100 was prepared. This solution shows a strong luminescence enhancement effect for EDTA−Eu3+ with a wide excitation wavelength range from UV to visible light (a maximum at 387 nm) and a long luminescence lifetime (520 μs), to provide a novel dissociation enhancement solution for time-resolved luminescence detection of EDTA−Eu3+. In the second approach, a ternary Eu3+ complex, 4,4′-bis(1′′,1′′,1′′,2′′,2′′,3′′,3′′-heptafluoro-4′′,6′′-hexanedion-6′′-yl)-chlorosulfo-o-terphenyl (BHHCT)−Eu3+−DPBT, was covalently bound to BSA to form a water-soluble BSA−BHHCT−Eu3+−DPBT conjugate. This biocompatible conjugate is of the visible-light excitable feature in aqueous media with a wide excitation wavelength range from UV to visible light (a maximum at 387 nm), a long luminescence lifetime (460 μs), and a higher quantum yield (27%). The conjugate was successfully used for streptavidin (SA) labeling and time-resolved luminescence imaging detection of three environmental pathogens, Giardia lamblia, Cryptosporidium muris, and Cryptosporidium parvum, in water samples. Our strategy gives a general idea for designing a visible-light-sensitized Eu3+ complex for time-resolved luminescence bioassay applications.
Co-reporter:Run Zhang, Xiaojing Yu, Zhiqiang Ye, Guilan Wang, Wenzhu Zhang and Jingli Yuan
Inorganic Chemistry 2010 Volume 49(Issue 17) pp:7898-7903
Publication Date(Web):August 2, 2010
DOI:10.1021/ic100810z
A unique ruthenium(II) complex, tris(4-methyl-2,2′-bipyridyl-4′-carboxaldehyde)Ru(II) hexafluorophosphate [Ru(CHO-bpy)3](PF6)2, has been designed and synthesized as a highly sensitive and selective luminescence probe for the recognition and detection of cysteine (Cys) and homocysteine (Hcy). The almost non-luminescent probe can rapidly react with Cys and Hcy to yield the corresponding thiazolidine and thiazinane derivatives, accompanied by the remarkable luminescence enhancement and a large blue-shift of the maximum emission wavelength from 720 to 635 nm. The dose-dependent luminescence enhancement of the probe shows a good linearity in the Cys/Hcy concentration range of 15 to 180 μM with the detection limits of 1.41 μM and 1.19 μM for Cys and Hcy, respectively. Furthermore, the luminescence response of the probe is highly specific to Cys/Hcy only even in the presence of various amino acids, protein, and DNA. The results of this work not only demonstrate the efficacy and advantages of the Ru(II) complex-based luminescence probe for the sensitive and selective detection of Cys/Hcy but also provide a useful strategy for the rational design of Ru(II) complex-based luminescence probes for various biological molecules.
Co-reporter:Run Zhang, Dr.;Guilan Wang ;Wenzhu Zhang Dr. ;Jingli Yuan
Chemistry - A European Journal 2010 Volume 16( Issue 23) pp:6884-6891
Publication Date(Web):
DOI:10.1002/chem.200903267
Abstract
A unique ruthenium(II) complex, bis(2,2′-bipyridine)(4-(3,4-diaminophenoxy)-2,2′-bipyridine)ruthenium(II) hexafluorophosphate ([(Ru(bpy)2(dabpy)][PF6]2), has been designed and synthesized as a highly sensitive and selective luminescence probe for the imaging of nitric oxide (NO) production in living cells. The complex can specifically react with NO in aqueous buffers under aerobic conditions to yield its triazole derivative with a high reaction rate constant at the 1010 M−1 s−1 level; this reaction is accompanied by a remarkable increase of the luminescence quantum yield from 0.13 to 2.2 %. Compared with organic probes, the new RuII complex probe shows the advantages of a large Stokes shift (>150 nm), water solubility, and a wide pH-availability range (pH independent at pH>5). In addition, it was found that the new probe could be easily transferred into both living animal cells and plant cells by the coincubation method, whereas the triazole derivative was cell-membrane impermeable. The probe was successfully used for luminescence-imaging detection of the exogenous NO in mouse macrophage cells and endogenous NO in gardenia cells. The results demonstrated the efficacy and advantages of the new probe for NO detection in living cells.
Co-reporter:Zhiqiang Ye, Guilan Wang, Jinxue Chen, Xiaoyan Fu, Wenzhu Zhang, Jingli Yuan
Biosensors and Bioelectronics 2010 Volume 26(Issue 3) pp:1043-1048
Publication Date(Web):15 November 2010
DOI:10.1016/j.bios.2010.08.056
Time-resolved luminescence detection technique using lanthanide chelates as luminescent probes or sensors is a highly sensitive and widely used tool for the luminescence detections of various biological and bioactive molecules. The essential of this technique is the developments of various functional luminescent probes or sensors that can selectively recognize the biological targets. In this work, a dual-chelating ligand N,N,N1,N1-{2,6-bis(3′-aminomethyl-1′-pyrazolyl)-4-[N,N-bis(2-picolyl)amino-methylenepyridine]} tetrakis(acetic acid) (BBATA) has been designed and synthesized. The luminescence of its Tb3+ chelate is very weak, but can be selectively and strongly enhanced upon reaction with Zn2+ ions. Thus a Tb3+ chelate-based luminescent chemosensor, BBATA-Tb3+, for highly selective and sensitive time-resolved luminescence detection of Zn2+ ions was developed. To confirm the utility of new chemosensor for the detection of intracellular Zn2+ ions, the performance of BBATA-Tb3+ as a chemosensor for time-resolved luminescent imaging detection of Zn2+ ions in living cells was investigated. The results demonstrated the efficacy and advantage of the new luminescent chemosensor for time-resolved luminescence detection of intracellular Zn2+ ions.
Co-reporter:Yan Liu, Haitao Dong, Wenzhu Zhang, Zhiqiang Ye, Guilan Wang, Jingli Yuan
Biosensors and Bioelectronics 2010 Volume 25(Issue 10) pp:2375-2378
Publication Date(Web):15 June 2010
DOI:10.1016/j.bios.2010.03.010
A novel colorimetric luminescence sensor strip for the detection of indole-3-acetic acid (IAA) has been fabricated by using green emissive quantum dots of cadmium telluride (CdTe QDs) as a background layer and a red emissive europium chelate, [4′-(9-anthryl)-2,2′:6′,2″-terpyridine-6,6″-diyl]bis(methylenenitrilo) tetrakis(acetate)-Eu3+ (ATTA-Eu3+), as a specific sensing layer coated on the surface of glass slide, respectively. The luminescence response of the sensor strip is given by the dramatic changes in emission colors from green to red at different IAA concentrations. This approach provides a simple, rapid, sensitive and accurate method for the detection of IAA without using any special scientific instruments.
Co-reporter:Haitao Dong;Yan Liu, ;Wenzhu Zhang;Guilan Wang;Zhiguang Liu ;Jingli Yuan
Helvetica Chimica Acta 2009 Volume 92( Issue 11) pp:2249-2256
Publication Date(Web):
DOI:10.1002/hlca.200900147
Abstract
Water-soluble thioglycolic acid (TGA)-capped CdTe quantum dots (QDs) were synthesized in aqueous medium, and then encapsulated in a silica nanosphere by copolymerization of the TGA-capped CdTe conjugated with (3-aminopropyl)triethoxysilane (APS-CdTe conjugate), free (3-aminopropyl)triethoxysilane (=3-(triethoxysilyl)propan-1-amine; APS), and tetraethyl orthosilicate (TEOS) in a H2O-in-oil reverse microemulsion consisting of Triton X-100, octanol, cyclohexane, and H2O in the presence of aqueous NH3 solution. The characterizations by transmission electron microscopy (TEM) and luminescence spectroscopy shows that the luminescent nanoparticles are monodisperse, spherical, and uniform in size, ca. 50 nm in diameter with a regular core–shell structure. In addition, primary amino groups directly introduced to the nanoparticle's surface by using free APS in the nanoparticle preparation enable the nanoparticles to be used easier as a biolabel. The effects of pH and metal cations on the luminescence of the nanoparticles also suggest that the new nanoparticles could be useful probes for luminescent sensings of pH and Cu2+ ion.
Co-reporter:Zhichao Dai, Lu Tian, Yunna Xiao, Zhiqiang Ye, Run Zhang and Jingli Yuan
Journal of Materials Chemistry A 2013 - vol. 1(Issue 7) pp:NaN927-927
Publication Date(Web):2013/01/08
DOI:10.1039/C2TB00350C
A unique cell-membrane-permeable europium complex has been developed as a probe for time-gated luminescence detection of singlet oxygen (1O2). Combined with the time-gated luminescence imaging technique, the probe was successfully used for investigating the time-dependent generation and distribution of 1O2 induced by the clinical drugs of photodynamic therapy in cancer cells.
Co-reporter:Yonggang Chen, Weihua Guo, Zhiqiang Ye, Guilan Wang and Jingli Yuan
Chemical Communications 2011 - vol. 47(Issue 22) pp:NaN6268-6268
Publication Date(Web):2011/05/06
DOI:10.1039/C0CC05658H
The first Eu3+ chelate-based luminescent probe specific for nitric oxide (NO) has been designed and synthesized for highly sensitive and selective time-gated luminescence detection of NO. Based on the probe, a time-gated luminescence imaging technique was developed for imaging the endogenous NO production in living plant cells/tissues.
![3,4-BIS[4-(4,4,5,5,6,6,6-HEPTAFLUORO-1,3-DIOXOHEXYL)PHENYL]BENZENESULFONYL CHLORIDE](http://img.cochemist.com/ccimg/200900/200862-70-0.png)
![3,4-BIS[4-(4,4,5,5,6,6,6-HEPTAFLUORO-1,3-DIOXOHEXYL)PHENYL]BENZENESULFONYL CHLORIDE](http://img.cochemist.com/ccimg/200900/200862-70-0_b.png)
![[2,2'-Bipyridine]-4-carboxylic acid, 4'-methyl-](/data/chemimg/117200/103946-54-9.png)
![[2,2'-Bipyridine]-4-carboxylic acid, 4'-methyl-](/data/chemimg/117200/103946-54-9_b.png)
![[2,2'-Bipyridine]-4-methanol, 4'-methyl-](/data/chemimg/1021700/81998-04-1.png)
![[2,2'-Bipyridine]-4-methanol, 4'-methyl-](/data/chemimg/1021700/81998-04-1_b.png)
