Yong-Fei Li

Colorimetric and fluorescent chemosensor for citrate based on a rhodamine and Pb2+ complex in aqueous solution

In this paper we unveil a novel rhodamine compound based fluorescent chemosensor (1-Pb(2+)) for colormetric and fluorescent detection of citrate in aqueous solution. This is the first fluorescent chemosensor for citrate based on rhodamine compound. The comparison of this method with some other fluorescence methods for citrate indicates that the method can detect citrate in aqueous solution by both color changes and fluorescent changes with long emission wavelength. In the new developed sensing system, 1-Pb(2+) is fluorescent due to Pb(2+)-induced fluorescence enhancement of 1. However, the addition of citrate may release 1 into the solution with quenching of fluorescence. The chemosensor can be applied to the quantification of citrate with a linear range covering from 1.0×10(-7) to 5.0×10(-5) M and a detection limit of 2.5×10(-8) M. The experiment results show that the response behavior of 1-Pb(2+) towards citrate is pH independent in medium condition (pH 6.0-8.0). Most importantly, the fluorescence changes of the chemosensor are remarkably specific for citrate in the presence of other anions (even those that exist in high concentration), which meet the selective requirements for practical application. Moreover, the response of the chemosensor toward citrate is fast (response time less than 1 min). In addition, the chemosensor has been used for determination of citrate in urine samples with satisfactory results.

A fluorescent chemosensor for Hg2+ based on naphthalimide derivative by fluorescence enhancement in aqueous solution

Naphthalimide derivative (compound 1) containing hydrophilic hexanoic acid group was synthesized and used to recognize Hg(2+) in aqueous solution. The fluorescence enhancement of 1 is attributed to the formation of a complex between 1 and Hg(2+) by 1:1 complex ratio (K=2.08×10(5)), which has been utilized as the basis of fabrication of the Hg(2+)-sensitive fluorescent chemosensor. The comparison of this method with some other fluorescence methods for the determination of Hg(2+) indicated that the method can be applied in aqueous solution rather than organic solution. The analytical performance characteristics of the proposed Hg(2+)-sensitive chemosensor were investigated. The chemosensor can be applied to the quantification of Hg(2+) with a linear range covering from 2.57×10(-7) to 9.27×10(-5) M and a detection limit of 4.93×10(-8) M. The experiment results show that the response behavior of 1 toward Hg(2+) is pH independent in medium condition (pH 4.0-8.0). Most importantly, the fluorescence changes of the chemosensor are remarkably specific for Hg(2+) in the presence of other metal ions, which meet the selective requirements for practical application. Moreover, the response of the chemosensor toward Hg(2+) is fast (response time less than 1 min). In addition, the chemosensor has been used for determination of Hg(2+) in hair samples with satisfactory results, which further demonstrates its value of practical applications.

Real-Time Monitoring ATP in Mitochondrion of Living Cells: A Specific Fluorescent Probe for ATP by Dual Recognition Sites

Adenosine triphosphate (ATP) is mainly produced in the mitochondrion and used as a universal energy source for various cellular events. Various fluorescent probes for ATP have been established successfully, but most of them are not appropriate for monitoring the fluctuation of the mitochondrial ATP level. Herein, a fluorescent probe named Mito-Rh is first synthesized and used to recognize ATP in mitochondrion. In the probe, rhodamine, diethylenetriamine, and triphenylphosphonium are selected as fluorophore, reaction site, and mitochondrion-targeting group, respectively. Probe Mito-Rh shows high sensitivity to ATP with 81-fold fluorescence enhancement, and the detection range (0.1-10 mM) can match the concentration level of ATP in the mitochondrion. Moreover, Mito-Rh provides excellent selectivity toward ATP over other biological anions (ADP, AMP, GTP, CTP, UTP) owing to a concurrent effect of dual recognition sites (hydrogen bond and π-π stacking). In particular, the probe can localize in mitochondrion specifically and demonstrates utility in the real-time detection of mitochondrial ATP concentration changes.

Facile and Sensitive Near-Infrared Fluorescence Probe for the Detection of Endogenous Alkaline Phosphatase Activity In Vivo

Alkaline phosphatase (ALP) is an essential enzyme and widely distributes in a variety of tissues. To date, various nanomaterial and small-molecule fluorescent probes for ALP have been constructed successfully, but the emission wavelengths of these probes are in the ultraviolet or visible range, which is not beneficial for bioimaging. Herein, a hemicyanine-based near-infrared (NIR) fluorescent probe named CyP is first synthesized and used to detect ALP activity. The characteristics of probe CyP are as follows: (1) The probe possesses a facile structure, which can be obtained by easy synthetic steps. (2) The fluorescence emission of the sensing system is at 738 nm belonging to NIR region, which is suitable for bioimaging in vivo. (3) The probe exhibits high sensitivity to ALP with 10-fold fluorescence enhancement and low detection limit (0.003 U/mL) can match the level of ALP in vivo. (4) The fluorescent change of the probe is attributed to the fact that ALP-catalyzed cleavage of the phosphate group in CyP induces the transformation of CyP (fluorescence off) into CyOH (fluorescence on), which is proved by HPLC, 31P NMR, MS, and DFT calculation. (5) The NIR fluorescent probe is applied for the detection of endogenous ALP activity in various biological samples such as cell, tissue, and living animal with satisfactory results.

A fluorescent chemosensor for silver ions based on porphyrin compound with high selectivity.

The design and synthesis of meso-tetra(p-methoxylpheny1)porphyrin (T(p-OCH(3))PPH(2)) and its application in fluorescent detections of Ag(I) in aqueous solution are reported. The fluorescence quenching of T(p-OCH(3))PPH(2) is attributed to the formation of a complex between T(p-OCH(3))PPH(2) and Ag(I) by 1:1 complex ratio (K=3.7 x 10(5)), which has been utilized as the basis of the fabrication of the Ag(I)-sensitive fluorescent chemosensor. The analytical performance characteristics of the proposed Ag(I)-sensitive chemosensor were investigated. The chemosensor can be applied to the quantification of Ag(I) with a linear range covering from 1.0 x 10(-7) to 5.0 x 10(-5)M with a detection limit of 2.5 x 10(-8)M. The experiment results show that the response behavior of T(p-OCH(3))PPH(2) towards Ag(I) is pH independent in medium condition(pH 4.0-8.0). Most importantly, the fluorescence changes of the chemosensor are remarkably specific for Ag(I) in the presence of other heavy and transition metal ions (even those that exist in high concentration), which meet the selective requirements for practical application. The proposed chemosensor has been used for direct measurement of Ag(I) content in river water samples with satisfying results, which further demonstrates its value of practical applications in environmental systems.

Ratiometric near-infrared chemosensor for trivalent chromium ion based on tricarboyanine in living cells.

A tricarboyanine derivative (IRPP) is applied as a ratiometric near-infrared chemosensor for detecting trivalent chromium ions (Cr(3+)) in living cells. Upon the addition of Cr(3+) to a solution of IRPP, large-scale shifts in the emission spectrum (from 755 nm to 561 nm) are observed. In the newly developed sensing system, these well-resolved emission peaks yield a sensing system that covers a linear range from 1.0×10(-7) to 1.0×10(-5) M with a detection limit of 2.5×10(-8) M. The experimental results show the response behavior of IRPP towards Cr(3+) is pH independent under neutral conditions (6.0-7.5). Most importantly, the fast response time (less than 3 min) and selectivity for Cr(3+) over other common metal ions provide a strong argument for the use of this sensor in real world applications. As a proof of concept, the proposed chemosensor has been used to detect and quantify Cr(3+) in river water samples and to image Cr(3+) in living cells with encouraging results.

A Dual-Response Fluorescent Probe for the Detection of Viscosity and H2S and Its application in Studying Their Cross-Talk Influence in Mitochondria

Intracellular viscosity is an essential microenvironmental parameter and H2S is a critical gaseous signaling molecule, which are both related to various physiological processes. It is reported that the change of viscosity and an imbalance of H2S production in the mitochondria are both associated with overexpression of amyloid betapeptide (Aβ), which is thought to play a central role in the pathogenesis of Alzheimers disease (AD). However, to our best knowledge, no fluorescent probe is found for dual detection of mitochondrial viscosity and H2S. Herein, a dual-response fluorescent probe (Mito-VS) is designed and synthesized to monitor the level of viscosity and H2S, respectively. Mito-VS itself is nonfluorescent due to a free intramolecular rotation between dimethylaniline and pyridine. After the increase of viscosity, the rotation is prohibited and an intense red fluorescence is released. Upon the addition of H2S, the probe can react with H2S to form compound 3 and a strong green fluorescence can be observed. Moreover, the probe possesses a good mitochondrion-targeting ability and is applied for imaging the change of viscosity on the red channel and visualizing the variation of exogenous and endogenous H2S concentration on the green channel in mitochondria. Most importantly, the probe is capable of studying the cross-talk influence of viscosity and H2S in mitochondria, which is very beneficial for knowing the pathogenesis of AD.

Detecting and Imaging of γ-Glutamytranspeptidase Activity in Serum, Live Cells, and Pathological Tissues with a High Signal-Stability Probe by Releasing a Precipitating Fluorochrome

γ-Glutamytranspeptidase (GGT) is a significant tumor-related biomarker that overexpresses in several tumor cells. Accurate detection and imaging of GGT activity in serum, live cells, and pathological tissues hold great significance for cancer diagnosis, treatment, and management. Recently developed small molecule fluorescent probes for GGT tend to diffuse to the whole cytoplasm and then translocate out of live cells after enzymatic reaction, which make them fail to provide high spatial resolution and long-term imaging in biological systems. To address these problems, a novel fluorescent probe (HPQ-PDG) which releases a precipitating fluorochrome upon the catalysis of GGT is designed and synthesized. HPQ-PDG is able to detect GGT activity with high spatial resolution and good signal-stability. The large Stokes shift of the probe enables it to detect the activity of GGT in serum samples with high sensitivity. To our delight, the probe is used for imaging GGT activity in live cells with the ability of discriminating cancer cells from normal cells. Whats more, we successfully apply it for pathological tissues imaging, with the results indicating that the potential application of HPQ-PDG in histopathological examination. All these results demonstrate the potential application of HPQ-PDG in the clinic.

Mitochondria-targeted near-infrared fluorescent probe for the detection of carbon monoxide in vivo

Carbon monoxide is a critical gasotransmitter in the body and related with mitochondrial respiration. To date, various fluorescent probes for CO have been well proposed, but two main problems remain. One is that most of the probes are not mitochondria-targeting, even if the probes claim to be able to detect CO in living cells. The other is that the probes for CO display excitation and emission within the ultraviolet or visible range, which hinders their applications in vivo. Herein, a hemicyanine-based near-infrared (NIR) fluorescent probe named CyAPC is first synthesized and used to detect mitochondrial CO. The characteristics of probe CyAPC are as follows: (1) The fluorescence emission of the sensing system is at 736 nm belonging to NIR region, which is suitable for bioimaging in vivo. (2) CyAPC, a positively charged molecule, would have a high tendency to localize in mitochondria of cells. (3) The fluorescence change of the probe is attributed to the fact that CO with Pd2+ induced cleavage of the allyl formate group from the probe and CyAPC (fluorescence off) is transformed into CyOH (fluorescence on), which is proved by HPLC, MS and DFT calculation. (4) The NIR fluorescent probe is applied for the detection of exogenous and endogenous CO in various biological samples such as cell, tissue and in vivo with satisfactory results.