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ANALYST · 2011 ·Vol. 137 ·期 4 ·932-938 · IF 3.913

An efficient rhodamine thiospirolactam-based fluorescent probe for detection of Hg2+ in aqueous samples

Yi-Jun Gong,Xiao-Bing Zhang,Zhuo Chen,Yuan Yuan,Zhen Jin,Lei Mei,Jing Zhang,Weihong Tan,Guo-Li Shen,Ru-Qin Yu

This paper described the optimized design, synthesis and application of a novel rhodamine thiospirolactam derivative as an ‘off-on’ fluorescent probe for the detection of Hg2+ in aqueous samples. The ‘off-on’ fluorescence and color signal change of the probe is based on an Hg2+-triggered domino reaction which brings on the opened-ring form of the rhodamine spirolactam to regain the conjugated system of the rhodamine skeleton. In the well designed probe, the thiospirolactam serves as both Hg2+ binding unit and electron-defect carbon centre, a phenolic hydroxyl with very strong nucleophilicity after deprotonation is chosen as the attacking unit, and a benzene ring is introduced on the linker to afford steric effects, which benefits an efficient nucleophilic reaction, with a high sensitivity towards Hg2+. It exhibits a stable response for Hg2+ from 1.0 × 10−8 to 1.0 × 10−6 M, with a detection limit of 3.0 × 10−9 M. The response of the probe to Hg2+ is highly selective and pH-insensitive, with a fast response time. All these unique features make it particularly favorable for cellular Hg2+ imaging applications. It has been preliminarily used for highly sensitive monitoring of Hg2+ levels in living cells with satisfying resolution.

CAS / MDL: 95-55-6 95-54-5 103-72-0
研究领域: 分析化学 · 环境科学 · 生物医学
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COLLOID AND POLYMER SCIENCE · 2015 ·Vol. 294 ·期 1 ·77-85 · IF 1.865

Micelle formation from hydrophobically end-capped poly(ethylene oxide) and its application for delivery of poorly water-soluble drug

Ding Guangzhu,Liu Huanyu,Jin Qianqian,Liu Jieping

The formation of micelle self-assembled from hydrophobically end-capped poly(ethylene oxide) (PEO) and its application for drug delivery have been investigated. As an important ABA-type associative triblock copolymer, a series of hydrophobically end-capped poly(ethylene oxide) [H(CH 2 ) n O(CH 2 CH 2 O) m (CH 2 ) n H], consisting of PEO (B) as hydrophilic segment and alkyl groups as hydrophobic block, are synthesized successfully according to 1 H NMR, Fourier transform infrared (FTIR), and differential scanning calorimetry (DSC) measurements. The triblock polymer is easy to form aggregates (micelles) under the appropriate conditions. The morphologies of micelles are found to be spherical confirmed by atomic force microscopy (AFM) measurement. Then, the polymeric micelles self-assembled from the triblock copolymer are used as a nanocarrier to solubilize poorly water-soluble drug spironolactone (a typical hydrophobicity drug). In vitro release behavior of spironolactone from triblock copolymer micelle is investigated carefully. It indicates interestingly that the drug can be released from triblock copolymer micelle stably and the release rate can be modulated by the variation of copolymer composition.

CAS / MDL: 7646-69-7
研究领域: 药剂学 · 材料科学 · 生物医学工程
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CHINESE JOURNAL OF ANALYTICAL CHEMISTRY · 2024 · IF 1.2

Overlooking pH Decrease Induced by ATP (or ATP-2Na) Results in False Positive Response of Rhodamine Spirolactam Derivatives to Millimolar ATP

Liyi Ma,Lixuan Mu,Lushan Huang,Guangwei She,Wensheng Shi

An outstanding fluorescent probe for adenosine 5′-triphosphate (ATP) in the millimolar range will shed deep light on the physiological role of ATP. Many fluorescent probes based on rhodamine spirolactam derivatives have been developed for this purpose and claimed to detect millimolar ATP excellently, where ATP or adenosine 5′-triphosphate disodium salt (ATP-2Na) dissolved in a buffer solution is employed to examine their response to ATP. However, in this work, it was found that both millimolar ATP and ATP-2Na could significantly decrease the pH of the common buffer solution even for several units. Considering the dependence of the rhodamine spirolactam fluorescence on pH, a series of rhodamine spirolactam-based probes was synthesized to investigate their fluorescence response to pH and ATP-2Na. The results demonstrated that the fluorescence response of the probes to millimolar ATP-2Na indeed resulted from both ATP-2Na itself and the pH decrease induced by ATP-2Na. Furthermore, it was evidenced that acidic pH was crucial for the probes to produce fluorescence response to millimolar ATP-2Na itself, and the rhodamine spirolactam-based probes would show poor sensitivity to millimolar ATP-2Na at near-natural pH. Accordingly, the previous conclusion that the rhodamine spirolactam-based probes could detect millimolar ATP excellently was almost erroneous, and might mislead the design and practice of intracellular ATP probe in the future. This work notes that attention should be paid to the physiochemical properties of the analyte and the environmental changes produced by the target analyte.

CAS / MDL: 590-92-1 989-38-8
研究领域: 分析化学 · 生物化学 · 分子生物学 · 荧光光谱学
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SENSORS AND ACTUATORS B-CHEMICAL · 2014 · IF 3.84

A new “off–on” fluorescent probe for Pd2+ in aqueous solution and live-cell based on spirolactam ring-opening reaction

Qi Huang,Yanmei Zhou,Qingyou Zhang,Enze Wang,Yinghao Min,Han Qiao,Junli Zhang,Tongsen Ma

Based on spirolactam ring-opening reaction, a chromogenic and “off–on” fluorescent sensor for determination of palladium (II) was developed in this paper. The novel sensor was easily synthesized from rhodamine B hydrazide and diacetyl monoxime named RBM. The structure of the sensor has been characterized by ESI-MS and NMR. EDTA-adding experiment indicated that the binding of chemosensor RBM and Pd 2+ was chemically reversible. The fluorescence intensity and absorbance of the sensor showed a good linearity with the concentration of Pd 2+ in the range of 0–15   μM and 0–17   μM, respectively, with detection limits of 0.015   μM and 0.200   μM. Moreover, it has been successfully applied to detect Pd 2+ in palladium-containing catalyst, natural water samples and imaging of Pd 2+ in living cells with satisfying results. The study indicated that this novel sensor could be an attractive approach to detect Pd 2+ in environmental systems and biological systems.

研究领域: 分析化学 · 环境科学 · 生物无机化学 · 分子影像 · 化学生物学
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JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY · 2017 · IF 2.625

Imaging dichromate in living cells with a fluorescence probe

Wenxi Xia,Jiangli Fan,Lizhu Zhang,Jingyun Wang,Jianjun Du,Xiaojun Peng

The dichromate as an industrial oxidant has a very extensive application. However, as one of the heavy metal elements, chromium has become a great threat to the organism and environment due to its carcinogenicity and mutageicity. So far, there is only a small number of detection and imaging methods for dichromate. In this work, a new fluorescent probe RhoCr for detecting dichromate based on in situ Cr 3+ -controlled opening of spirolactam-ring in a rhodamine dye after Cr 2 O 7 2− reduced to Cr 3+ by NaHSO 3 in solution and self-reduction in organism is reported, which displays a strong enhancement of fluorescence emission (λ em 582   nm), fast response (completed within 2   min) and excellent sensitivity (DL 1.18   nM). RhoCr successfully obtained fluorescence images of the intracellular Cr 2 O 7 2− . In addition, the effect have been exhibited in tap water and pool water, which will be crucial to the detection of dichromate in the environment.

CAS / MDL: 81-88-9
研究领域: 分析化学 · 环境科学 · 细胞生物学 · 材料科学
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SENSORS AND ACTUATORS B-CHEMICAL · 2014 · IF 3.84

A rhodamine-based fluorescent probe for Hg2+ and its application for biological visualization

Jiwen Hu,Zhangjun Hu,Yang Cui,Xuanjun Zhang,Hong-Wen Gao,Kajsa Uvdal

A new visible light excitable fluorescent probe ( 1 ) is synthesized by appending a hydroxymethyl-pyridine to rhodamine B hydrazide. The probe displays very specific Hg 2+ -induced colour change and fluorescent enhancement in the aqueous systems. The “turn-on” response of fluorescence is based on a binding-induced ring-opening process from the spirolactam (nonfluorescent) to acyclic xanthene (fluorescent) in rhodamine B. The coordinating atoms O–N–N–O from the hydroxymethyl-pyridine and rhodamine B hydrazide play dominant role in the formation of a complex with 1:1 stoichiometry of Hg 2+ to 1 . It exhibits a linear response in the range of 0.1–5   μM with the limit of detection (LOD) of 15.7   nM (3 σ /slope), while the calculated value of the association constant of Hg 2+ / 1 is 0.70   ×   10 5   M −1 . Furthermore, confocal microscopy imaging experiment demonstrates the probe 1 can be applied as a fluorescent probe for visualization of Hg 2+ in living HeLa cells.

研究领域: 化学 · 生物化学 · 材料科学 · 分析化学 · 细胞生物学
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SCIENCE OF THE TOTAL ENVIRONMENT · 2025 · IF 8

Benzo(a)pyrene induces cardiac hypertrophy via the aryl hydrocarbon receptor-mediated DNA damage

Fan Zhang,Yan Jiang,PinYi Chen,Huixian Chen,Tao Chen

Benzo( a )pyrene (BaP), one of the most extensively studied polycyclic aromatic hydrocarbons, is prevalent in the environment. BaP exposure has been linked to cardiovascular diseases, but the underlying mechanisms remain elusive. In this study, we observed that BaP exposure induces cardiac hypertrophic effects (enlarged cell surface area and increased expression of Nppa , Nppb , and Myh7 ) in rat H9c2 cardiomyoblasts. Notably, these effects are dependent on the aromatic hydrocarbon receptor (AHR)-Cyp1a1/Cyp1b1 axis. AHR-Cyp1a1/Cyp1b1 signaling also mediates BaP-induced cellular senescence, evidenced by an increased percentage of β-galactosidase-positive cells, p21 overexpression, and Lamin B1 deficiency. We then demonstrated that AHR activation by BaP promotes BPDE-DNA adducts and γ-H2AX foci formation, not only by upregulating Cyp1a1/Cyp1b1 expression but also by repressing nucleotide excision repair (NER). Further experiments revealed that BaP-activated AhR suppresses Sirt1 expression, which may inhibit NER by downregulating Ddb2 expression. Additionally, inhibition of cellular senescence through P21 inhibition counteracted BaP-induced cardiac hypertrophy. Furthermore, we demonstrated that either AHR inhibition or Sirt1 activation attenuated BaP-induced cardiac hypertrophy in zebrafish larvae. In conclusion, our findings indicate that AhR activation by BaP induces DNA damage both by promoting its conversion to BPDE and by repressing NER, leading to cellular senescence and ultimately resulting in cardiac hypertrophy.

CAS / MDL: 50-32-8 52-01-7
研究领域: 毒理学 · 心血管研究 · 分子生物学 · 环境健康
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SCIENCE OF THE TOTAL ENVIRONMENT · 2023 · IF 9.8

AHR-mediated DNA damage contributes to BaP-induced cardiac malformations in zebrafish

Hongmei Zou,Mingxuan Zhang,Jin Chen,Stanley Aniagu,Yan Jiang,Tao Chen

Benzo[ a ]pyrene (BaP) is a representative polycyclic aromatic hydrocarbon widely present in the environment. We previously reported that the aryl hydrocarbon receptor (AHR) mediates BaP-induced apoptosis and cardiac malformations in zebrafish embryos, but the underlying molecular mechanisms were unclear. Since BaP is a mutagenetic compound, we hypothesize that BaP induces apoptosis and heart defects via AHR-mediated DNA damage. In this study, zebrafish embryos were exposed to BaP at a concentration of 0.1 μM from 2 to 72 h post fertilization, either with or without inhibitors/agonists. AHR activity and levels of reactive oxygen species (ROS) were examined under a fluorescence microscope. mRNA expression levels were quantified by qPCR. DNA damage and apoptosis were detected by immunofluorescence. Our findings revealed that BaP exposure significantly increased BPDE-DNA adducts, mitochondrial damage, apoptosis and heart defects in zebrafish embryos. These effects were counteracted by inhibiting AHR/cyp1a1 using pharmaceutical inhibitors or genetic knockdown. Furthermore, we observed that spironolactone, an antagonist of nucleotide excision repair (NER), significantly enhanced BaP-induced BPDE-DNA adducts, mitochondrial damage, apoptosis and heart malformation rates. Conversely, SRT1720, a SIRT1 agonist, reduced the adverse effects of BaP. Supplementation with spironolactone also enhanced γ-H2AX signals in the heart of zebrafish embryos exposed to BaP. Additional experiments demonstrated that BaP suppressed the expression of SIRT1. We further established that AHR, when activated by BaP, directly inhibited SIRT1 transcription, leading to downregulation of XPC and XPA, which are essential NER genes involved in the recognition and verification steps of the NER process. Taken together, our results indicate that AHR mediates BaP-induced DNA damage in the heart of zebrafish embryos by inducing BPDE-DNA adduct formation via the AHR/Cyp1a1 signalling pathway, as well as suppressing NER via AHR-mediated inhibition of SIRT1.

CAS / MDL: 13517-08-3 52-01-7
研究领域: 毒理学 · 发育生物学 · 分子生物学
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