Probe For Hydrogen Sulfide Research Articles

Activity-Based Fluorescent Probes for Hydrogen Sulfide and Related Reactive Sulfur Species.

Hydrogen sulfide (H2S) is not only a well-established toxic gas but also an important small molecule bioregulator in all kingdoms of life. In contemporary biology, H2S is often classified as a "gasotransmitter," meaning that it is an endogenously produced membrane permeable gas that carries out essential cellular processes. Fluorescent probes for H2S and related reactive sulfur species (RSS) detection provide an important cornerstone for investigating the multifaceted roles of these important small molecules in complex biological systems. A now common approach to develop such tools is to develop "activity-based probes" that couple a specific H2S-mediated chemical reaction to a fluorescent output. This Review covers the different types of such probes and also highlights the chemical mechanisms by which each probe type is activated by specific RSS. Common examples include reduction of oxidized nitrogen motifs, disulfide exchange, electrophilic reactions, metal precipitation, and metal coordination. In addition, we also outline complementary activity-based probes for imaging reductant-labile and sulfane sulfur species, including persulfides and polysulfides. For probes highlighted in this Review, we focus on small molecule systems with demonstrated compatibility in cellular systems or related applications. Building from breadth of reported activity-based strategies and application, we also highlight key unmet challenges and future opportunities for advancing activity-based probes for H2S and related RSS.

A Highly Selective Fluorescent Probe for Hydrogen Sulfide and its Application in Living Cell.

A new Near-infrared fluorescent probe for hydrogen sulfide detection was synthesized by employing dicyanoisophorone based fluorescence dye as a fluorophore and methyl 3-(2-(carbonyl)phenyl)-2-cyanoacrylate group as the response unit. The Probe DCI-H2S showed a long emission wavelength (λem = 674nm). Based on the H2S-induced addition-cyclization of deprotecting methyl 3-(2-(carbonyl)phenyl)-2-cyanoacrylate group, the probe DCI-H2S showed high selectivity, sensitivity and response speed toward hydrogen sulfide under room temperature. These numerous advantages of the probe DCI-H2S make it to potentially detect endogenous hydrogen sulfide in living organisms.

Application and Cell Imaging of Turn-On Fluorescent Probe for Hydrogen Sulfide Based on Benzopyran in Food Samples

Application and Cell Imaging of Turn-On Fluorescent Probe for Hydrogen Sulfide Based on Benzopyran in Food Samples

Red-emitting fluorescent probe for hydrogen sulfide detection and its applications in food freshness determination and in vivo bioimaging.

We report the development of a red-emitting fluorescence probe (XDS) for hydrogen sulfide (H2S) detection in biosystems, real-world food samples, and application of this probe for monitoring of H2S production during food spoilage. The XDS probe is developed by coupling of coumarin derivative to rhodanic-CN through a H2S responsive CC bond. Remarkable fluorescence quenching of XDS is observed as a result of the response to H2S. Semi-quantitative detection of H2S in three real-world water and two beer samples and monitoring of H2S production during food spoilage in real-time by "naked-eye" and smartphone colorimetric analysis are then achieved using XDS as the probe. Moreover, XDS is low toxicity, allowing it being used for visualizing endogenous and exogenous H2S in vivo in a mouse model. It is expected that the successful development of XDS could provide an effective tool for investigating the roles of H2S in biomedical system and for future food safety evaluation.

Interactive Twin Intramolecular Hydrogen Bonds Enable Bright, S‐Blue Emissive, Environment‐Insensitive Single‐Benzene Fluorophores

AbstractSmall‐molecule dyes that emit blue fluorescence, particularly those that emit in the S‐blue region, are limited in number. Functionalization of benzene with electron‐donating and ‐accepting groups generates single‐benzene fluorophores (SBFs) with tunable emission properties. By exploring the unprecedented, interactive twin intramolecular H‐bonds, a novel type of SBFs that exhibits several notable features for bioimaging applications is developed. Specifically, aniline derivatives bearing two carbonyl/carboxyl groups at ortho‐positions have interactive H‐bonds, which lead to conformational restriction, suppressed solvation, and increased HOMO‐LUMO energy gaps from those of the conventional SBFs that have non‐interactive H‐bonds. The interactive H‐bonds are manifested by notable photophysical properties among the new SBFs, such as S‐blue emissive, bright, photo‐ and chemo‐stable, solid‐state‐emissive, and environment (pH, polarity, and viscosity)‐insensitive. The use of the highly faceted dye system to develop a reliable fluorescent probe, organelle‐staining dyes, and a fluorescence‐resonance‐energy‐transfer probe for hydrogen sulfide demonstrates its potential in bioimaging applications.

A selective fluorescent probe for hydrogen sulfide from a series of flavone derivatives and intracellular imaging

In this work, through the orthogonal design of two fluorophores and two recognition groups, a series of fluorescent probes were developed from the flavone derivatives for hydrogen sulfide (H2S). The probe FlaN-DN stood out from the primarily screening on the selectivity and response intensities. It could respond to H2S with both the chromogenic and fluorescent signals. Among the recent reported probes for the H2S detection, FlaN-DN indicated the most highlighted advantages including the rapid response (within 200 s) and the high response multiplication (over 100 folds). FlaN-DN was sensitive to the pH condition, thus could be applied to distinguish the cancer micro-environment. Moreover, FlaN-DN suggested practical capabilities including a wide linear range (0–400 μM), a relatively high sensitivity (limit of detection 0.13 μM), and high selectivity towards H2S. As a low cytotoxic probe, FlaN-DN achieved the imaging in living HeLa cells. FlaN-DN could detect the endogenous generation H2S and visualize the dose-dependent responses to the exogenous H2S level. This work provided a typical case of natural-sourced derivatives as functional implements, which might inspire the future investigations.

Dye-embedded NanoMOF as a turn-on fluorescent sensor for selective and sensitive detection of hydrogen sulfide

Developing high-performance fluorescent probes for hydrogen sulfide (H2S) has drawn enormous attention recently. In this paper, we report a stable nanoscale dual-emitting probe RB@UiO-66-NO2 for H2S detection, which was obtained by embedding the red-emitting rhodamine B (RB) in the blue-emitting nitryl-functionalized metal−organic framework (MOF) UiO-66-NO2. The accommodated RB is designed as a reference signal, and the nitro groups on the host skeleton can serve as accessible reactive sites to allow for the selective sensing of H2S by RB@UiO-66-NO2. As a result of H2S's ability to dioxide the nitro group on the ligand and improve the intramolecular charge transfer, RB@UiO-66-NO2 shows enhanced blue fluorescence as well as ratiometric response to H2S. Our investigation shows that RB@UiO-66-NO2 nanoprobe has good stability, fast response (<2 min), distinct color change, and high selectivity and sensitivity (LOD = 5.128 μM) to H2S in the HEPES solution, demonstrating its potential application for H2S detection under various solution conditions.

Construction and Application of Multipurpose metal-organic frameworks -based Hydrogen Sulfide Probe.

Hydrogen sulfide (H2S) is a toxic gas derived from the sulfur industry and trace H2S in the environment can cause serious ecological damage while inhalation can cause serious damage and lead to disease. Therefore, the real-time and accurate detection of trace sulfur ions is of great significance for environmental protection and early disease detection. Considering the shortcoming of current H2S probes in terms of stability and sensitivity, the development of novel probes is necessary. Herein, a novel metal-organic frameworks (MOF)-based material, UiO-66-NH2@BDC, was designed and prepared for the visual detection of H2S with rapid response (< 6s) and low detection limit of S2- (0.13 µM) by hydrogen bonding. Based on its good optical performance, the UiO-66-NH2@BDC probe can detect S2- in various water environments. More importantly, UiO-66-NH2@BDC probe realize imaging S2- in cells and live zebrafish.

Synthesis of a Turn-On Fluorescent Probe for Hydrogen Sulfide and Its Application in Red Wine and Living Cells

Synthesis of a Turn-On Fluorescent Probe for Hydrogen Sulfide and Its Application in Red Wine and Living Cells

A new fluorescent probe for hydrogen sulfide based on naphthalimide derivatives and its biological application

• • A novel fluorescent probe SBD for the detection of H 2 S was constructed. • • Probe SBD displayed excellent recognition performance of H 2 S, and its solution color changed from yellow to pink. • • Probe SBD showed good cytocompatibility and could be applied to fluorescence imaging. As a signal transduction molecule in organism, H 2 S plays an important role in many physiological processes. In this paper, a novel H 2 S fluorescent probe SBD was designed based on 1,8-naphthalimide and dinitrobenzenesulfonyl group. In DMSO-PBS solution, probe SBD could recognize H 2 S and change the color of solution from yellow to pink, realizing the naked eye recognition for H 2 S. In addition, probe SBD displayed high fluorescence enhancement rate (45-fold), good selectivity, strong anti-interference ability and the detection limit was as low as 152 nM. Most importantly, probe SBD showed very low cytotoxicity and had been successfully applied to image exogenous H 2 S in living cells.

A novel near-infrared colorimetric-fluorescent probe for hydrogen sulfide and application in bioimaging

As a kind of gas signal molecules, H2S is related to in human health and disease. Herein, we developed a novel probe with near-infrared fluorescent emission (750 nm) and a large Stokes shift (118 nm) for the detection of H2S. The probe can specific and sensitive detection (LOD as low as 4.5 × 10–8 M) of H2S, accompanying an ideal color changes from purple to green natural light. Based on the advantages of excellent cell permeability and cytotoxicity data, the probe was be utility for H2S image in cells and mice.

A “turn-on” chalcone-based probe for hydrogen sulfide and imaging applications in lysosomes of living cells and zebrafish

A chalcone-based probe was designed to hydrogen sulfide (H2S) detection by employing 2,4-dinitrophenyl either as a recognition group. This probe can rapidly and specifically detect H2S in semi-aqueous solutions with the detection limit of 120 nM and a wide pH range from 2.0 to 9.0. The sensing mechanism was determined by UV–Vis, fluorescence spectra, mass spectra, 1H NMR studies and density functional theory calculations, respectively. Additionally, the probe can target lysosomes and monitor H2S in living cells and zebrafish by fluorescence imaging.

A Novel Fast and Sensitive Fluorescent Hydrogen Sulfide Probe with Large Stokes Shift for Imaging Living Cells and Zebrafish

As an important physiological gas transmitter, hydrogen sulfide (H2S) plays an important role in the immune system and is closely related to the occurrence of many diseases, such as cirrhosis, arterial disease, down syndrome, heart disease, and Alzheimer’s disease. In recent years, H2S probes have been reported frequently, but they still have some shortcomings, such as slow response time, small Stokes shift and insufficient sensitivity. Herein, a novel H2S probe NM–H2S was designed and synthesized. The probe NM–H2S emitted red fluorescence at 625 nm, and had a large Stokes shift (130 nm), which significantly reduces the background interference of the probe NM–H2S in biological imaging. The probe NM–H2S showed remarkable fluorescence color change, rapid response (within 10 min) and high sensitivity (0.4 μM detection limit) to the analyte H2S. Not only that, the probe NM–H2S showed good selectivity in a series of chemical analytes. In addition, the probe NM–H2S was also capable of detecting H2S in Hela cells and zebrafish by turning on fluorescence in biological applications.

A “Turn-On” Chalcone-Based Probe for Hydrogen Sulfide and Imaging Applications in Lysosomes of Living Cells and Zebrafish

A “Turn-On” Chalcone-Based Probe for Hydrogen Sulfide and Imaging Applications in Lysosomes of Living Cells and Zebrafish

A dual-emission fluorescence-enhanced probe for hydrogen sulfide and its application in biological imaging

A fluorescence-enhanced probe with unique dual-channel emissions was designed for the detection and bioimaging of hydrogen sulfide.

Near-infrared fluorescent probe for hydrogen sulfide: high-fidelity ferroptosis evaluation in vivo during stroke.

Ferroptosis is closely associated with cancer, neurodegenerative diseases and ischemia-reperfusion injury and the detection of its pathological process is very important for early disease diagnosis. Fluorescence based sensing technologies have become excellent tools due to the real-time detection of cellular physiological or pathological processes. However, to date the detection of ferroptosis using reducing substances as markers has not been achieved since the reducing substances are not only present at extremely low concentrations during ferroptosis but also play a key role in the further development of ferroptosis. Significantly, sensors for reducing substances usually consume reducing substances, instigating a redox imbalance, which further aggravates the progression of ferroptosis. In this work, a H2S triggered and H2S releasing near-infrared fluorescent probe (HL-H2S) was developed for the high-fidelity in situ imaging of ferroptosis. In the imaging process, HL-H2S consumes H2S and releases carbonyl sulfide, which is then catalyzed by carbonic anhydrase to produce H2S. Importantly, this strategy does not intensify ferroptosis since it avoids disruption of the redox homeostasis. Furthermore, using erastin as an inducer for ferroptosis, the observed trends for Fe2+, MDA, and GSH, indicate that the introduction of the HL-H2S probe does not exacerbate ferroptosis. In contrast, ferroptosis progression was significantly promoted when the release of H2S from HL-H2S was inhibited using AZ. These results indicate that the H2S triggered and H2S releasing fluorescent probe did not interfere with the progression of ferroptosis, thus enabling high-fidelity in situ imaging of ferroptosis.

A ratiometric fluorescent probe for hydrogen sulfide in neat aqueous solution and its application in lysosome-targetable cell imaging

Hydrogen sulfide (H2S) has been recently regarded as one of the most important gasotransmitters in the metabolic system, while abnormal H2S concentration is associated with various diseases. Although numerous fluorescent probes have been developed for the detection of cellular H2S, only a few of them can monitor lysosomal H2S with ratiometric fluorescent output. Here, we developed a water-soluble probe 1 toward H2S by introducing 2,4-dinitrophenyl ether into a novel merocyanine-based dye. As expected, H2S induced an obvious red-shift of the probe from 520 nm to 580 nm in neat aqueous solution, and this fluorescent ratiometric response is highly selective and sensitive (with the detection limit of 0.81 nM), rapid (within 10 s), and effective in a wide pH range (2.0–10.0). In particular, the probe was successfully applied for tracing H2S in the lysosomes of living cells and in zebrafish.

Sensing mechanism of a new fluorescent probe for hydrogen sulfide: photoinduced electron transfer and invalidity of excited-state intramolecular proton transfer.

It is of great significance for biological research to develop efficient detection methods of hydrogen sulfide (H2S). When DFAN reacts with H2S, 2,4-dinitrophenyl ether group acting as an electron acceptor generates a hydroxyl-substituted 2,4-dinitrophenyl ether group, resulting in the disappearance of photoinduced electron transfer (PET), and the new formed DFAH can be observed, while being accompanied by a significant fluorescence. In the present study, the PET sensing mechanism of probe DFAN and the excited state intramolecular proton transfer (ESIPT) process of DFAH have been explored in detail based on the density functional theory (DFT) and time-dependent density functional theory (TD-DFT) methods. Our theoretical results show that the fluorescence quenching of DFAN is caused by the PET mechanism, and the result of ESIPT mechanism is not due to the large Stokes shift fluorescence emission of DFAH. We also optimized the geometric structure of the transition state of DFAH. The frontier molecular orbitals and potential barrier show that the ESIPT process does not easy occur easily for DFAH. The enol structure of DFAH is more stable than that of the keto structure. The absence of the PET process resulted in the enol structure emitting strong fluorescence, which is consistent with the single fluorescence in the experiment. Above all, our calculations are sufficient to verify the sensing mechanism of H2S using DFAN.

Recent advances in probe design to detect reactive sulfur species and in the chemical reactions employed for fluorescence switching.

Reactive sulfur species, including hydrogen sulfide, hydropersulfide, and polysulfide, have many roles in biological systems. For example, hydrogen sulfide is involved in the relaxation of vascular smooth muscles and mediation of neurotransmission, while sulfane sulfur, which exists in cysteine persulfide/polysulfide, and glutathione persulfide/polysulfide, is involved in physiological antioxidation and cytoprotection mechanisms. Fluorescence imaging is well suited for real-time monitoring of reactive sulfur species in living cells, and many fluorescent probes for reactive sulfur species have been reported. In such probes, the choice of detection chemistry is extremely important, not only to achieve effective fluorescence switching and high selectivity, but also because the reactions may be applicable to develop other chemical tools, such as reactive sulfur species donors/scavengers. Here, we present an overview of both widely used and recently developed fluorescent probes for reactive sulfur species, focusing especially on the chemical reactions employed in them for fluorescence switching. We also briefly introduce some applications of fluorescent probes for hydrogen sulfide and sulfane sulfur.

A fluorescence turn-on probe for hydrogen sulfide and biothiols based on PET & TICT and its imaging in HeLa cells.

In this paper, a photoinduced electron transfer (PET)& twisted intramolecular charge transfer (TICT)-based fluorescent probe (1) for detecting biothiols (GSH/Cys/Hcy) and hydrogen sulfide with fluorescence turn on was developed. The probe could recognize hydrogen sulfide over primary ions and selectively detect GSH/Cys/Hcy over other amino acids with fluorescence turn-on (an ESIPT process). H2S can be distinguished from GSH/Cys/Hcy with wavelength shift by UV-Vis spectra. In addition, detection limits for H2S/GSH/Cys/Hcy of probe 1 were 1.42μM (0-100μM), 0.13μM (0-40μM), 0.27 (0-30μM), 0.22μM (0-40μM), respectively. The proposed thiolysis of the 2,4-dinitrochlorophenyl ether reaction in identification process was verified by the characteristic peak in 1H NMR and HRMS spectra. Finally, the biological imaging experiments and low cytotoxicity investigations in HeLa cells demonstrated that probe 1 could provide a promising method for the determination of H2S and biothiols in aqueous solution and living cells.