Selective Detection Of H2S Research Articles

Hybrid organic-inorganic composite based on electroactive aniline trimer decorated MIL-88B(Fe) as hydrogen sulfide sensor

This study presents a novel approach to enhancing MIL-88B(Fe) for H₂S sensing by incorporating aniline trimer (ACAT). The successful synthesis and comprehensive characterization of ACAT, MIL-88B(Fe), and their composite, ACAT-MIL-88B(Fe), are detailed. The ACAT-MIL-88B(Fe) sensor demonstrates significantly superior performance, with a sensitivity increase to 643.5 % at 9–10 ppm H₂S and a rapid response time of 288 seconds. It maintains high sensitivity (450 % response) even at 90 % relative humidity and shows excellent selectivity for H₂S over other gases. Stability tests confirm over 600 % responsiveness over 16 days. Density Functional Theory (DFT) calculations validate that H₂S adsorption is most stable at the Fe site of MIL-88B(Fe), with ACAT enhancing this interaction. This innovative sensor holds promise for highly sensitive, selective, and stable H₂S detection in industrial applications.

An AIE-based ratiometric fluorescent probe for highly selective detection of H2S in plant stress responses

Hydrogen sulfide (H2S) has emerged as a crucial signaling molecule in plant stress responses, playing a significant role in regulating various physiological and biochemical processes. In this study, we report an aggregation-induced emission (AIE)-based ratiometric fluorescent probe TPN-H2S for the highly selective detection of H2S in plant tissues. The probe exhibited excellent sensitivity and selectivity towards H2S over other analytes, enabling real-time monitoring of H2S dynamics in living cell. Furthermore, the AIE-based ratiometric probe TPN-H2S allowed for accurate quantification of H2S levels, providing valuable insights into the spatiotemporal distribution of Cys metabolism produces H2S. Importantly, the physiological pathways and signaling mechanisms of H2S production of was investigated in plant tissues under Cr and nano-plastics stress. Utilizing a high-throughput screening approach, we identified exogenous substances such as calcium chloride (CaCl2) and abscisic acid (ABA) that could induce higher level of H2S production during the stress response in plants. Overall, those findings demonstrate the potential of the AIE-based ratiometric fluorescent probe TPN-H2S as a powerful tool for unraveling the role of H2S in plant stress responses and pave the way for further exploration of H2S-mediated signaling pathways in plants.

Responsive β-Diketonate-europium(III) Complex-Based Probe for Time-Gated Luminescence Detection and Imaging of Hydrogen Sulfide In Vitro and In Vivo.

As a crucial biological gasotransmitter, hydrogen sulfide (H2S) plays important roles in many pathological and physiological processes. Highly selective and sensitive detection of H2S is significant for the precise diagnosis and evaluation of diverse diseases. Nevertheless, challenges remain in view of the interference of autofluorescence in organisms and the stronger reactivity of H2S itself. Herein, we report the design and synthesis of a novel H2S-responsive β-diketonate-europium(III) complex-based probe, [Eu(DNB-Npketo)3(terpy)], for background-free time-gated luminescence (TGL) detection and imaging of H2S in autofluorescence-rich biological samples. The probe, consisting of a 2,4-dinitrobenzenesulfonyl (DNB) group coupled to a β-diketonate-europium(III) complex, shows almost no luminescence owing to the existence of intramolecular photoinduced electron transfer. The cleavage of the DNB group by a H2S-triggered reaction results in the recovery of the long-lived luminescence of the Eu3+ complex, allowing the detection of H2S in complicated biological samples to be performed in TGL mode. The probe showed a fast response, high specificity, and high sensitivity toward H2S, which enabled it to be successfully used for the quantitative TGL detection of H2S in tissue homogenates of mouse organs. Additionally, the low cytotoxicity of the probe allowed it to be further used for the TGL imaging of H2S in living cells and mice under different stimuli. All of the results suggested the potential of the probe for the investigation and diagnosis of H2S-related diseases.

Bimetal−organic framework-integrated electrochemical sensor for on-chip detection of H2S and H2O2 in cancer tissues

Studies on the interaction between hydrogen sulfide (H2S) and hydrogen peroxide (H2O2) in redox signaling motivate the development of a sensitive sensing platform for their discriminatory and dynamic detection. Herein, we present a fully integrated microfluidic on-chip electrochemical sensor for the online and simultaneous monitoring of H2S and H2O2 secreted by different biological samples. The sensor utilizes a cicada-wing-like RuCu bimetal−organic framework with uniform nanorods architecture that grows on a flexible carbon fiber microelectrode. Owing to the optimized electronic structural merits and satisfactory electrocatalytic properties, the resultant microelectrode shows remarkable electrochemical sensing performance for sensitive and selective detection of H2S and H2O2 at the same time. The result exhibits low detection limits of 0.5 μM for H2S and 0.1 μM for H2O2, with high sensitivities of 61.93 μA cm−2 mM−1 for H2S, and 75.96 μA cm−2 mM−1 for H2O2. The integration of this biocompatible microelectrode into a custom wireless microfluidic chip enables the construction of a miniature intelligent system for in situ monitoring of H2S and H2O2 released from different living cells to differentiate between cancerous and normal cells. When applied for real-time tracking of H2S and H2O2 secreted by colorectal cancer tissues, it allows the evaluation of their chemotherapeutic efficacy. These findings hold paramount implications for disease diagnosis and therapy.

Single Side-Chain-Modulatory of Hemicyanine for Optimized Fluorescence and Photoacoustic Dual-Modality Imaging of H2S In Vivo.

Near-infrared fluorescence (NIRF)/photoacoustic (PA) dual-modality imaging integrated high-sensitivity fluorescence imaging with deep-penetration PA imaging has been recognized as a reliable tool for disease detection and diagnosis. However, it remains an immense challenge for a molecule probe to achieve the optimal NIRF and PA imaging by adjusting the energy allocation between radiative transition and nonradiative transition. Herein, a simple but effective strategy is reported to engineer a NIRF/PA dual-modality probe (Cl-HDN3) based on the near-infrared hemicyanine scaffold to optimize the energy allocation between radiative and nonradiative transition. Upon activation by H2S, the Cl-HDN3 shows a 3.6-fold enhancement in the PA signal and a 4.3-fold enhancement in the fluorescence signal. To achieve the sensitive and selective detection of H2S in vivo, the Cl-HDN3 is encapsulated within an amphiphilic lipid (DSPE-PEG2000) to form the Cl-HDN3-LP, which can successfully map the changes of H2S in a tumor-bearing mouse model with the NIRF/PA dual-modality imaging. This work presents a promising strategy for optimizing fluorescence and PA effects in a molecule probe, which may be extended to the NIRF/PA dual-modality imaging of other disease-relevant biomarkers.

A Turn-On Fluorescent Probe for Highly Selective Detection and Visualization of Hydrogen Sulfide in Fungi.

Hydrogen sulfide (H2S) is a significant actor in the virulence and pathogenicity of fungi. The analysis of endogenous H2S in fungi benefits the prevention and treatment of pathogenic infections. Herein, a H2S-activated turn-on fluorescent probe named DDX-DNP was developed for the sensitive and selective detection of H2S. Using DDX-DNP, the ability of several oral fungi strains to produce H2S was identified, which was also validated using a typical chromogenic medium. In addition, DDX-DNP was successfully used for the visual sensing of endogenous H2S in fungal cells via microscope, flow cytometry, and colony imaging, along with a specific validation with the co-incubation of H2S production inhibitors in living cells. Above all, DDX-DNP could be used for H2S detection, the fluorescent imaging of fungi, and even the identification of related fungi.

Construction of a coumarin-based fluorescent probe for accurately visualizing hydrogen sulfide in live cells and zebrafish.

Hydrogen sulfide (H2S), an important gas signaling molecule, is a regulator of many physiological processes, and its abnormal levels are closely related to the onset and progression of disease. It is vital to develop methods for specific tracking of H2S in clinical diagnosis and treatment. In this study, we designed an ultrasensitive and highly stable coumarin-based fluorescent probe Cou-H2S. Through the H2S-initiated tandem reaction, Cou-H2S successfully achieved highly selective and super-fast detection of H2S. Cou-H2S was successfully applied to the monitoring of endogenous and exogenous H2S at the cellular level and verified the validity of the detection of H2S in the LPS-induced zebrafish model. Therefore, Cou-H2S might provide new insights into the study of H2S-related diseases.

W-CeO2 nanospheres gas sensor array for accurate and selective H2S detection in exhaled breath

Hydrogen sulfide (H2S), an endogenous gas intricately linked with various physiological disorders, carries paramount importance for medical diagnostics. Despite its significance, rapid and precise H2S detection in the complex atmosphere of exhaled breath remains a formidable challenge. In this study, W-CeO2 core@shell nanospheres were synthesized employing a facile one-step hydrothermal method. Particularly, the 7 % W-CeO2 composite showcased exceptional gas sensing capabilities, characterized by a response of 18.4 and an effective detection threshold of 50 ppb at 225 °C with 80 % RH. The underlying gas-sensing mechanism was meticulously expounded. To enhance the discrimination of sensor responses towards diverse gases, a sensor array encompassing four distinct W-CeO2 sensors was meticulously devised. By synergizing this sensor array with an algorithmic approach, the discrimination accuracy for qualitative (100 %) and quantitative (89 %) classification of H2S, ethanol, and their mixtures within a high humidity range. Furthermore, the proposed sensor array's utility was extended to the design of an electronic nose system tailored for H2S detection in exhaled breath. This platform effectively evaluated its diagnostic efficacy for halitosis, evidencing its capability to discern exhaled breath samples from healthy exhaled samples and simulated halitosis exhaled samples accurately.

Metal–organic frameworks modified electrode for H2S detections in biological and pharmaceutical agents

AbstractThe development of hydrogen sulfide (H2S) sensors is essential to address H2S‐related pharmacology since slow‐releasing H2S medications have been identified to be prospective options for cancer treatments. Here, we described an electrochemical sensor for highly selective and sensitive detection of aqueous H2S, using a thin film of fumarate‐based face‐centered cubic (fcu)‐based metal–organic frameworks (fum‐fcu‐MOF) modified on laser‐scribed graphene (LSGE). The fum‐fcu‐MOF has shown a strong affinity and chemical stability to H2S analysis. The electrochemical and H2S catalytic properties were studied for fum‐fcu‐MOF/LSGE. An amperometry and differential pulse voltammetry techniques were demonstrated to validate the sensor. The resulting sensor delivered acceptable analytical parameters in terms of; detection limit (3.0 µM), dynamic range (10–500 µM), reproducibility, and stability (94.7%). The sensor's practical validity was demonstrated in bacterial cells and H2S‐releasing drug, where the sensor was able to monitor the continuous release of in‐situ H2S. The pharmacokinetics of a slow releasing H2S donor is accessed at different time intervals and different concentration levels. Our research indicate that this fum‐fcu‐MOF based H2S sensor holds potential in understanding pharmacokinetics of H2S releasing drugs.

Monitoring disease-implicated hydrogen sulfide in blood using a facile deproteinization-based electrochemiluminescence chemosensor system

Hydrogen sulfide (H2S), an antioxidant and cell signaling molecule, plays a critical role in redox reactions in the biological system, and its imbalances in blood levels have been implicated in various diseases. Here, we demonstrate a novel chemosensor-based “turn-on” electrochemiluminescence (ECL) system for the selective and sensitive detection of H2S in a type 1 diabetes rat model. Our luminogenic chemosensor (Probe) is a redox-stable cyclometalating iridium (III) complex with emission-quenching 2,4-dinitrophenyl ether (DNP) that shows a significant enhancement in emission intensity upon cleavage of DNP by selective reaction towards H2S. To achieve robust and reliable ECL emission of Probe for biological analysis, we developed a facile deproteinization protocol based on organic solvent-induced protein precipitation/syringe filtration that eliminates uncontrolled protein adsorption on the electrode surface from protein-rich biological samples. Our deproteinization-assisted ECL chemosensor system showed effectiveness in detecting disease-associated H2S levels in biological media with a linear response in the range of 0–250 µM (R2: 0.992). It enables reliable in vitro monitoring of H2S level changes in blood samples of a type 1 diabetes rat model (P = 0.0296). This strategy to integrate chemosensor-based ECL and facile deproteinization protocol provides a sensitive and rapid disease-monitoring platform for detecting small-molecule biomarkers.

An activatable AIEgen for imaging of endogenous H2S: Reticulation based H2S gas sensor

Novel 2,4-dinitrophenylether functionalized hydroxybenzothiazole derivative (HBT 3) has been synthesized and characterized for selective and rapid detection of H2S in aqueous medium, gas phase and live cells. The H2S induced thiolysis of 2,4-dinitrophenylether leads to morphological transformation in HBT 3 from spherical to reticulate with aggregation induced emission (AIE + ESIPT) at 550 nm (greenish yellow aggregates) as evidenced by optical, DLS, NMR and AFM studies. The HBT 3 can specifically detect H2S with limits of detection as low as 0.45 and 1.22 µM in CH3CN; 2.9 µM and 6.8 µM in 70% HEPES buffer–CH3CN solution. The HBT 3 based solution- and solid- supported point-of-care testing (POCT) kits have been explored for detection of 75–400 ppm H2S gas; 2.4 µg H2S with fluorescence color change from non-fluorescent to fluorescent yellow. HBT 3 has been successfully utilized for endogenous and exogenous detection of H2S in live L929 cells.

Inorganic Chemistry in Dalian University of Technology: Fundamental Science and Solution for Renewable Energy, Environment, Health, and Materials

Inorganic Chemistry in Dalian University of Technology: Fundamental Science and Solution for Renewable Energy, Environment, Health, and Materials

Construction of a novel ESIPT and AIE-based fluorescent sensor for sequentially detecting Cu2+ and H2S in both living cells and zebrafish

The development of effective methods for tracking Cu2+ and H2S in living organisms is urgently required due to their vital function in a variety of pathophysiological processes. In this work, a new fluorescent sensor BDF with excited-state intramolecular proton transfer (ESIPT) and aggregation-induced emission (AIE) features for the successive detection of Cu2+ and H2S was constructed by introducing 3,5-bis(trifluoromethyl)phenylacetonitrile into the benzothiazole skeleton. BDF showed a fast, selective and sensitive fluorescence “turn off” response to Cu2+ in physiological media, and the situ-formed complex can serve as a fluorescence “turn on” sensor for highly selective detection of H2S through the Cu2+ displacement approach. In addition, the detection limits of BDF for Cu2+ and H2S were determined to be 0.05 and 1.95 μM, respectively. Encouraged by its favourable features, including strong red fluorescence from the AIE effect, large Stokes shift (285 nm), high anti-interference ability and good function at physiological pH as well as a low toxicity, BDF was successfully applied for the consequent imaging of Cu2+ and H2S in both living cells and zebrafish, making it an ideal candidate for detecting and imaging of Cu2+ and H2S in live systems.

A new highly selective fluorescent probe design for visualizing hydrogen sulfide in food sample

We report herein a new highly selective fluorescent probe QVPB-DNP for selective evaluation of H2S in the solid states and food samples. In this probe, a quinoline-phenol vinylic conjugated skeleton as well as the expanded benzothiazole moiety (QVPB-OH) is selected as the fluorophore and a 2,4‑dinitrophenyl (DNP) ether is chosen as binding site of H2S. The probe shows significant variations in UV/visible absorption (Stokes Shift = 160 nm) and fluorescence emission enhancement at 605 nm for selective detection of H2S in DMSO/PBS system (v/v, 7:3, PBS buffer; pH 7.4). Moreover, probe QVPB-DNP-loaded test strips are successfully applied for the visual and real-time detection of gaseous H2S in practical food samples.

The effect of acids precipitants on the synthesis of WO3 hierarchical nanostructures for highly selective and sensitive H2S detection

The detection and monitoring of H2S gas at high and lower concentrations is very crucial since this gas is highly toxic and can affect tissues and organs, especially in occupational environment. This work reports on the synthesis of WO3 nanostructures-based sensors for highly sensitive and selective H2S detection at low operating temperatures. These WO3 nanostructures were synthesized using pressurized hydrothermal process. Different acids from weak to strong (HNO3, H2SO4, and HCl) were employed as precipitants to form supposedly hierarchical and cube-like nanostructures of WO3. These WO3 nanostructures were characterized by XRD, SEM, TEM, XPS and BET analysis. The fabricated WO3 sensors were exposed to different target gases (CO2, H2, CH4, NH3, LPG and H2S) at different concentrations. They were found to be selective to H2S, and the WO3 precipitated by HCl otherwise referred to as WO3-HCl was found to be highly sensitive, with high response of S = 1394.04 towards 150 ppm of H2S at 125°C operating temperature. The WO3 precipitated by H2SO4 named WO3-H2SO4 showed a high response of 141.64 at 125°C operating temperature. Lastly, WO3 precipitated by HNO3 called WO3-HNO3, recorded a H2S response of 125.75 also at 125°C operating temperature. The HCl-precipitated WO3 is a promising candidate for selective detection of H2S, being the most sensitive in the series.

Adsorption of chalcogenide gas by 2H-MoSe2 monolayer modified by transition metal

Nowadays, detecting the more hazardous sulphur group of gases (H2S, SO2) is increasingly essential, and there is a need to find a readily fabricated, low-cost, high-performance 2D material. This study investigated the selective detection of H2S and SO2 by MoSe2 monolayers and Pt-doped MoSe2 monolayers using first-principles calculations. Our results show that the dopant dramatically enhances the activity of the material, creating solid interactions with the material surface and that Pt-doped MoSe2 monolayers have the potential to selectively detect these toxic gases because of their different conductive tendencies. This work provides insights into the potential application of unexplored TMDs as chemically resistant sensors for the detection of poisonous gases, which may be of importance for environmental monitoring and industrial manufacturing.

A fluorous-tag-assisted fluorescent probe for simple and selective detection of hydrogen sulfide: application for turbid dyeing solutions.

Accurate hydrogen sulfide (H2S) detection has attracted much attention because its toxicity may affect aquatic environments and human health. However, recognizing H2S levels by conventional fluorescent probes in turbid wastewater has been challenging because the opaque environment interferes with their photophysical properties. To overcome this limitation, a fluorous-tagging strategy can be used for the development of fluorescent sensors to detect H2S in turbid solutions. The use of fluorescent probe assisted with fluorous-tag allowed for easy isolation of the probe using polytetrafluoroethylene (PTFE) material, while disturbing species were eliminated through a simple aqueous wash. This approach enabled the fluorescent probe to effectively quantify H2S, even in opaque solutions containing organic dyes that could interfere with fluorescence emission.

A ruthenium nitrosyl complex-based highly selective colorimetric sensor for biological H2S and H2S-NO cross-talk regulated release of NO.

A ruthenium nitrosyl complex (1·NO) and 1·NO incorporated phospholipid-based liposomes (Lip-1·NO) were reported for highly selective colorimetric detection of H2S. The probe 1·NO "cross-talks" with H2S and releases nitric oxide (NO) in the process. The detection limit for H2S was found to be 0.31 μM and 0.45 μM in the cases of 1·NO and Lip-1·NO, respectively. The DAF-FM DA assay has been performed to confirm the H2S-induced NO release from 1·NO and Lip-1·NO. The sensing of H2S was also verified by ESI-MS and FT-IR spectroscopy. It was also observed that external stimuli, H2S and light worked in an almost similar way to release NO as observed by UV-Vis spectroscopy. A molecular logic gate operation "OR" was applied to the probe 1·NO in combination with inputs 'light' and 'H2S' to give the output 'NO release'. Hence, the probe 1·NO performs the dual work of sensing H2S with a colorimetric response, releasing NO upon cross-talk between NO and H2S.

A turn-on fluorescent probe for selective detection of H2S in environmental samples and bio-imaging in human breast cancer cells.

A triphenylamine-benzothaizole-based turn-on fluorescent probe TPB-NO2 was designed and synthesized for tracking H2S in both environmental and biological samples depending upon the sensing strategy of thiolysis of 2,4-dinitrophenyl (DNP) ether. Due to PET (photoinduced electron transfer), occurring from donor triphenylamine moiety to acceptor DNP moiety, the probe TPB-NO2 itself is very weakly fluorescent and colorless in DMSO/H2O solution (1 : 1, v/v; 10 mM HEPES buffer, pH 7.4). But the addition of H2S leads to thiolysis of 2,4-dinitrophenyl ether to block the initial PET process and hence it exhibits naked eye detectable turn-on response with bright cyan fluorescence and intense brown color. Not only that, the probe exhibits excellent selectivity over other bio-thiols like Cysteine (Cys), homocysteine (Hcy), and glutathione (GSH), fast response time (<2 min), and high sensitivity with a detection limit of 9.81 nM. Moreover, to explore the practical applicability of our probe we employed it to monitor H2S successfully in environmental water samples, solid-state TLC strip study, Quantitative determination of H2S in eggs, and in the bioimaging of human breast cancer cells (MDA-MB 231).

A Golgi Apparatus‐Targetable Probe Based on Lanthanide Complexes for Ratiometric Time‐Gated Luminescence Detection of Hydrogen Sulfide

AbstractDevelopment of bioanalytical methods for selective and accurate detection of H2S in living samples is essential for understanding the pathological and physiological functions of this gasotransmitter in biological systems. Here we report a Golgi apparatus‐targetable lanthanide complex‐based luminescent probe, Golgi‐ABTTA‐Eu3+/Tb3+, that can be used for accurately determining H2S in aqueous solution and living cells via the ratiometric time‐gated luminescence (RM‐TGL) technique. This probe is composed of 2,2′:6′,2′′‐terpyridine‐Eu3+/Tb3+ mixed complexes as the luminophore, 4‐azidobenzyl‐ether as the responsive moiety, and sulfanilamide as the Golgi apparatus‐targeting moiety. Upon reaction with H2S, accompanied by the cleavage of 4‐azidobenzyl group from the probe molecule, the long‐lived emission of Tb3+ complex at 540 nm is significantly enhanced, while that of Eu3+ complex at 610 nm is obviously reduced. It was noted that the I540/I610 ratio increased by 8.8 times after the probe was exposed to H2S, which enabled H2S to be detected with RM‐TGL method. After being incubated with living cells, the probe molecules were selectively accumulated in the Golgi apparatus, which allowed H2S in the Golgi apparatus to be successfully imaged in RM‐TGL mode.