Monitoring Of H2S Research Articles

A 1,3,4-thiadiazole based turn-on probe with large Stoke’s shift and ESIPT effect for fluorescent detection of H2S and its applications

Based on a useful 1,3,4-thiadiazole scaffold in our lab, a turn-on fluorescent probe for sensing H2S in environment, biological imaging and food analysis was rationally designed and synthesized. In this probe, 1,3,4-thiadiazole unit was used as fluorophore with ESIPT effect and 2,4-dinitrophenyl moiety was used as recognition fragment and fluorescent bursting agent to inhibt ESIPT. Thus, a PET process was formed and an “off–on” procedure arose after added target analyte. These brought the probe could specifically detect H2S without being interfered by other biological thiols. It showed high sensitivity (LOD=60.8 nM), large Stoke’s shift (133 nm) and had a stable performance over pH range of 6.0–9.0 in H2S monitoring system. More importantly, probe could be used for detection of H2S in real water, three beer samples and red wine sample. Furthermore, probe was successfully utilized for visualizing H2S in HeLa cells and applied for real-time monitoring of H2S during food spoilage by “naked eye” and smartphone colorimetric analysis.

2D electrodeposition assembly of Cu/Cu2O nanoarrays for low temperature H2S sensing

Ultra-sensitive hydrogen sulfide (H2S) detection technology at low temperatures provides critical support for the application of one-time alert systems under extreme conditions, ensuring reliable monitoring of H2S in low-temperature environments and enhancing safety and practicability. In this study, we developed a novel low-temperature H2S sensor based on Cu/Cu2O nanoarrays, prepared through a combination of 2D electrodeposition in situ assembly and the hydrothermal method. The heterointerface between Cu nanowires and Cu2O nanocubes presents a high barrier, which can be modulated to zero through the formation of continuous CuxS conductive channels via the vulcanization reaction, thereby achieving excellent sensitivity and selectivity towards H2S at low temperatures. At freezing temperatures and low H2S concentrations (≤20 ppm), the sensors show ideal recovery and reasonable sensitivity (R=150 to 10 ppm H2S at 0 °C). However, the response significantly increases (R=5624 at 10 ppm H2S at 50 °C) and recovery is lost under reversed conditions. First-principles calculations have confirmed that the enhanced H2S adsorption at the heterointerface is the primary reason for the robust response observed at 0 °C. Experimental results demonstrate that the Cu/Cu2O nanoarrays were capable of rapid detection of H2S at low temperatures through modulation of heterointerface barriers.

Visual Tracking of Hydrogen Sulfide: Application of a Novel Lysosome-Targeted Fluorescent Probe for Bioimaging and Food Safety Assessment.

The equilibrium state of hydrogen sulfide (H2S), a gaseous signaling molecule produced by lysosomal metabolites, in vivo is crucial for cellular function. Abnormal fluctuations in H2S concentration can interfere with the normal function of lysosomes, which has been closely linked to the pathogenesis of a variety of diseases. In view of this, a novel fluorescent probe Lyso-DPP based on 1,3,5-triarylpyrazolines was developed for the precise detection of H2S in lysosomes by using the hydrophilic morpholine moiety as a lysosomal targeting unit, and 2,4-dinitroanisole as a fluorescence-quenching and H2S-responsive unit. The probe cleverly combines the advantages of simple synthesis, sensitive blue fluorescence turn-on with a limit of detection, LOD, of 97.3 nM, good stability, and fast response time (10 min), which makes Lyso-DPP successful in portable monitoring of meat freshness in the form of test strips. Moreover, the excellent biocompatibility and precise targeting capability of the probe Lyso-DPP make it perform well in the monitoring of H2S in lysosomes, living cells, and zebrafish. This work not only provides new technical tools for food quality control but also paves up new ideas for early diagnosis and treatment of H2S-related diseases.

Bodipy-Based highly sensitive hydrogen sulfide fluorescent probe and its fluorescence imaging in cells and zebrafish

Hydrogen sulfide (H2S) is a crucial endogenous gasotransmitter that plays a role in various physiological and pathological processes. Therefore, accurate and rapid monitoring of H2S in organisms is highly significant for understanding the underlying pathological mechanisms and facilitating early diagnosis of related diseases. In this study, we developed a novel fluorescent probe, B-CHO-NO2, based on a bodipy fluorophore, which exhibits excellent sensitivity and selectivity towards H2S. The design of the probe exploits the nucleophilicity of H2S by introducing a formyl group as the ortho-participating moiety, significantly enhancing the reaction rate with H2S. In cellular and zebrafish models, the probe B-CHO-NO2 successfully achieved fluorescence imaging of endogenous and exogenous H2S. The development of probe B-CHO-NO2 provides a powerful tool for biological studies of H2S and diagnosis of related diseases.

An easily accessible probe for H2S based on AIE mechanism and its application in cell imaging

Hydrogen sulfide (H2S) is a crucial endogenous gas transmitter, maintaining the redox homeostasis in biological systems. Thus, a real-time and specific H2S detection approach is urgently necessary to study the attack and management of disorders linked to H2S. In this paper, a novel fluorescent probe HMP based on AIE property for the detection of H2S was elaborately conducted. In PBS buffer solution HMP exhibited high photostability, low detection limit (0.82 μM), significant anti-interference ability and fast response time and specificity to H2S. What’s more, it could be employed for the monitoring and luminescent imaging of H2S with Hela cells, thereby broadening the prospective capacity for diagnosing associated 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.

Ozone-enhanced photoionization ion mobility spectrometry coupled with time-resolved dynamic diluter for on-site monitoring of H2S in humid atmosphere

The online monitoring of hydrogen sulfide (H2S) presents a critical advancement for environmental protection and public health, yet existing methodologies struggle to achieve on-site, on-line and highly sensitive detection in atmospheric conditions. This study introduces a novel approach employing ozone-enhanced photoionization ion mobility spectrometry (IMS) in conjunction with a time-resolved dynamic diluter (TRDD) for the efficacious identification of H2S within environments of high humidity, such as sewers. This method ingeniously addresses the challenge of distinguishing H2S in the presence of water vapor through a dual strategy of ozone oxidization pretreatment and TRDD injection. The strategic placement of ozone within the drift region significantly amplifies the sensitivity of the IMS detection, showcasing the method's superior sensitivity, stability, and humidity interference resilience. Notably, this technique achieves a detection limit for H2S at an impressive 2.5 parts per billion (ppb), maintaining a consistent relative standard deviation (RSD) of 2.5 % over three consecutive days. Furthermore, the approach effectively mitigates the effects of moisture, maintaining an RSD of 3.0 % despite a relative humidity (RH) increase from 22 % to 95 %. Applied to the on-site measurement of H2S in sewer systems, the method demonstrated all the aforementioned performance characteristics, marking it a promising way of high humidity environment H2S monitoring.

NIR-activated water-soluble molecular probe based on Cu(ii) ion quenching mechanisms and substituted strategies: For in vitro/in vivo H2S detection

Human health, environmental contamination, and food safety are tightly associated with hydrogen sulfide (H2S). The safe and highly sensitive monitoring of H2S in tissues, organs, and blood has presented ongoing challenges. Herein, a novel near-infrared (NIR)-activated water-soluble molecular probe, denoted as IR820-TPY-Cu was developed for detecting hydrogen sulfide. This probe is built upon the fluorescent molecule IR820, a derivative of Indocyanine green (ICG). Upon reacting with H2S, IR820-TPY-Cu exhibits active fluorescence (670–750 nm), which is attributed to the Cu (II) ion quenching mechanism and substitution strategy. IR820-TPY-Cu exhibits selectively activated near-infrared fluorescence signal changes, a low detection limit of 0.114 μM, and a rapid in vitro response (3 min) for H2S detection. Moreover, the biocompatible probe IR820-TPY-Cu not only quantitatively monitors H2S in environmental water and various food specimens (red wine, beer, meat, milk, and sweet potato) through colorimetric sensing but also successfully images endogenous and exogenous H2S in living cells, zebrafish, and mice. This research provides a promising approach for monitoring H2S in environmental contamination, ensuring food safety, and studying living systems.

An AND-Gate Photoacoustic Probe for Cys and H2S Precise Photoacoustic Sensing in Localized Tumors.

Photoacoustic (PA) tomography has shown many promising aspects in noninvasive and precise imaging of deep-localized biomarkers. However, these traditional single-locked PA probes always face challenges in precise PA imaging with high specificity. Here, we report a novel AND-gate photoacoustic probe, BAE, to improve tumor imaging accuracy via the combination of two tumor-associated biomarkers, cysteine (Cys) and hydrogen sulfide (H2S). Only when Cys and H2S are concurrently introduced into the detection system does the absorption of BAE red-shift from the initial 680 to 810 nm, thereby showing a 5.29-fold enhancement in its PA signal at 810 nm. The good specificity of BAE is proven, since an obvious PA signal could be observed only in the solution containing both Cys and H2S and was not affected by other reactive sulfur species. After being taken up by tumors with the assistance of a nanomicelle, the AND-gate PA probe BAE was applied for dynamic real-time monitoring of Cys and H2S in vivo, achieving precise identification of tumors. This AND-gate PA probe provides a potential technical tool for precise sensing analysis of deep-seated diseases.

Hierarchical PVDF/ZnO/Ag/ZIF-8 nanofiber membrane used in trace-level Raman detection of H2S

surface enhanced Raman scattering (SERS) detection of gases has always been difficult due to the low affinity and poor Raman cross section of the moving molecules. To mitigate the impact of these problems on detection of gases, a structure of zinc oxide/silver nanowires coated with zeolitic imidazolate framework-8 (ZnO NWs/Ag/ZIF-8) was constructed on polyvinylidene fluoride (PVDF) nanofiber membrane (PVDF/ZnO NWs/Ag/ZIF-8) and in detail researched in this work. Benefitting from the quadruple synergistic effect of efficient Knudsen diffusion of gas molecules inside ZIF-8, enrichment of ZIF-8 microsponges for gaseous molecules, regulation of ZIF-8 dielectric layer for light and reverse light scattering of ZnO NW/Ag tip, the structure was proven to have precise co-confinement on both hot spots and gaseous molecules. As a result, this PVDF/ZnO NWs/Ag/ZIF-8 achieved excellent detection for hydrogen sulfide (H2S), with a limit of detection of 1 × 10−10 v/v and the minimum relative standard deviation value of ca. 7.13 %. Furthermore, as a proof of concept, in practical application, we designed and assembled our substrate (3.5 cm × 3.5 cm) into a SERS face mask and realized efficient monitoring of H2S in human’s exhaled breath.

Near-infrared fluorescent probe for detection of hydrogen sulfide in water samples and food spoilage

Hydrogen sulfide (H2S) is a common toxic gas that threatens the quality and safety of environmental water and food. Herein, a new near-infrared fluorescent probe DTCM was synthesized and characterized by single crystal X-ray diffraction for sensing H2S. It exhibited a remarkable “turn-on” near-infrared (NIR) emission response at 665 nm with a remarkably massive Stokes shift of 175 nm, super-rapid detection ability (within 30 s), excellent photostability, high selectivity and sensitivity (limit of detection, LOD = 58 nM). Additionally, the probe was successfully utilized for the detection of H2S in environmental water samples. The DTCM-loaded test papers enabled convenient and real-time monitoring of H2S produced by food spoilage.

Preparation of a high-performance H2S gas sensor based on CuO/Co3O4 composite derived from bimetallic MOF

The bimetallic metal–organic frameworks (MOFs), Cu/Co-MOF, was synthesized through a solvothermal method and calcined to obtain CuO/Co3O4 composites. By adjusting the molar ratio between Cu and Co ions, a composite material of CuO/Co3O4 (Cu:Co = 1:1) was developed and showed excellent sensing capabilities, and the response reached as high as 196.3 for 10 ppm H2S detection. Furthermore, the optimal operating temperature as low as 40 °C was found. In comparison with the sensors prepared by pristine CuO and pristine Co3O4, the sensor based on CuO/Co3O4 composite exhibited a significant response. Additionally, the sensor can detect H2S gas down to 300 ppb. The gas sensing mechanism is discussed in depth from the perspective of p–p heterojunction formation between the p-type CuO and p-type Co3O4. The as-prepared CuO/Co3O4 composite-based sensor is expected to find practical application in the low-power monitoring of H2S.

A Potentiometric Dual‐Channel Microsensor Reveals that Fluctuation of H2S is Less pH‐Dependent During Spreading Depolarization in the Rat Brain

AbstractSpreading depolarization (SD) is one of the most common neuropathologic phenomena in the nervous system, relating to numerous diseases. However, real‐time monitoring the rapid chemical changes during SD to probe the molecular mechanism remains a great challenge. We develop a potentiometric dual‐channel microsensor for simultaneous monitoring of H2S and pH featuring excellent selectivity and spatiotemporal resolution. Using this microsensor we first observe real time changes of H2S and pH in the rat brain induced by SD. This changes of H2S are completely suppressed when the rat pre‐treats with aminooxyacetic acid (AOAA), a blocker to inhibit the H2S‐producing enzyme, indicating H2S fluctuation might be related to enzyme‐dependent pathway during SD and less pH‐dependent. This study provides a new perspective for studying the function of H2S and the molecular basis of SD‐associated diseases.

Ultrahigh Sensitive Trace Gas Sensing System with Dual Fiber-Optic Cantilever Multiplexing-Based Differential Photoacoustic Detection.

An ultrahigh sensitive trace gas sensing system was presented with dual cantilever-based differential photoacoustic detection. By combining the double enhancement of multipass absorption and optical differential detection, the gas detection sensitivity was significantly improved. The dual-channel synchronous photoacoustic detection was realized by fiber-optic Fabry-Perot interference spectrum multiplexing. The photoacoustic signals detected by two fiber-optic cantilever microphones installed in a differential photoacoustic cell (DPAC) were out of phase, while the detected gas flow noises were in phase. The optical differential detection method achieved both highly sensitive optical interference measurement and differential noise suppression. In the multipass configuration, the interaction path between excitation light and target gas achieved 4.1 m, which improved the photoacoustic signal by an order of magnitude compared with a single reflection. The maximum gas flow allowed by the system based on the DPAC was 250 sccm, which realized the dynamic monitoring of H2S in the SF6 background. The detection limit for H2S in SF6 background was 5.1 ppb, which corresponds to the normalized noise equivalent absorption coefficient of 9 × 10-10 cm-1 W Hz-1/2.

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.

Sensitive detection of H2S based on Ce doped ZnCo2O4 hollow microspheres at low working temperature.

In order to develop a highly efficient H2S gas sensor at low working temperature, in this work, a kind of novel Ce-doped ZnCo2O4 hollow microspheres (Ce/ZnCo2O4 HMSs) were successfully synthesized using a template-free one-pot method, showing a sensitive response toward H2S. The microstructure and morphology of the material were characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The gas-sensing performance of the composite was investigated, showing that the ZnCo2O4 doped with 6 mol% Ce had the highest response to 20 ppm H2S at a low operating temperature of 160 °C with a response value of 67.42, which was about 2 times higher than that of original ZnCo2O4. The prepared Ce/ZnCo2O4 HMS sensor in response to H2S exhibited a linear range of 0.1-200 ppm with a low detection limit of 0.1 ppm under the conditions of ambient humidity of 45% and ambient temperature of 20 °C. Meanwhile, it also possessed good selectivity, repeatability and reproducibility. The response value of the sensor decreased by 5.32% after 7 months of continuous monitoring of H2S in an atmospheric environment of a pig farm, indicating that the sensor had a long-term stability and continuous service life with important application prospects.

Activatable Nanoprobes for Dual‐Modal NIR‐II Photoacoustic and Fluorescence Imaging of Hydrogen Sulfide in Colon Cancer

AbstractHigh hydrogen sulfide (H2S) expression has been shown to play a crucial role in tumor growth and proliferation in colon cancer. So far, most probes used for monitoring H2S offer single‐modal imaging, which makes the collection of accurate information for tumor diagnosis difficult. In the present study, a novel dual‐modal imaging probe in the second near‐infrared (NIR‐II, 950‐1700) window is proposed and constructed by coating a uniform shell of polydopamine (PDA) on the surface of cuprous oxide (Cu2O)‐conjugated downconversion nanoparticles (DCNPs). Of note, DCNP‐Cu2O@PDA is in the “on” state, with emission centered at 1550 nm (irradiation using a 980nm laser) in non‐neoplastic tissues. Colon tumors with endogenous H2S overexpression can induce the in situ transformation of Cu2O to copper sulfide (Cu2‐XS）. Owing to the competitive absorption between Cu2‐XS and DCNPs at a wavelength of 980 nm, the generated DCNP‐Cu2‐XS@PDA exhibits a quenched NIR‐II fluorescence (FL) signal. Meanwhile, Cu2‐XS exhibits a strong absorbance at 1250 nm, enhancing the NIR‐II photoacoustic (PA) signal accompanied by NIR‐II FL attenuation. The switching in PA and FL signals at the tumor site offered “double assurances” for the accurate monitoring of H2S.

A metal–organic framework-derived ruthenium–nitrogen–carbon nanozyme for versatile hydrogen sulfide and cystathionine γ-lyase activity assay

In this study, a novel approach exploiting the interactions between hydrogen sulfide (H2S) and ruthenium-nitrogen-carbon (Ru–N–C) nanozymes is presented, advancing H2S and cystathionine γ-lyase (CSE) biosensing techniques. Utilizing the intrinsic peroxidase-like activity of Ru–N–C nanozymes and the noticeable inhibition effect caused by H2S, an efficient, simple, and economical assay has been developed. This innovative method allows for the versatile real-time monitoring of H2S from various sources, including specialized donors and native bacterial production. Furthermore, the assay has been applied to reveal the interactions within tumor cells and tissues ex vivo, providing a clearer and simpler view of CSE expression levels through an improved colorimetric method. This contribution enhances our understanding of the complex roles of H2S metabolism and represents a significant advancement in the versatile application of nanozymes in biomedical research.

Highly Selective and Fast Response/Recovery Cataluminescence Sensor Based on SnO2 for H2S Detection.

In the present work, three kinds of nanosized SnO2 samples were successfully synthesized via a hydrothermal method with subsequent calcination at temperatures of 500 °C, 600 °C, and 700 °C. The morphology and structure of the as-prepared samples were characterized using X-ray diffraction, transmission electron microscopy, selected area electron diffraction, Brunauer-Emmett-Teller analysis, and X-ray photoelectron spectroscopy. The results clearly indicated that the SnO2 sample calcined at 600 °C had a higher amount of chemisorbed oxygen than the SnO2 samples calcined at 500 °C and 700 °C. Gas sensing investigations revealed that the cataluminescence (CTL) sensors based on the three SnO2 samples all exhibited high selectivity toward H2S, but the sensor based on SnO2-600 °C exhibited the highest response under the same conditions. At an operating temperature of 210 °C, the SnO2-600 °C sensor showed a good linear response to H2S in the concentration range of 20-420 ppm, with a detection limit of 8 ppm. The response and recovery times were 3.5 s/1.5 s for H2S gas within the linear range. The study on the sensing mechanism indicated that H2S was oxidized into excited states of SO2 by chemisorbed oxygen on the SnO2 surface, which was mainly responsible for CTL emission. The chemisorbed oxygen played an important role in the oxidation of H2S, and, as such, the reason for the SnO2-600 °C sensor showing the highest response could be ascribed to the highest amount of chemisorbed oxygen on its surface. The proposed SnO2-based gas sensor has great potential for the rapid monitoring of H2S.

AirQuality Lab-on-a-Drone: A Low-Cost 3D-Printed Analytical IoT Platform for Vertical Monitoring of Gaseous H2S.

The measurement of gaseous compounds in the atmosphere is a multichallenging task due to their low concentration range, long and latitudinal concentration variations, and the presence of sample interferents. Herein, we present a quadcopter drone deployed with a fully integrated 3D-printed analytical laboratory for H2S monitoring. Also, the analytical system makes part of the Internet of Things approach. The analytical method applied was based on the reaction between fluorescein mercuric acetate and H2S that led to fluorescence quenching. A 5 V micropump at a constant airflow of 50 mL min-1 was employed to deliver constant air into a flask containing 800 μL of the reagent. The analytical signal was obtained using a light-emitting diode and a miniaturized digital light detector. The method enabled the detection of H2S in the range from 15 to 200 ppbv, with a reproducibility of 5% for a sampling time of 10 min and an limit of detection of 9 ppbv. All devices were controlled using an Arduino powered by a small power bank, and the results were transmitted to a smartphone via Bluetooth. The proposed device resulted in a weight of 300 g and an overall cost of ∼50 USD. The platform was used to monitor the concentration of H2S in different intervals next to a wastewater treatment plant at ground and vertical levels. The ability to perform all analytical steps in the same device, the low-energy requirements, the low weight, and the attachment of data transmission modules offer new possibilities for drone-based analytical systems for air pollution monitoring.