Sensitive Detection Of Hydrogen Sulfide Research Articles

A new-style pohotoelectrochemical sensing device based on NH2-UiO-66@Bi2O3 for the sensitive detection of hydrogen sulfide

Hydrogen sulfide (H2S) has been regarded as an environmentally hazardous substance and its abnormal level in the atmosphere can cause great harm for human body. Therefore, the development of a rapid and sensitive method for H2S detection is valuable for both human health and ecosystem safety. Herein, a new-style photoelectrochemical (PEC) sensing device integrated with a headspace separation system for sensing H2S was constructed by assembling a NH2-UiO-66@Bi2O3 modified photoelectrode array which was prepared by a vacuum filtration technique. According to the experimental results, the H2S gas volatilized from the test sample induces partial in situ transformation of the NH2-UiO-66@Bi2O3 modified on photoelectrode array into NH2-UiO-66@Bi2S3 which promotes electron-holes separation and visible light absorption, thus leading to the enhancement of photocurrent response. Correspondingly, a signal-on PEC sensing device was thereby constructed for sensing H2S concentration linearly ranging from 2.5 to 100 µM, with a detection limit of about 0.78 µM. Beyond that, the feasibility of sensing H2S in environment samples was further confirmed by recovery assays. This work could broaden a new vision of the elegant design of portable PEC sensor for rapid and sensitive environmental analysis.

A Near-Infrared Fluorescent Probe with Large Stokes Shift for Sensitive Detection of Hydrogen Sulfide in Environmental Water, Food Spoilage, and Biological Systems.

Hydrogen sulfide (H2S) is an important endogenous gas transmitter that plays a critical role in various physiological and pathological processes and can also cause a negative impact on foodstuffs. In this study, we designed and synthesized a simple, easily available, high-yield, and low-cost near-infrared (λem = 710 nm) fluorescent probe, DEM-H2S, with a substantial Stokes shift (205 nm) for the detection of H2S. DEM-H2S features high selectivity and sensitivity (LOD = 80 nM) toward H2S, accompanied by a noticeable color change. Upon interaction with H2S, DEM-H2S exhibits a restored ICT (Intramolecular Charge Transfer) process, thereby manifesting near-infrared fluorescence. DEM-H2S has been successfully utilized to detect H2S in actual water samples and to monitor the spoilage of food items, such as pork, shrimp, and eggs. Furthermore, DEM-H2S enables the imaging of endogenous and exogenous H2S in living MCF-7 cells and zebrafish. Hence, DEM-H2S provides an attractive method for the detection of H2S in environmental, food, and biological systems, holding potential value in physiological and pathological research.

A ratiometric near-infrared fluorescent probe with a large Stokes shift for rapid and sensitive detection of hydrogen sulfide in food samples and imaging in biological system

Hydrogen sulfide (H2S) has multiple contributions to living organisms and is also linked to the freshness of most high-protein foodstuffs. Therefore, developing a highly sensitive technology for on-site detection of H2S is promising and crucial. In this paper, a novel ratiometric near-infrared fluorescent probe 1,1,3-trimethyl-2-(4-(5,5,7-trimethyl-4,5,6,7-tetrahydro-3H-4,6-methanobenzo[d]imidazol-2-yl)styryl)− 1H-benzo[e]indol-3-ium iodide (TIBI) was designed and synthesized from α-pinene derivative 4,6,6-trimethylbicyclo[3.1.1]heptane-2,3-dione for the specific detection of H2S. TIBI displayed several excellent merits during the detection of H2S including low detection limit (19.43 nM), short response time (50 s), and wide pH detection range (59). The emission wavelength of TIBI blue-shifted from 690 nm to 460 nm accompanying with the fluorescence color changed from red to blue at the presence of H2S, and its fluorescence intensity ratio (I460 nm/I690 nm) enhanced up by 540 folds. The TIBI-loaded test strips could successfully achieved the real-time and convenient monitoring of H2S produced from food spoilage. Besides, probe TIBI could be also applied for imaging H2S level in living cells and zebrafish.

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.

A Novel Turn-On Fluorescent Probe Based on Naphthalimide for Highly Selective and Sensitive Detection of Hydrogen Sulfide in Solution and Gas

A Novel Turn-On Fluorescent Probe Based on Naphthalimide for Highly Selective and Sensitive Detection of Hydrogen Sulfide in Solution and Gas

Dye-Embedded Nanomof as a Turn-On Fluorescent Sensor for Selective and Sensitive Detection of Hydrogen Sulfide

Dye-Embedded Nanomof as a Turn-On Fluorescent Sensor for Selective and Sensitive Detection of Hydrogen Sulfide

Ruthenium(II) complex encapsulated multifunctional metal organic frameworks based electrochemiluminescence sensor for sensitive detection of hydrogen sulfide

Metal organic frameworks (MOFs) based sensors exhibited a good deal of merits on sensitive detection like low reagent consumption, good chemical stability and high detection efficacy. Here, we reported a novel electrochemiluminescence (ECL) sensor which was based on tris(2,2′-bipyridyl) ruthenium(II) (Ru(bpy)32+) encapsulated multifunctional metal organic frameworks (Ru-MOFs) as nanocarrier and nanoreactor for sensitive detection of H2S. Moreover, novel co-reactants NBD-amine was introduced into the ECL sensor as recognition probe. The introducing of Ru-MOFs successfully increased the amount of luminescent probe in the sensing system. At the same time, the Ru-MOFs as nanoreactors improved the molecule reaction efficiency inside the MOFs, including Ru(bpy)32+/co-reactants, and NBD-amine/H2S. Furthermore, the Ru-MOFs has superior adsorption capacity for H2S, which will facilitate the enrichment of H2S at the sensing interface. These were all contributed to enhance the ECL signal and improve the sensitivity of proposed ECL sensor. As a result, the proposed ECL sensor had excellent detection performance for H2S with the dynamic range from 1.0 × 10−11 mol L−1 to 1.0 × 10−4 mol L−1 and the detection limit was 2.5 × 10−12 mol L−1.

BODIPY-NBD dyad for highly selective and sensitive detection of hydrogen sulfide in cells and zebrafish

Hydrogen sulfide (H2S) has been regarded as the third endogenous gas signaling molecule. The development of suitable tools for H2S detection in vitro and in vivo has always been a focus of research. In this work, three BODIPY-NBD dyads (o/m/p-BNP) were designed and synthesized using BODIPY and NBD as the fluorophore and quencher, respectively. The position of the NBD moiety in the probe showed different fluorescence quenching abilities. All probes showed highly selective to H2S. Probe o-BNP displayed the maximum fluorescence enhancement (c.a. 1300-fold) and the lowest detection limit (105 nM). Probe o-BNP can visualize the production of endogenous H2S in HeLa cells and zebrafish.

ZnO@CuO hollow nanosphere-based composites used for the sensitive detection of hydrogen sulfide with long-term stability.

In this study, zinc oxide@cupric oxide hollow nanospheres (ZnO@CuO HNS, 330 nm in diameter) were successfully prepared by a hard-template method using amino-phenolformaldehyde resin spheres (APF) as the templates. A new type of thin-film gas sensor toward hydrogen sulfide (H2S) was fabricated by means of drop-coating on the gold electrode of an alumina ceramic tube. The microstructure and morphology of the nanosphere composites were characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM), and the gas-sensing performance of the composites toward the detection of H2S were investigated. The ZnO@CuO nanocomposite with a hollow structure exhibited good gas-sensing properties. Under the optimum operating temperature of 260 °C, ambient temperature of 30 °C, and ambient humidity of 70%, the linear response of the sensor to H2S was in the concentration range of 0.1-100 ppm, and its detection limit reached 0.0611 ppm, with a quick response time of 78 s. Also, the sensor possessed good repeatability, selectivity, and stability. The long-term stability and run duration of such sensors were pronounced, with only a 1.9% reduction in the signal after the continuous monitoring of H2S gas in a pig farm for 18 months using Alibaba's cloud remote transmission system, which presents an important practical application prospect in atmosphere environment monitoring on livestock-raising fields.

Silver transfer based plasmonic nanoprobe for highly sensitive detection of hydrogen sulfide

Hydrogen sulfide plays a non-negligible role in regulating the redox state and other signaling processes in cells, and the abnormal level of H2S in the organism is recognized as an important indicator of various diseases. To disclose the physiological and pathological effects of H2S, accurate and sensitive detection technology is imperatively required. In this report, we designed a mix-detect model plasmonic nanoprobe for the rapid and efficient detection of H2S based on the silver transfer. In the presence of H2S, silver can be transferred to the surface of AuNRs to form an Ag2S layer during the etching process of Ag nanoparticles, thereby detecting a significant SPR peak shift to determine the H2S content. This method has good anti-interference ability and a good linear relationship ranging from 1 to 10 nM, with a detection limit of 0.3 nM. Besides, this plasmonic nanoprobe is more suitable for H2S detection in actual biological samples due to its SPR shift in the NIR region, which makes the plasmonic nanoprobe more valuable for H2S detection in actual biological samples.

Highly Selective and Sensitive Detection of Hydrogen Sulfide by the Diffraction Peak of Periodic Au Nanoparticle Array with Silver Coating

The two-dimensional (2D) periodic Au nanosphere array with silver coating was prepared by using a colloidal monolayer template to obtain a Au nanosphere array and subsequently depositing silver thin coating on it, which could be used as an optical sensor to effectively detect H2S. Such periodic Au nanosphere array with silver coating displayed a surface plasmonic resonance (SPR) peak and an optical diffraction peak. Compared with the SPR peak, the diffraction peak, originated from the periodic arrangements of the obtained array, demonstrated a more sensitive optical change to detect H2S with a significant redshift as the H2S concentration increased. It was attributed to the increase of the refractive index of the environment around the Au nanosphere arrays with silver coating due to the partial formation of Ag2S after detecting H2S. Furthermore, the H2S sensor based on the change of the optical diffraction peak, showed an excellent selectivity and it was very sensitive to detect H2S from 2 to 30 μM. This method was investigated by the analysis in H2S-spiked blood samples, which indicates that the method has the potential to detect H2S in blood samples. The presented work provides a new strategy of utilizing the optical diffraction peak of the periodic array to develop promising sensors.

Highly selective and sensitive detection of hydrogen sulfide in aqueous medium and live cells using peptide-based bioprobe to mimic the binding sites of the ceruloplasmin for Cu(II) ions

Hydrogen sulfide (H2S) plays a vital role in biological systems, so it is important to develop new methods for monitoring H2S with high selectively and sensitivity. In this study, we report the efficient solid phase synthesis of a new peptide-based bioprobe L that mimics the Cu(II) binding sites of ceruloplasmin. L exhibits highly sensitive colorimetric and fluorescent “turn off” responses to Cu2+ with high selectively among various metal ions over a broad pH range in 100% aqueous solutions. Interestingly, as a new promising analytical bioprobe, the L-Cu ensemble can monitor H2S by both colorimetric and fluorescent changes, and the limit of detection (LOD) is found to be as low as 14.7 nM. The reversibility experiment indicated that L could be recycled many times as reversible bioprobe. It is worth noting that L could be used to detect Cu2+ and H2S specifically in two real samples. Moreover, L exhibited excellent water-solubility and low biotoxicity even at high concentrations based on MTT study, and cell imaging results indicated that it can be applied to detecting Cu(II) and H2S in living RKO cells monitored by confocal fluorescence microscopy imaging.

A FRET-based upconversion nanoprobe assembled with an electrochromic chromophore for sensitive detection of hydrogen sulfide in vitro and in vivo.

Hydrogen sulfide (H2S) as an important gaseous signaling molecule is closely related to numerous biological processes in living systems. To further study the physiological and pathological roles of H2S, convenient and efficient detection techniques for endogenous H2S in vivo are still in urgent demand. In this study, an electrochromic chromophore, dicationic 1,1,4,4-tetra-aryl butadiene (EM1), was innovatively introduced into upconversion nanoparticles (UCNPs) and a nanoprobe, PAAO-UCNPs-EM1, was constructed for the detection of H2S. This nanosystem was made of core-shell upconversion nanoparticles (NaYF4:Yb,Tm@NaYF4:Yb,Er), EM1, and polyacrylic acid (PAA)-octylamine. The EM1 with strong absorption ranging from 500 to 850 nm could serve as an energy acceptor to quench the upconversion luminescence of UCNPs through the Förster resonance energy transfer (FRET) process. In the presence of H2S, the EM1 in the nanoprobe was reduced to a colorless diene (EM2), resulting in the linear enhancement of luminescence emissions at 660 nm and 800 nm under the excitation of 980 nm light because the FRET was switched off. The nanoprobe PAAO-UCNPs-EM1PAAO-UCNPs-EM1 exhibited fast response and high sensitivity to H2S with a LoD of 1.21 × 10-7 M. Moreover, it was successfully employed in detecting the endogenous and exogenous H2S in living cells with high selectivity and low cytotoxicity. Also, this nanoprobe could distinguish normal and tumor cells by an upconversion luminescence imaging of endogenous H2S. Furthermore, the nanoprobe could significantly monitor H2S in a tumor-bearing nude mouse model. Therefore, we anticipate that this novel nanoprobe assembled with an electrochromic chromophore for responding to H2S and for bioimaging this molecule would have a promising prospect in biological and clinical investigations.

Fast response near-infrared fluorescent probe for hydrogen sulfide in natural waters

Rapid and sensitive detection of hydrogen sulfide (H2S) is of great importance for the environmental monitoring. Near-infrared fluorescent probes are recently developed for the sensitive H2S detection thanks to their low background interference, while often hampered by relatively long response time (around 30 min). In this work, we reported a fast response (within 5 min), highly sensitive near-infrared (NIR) fluorescent probe (DCM-OCN) for H2S. The rapid nucleophilic reaction between cyanate moiety and H2S endowed fast response of the NIR probe. The influence of experimental parameters (including CTAB concentration, reaction time, pH value etc.), interference study, and possible mechanism were investigated in detail. The fluorescence increment was linear with H2S concentration in 1–10 μM with a detection limit of 0.28 μM (3σ). The probe was successfully applied to environmental water samples including river water, tap water, lake water, mineral water and artificial wastewater.

Smartphone Nanocolorimetric Determination of Hydrogen Sulfide in Biosamples after Silver–Gold Core–Shell Nanoprism-Based Headspace Single-Drop Microextraction

In this work, the sensitive detection of hydrogen sulfide (H2S) was realized at low cost and high efficiency through the application of silver-gold core-shell nanoprism (Ag@Au-np) combined with headspace single-drop microextraction (HS-SDME). After SDME, smartphone nanocolorimetry (SNC), with the aid of a smartphone camera and color picker software, was used to detect and quantify the H2S. The method took advantage of the inhibition of the ultraviolet-visible (UV-vis) signal caused by H2S etching of the Ag@Au-np preadded to the SDME solvent to measure the H2S concentration. The coating of the gold layer not only ensured the high stability of the nanomaterial but also enhanced the selectivity toward H2S. The HS-SDME method was simple to process and required only a droplet of solvent for analysis to be realized. This HS-SDME-SCN approach exhibited a calibration graph linearity of between 0.1 and 100 μM and a limit of detection of 65 nM (relative standard deviations of N% ( n = 3) < 4.80). A comparison with UV-vis spectrophotometry was conducted. The practical applicability of HS-SDME-SNC was successfully demonstrated by determining H2S in genuine biosamples (egg and milk).

A coumarin-based colorimetric fluorescent probe for rapid response and highly sensitive detection of hydrogen sulfide in living cells

Hydrogen sulfide (H2S) plays a vital role in numerous biological processes in living organisms. To better understand its functions, a fluorescent probe to fast and sensitively detect H2S is imminently needed. Keep this in mind, we reasonably designed probe DHC for detecting H2S based on α, β-unsaturated ethanoylcoumarin fluorophore. The limit of detection (LOD) is found to be as low as 5 × 10−8 M, which is superior to most reported fluorescent probes to detect H2S. Furthermore, the wide pH range of 4–11 makes it capable of application in biological systems. Most importantly, MTT assays and cell imaging experiments indicate that probe DHC has hypotoxicity and outstanding membrane permeability, which makes DHC successful imaging of H2S in Baby Hamster Syrian Kidney (BHK) cells.

Dual-Emitting Eu(III)–Cu(II) Heterometallic–Organic Framework: Simultaneous, Selective, and Sensitive Detection of Hydrogen Sulfide and Ascorbic Acid in a Wide Range

As important biomolecules, the deficiency or maladjustment of hydrogen sulfide (H2S) or ascorbic acid (AA) is associated with the symptoms of the same disease (e.g., cardiovascular disease or cancer). There is an urgent need to develop a fluorescent probe capable of distinguishing between H2S and AA simultaneously. Here, we report the syntheses, structure, and property of the first dual-detection fluorescent probe which can differentiate H2S or/and AA in aqueous media. Accordingly, a novel [EuCu(pydc)2(ox)0.5(H2O)3·1.5H2O]2 n (1, H2pydc = 2,3-pyridinedicarboxylic acid and ox = oxalic acid) for selective and sensitive detection of H2S and AA in a wide range has been constructed (H2S: [130 nM, +∞); AA: [55 nM, +∞)), exhibiting excellent catalytic activity comparable to horseradish peroxidase. In addition, the highly efficient detection in human serum sample also proves the potential application in medical diagnosis. Meanwhile, a combinatorial logic gate (AND(INH)-OR) based on activated 1 has also been constructed. Furthermore, this approach for simultaneous H2S and AA detection suggests that the current work will expand the potential application of metal-organic frameworks for dual or multiple detections in biomedical fields.

A Benzooxazole‐Based Probe for the Sensitive Detection of Hydrogen Sulfide: Kinetic and Transition‐State Studies and In Vitro Application in HepG2 Cells

AbstractA benzooxazole based probe, 2‐[4‐(2, 4‐dinitrophenoxy)‐phenyl]‐benzooxazole has been synthesized and thoroughly characterized by mass, 1H‐NMR and FT‐IR spectroscopy. The probe exhibits sensitive and selective response towards H2S in DMSO:PBS buffer (6:4, v/v, pH 7.4) over the other reactive sulfur species especially the biological thiols like cysteine, homocysteine and glutathione. Due to thiolysis of dinitrophenyl ether, this probe displays turn‐on fluorescence response where the sensing mechanism follows inhibited photoinduced electron transfer (d‐PET) process. This thiolysis reaction proceeds through aromatic nucleophilic substitution (SNAr) type mechanism. Moreover, the transition state study shows that this process is exoergic with favorable energy barrier of 5.0 kcal/mol. The kinetic studies of the probe with HS– at various pH assist to evaluate the acid dissociation constant value (Ka1 =1.09 × 10−8 M−1) of H2S that illustrate a reasonable agreement with the literature value, Ka (9.5 x 10−8 M−1). Finally, this probe is cell permeable, non‐cytotoxic and suitable for intracellular cytoplasmic HS– sensing in live cells with a very low detection limit (51.8 nM).

Two colorimetric and ratiometric fluorescence probes for hydrogen sulfide based on AIE strategy of α–cyanostilbenes

Aggregation-induced emission (AIE) active fluorescent probes have attracted great potential in biological sensors. In this paper two cyanostilbene based fluorescence chemoprobe Cya–NO2 (1) and Cya–N3 (2) were developed and evaluated for the selective and sensitive detection of hydrogen sulfide (H2S). Both of these probes behave aggression-induced emission (AIE) activity which fluoresces in the red region with a large Stokes shift. They exhibit rapid response to H2S with enormous colorimetric and ratiometric fluorescent changes. They are readily employed for assessing intracellular H2S levels.

Naked-eye and ratiometric fluorescence probe for fast and sensitive detection of hydrogen sulfide and its application in bioimaging

A sensitive and ultrafast ratiometric fluorescence probe for the detection of hydrogen sulfide (H2S) in HeLa cells and zebrafish.