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Reaction-based turn-on electrochemiluminescent sensor with a ruthenium(II) complex for selective detection of extracellular hydrogen sulfide in rat brain.
Anal Chem. 2015 Feb 03; 87(3):1839-45.AC

Abstract

Hydrogen sulfide (H2S) has been drawing increasing attention because it plays an important role in the nervous system and has been deemed as a third endogenous gas signal molecule besides nitric oxide (NO) and carbon monoxide (CO). In this study, using a ruthenium complex, [Ru(bpy)2(bpy-DPA)Cu](4+) (where bpy = 2,2'-bipyridine and bpy-DPA = 4-methyl-4'-[N,N-bis(2-picolyl)aminomethylene]-2,2'-bipyridine) as recognition unit, we report a new reaction-based turn-on electrochemiluminescent (ECL) sensor to selectively detect extracellular H2S in rat brain, coupled with in vivo microdialysis for dialysate sampling. To prepare the sensor for sensing endogenous H2S, [Ru(bpy)2(bpy-DPA)](2+) is first designed and synthesized, showing high ECL efficiency with tri-n-propylamine (TPA) as a coreactant and quenching after reaction with Cu(2+) (forming [Ru(bpy)2(bpy-DPA)Cu](4+)). Then a Nafion membrane is coated on the surface of glassy carbon (GC) electrode and [Ru(bpy)2(bpy-DPA)Cu](4+) is confined onto the Nafion membrane through ion exchange. The resulting [Ru(bpy)2(bpy-DPA)Cu](4+)/Nafion/GC sensor exhibits a low ECL signal. The [Ru(bpy)2(bpy-DPA)Cu](4+)/Nafion/GC sensor demonstrates enhanced ECL signal after reacting with volatile H2S due to the high-affinity binding between sulfur and Cu(2+), returning to [Ru(bpy)2(bpy-DPA)](2+)/Nafion/GC. The changes of ECL signal at the sensor depend linearly on the concentration of Na2S in the range from 0.5 to 10 μM, with a detection limit of 0.25 μM. Moreover, the sensor demonstrates high selectivity, free from interference especially by other nonvolatile thiol-containing species, such as cysteine and glutathione. The basal dialysate level of H2S in the microdialysate from the cortex of adult male Sprague-Dawley rats is determined to be 2.3 ± 0.9 μM (n = 4). This method is reliable and is envisaged to help understand the regulation of H2S in physiological and pathological events.

Authors+Show Affiliations

Department of Chemistry, Renmin University of China , Beijing 100872, China.No affiliation info availableNo affiliation info availableNo affiliation info available

Pub Type(s)

Evaluation Study
Journal Article
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

25574779

Citation

Yue, Xiaoxiao, et al. "Reaction-based Turn-on Electrochemiluminescent Sensor With a ruthenium(II) Complex for Selective Detection of Extracellular Hydrogen Sulfide in Rat Brain." Analytical Chemistry, vol. 87, no. 3, 2015, pp. 1839-45.
Yue X, Zhu Z, Zhang M, et al. Reaction-based turn-on electrochemiluminescent sensor with a ruthenium(II) complex for selective detection of extracellular hydrogen sulfide in rat brain. Anal Chem. 2015;87(3):1839-45.
Yue, X., Zhu, Z., Zhang, M., & Ye, Z. (2015). Reaction-based turn-on electrochemiluminescent sensor with a ruthenium(II) complex for selective detection of extracellular hydrogen sulfide in rat brain. Analytical Chemistry, 87(3), 1839-45. https://doi.org/10.1021/ac503875j
Yue X, et al. Reaction-based Turn-on Electrochemiluminescent Sensor With a ruthenium(II) Complex for Selective Detection of Extracellular Hydrogen Sulfide in Rat Brain. Anal Chem. 2015 Feb 3;87(3):1839-45. PubMed PMID: 25574779.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Reaction-based turn-on electrochemiluminescent sensor with a ruthenium(II) complex for selective detection of extracellular hydrogen sulfide in rat brain. AU - Yue,Xiaoxiao, AU - Zhu,Ziyu, AU - Zhang,Meining, AU - Ye,Zhiqiang, Y1 - 2015/01/09/ PY - 2015/1/10/entrez PY - 2015/1/13/pubmed PY - 2015/9/10/medline SP - 1839 EP - 45 JF - Analytical chemistry JO - Anal Chem VL - 87 IS - 3 N2 - Hydrogen sulfide (H2S) has been drawing increasing attention because it plays an important role in the nervous system and has been deemed as a third endogenous gas signal molecule besides nitric oxide (NO) and carbon monoxide (CO). In this study, using a ruthenium complex, [Ru(bpy)2(bpy-DPA)Cu](4+) (where bpy = 2,2'-bipyridine and bpy-DPA = 4-methyl-4'-[N,N-bis(2-picolyl)aminomethylene]-2,2'-bipyridine) as recognition unit, we report a new reaction-based turn-on electrochemiluminescent (ECL) sensor to selectively detect extracellular H2S in rat brain, coupled with in vivo microdialysis for dialysate sampling. To prepare the sensor for sensing endogenous H2S, [Ru(bpy)2(bpy-DPA)](2+) is first designed and synthesized, showing high ECL efficiency with tri-n-propylamine (TPA) as a coreactant and quenching after reaction with Cu(2+) (forming [Ru(bpy)2(bpy-DPA)Cu](4+)). Then a Nafion membrane is coated on the surface of glassy carbon (GC) electrode and [Ru(bpy)2(bpy-DPA)Cu](4+) is confined onto the Nafion membrane through ion exchange. The resulting [Ru(bpy)2(bpy-DPA)Cu](4+)/Nafion/GC sensor exhibits a low ECL signal. The [Ru(bpy)2(bpy-DPA)Cu](4+)/Nafion/GC sensor demonstrates enhanced ECL signal after reacting with volatile H2S due to the high-affinity binding between sulfur and Cu(2+), returning to [Ru(bpy)2(bpy-DPA)](2+)/Nafion/GC. The changes of ECL signal at the sensor depend linearly on the concentration of Na2S in the range from 0.5 to 10 μM, with a detection limit of 0.25 μM. Moreover, the sensor demonstrates high selectivity, free from interference especially by other nonvolatile thiol-containing species, such as cysteine and glutathione. The basal dialysate level of H2S in the microdialysate from the cortex of adult male Sprague-Dawley rats is determined to be 2.3 ± 0.9 μM (n = 4). This method is reliable and is envisaged to help understand the regulation of H2S in physiological and pathological events. SN - 1520-6882 UR - https://www.unboundmedicine.com/medline/citation/25574779/Reaction_based_turn_on_electrochemiluminescent_sensor_with_a_ruthenium_II__complex_for_selective_detection_of_extracellular_hydrogen_sulfide_in_rat_brain_ DB - PRIME DP - Unbound Medicine ER -