硫化氢(H2S)是一种具有臭鸡蛋气味的有毒气体,酒类中过量的H2S不仅会影响其饮用风味,而且会对人体造成危害,因此对于酒类中H2S含量的检测是非常必要的。该文构建了一种基于H2S引起的特殊还原反应的表面增强拉曼散射(surface-enhanced Raman scattering,SERS)纳米探针,用于葡萄酒和啤酒中H2S的快速灵敏检测。首先制备了金纳米星(gold nanostars,AuNSs)、金纳米立方体(gold nanocubes,AuNCs)和金纳米球(gold nanospheres,AuNPs),然后通过Au-S键分别共价连接上H2S的供体4-硝基苯硫酚(4-nitrophenylthiophenol,4-NTP),获得3种探针AuNPs@4-NTP、AuNCs@4-NTP和AuNSs@4-NTP。通过比较三者的拉曼图谱,筛选出拉曼增强效果最好的AuNSs@4-NTP作为SERS纳米探针开展H2S的检测。当H2S存在时,SERS纳米探针中的4-NTP的硝基被H2S还原成氨基,使得硝基峰的拉曼信号强度明显降低,从而实现对H2S的灵敏检测。实验结果表明,H2S在10~200 nmol/L范围内,SERS纳米探针对其表现出良好的线性响应,检测限为3.24 nmol/L。该SERS纳米探针具有良好的H2S检测特异性,对其他干扰物质的响应能力较弱。重要的是,该SERS纳米探针可应用于检测市售葡萄酒和啤酒样品中的H2S,回收率在97.54%~101.78%,具有良好的实际应用潜能。
Hydrogen sulfide (H2S) is a toxic gas with a characteristic rotten egg odor.Elevated levels of H2S in alcoholic beverages not only compromise their flavor but also pose health risks.Therefore, effective monitoring of H2S concentration in such products is critical.This study developed a surface-enhanced Raman scattering (SERS) nanoprobe for the rapid and sensitive detection of H2S in wine and beer.Firstly, gold nanostars (AuNSs), gold nanocubes (AuNCs), and gold nanospheres (AuNPs) were synthesized, and the donor molecule 4-nitrophenylthiophenol (4-NTP) was covalently attached to the nanoparticles via Au-S bonds to form three nanoprobes:AuNSs@4-NTP, AuNCs@4-NTP and AuNPs@4-NTP.Among them, AuNSs@4-NTP exhibited the strongest Raman enhancement and was selected as the optimal SERS nanoprobe for H2S detection.Upon exposure to H2S, the nitro group in 4-NTP was reduced to an amino group, resulting in a marked decrease in the Raman signal intensity of the nitro peak, thereby enabling sensitive detection of H2S.Experimental results demonstrated that the SERS nanoprobe exhibited a good linear response to H2S over the concentration range of 10-200 nmol·L-1, with a detection limit of 3.24 nmol/L.The nanoprobe also exhibited high specificity for H2S, with minimal interference from other substances.Furthermore, it was successfully applied to detect H2S in commercial wine and beer samples, achieving recovery rates between 97.54% and 101.78%, highlighting its practical applicability.
[1] KOLLURU G K, SHACKELFORD R E, SHEN X G, et al.Sulfide regulation of cardiovascular function in health and disease[J].Nature Reviews Cardiology, 2023, 20(2):109-125.
[2] LI S P, HU K D, HU L Y, et al.Hydrogen sulfide alleviates postharvest senescence of broccoli by modulating antioxidant defense and senescence-related gene expression[J].Journal of Agricultural and Food Chemistry, 2014, 62(5):1119.
[3] SHANG Z Y, MENG Q T, TIAN D H, et al.Red-emitting fluorescent probe for hydrogen sulfide detection and its applications in food freshness determination and in vivo bioimaging[J].Food Chemistry, 2023, 427:136701.
[4] YU Y X, LI G L, WU D, et al.Determination of hydrogen sulfide in wines based on chemical-derivatization-triggered aggregation-induced emission by high-performance liquid chromatography with fluorescence detection[J].Journal of Agricultural and Food Chemistry, 2020, 68(3):876-883.
[5] VELA E, HERNÁNDEZ-ORTE P, FRANCO-LUESMA E, et al.The effects of copper fining on the wine content in sulfur off-odors and on their evolution during accelerated anoxic storage[J].Food Chemistry, 2017, 231:212-221.
[6] XING X, WU L Y, ZHANG Y C, et al.Femtomolar hydrogen sulfide detection via hybrid small-molecule nano-arrays[J].Nature Communications, 2024, 15:10831.
[7] ZHAI X R, LI S, WANG Y K, et al.A magnet-renewable electroanalysis strategy for hydrogen sulfide in aquaculture freshwater using magnetic silver metal-organic frameworks[J].Analytica Chimica Acta, 2022, 1195:339450.
[8] CAO J, LOPEZ R, THACKER J M, et al.Chemiluminescent probes for imaging H2S in living animals[J].Chemical Science, 2015, 6(3):1979-1985.
[9] ZHANG Y Q, GU Y Q, HE J, et al.Ultrabright gap-enhanced Raman tags for high-speed bioimaging[J].Nature Communications, 2019, 10(1):3905.
[10] HANG Y J, BORYCZKA J, WU N Q.Visible-light and near-infrared fluorescence and surface-enhanced Raman scattering point-of-care sensing and bio-imaging:A review[J].Chemical Society Reviews, 2022, 51(1):329-375.
[11] QI X Y, YE Y F, WANG H, et al.An ultrasensitive and dual-recognition SERS biosensor based on Fe3O4@Au-Teicoplanin and aptamer functionalized Au@Ag nanoparticles for detection of Staphylococcus aureus[J].Talanta, 2022, 250:123648.
[12] TONG L M, ZHU T, LIU Z F.Approaching the electromagnetic mechanism of surface-enhanced Raman scattering:From self-assembled arrays to individual gold nanoparticles[J].Chemical Society Reviews, 2011, 40(3):1296-1304.
[13] ZHONG Q M, ZHANG R R, YANG B B, et al.A rational designed bioorthogonal surface-enhanced Raman scattering nanoprobe for quantitatively visualizing endogenous hydrogen sulfide in single living cells[J].ACS Sensors, 2022, 7(3):893-899.
[14] ZHANG W S, WANG Y N, XU Z R.High sensitivity and non-background SERS detection of endogenous hydrogen sulfide in living cells using core-shell nanoparticles[J].Analytica Chimica Acta, 2020, 1094:106-112.
[15] CHEN S, FAN J Y, LV M Y, et al.Internal standard assisted surface-enhanced Raman scattering nanoprobe with 4-NTP as recognition unit for ratiometric imaging hydrogen sulfide in living cells[J].Analytical Chemistry, 2022, 94(42):14675-14681.
[16] WANG X L, YANG H R, SUN T, et al.A fluorescence and SERS dual-mode biosensor for quantification and imaging of Mucin1 in living cells[J].Biosensors and Bioelectronics, 2025, 270:116964.
[17] WANG J W, MA S, GE K Z, et al.Face-to-face assembly strategy of Au nanocubes:Induced generation of broad hotspot regions for SERS-fluorescence dual-signal detection of intracellular miRNAs[J].Analytical Chemistry, 2024, 96(22):8922-8931.
[18] LIU H, CHEN R, WU K X, et al.Ratiometric fluorescent biosensor for detection and real-time imaging of nitric oxide in mitochondria of living cells[J].Biosensors and Bioelectronics, 2024, 248:116000.
[19] ZHU A F, ALI S, JIAO T H, et al.Facile synthesis of fluorescence-SERS dual-probe nanocomposites for ultrasensitive detection of sulfur-containing gases in water and beer samples[J].Food Chemistry, 2023, 420:136095.
