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Ag–Au–Cu Trimetallic Alloy Microflower: A Highly Sensitive SERS Substrate for Detection of Low Raman Scattering Cross-Section Thiols
Langmuir ( IF 3.7 ) Pub Date : 2023-11-09 , DOI: 10.1021/acs.langmuir.3c02528 Sravani Kaja 1 , Amit Nag 1
Langmuir ( IF 3.7 ) Pub Date : 2023-11-09 , DOI: 10.1021/acs.langmuir.3c02528 Sravani Kaja 1 , Amit Nag 1
Affiliation
Trimetallic Ag–Au–Cu alloy microflowers (MFs) with various surface compositions were synthesized on a glass coverslip and used as efficient surface-enhanced Raman spectroscopy (SERS) substrates for highly sensitive label-free detection of smaller Raman scattering cross-section molecules, namely, L-cysteine and toxic thiophenols. MFs of different compositions were synthesized via appropriate mixing of metal–alkyl ammonium halide precursors followed by a single-step thermolysis at 350 °C. While the Ag percentage was kept constant at 90% for all the substrates, the composition of Au and Cu was varied between 1 and 9% sequentially. The synthesized MFs were thoroughly characterized by using field emission scanning electron microscopy (FE-SEM), wide-angle X-ray scattering, X-ray photoelectron spectroscopy (XPS), and X-ray fluorescence techniques. FE-SEM studies revealed that the MFs were present throughout the substrate, and the average size varied from 20 to 40 μm. XPS studies showed that the top surface of the alloy substrates was rich in either Au or Cu atoms, while Ag remained underneath. The performance of the trimetallic MFs as SERS substrates was evaluated using Rhodamine 6G as a probe molecule, which showed that the MFs with Ag–Au–Cu compositions 90–7–3 and 90–3–7 were found to be the best and of equal SERS efficiency. The SERS enhancement factor (EF) of both these MFs was found to be the same, approximately 9 × 107, when calculated using 1,2,3-benzatriazole as the probe molecule. Between the two, the trimetallic substrate with a higher Au percentage (Ag–Au–Cu as 90–7–3) was used for the sensitive SERS-based detection of thiols to exploit the strong Au–S binding interaction. By virtue of the high EF of the substrate, the inherently low Raman scattering cross-sections of the probe molecules were greatly enhanced in SERS mode. The 'limit of quantification (LOQ)' values were found to be 1 nM for aliphatic L-Cysteine and 1–0.1 pM for aromatic thiols using the trimetallic SERS sensor.
中文翻译:
Ag-Au-Cu 三金属合金 Microflower:用于检测低拉曼散射截面硫醇的高灵敏度 SERS 基底
在玻璃盖玻片上合成了具有各种表面成分的三金属银-金-铜合金微花(MF),并用作高效的表面增强拉曼光谱(SERS)基底,用于对较小拉曼散射截面分子进行高灵敏度无标记检测,即L-半胱氨酸和有毒的苯硫酚。通过适当混合金属烷基卤化铵前体,然后在 350 °C 下进行一步热解,合成了不同成分的 MF。虽然所有基材的 Ag 百分比保持恒定在 90%,但 Au 和 Cu 的成分依次在 1% 和 9% 之间变化。通过使用场发射扫描电子显微镜 (FE-SEM)、广角 X 射线散射、X 射线光电子能谱 (XPS) 和 X 射线荧光技术对合成的 MF 进行了彻底表征。 FE-SEM 研究表明,MF 存在于整个基材中,平均尺寸为 20 至 40 μm。 XPS 研究表明,合金基底的顶面富含金或铜原子,而银则保留在下面。使用罗丹明 6G 作为探针分子评估了三金属 MF 作为 SERS 基底的性能,结果表明,Ag-Au-Cu 成分为 90-7-3 和 90-3-7 的 MF 是最好的,并且是最佳的。相同的 SERS 效率。当使用 1,2,3-苯并三唑作为探针分子计算时,发现这两个 MF 的 SERS 增强因子 (EF) 相同,约为 9 × 10 7 。在两者之间,具有较高 Au 百分比(Ag-Au-Cu 为 90-7-3)的三金属基板用于基于 SERS 的硫醇敏感检测,以利用强 Au-S 结合相互作用。 凭借基底的高EF,探针分子固有的低拉曼散射截面在SERS模式下得到极大增强。使用三金属 SERS 传感器发现,脂肪族 L-半胱氨酸的“定量限 (LOQ)”值为 1 nM,芳香族硫醇的“定量限 (LOQ)”值为 1–0.1 pM。
更新日期:2023-11-10
中文翻译:
Ag-Au-Cu 三金属合金 Microflower:用于检测低拉曼散射截面硫醇的高灵敏度 SERS 基底
在玻璃盖玻片上合成了具有各种表面成分的三金属银-金-铜合金微花(MF),并用作高效的表面增强拉曼光谱(SERS)基底,用于对较小拉曼散射截面分子进行高灵敏度无标记检测,即L-半胱氨酸和有毒的苯硫酚。通过适当混合金属烷基卤化铵前体,然后在 350 °C 下进行一步热解,合成了不同成分的 MF。虽然所有基材的 Ag 百分比保持恒定在 90%,但 Au 和 Cu 的成分依次在 1% 和 9% 之间变化。通过使用场发射扫描电子显微镜 (FE-SEM)、广角 X 射线散射、X 射线光电子能谱 (XPS) 和 X 射线荧光技术对合成的 MF 进行了彻底表征。 FE-SEM 研究表明,MF 存在于整个基材中,平均尺寸为 20 至 40 μm。 XPS 研究表明,合金基底的顶面富含金或铜原子,而银则保留在下面。使用罗丹明 6G 作为探针分子评估了三金属 MF 作为 SERS 基底的性能,结果表明,Ag-Au-Cu 成分为 90-7-3 和 90-3-7 的 MF 是最好的,并且是最佳的。相同的 SERS 效率。当使用 1,2,3-苯并三唑作为探针分子计算时,发现这两个 MF 的 SERS 增强因子 (EF) 相同,约为 9 × 10 7 。在两者之间,具有较高 Au 百分比(Ag-Au-Cu 为 90-7-3)的三金属基板用于基于 SERS 的硫醇敏感检测,以利用强 Au-S 结合相互作用。 凭借基底的高EF,探针分子固有的低拉曼散射截面在SERS模式下得到极大增强。使用三金属 SERS 传感器发现,脂肪族 L-半胱氨酸的“定量限 (LOQ)”值为 1 nM,芳香族硫醇的“定量限 (LOQ)”值为 1–0.1 pM。