Abstract：
BACKGROUND: Histamine is a kind of biogenic amine with strong toxicity and potential carcinogenicity. Many traditional methods of detecting histamine have the disadvantages of cumbersome detection steps, expensive equipment, and high professional requirements for staff. In contrast, SERS has become the preferred method for quantitative analysis of histamine because of rich fingerprint information, rapidity and economy. However, most of SERS substrates still have technical problems, such as poor stability, low sample collection rate, and detection efficiency. Therefore, there is a great need for new strategies to develop high-performance SERS substrates based sensors.
RESULTS: In our study, a sensitive SERS aptasensor for the detection of histamine was synthesized. The assembly was formed between IRMOF-3@Au/PDMS (flexible SERS substrate) and AuNR-DTNB@Ag-HA apt (Raman signal probe with both the target capture ability) via π-π stacking interaction from HA aptamer and IRMOF-3. Consequently, the SERS signal of the assembly derived from DTNB reached highest due to the synergistic enhancement effect by AuNR@Ag and IRMOF-3@Au. Meanwhile, HA aptamer can specifically capture histamine, therefore histamine addition competitively bound to the probe, leading to a corresponding decrease in the DTNB signal value on the SERS substrate. The SERS intensity at 1331 cm-1 presented a good linear relationship towards the logarithmic value of histamine concentrations ranging from 0.0001 mg/L to 400 mg/L (R2 = 0.990) with the LOD of 3.6 × 10-5 mg/L. Furthermore, the application in wine samples demonstrated the accuracy and applicability of the developed sensor.
CONCLUSIONS: This method effectively improves substrate stability, detection sensitivity and signal response immediacy to amplify the SERS sensor, thus satisfying the histamine detection requirements of various systems. According to this aptasensor design, our strategy can be extended to create other MOF-based SERS substrates for accurately detecting relative targets to ensure food safety.
RESULTS: In our study, a sensitive SERS aptasensor for the detection of histamine was synthesized. The assembly was formed between IRMOF-3@Au/PDMS (flexible SERS substrate) and AuNR-DTNB@Ag-HA apt (Raman signal probe with both the target capture ability) via π-π stacking interaction from HA aptamer and IRMOF-3. Consequently, the SERS signal of the assembly derived from DTNB reached highest due to the synergistic enhancement effect by AuNR@Ag and IRMOF-3@Au. Meanwhile, HA aptamer can specifically capture histamine, therefore histamine addition competitively bound to the probe, leading to a corresponding decrease in the DTNB signal value on the SERS substrate. The SERS intensity at 1331 cm-1 presented a good linear relationship towards the logarithmic value of histamine concentrations ranging from 0.0001 mg/L to 400 mg/L (R2 = 0.990) with the LOD of 3.6 × 10-5 mg/L. Furthermore, the application in wine samples demonstrated the accuracy and applicability of the developed sensor.
CONCLUSIONS: This method effectively improves substrate stability, detection sensitivity and signal response immediacy to amplify the SERS sensor, thus satisfying the histamine detection requirements of various systems. According to this aptasensor design, our strategy can be extended to create other MOF-based SERS substrates for accurately detecting relative targets to ensure food safety.
摘要：
背景：组胺是一种具有强毒性和潜在致癌性的生物胺。许多传统的组胺检测方法具有检测步骤繁琐的缺点,昂贵的设备,对员工的专业要求很高。相比之下,SERS因其丰富的指纹信息而成为组胺定量分析的首选方法,速度和经济。然而,大多数SERS基板仍然存在技术问题，比如稳定性差，低样本收集率，和检测效率。因此,非常需要新的策略来开发基于SERS衬底的高性能传感器。
结果：在我们的研究中，合成了一种用于检测组胺的灵敏SERS传感器。通过HA适体和IRMOF-3的π-π堆叠相互作用，在IRMOF-3@Au/PDMS（柔性SERS基底）和AuNR-DTNB@Ag-HAapt（具有靶标捕获能力的拉曼信号探针）之间形成组装体。因此,由于AuNR@Ag和IRMOF-3@Au的协同增强作用，来自DTNB的组件的SERS信号达到最高。同时,HA适体可以特异性捕获组胺，因此，组胺添加竞争性地结合到探针，导致SERS衬底上的DTNB信号值的相应减小。1331cm-1处的SERS强度与组胺浓度的对数值呈良好的线性关系，范围为0.0001mg/L至400mg/L（R2=0.990），LOD为3.6×10-5mg/L。此外，在葡萄酒样品中的应用证明了所开发传感器的准确性和适用性。
结论：该方法有效地提高了底物的稳定性，检测灵敏度和信号响应即时性放大SERS传感器，从而满足各种系统的组胺检测要求。根据这个aptasensor设计，我们的策略可以扩展到创建其他基于MOF的SERS底物，以准确检测相关目标，以确保食品安全。
结果：在我们的研究中，合成了一种用于检测组胺的灵敏SERS传感器。通过HA适体和IRMOF-3的π-π堆叠相互作用，在IRMOF-3@Au/PDMS（柔性SERS基底）和AuNR-DTNB@Ag-HAapt（具有靶标捕获能力的拉曼信号探针）之间形成组装体。因此,由于AuNR@Ag和IRMOF-3@Au的协同增强作用，来自DTNB的组件的SERS信号达到最高。同时,HA适体可以特异性捕获组胺，因此，组胺添加竞争性地结合到探针，导致SERS衬底上的DTNB信号值的相应减小。1331cm-1处的SERS强度与组胺浓度的对数值呈良好的线性关系，范围为0.0001mg/L至400mg/L（R2=0.990），LOD为3.6×10-5mg/L。此外，在葡萄酒样品中的应用证明了所开发传感器的准确性和适用性。
结论：该方法有效地提高了底物的稳定性，检测灵敏度和信号响应即时性放大SERS传感器，从而满足各种系统的组胺检测要求。根据这个aptasensor设计，我们的策略可以扩展到创建其他基于MOF的SERS底物，以准确检测相关目标，以确保食品安全。
