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处于太赫兹频段的电磁波表现出许多极具发展前景的特点, 如非电离、“指纹”谱、对弱共振敏感、对非极性物质穿透性强等特性, 并逐步发展成物理、信息、材料、生物、化学等学科基础与应用研究关注的热点. 然而, 在生物、化学物质的传感检测应用中, 当待测物尺度小于入射太赫兹波长时, 微小扰动和细微特征难以被太赫兹波检测到, 并且无法与太赫兹波之间产生充分的相互作用, 这无疑阻碍了太赫兹生物化学传感检测技术的进一步发展. 而太赫兹超材料的迅速发展提供了解决这一问题的全新思路. 近年来, 一系列基于太赫兹超材料的研究工作与新材料、新结构、新机制结合, 为实现高灵敏太赫兹生物化学传感检测带来了新的机遇. 本文主要综述了最近太赫兹超材料应用于生物化学传感检测技术的研究进展, 并简述了评价器件性能的关键参数. 根据材料特性、设计策略的不同, 对基于金属-介质、碳基纳米材料、全硅等太赫兹超材料生物化学传感检测相关工作做了总结, 并在文末对太赫兹超材料传感检测技术的未来发展方向做出了展望.The electromagnetic wave in the terahertz region shows many promising properties, such as non-ionizing, sensitivity to weak resonance, and gradually becomes a basic and applied research hotspot of physics, information, materials, biology, chemistry and other disciplines. However, the analyte molecules tend to be of subwavelength size, and cannot have sufficient interaction with the incident terahertz wave. Small disturbances and subtle features are difficult to detect, which undoubtedly hinders the further development of the terahertz biochemical sensing and detection. The rapid development of terahertz metamaterials provides an alternative method to overcome this obstacle. The intense electromagnetic field enhancement induced by metamaterials allows the sensing and detection application to surpass the limitation of classical terahertz spectroscopy, which is due to the enhancement of the interaction between the analyte and terahertz. In recent years, a series of researches based on terahertz metamaterials combined with new materials, new structures and new mechanisms has offered new opportunities for the application of highly sensitive terahertz biochemical sensing and detection. In this paper, the recent advances in the application of terahertz metamaterials biochemical sensing are reviewed. The related concepts are briefly introduced and the influences of different factors on the sensing performance of metamaterial sensor are analyzed. According to the material selection and design strategies, the related researches of terahertz metamaterial biochemical sensing and detection are summarized. Furthermore, the novel strategy of terahertz metamaterial sensing and detection application based on multidisciplinary are presented, and the future development directions are also discussed, which will greatly conduce to expanding the practicality of terahertz sensing and detection.
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Keywords:
- terahertz /
- metamaterial /
- biological /
- sensing
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图 2 金属基太赫兹超材料生物传感器 (a) 用于检测细胞凋亡的周期性同心金圆环结构太赫兹超材料[147]; (b)可实现葡萄糖溶液和尿素检测的金属太赫兹谐振器[171]; (c) 用于农药浓度传感的多频带太赫兹超材料吸收器[172]; (d) 用于病毒检测的银纳米线太赫兹超材料[173]
Fig. 2. Metal-based terahertz metamaterial biosensors: (a) Periodic concentric gold ring terahertz metamaterial for cell apoptosis sensing[147]; (b) metal-base terahertz resonator for glucose and urea detection[171]; (c) multiband terahertz metamaterial absorber for pesticide concentration sensing[172]; (d) silver nanowires terahertz metamaterial for virus detection[173].
图 3 全硅太赫兹超材料传感器 (a)基于周期性同轴环和圆柱结构的太赫兹超材料吸收器, 可实现对毒死蜱溶液的灵敏检测[135]; (b) 单带全硅太赫兹超材料传感器, 用于2, 4-D农药检测[139]; (c) 一种可用于毒死蜱检测的全硅光栅结构的太赫兹超材料吸收器[140]
Fig. 3. All-silicon terahertz metamaterial sensors: (a) Terahertz metamaterial absorber based on periodic coaxial ring and cylindrical structure for the sensitive detection of chlorpyrifos solution[135]; (b) single-band all-silicon terahertz metamaterial absorbers for 2, 4-D pesticide sensing[139]; (c) an all-silicon grating metamaterial absorber for chlorpyrifos detection [140].
图 4 碳基太赫兹超材料传感器 (a) 石墨烯复合纳米槽基太赫兹超材料, 用于识别单链DNA (ssDNA)[181]; (b) 一种碳纳米管超材料, 可用于农药浓度检测[138]
Fig. 4. Carbon-based terahertz metamaterial sensors: (a) Graphene composite nanoslot-based terahertz metamaterial for ssDNA detection[181]; (b) a carbon nanotubes metamaterial which can be used for pesticide concentration detection[138].
图 5 基于指纹光谱的太赫兹超材料传感器 (a) 利用金属狭缝天线对不同种类碳水化合物进行区分和定量检测[182]; (b) 用于检测果糖和L-组氨酸的金属超材料[185]
Fig. 5. Terahertz metamaterial sensor based on fingerprint spectrum: (a) Using nano-antenna array to distinguish and quantitatively detect different types of carbohydrates[182]; (b) metal-based metamaterials for detection of fructose and L-histidine[185].
图 6 与抗体结合的太赫兹超材料传感器 (a) 使用大肠杆菌抗体做表面修饰的超材料, 实现在水环境中对大肠杆菌进行特异性检测[192]; (b) 用于特异性检测ZIKV的超材料[193]; (c) 将抗体修饰的GNPs引入超材料来实现EGFR的特异性检测[194]
Fig. 6. Terahertz metamaterial sensor combined with antibody: (a) Specific detection of E. coli in water environment realized by metamaterial with surface modification of E. coli antibody[192]; (b) metamaterial for the specific detection of ZIKV[193]; (c) antibody-modified GNPs are introduced into the metamaterial to achieve specific detection of EGFR[194].
图 7 集成微流体的太赫兹超材料生物传感器 (a)纳米流体太赫兹超材料传感器用于醇水混合物和三磷酸腺苷(ATP)检测[207]; 用SRR (b) 和Fano谐振器(c)制作的THz超材料芯片的扫描电子显微镜图像及模拟电场分布[207]; (d)集成微流体的太赫兹超材料生物传感器用于早期肝癌生物标志物检测[208]
Fig. 7. THz metamaterials biosensor chip integrated with microfluidics. (a) Nanofluidic THz metamaterial sensor and its cross-sectional device structure for alcohol-water mixture and adenosine triphosphate (ATP)[207]. Scanning electron microscopic image of the fabricated THz metamaterial chip with SRR (b) and Fano resonator (c) and their simulated electric field distribution[207]. (d) THz metamaterials biosensor chip integrated with microfluidics for liver cancer biomarker testing[208].
图 8 太赫兹超材料生化传感检测技术中的新方法 (a) 利用适体水凝胶功能化太赫兹超材料制成的分子特异性太赫兹生物传感器[209]; (b) 应用于太赫兹偏振转换和薄膜厚度检测的双层手性超材料[210]
Fig. 8. New methods in terahertz metamaterial biochemical sensing and detection: (a) Molecule-specific THz biosensor was fabricated from an aptamer hydrogel-functionalized THz metamaterial[209]; (b) double-layer chiral metamaterial for terahertz polarization conversion and film thickness detection[210].
表 1 各种太赫兹超材料生物化学传感器对比
Table 1. List of various THz metamaterial biochemical sensors.
传感检测
实现方式核心
材料功能 性能 文献 直接滴加 金属 黄曲霉毒素B1和B2 最小剂量为5 μL [167] 滴加-干燥 金属 牛血清蛋白浓度检测 最低检测浓度为0.1 mg/mL, 17.6 mg/mL
浓度引起的频移量为137 GHz[141] 滴加-干燥 全金属结构 牛血清蛋白检测 灵敏度为72.81 GHz/(ng/mm2),
检测限为0.035 mg/mL[70] 滴加-干燥 硅 毒死蜱浓度检测 最低浓度20 ppt [140] 滴加-干燥 碳纳米管 2, 4-D 和毒死蜱浓度检测 最低检测量10 ng,
灵敏度为1.38 × 10–2/ppm (2, 4-d)
2.0 × 10–3/ppm (毒死蜱)[138] 特异性抗体修饰 金属 恶性神经胶质瘤细胞检测 最大灵敏度248.75 kHz/(cell mL–1) [57] 特异性抗体修饰 金属 癌胚抗原浓度的检测 检测限为0.1 ng/mL [37] 微流通道 金属 乙醇-水混合物浓度检测 124.3 GHz/RIU [205] 衰减全反射 金属 水环境蔗糖溶液浓度检测 最低检测浓度为0.03125 mol/L [168] 使用石墨烯-超表面混合结构, 微流通道-特异性结合 石墨烯 DNA检测 100 nmol/L DNA 溶液 [206] 特异性适体水凝胶 金属 水环境特异性h-TB检测 检测限为0.40 pmol/L [209] 金纳米颗粒-RCA 金属 金黄色酿脓葡萄球菌 检测限为0.08 pg/mL [188] 石墨烯超表面
手性传感石墨烯 禽流感病毒检测 对H1N1, H5N2, N9N2三种不同类型
禽流感病毒特异性识别[180] 手性传感 金属 纳米颗粒浓度 灵敏度为5.5 GHz%–1 [204] -
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