1.上海理工大学 光电信息与计算机工程学院, 上海 200093
2.上海理工大学 机械工程学院, 上海 200093
张可非,2335060459@st.usst.edu.cn
邵咏妮,ynshao@usst.edu.cn
收稿:2026-01-18,
修回:2026-07-07,
录用:2026-07-13,
移动端阅览
张可非,邵雨霆,唐伟然,等. 太赫兹超材料传感器用于川芎腐霉利残留的高灵敏检测[J].光子学报,2026,55(8):0828001
ZHANG Kefei, SHAO Yuting, TANG Weiran, et al. High-Sensitivity Detection of Procymidone Residues in Ligusticum chuanxiong Using a Terahertz Metamaterial Sensor[J]. Acta Photonica Sinica, 2026, 55(8):0828001
张可非,邵雨霆,唐伟然,等. 太赫兹超材料传感器用于川芎腐霉利残留的高灵敏检测[J].光子学报,2026,55(8):0828001 DOI: 10.3788/gzxb20265508.0828001. CSTR: 32255.14.gzxb20265508.0828001.
ZHANG Kefei, SHAO Yuting, TANG Weiran, et al. High-Sensitivity Detection of Procymidone Residues in Ligusticum chuanxiong Using a Terahertz Metamaterial Sensor[J]. Acta Photonica Sinica, 2026, 55(8):0828001 DOI: 10.3788/gzxb20265508.0828001. CSTR: 32255.14.gzxb20265508.0828001.
腐霉利(C₁₃H₁₁Cl
2
NO₂)是一种常用的有机氯类杀菌剂,在川芎的种植过程中被广泛用于防治菌核病和灰霉病,其残留问题严重威胁中药材的质量安全。设计并制备了一种基于非对称方环链结构的太赫兹超材料传感器,用于川芎中痕量农药残留的快速检测。电磁仿真分析证明,在
x
方向偏振波激发下,该结构产生了电偶极子共振,其理论灵敏度达346 GHz/RIU。实验结果显示,通过建立谐振峰频移量与腐霉利浓度的定量模型,传感器在浓度范围内表现出良好的非线性响应特征(拟合系数
R
² 0.98),川芎中腐霉利残留的最低检测限为0.52 μg/L,且整个检测流程可在30 min内完成。研究结果表明,太赫兹光谱与超材料传感器的结合为中药材中农药残留的快速、高灵敏检测提供了一种具有应用前景的技术方案。
Traditional Chinese Medicine (TCM) plays a crucial role in global healthcare; however, the growing popularity of herbal medicinal products has raised significant concerns regarding potentially hazardous pesticide residues.
Ligusticum chuanxiong
, a widely used TCM prized for its analgesic, anti-tumor, and anti-inflammatory properties, is highly susceptible to fungal infections such as
Sclerotinia sclerotiorum
and
Botrytis cinerea
during its artificial cultivation. To combat these diseases, procymidone, a cost-effective and highly efficient organochlorine fungicide, is frequently applied. Due to its high chemical stability and prolonged environmental half-life, persistent procymidone residues can easily accumulate within ecosystems and herbal matrices. Toxicological research demonstrates that excessive dietary exposure to procymidone can inhibit androgenic activity, disrupt endocrine functions, and induce adverse effects on the reproductive, digestive, and nervous systems. Consequently, stringent Maximum Residue Limits (MRLs) have been established globally, with the European Union mandating an MRL of 0.02 mg/kg for herbal products. Conventional pesticide residue detec
tion methods, including Gas Chromatography-tandem Mass Spectrometry (GC-MS) and High-performance Liquid Chromatography (HPLC), offer high sensitivity but are fundamentally limited by prolonged detection times, complex sample pretreatment procedures, and the need for specialized personnel. Conversely, standard spectroscopic analysis methods can reduce operational time but generally possess lower detection sensitivity, rendering them inadequate for trace-level residue analysis. Therefore, the objective of this study is to develop a rapid and highly sensitive detection method utilizing a terahertz (THz) metamaterial sensor to quantify trace procymidone residues in complex TCM matrices.To address the critical limitations of conventional analytical techniques, this study proposes a novel sensing platform combining THz time-domain spectroscopy with a specifically designed metamaterial sensor. THz waves exhibit high penetration, low photon energy, and distinct spectral features, making them highly suitable for non-destructive and label-free chemical detection. The fabricated THz metamaterial sensor features an artificially engineered asymmetric square ring chain resonator composed of periodically arranged subwavelength structures. This specific structural design introduces asymmetric microperturbations that significantly enhance the localized electromagnetic field and improve the quality factor of the dipole resonance compared to symmetric designs. When pesticide molecules adhere to the sensor surface, small local electric field perturbations are generated in the surrounding dielectric environment, which ultimately manifest as highly sensitive changes in the THz resonance peak frequency. In the experimental procedure, procymidone standard solutions were systematically prepared across a trace concentration gradient ranging from 1 to 82 μg/L. Subsequently, organically cultivated and commercial
Ligusticum chuanxiong
samples were ground into powder and subjected to an extraction process using dimethyl sulfo
xide as the solvent due to its optimal solubility. Small volumes of the resulting supernatants were accurately pipetted onto the surface of the THz metamaterial sensor and dried in a controlled environment. The THz absorbance spectra were then continuously recorded, and the resonance peak frequency shifts were extracted to establish quantitative regression models linking the frequency shift to the exact pesticide concentration.Experimental evaluations of the proposed THz metamaterial sensor revealed exceptional localized electromagnetic field enhancement and superior sensing capabilities. Upon the application of the pure procymidone standard solutions, the THz-TDS system captured stable and highly distinguishable frequency shifts, demonstrating that as the pesticide concentration increased, the resonance peaks of the metamaterial exhibited a clear red-shift toward lower frequencies. A quantitative concentration-frequency shift model was successfully established utilizing the Michaelis-Menten equation, yielding a remarkably high fitting coefficient (
R
2
0.98). Most notably, the asymmetric metamaterial sensor achieved an ultra-low limit of detection of 0.52 μg/L for procymidone, significantly outperforming previously reported THz biosensors. During the practical validation phase involving the complex TCM matrix, the sensor successfully maintained its high detection sensitivity. The regression curves constructed for procymidone within the
Ligusticum chuanxiong
DMSO extracts similarly demonstrated a strong nonlinear fitting correlation, proving that the unique subwavelength structure effectively amplifies the dielectric perturbation caused by the target molecules while overcoming residual background interferences from the herbal matrix. Furthermore, the entire sample preparation and detection workflow could be seamlessly completed within 30 minutes, drastically reducing the operational timeframe compared to traditional chromatographic analyses.In summary, this study experi
mentally demonstrates the feasibility and substantial advantages of utilizing a highly sensitive THz metamaterial sensor for the quantitative detection of trace procymidone residues in the TCM
Ligusticum chuanxiong
. By rationally designing an asymmetric square ring chain structure, the localized electromagnetic interactions between the THz waves and the pesticide molecules are significantly amplified, enabling an unprecedented μg/L-scale detection limit. This detection threshold strictly complies with the stringent MRLs established by international regulatory bodies. This approach successfully circumvents the time-consuming and expensive drawbacks of conventional GC-MS methods while entirely resolving the sensitivity bottlenecks of standard optical spectroscopy. Ultimately, combining the physical characteristics of the THz metamaterial sensor with reliable mathematical modeling provides a label-free, rapid, and highly effective technological strategy. This study offers a promising new testing solution for the rigorous safety monitoring and quality control of TCM materials, contributing significantly to the prevention of potential pesticide-related health risks.
CHEN Li , LI Xuesheng , WANG Zhengquan , et al . Residue dynamics of procymidone in leeks and soil in greenhouses by smoke generator application [J]. Ecotoxicology and Environmental Safety , 2010 , 73 : 73 - 77 .
LU Juan , GUO Yanjia , SHAN Xiangyu , et al . Solid electrochemiluminescence sensor by immobilization luminol in Zn-Co-ZIF CNFs for sensitive detection of procymidone in vegetables [J]. Microchimica Acta , 2024 , 191 : 508 .
XU Di , ZHANG Lili , ZHANG Guangying , et al . Novel and portable test strip platform for rapid and sensitive on-site detection of procymidone pesticide [J]. Microchimica Acta , 2023 , 190 : 392 .
RIFAI A , SOUISSI Y , GENTY C , et al . Ultraviolet degradation of procymidone – structural characterization by gas chromatography coupled with mass spectrometry and potential toxicity of photoproducts using in silico tests [J]. Rapid Communications in Mass Spectrometry , 2013 , 27 : 1505 - 1516 .
ZHUANG Zhuang , WANG Zihao , HUANG Yueyue , et al . Protective effect and possible mechanisms of ligustrazine isolated from Ligusticum wallichii on nephropathy in rats with diabetes: a preclinical systematic review and meta-analysis [J]. Journal of Ethnopharmacology , 2020 , 252 : 112568 .
ZHANG Ziang , LIN Hong , SUI Jianxin , et al . The effect of chlorophyll on the enzyme-linked immunosorbent assay (ELISA) of procymidone in vegetables and the way to overcome the matrix interference [J]. Journal of the Science of Food and Agriculture , 2022 , 102 : 3393 - 3399 .
SREEDHAR N Y , BABU T R , SAMATHA K , et al . Differential pulse polarographic determination of procymidone in formulations and wine [J]. Journal of AOAC International , 2002 , 85 : 731 - 735 .
LI Li , ZHAO Tingting , LIU Yu , et al . Method validation, residues and dietary risk assessment for procymidone in green onion and garlic plant [J]. Foods , 2022 , 11 : 1856 .
LI Yongbo , QIN Guofu , HE Fengrui , et al . Investigation and analysis of pesticide residues in edible fungi produced in the mid-western region of China [J]. Food Control , 2022 , 136 : 108857 .
ARMENTA S , GARRIGUES S , DE LA GUARDIA M . Determination of iprodione in agrochemicals by infrared and Raman spectrometry [J]. Analytical and Bioanalytical Chemistry , 2007 , 387 : 2887 - 2894 .
HUANG Ming , YANG Jingjing , PETRIN A . Microwave sensor using metamaterials [J]. Wave Propagation , 2011 , 13 : 36 .
DEGL’INNOCENTI R , LIN H , NAVARRO-CÍA M . Recent progress in terahertz metamaterial modulators [J]. Nanophotonics , 2022 , 11 : 1485 - 1514 .
YANG Ke , LI Jining , DE LA CHAPELLE M L , et al . A terahertz metamaterial biosensor for sensitive detection of microRNAs based on gold-nanoparticles and strand displacement amplification [J]. Biosensors and Bioelectronics , 2021 , 175 : 112874 .
ZHANG Huo , LI Zhi , HU Fangrong , et al . Sensitive detection of chlorpheniramine maleate using THz combined with metamaterials [J]. Optical and Quantum Electronics , 2017 , 49 : 258 .
TANTIWANICHAPAN K , DURMAZ H . Herbicide/pesticide sensing with metamaterial absorber in THz regime [J]. Sensors and Actuators A: Physical , 2021 , 331 : 112960 .
LIU Jianjun . High-sensitivity detection method for organochlorine pesticide residues based on loop-shaped absorber [J]. Materials Chemistry and Physics , 2020 , 242 : 122542 .
XU Wendao , WANG Qi , ZHOU Ruiyun , et al . Defect-rich graphene-coated metamaterial device for pesticide sensing in rice [J]. RSC Advances , 2022 , 12 : 28678 - 28684 .
YE Yunxia , ZHANG Yixing , ZHAO Yu , et al . Sensitivity influencing factors during pesticide residue detection research via a terahertz metasensor [J]. Optics Express , 2021 , 29 : 15255 - 15268 .
MAO Xiaodong , YANG Shimin , HUANG Zhikai , et al . A novel INFO-SVR-based strategy integrated with terahertz metamaterial sensing for detecting trace thiabendazole residues [J]. Measurement , 2026 , 258 : 119092 .
WANG Dongxu , LUO Siyuan , XU Kaida . A flexible terahertz metamaterial sensor for pesticide sensing and detection [J]. ACS Applied Materials and Interfaces , 2024 , 16 : 27969 - 27978 .
LIU Bingwei , PENG Yan , JIN Zuanming , et al . Terahertz ultrasensitive biosensor based on wide-area and intense light-matter interaction supported by QBIC [J]. Chemical Engineering Journal , 2023 , 462 : 142347 .
ARDESHANA M A , THAKKAR F N , DOMADIA S G . Robust Multi-Band DNG metamaterial absorber for GPS (L1), ISM, and 5G application with Enhanced polarization and angle stability [J]. Journal of Magnetism and Magnetic Materials , 2024 , 610 : 172554 .
BEDDOES B , KACZMAREK M , APOSTOLOPOULOS V , et al . All-optical switching of liquid crystals at terahertz frequencies enabled by metamaterials [J]. Optics Express , 2023 , 31 : 18336 - 18345 .
MIKHAILOVSKII M S , POLEVA M A , SOLODOVCHENKO N S , et al . Engineering of high-Q states via collective mode coupling in chains of mie resonators [J]. ACS Photonics , 2024 , 11 : 1657 - 1663 .
LANG Tingting , ZHANG Jinhui , QIU Yanqing , et al . Flexible terahertz metamaterial sensor for sensitive detection of imidacloprid [J]. Optics Communications , 2023 , 537 : 129430 .
LI Xue , SUN Jingye , YAO Xuan , et al . Liquid metal-based terahertz metamaterial sensors with integrated microfluidic channels for sensitive biosensing applications [J]. Optics Express , 2025 , 33 : 23476 - 23490 .
NIE Pengcheng , ZHU Dongying , CUI Zijian , et al . Sensitive detection of chlorpyrifos pesticide using an all-dielectric broadband terahertz metamaterial absorber [J]. Sensors and Actuators B: Chemical , 2020 , 307 : 127642 .
LANG Tingting , XIAO Meiyu , CEN Wenyang . Graphene-based metamaterial sensor for pesticide trace detection [J]. Biosensors , 2023 , 13 : 560 .
LI Gaozhen , SUN Jiashuai , LI Jiahuan , et al . Paper-based biosensors relying on core biological immune scaffolds for the detection of procymidone in vegetables [J]. Talanta , 2023 , 265 : 124843 .
XU Wendao , XIE Lijuan , ZHU Jianfei , et al . Terahertz sensing of chlorpyrifos-methyl using metamaterials [J]. Food Chemistry , 2017 , 218 : 330 - 334 .
0
浏览量
1
下载量
0
CSCD
关联资源
相关文章
相关作者
相关机构
京公网安备11010602201714号