Abstract-Spectral Characterization and Molecular Dynamics Simulation of Pesticides Based on Terahertz Time-Domain Spectra Analyses and Density Functional Theory (DFT) Calculations

Fangfang Qu,  Lei Lin, Yong He,  Pengcheng Nie, Chengyong Cai, Tao Dong,  Yi Pan,  Yu Tang,  Shaoming Luo

http://www.mdpi.com/1420-3049/23/7/1607

This work provides the experimental and theoretical fundamentals for detecting the molecular fingerprints of six kinds of pesticides by using terahertz (THz) time-domain spectroscopy (THz-TDS). The spectra of absorption coefficient and refractive index of the pesticides, chlorpyrifos, fipronil, carbofuran, dimethoate, methomyl, and thidiazuron are obtained in frequencies of 0.1–3.5 THz. To accurately describe the THz spectral characteristics of pesticides, the wavelet threshold de-noising (WTD) method with db 5 wavelet fucntion, 5-layer decomposition, and soft-threshold de-noising was used to eliminate the spectral noise. The spectral baseline correction (SBC) method based on asymmetric least squares smoothing was used to remove the baseline drift. Spectral results show that chlorpyrifo had three characteristic absorption peaks at 1.47, 1.93, and 2.73 THz. Fipronil showed three peaks at 0.76, 1.23, and 2.31 THz. Carbofuran showed two peaks at 2.72 and 3.06 THz. Dimethoate showed three peaks at 1.05, 1.89, and 2.92 THz. Methomyl showed five peaks at 1.01, 1.65, 1.91, 2.72, and 3.20 THz. Thidiazuron showed four peaks at 0.99, 1.57, 2.17, and 2.66 THz. The density functional theory (DFT) of B3LYP/6-31G+(d,p) was applied to simulate the molecular dynamics for peak analyzing of the pesticides based on isolated molecules. The theoretical spectra are in good agreement with the experimental spectra processed by WTD + SBC, which implies the validity of WTD + SBC spectral processing methods and the accuracy of DFT spectral peak analysis. These results support that the combination of THz-TDS and DFT is an effective tool for pesticide fingerprint analysis and the molecular dynamics simulations.

Abstract-Terahertz Multivariate Spectral Analysis and Molecular Dynamics Simulations of Three Pyrethroid Pesticides

Fangfang Qu, Lei Lin,Yong He,Pengcheng Nie,Chengyong Cai,TaoDong, Yi Pan,Yu Tang,Shaoming Luo

https://link.springer.com/article/10.1007%2Fs10762-018-0519-x

The terahertz (THz) multivariate spectral characteristics and the molecular dynamics of three pyrethroid pesticides, including deltamethrin, fenvalerate, and beta-cypermethrin, were studied in this paper. THz spectra of the pesticides were measured in frequency range of 0.06–3.5 THz by using THz time-domain spectroscopy (THz-TDS). To improve the THz spectral quality, the wavelet threshold de-noising (WTD) method was used to remove spectral noise and the spectral baseline correction (SBC) method was used to remove baseline drift. Specific absorption peaks were observed in the processed THz spectra of the three pesticides. Deltamethrin showed three peaks at 0.90, 1.49, and 2.32 THz. Fenvalerate had five peaks at 1.13, 1.43, 1.61, 1.98, and 2.58 THz. Beta cypermethrin had four peaks at 1.27, 1.84, 2.12, and 2.92 THz. The density functional theory (DFT) was used to characterize the molecular dynamics and formation mechanism of the absorption peaks. Results showed that there was a good matching effect between the THz experimental spectra and the DFT quantum calculation spectra. Based on the characterized fingerprint absorption peaks, the linear addition model was used to simulate the THz spectra of mixed pesticides. The simulated spectra of multicomponent pesticides were demonstrated to be in good agreement with those obtained by THz-TDS. By analyzing the absorption peaks of THz spectra, the composition and concentration of multicomponent pesticides could be determined. The proposed strategy presented an analytical methodology for studying the THz spectral characteristics of pesticides. In addition, this work provided experimental and theoretical basis for the detection potential of pesticides in agricultural products based on THz technology.

Abstract-Ultrasensitive Detection of Residual Pesticides Using THz Near-Field Enhancement

Lee Dong-Kyu, Kim Giyoung Chulki, Min  Jhon Young, Kim Jae Hun,  Lee Taikjin,  Son Joo-Hiuk, Seo Minah,
http://www.ieeeexplore.ws/xpl/articleDetails.jsp?arnumber=7454771&filter%3DAND%28p_IS_Number%3A5741778%29

We present a novel type of highly sensitive and selective detection method for residual pesticide molecules including, e.g., methomyl using nanoscale metamaterials based terahertz (THz) time-domain spectroscopy (TDS) system. Nanoscale slot-antenna-based metamaterials were designed for the strong THz resonance at a certain frequency, where the specific molecule has intramolecular or intermolecular collective vibrational mode. Enhanced THz near-field via a nano-antenna metamaterial strongly increases absorption cross section, and this leads to the detection sensitivity up to parts-per-billion level even in a solution state of pesticide sample. Measured transmittance and reflectance spectrum results show excellent performances in both sensitivity and selectivity. We also imaged reflected THz signals though our THz nano-metamaterials in a nondestructive manner to simply detect the contained residual pesticide at the surface of an apple as it is, without any treatment. This observation can offer the possibility for further various applications as prompt and accurate molecule sensing tools in real time.

Abstract-Optical characteristics of pesticides measured by terahertz time domain spectroscopy

Dong-Kyu Lee, Joo-Hiuk Son

Univ. of Seoul (Korea, Republic of)

Giyoung Kim

National Academy of Agricultural Science (Korea, Republic of)

Proc. SPIE 9655, Fifth Asia-Pacific Optical Sensors Conference, 965516 (July 1, 2015); doi:10.1117/12.2184387

http://proceedings.spiedigitallibrary.org/proceeding.aspx?articleid=2388821

In this study, we measured the optical characteristics of pesticides by terahertz time-domain spectroscopy. Pesticide samples were prepared as pellets that were mixed with polyethylene powder and placed in the center of the path of a terahertz electromagnetic (EM) wave in the spectroscopy system. The absorbance of each sample showed obvious differences in absorption peaks. From this result, we showed that these pesticide products had resonance modes in the terahertz range, and this method can be used to make a sensor that is able to measure low concentrations of pesticides in farm produce.
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