Theae nigrae folium: Comparing the analytical performance of benchtop and handheld near-infrared spectrometers

We investigated caffeine and l-theanine, quality characteristics for camellia sinensis, in milled and ground black tea samples with near-infrared (NIR) spectroscopy giving a direct comparison between the performances of benchtop and handheld NIR spectrometers. The constructed partial least squares regression (PLSR) models for all spectrometers were validated by test-set-validation and according to the obtained root mean square errors of prediction (RMSEP). The performances of the spectrometers were as follows: The benchtop spectrometer NIRFlex N-500 (Büchi, Flawil, Switzerland) showed the best results for milled samples with a RMSEP of 0.14% for caffeine and 0.12% for l-theanine. For the ground samples, a RMSEP of 0.17% for caffeine and 0.12% for l-theanine was gained. While the handheld spectrometers MicroNIR 2200 (Viavi Solutions (former: JDS Uniphase Corporation), Milpitas, USA) and the microPHAZIR (Thermo Fisher Scientific, Waltham, USA) both provided good results for the prediction of caffeine in milled samples (RMSEP of 0.22% and 0.26%), only the microPHAZIR was able to satisfactorily determine the caffeine content in ground samples (RMSEP of 0.28%). The investigation of l-theanine with handheld spectrometers did not lead to convincing results, since R² was 0.75 for milled samples while ground samples could not be calculated. Decisive differences were concluded in how different NIR instruments capture the chemical information on caffeine vs. l-theanine. The handheld spectrometers manifested limited applicability to l-theanine. Deeper insight was obtained through the detailed NIR band assignments of caffeine and l-theanine derived from quantum mechanical simulation. Narrow working spectral region of handhelds omits the characteristic absorption bands of l-theanine. Therefore, information on l-theanine content measured by the evaluated miniaturized spectrometers is insufficient to enable its effective quantification. In contrast, the most characteristic NIR absorption of caffeine matches the working spectral regions of the handheld NIR spectrometers, hence their performance is comparable with the benchtop device.