Rapid identification and on-site analysis by miniature mass spectrometry of chemical markers for fragrant rosewood authentication

Dalbergia odorifera T. Chen (Dalbergiae Odoriferae Lignum, DOL), renowned for its therapeutic applications in raditional Chinese medicine and its value in crafting luxury items, faces challenges due to the slow heartwood formation process and subsequent market adulteration. The proliferation of counterfeit products necessitates reliable methods for rapid, on-site authentication. This study aims to establish a rapid, green, and on-site method to identify the authenticity of DOL. A comprehensive analysis was conducted on 10 batches of DOL samples sourced from diverse locations, utilizing a miniature mass spectrometer (mini MS) equipped with a paper capillary spray (PCS) technique. Multivariate statistical approaches were employed to classify the samples and pinpoint chemical markers indicative of authenticity. Subsequent MS-guided separation and thin-layer chromatography (TLC) verified the markers’ validity and assessed the greenness profile by Analytical Eco-scale (AES), Green Analytical Procedure Index (GAPI), and Analytical GREEnness (AGREE). A total of 10 batches of DOL samples detected by PCS-mini MS were classified into authentic and counterfeit, by unsupervised cluster analysis. Sativanone (m/z301.1, VIP=6.0, p=0.000001) and 3’-O-methylviolanone (m/z331.1, VIP=3.2, p=0.000382) were regarded as the chemical markers for the rapid identification of DOL. The results of the TLC method were consistent with this method, and the new method is greener. The application of mini MS for on-site authentication of DOL via specific chemical markers offers significant advantages, including operational simplicity, high efficiency, greenness, and accuracy. The deployment of this strategy promises to facilitate the effective regulation of DOL, ensuring authenticity and quality.

DOL heartwood is usually confused with closely related species, such as Dalbergia sissoo Roxb. and Dalbergia pinnata (Lour.) Merr. Through the application of the PCS-mini MS technique, two distinctive components, Sativanone and 3’-O-methylviolanone, were identified as chemical markers capable of swiftly verifying the authenticity of DOL. The reliability of this method was corroborated through TLC, wherein the characteristic compounds were isolated from DOL and duly identified. The utility of mini MS in the analysis of precious and scarce botanicals like DOL extends beyond fewer sample materials, it offers simplicity in operation, minimal time investment, and the capacity to accurately discern genuine specimens from counterfeits without necessitating reference standards or crude drug samples. This finding complements existing identification methodologies for DOL, complies with the requirements of green analytical chemistry, and serves as a versatile tool in traditional Chinese medicine identification and botanical conservation efforts.