The Tandem of Full Spin Analysis and qHNMR for the Quality Control of Botanicals Exemplified with Ginkgo biloba

Abstract

Botanical dietary supplements and herbal remedies are widely used for health promotion and disease prevention. Due to the high chemical complexity of these natural products, it is essential to develop new analytical strategies to guarantee their quality and consistency. In particular, the precise characterization of multiple botanical markers remains a challenge. This study demonstrates how a combination of computer-aided spectral analysis and 1D quantitative 1H NMR spectroscopy (qHNMR) generates the analytical foundation for innovative means of simultaneously identifying and quantifying botanical markers in complex mixtures. First, comprehensive 1H NMR profiles (fingerprints) of selected botanical markers were generated via 1H iterative Full Spin Analysis (HiFSA) with PERCH. Next, the 1H fingerprints were used to assign specific 1H resonances in the NMR spectra of reference materials, enriched fractions and crude extracts of Ginkgo biloba leaves. These 1H fingerprints were then used to verify the assignments by 2D NMR. Subsequently, a complete purity and composition assessment by means of 1D qHNMR was conducted. As its major strengths, this tandem approach enables the simultaneous quantification of multiple constituents without the need for identical reference materials, the semi-quantitative determination of particular sub-classes of components, and the detection of impurities and adulterants.

Orthogonal analytical methods for botanical standardization: Determination of green tea catechins by qNMR and LC–MS/MS

“…The present study combines a recently validated qHNMR method, specifically developed for the analysis of natural products [19], with a computational approach called 1 H iterative Full Spin Analysis (HiFSA) [20], which enables the unequivocal identification of individual phytoconstituents in complex green tea samples. The computer-aided HiFSA method involves (i) the development of characteristic 1 H NMR profiles (NMR fingerprints) of the seven marker compounds, and (ii) the subsequent identification and quantification of these markers in complex mixtures using their NMR fingerprints.…”

Proton Fingerprints Portray Molecular Structures: Enhanced Description of the1H NMR Spectra of Small Molecules

“…The application of 1 H iterative Full Spin Analysis (HiFSA) 6 using PERCH software 7,8 and the Automated Consistency Analysis (ACA) 9,10 module enables a thorough analysis of 1 H NMR spectra, as demonstrated for a series of increasingly complex organic molecules. This approach produces replicas of 1 H NMR spectra (i.e., 1 H fingerprints ), provides complete assignments, and extracts important spectral parameters including chemical shifts (δ), coupling constants ( J ), and effective linewidths (Δν ½ ).…”

Diarylheptanoids from Dioscorea villosa (Wild Yam)

“…13 By presenting the HiFSA profiles of compounds, 1 – 7 , the present study facilitates future studies of Dioscorea botanicals at the chemistry/biology interface by supplying comprehensive information for dereplication. As shown recently, this knowledge also enables the precise quantification of multiple marker compounds by a combination of HiFSA and qHNMR, 35 thus laying the groundwork for the quantifiable assessment of the RC of Dioscorea preparations.…”

“…35 Molecular structures of the selected diarylheptanoids were used as starting points to analyze each discrete spin system and predict the basic 1 H NMR parameters ( δ and J ). Then, the predicted NMR parameters were optimized through iterative spin system calculations using the PERCHit iterator, until the quantum-mechanical simulations replicated the experimental 1 H NMR spectra (S4, Supporting Information).…”

“…38 The digital HiFSA spectra of these secondary metabolomic markers can also serve as references for future metabolomic standardization of wild yam botanicals. 35 …”