Near infrared (NIR) spectroscopy with chemometric techniques was applied to discriminate the geographical origins of crude drugs (i.e., dried ripe fruits of Trichosanthes kirilowii) and prepared slices of Trichosanthis Fructus in this work. The crude drug samples (120 batches) from four growing regions (i.e., Shandong, Shanxi, Hebei, and Henan Provinces) were collected, dried, and used and the prepared slice samples (30 batches) were purchased from different drug stores. The raw NIR spectra were acquired and preprocessed with multiplicative scatter correction (MSC). Principal component analysis (PCA) was used to extract relevant information from the spectral data and gave visible cluster trends. Four different classification models, namely K-nearest neighbor (KNN), soft independent modeling of class analogy (SIMCA), partial least squares-discriminant analysis (PLS-DA), and support vector machine-discriminant analysis (SVM-DA), were constructed and their performances were compared. The corresponding classification model parameters were optimized by cross-validation (CV). Among the four classification models, SVM-DA model was superior over the other models with a classification accuracy up to 100% for both the calibration set and the prediction set. The optimal SVM-DA model was achieved when C =100, γ = 0.00316, and the number of principal components (PCs) = 6. While PLS-DA model had the classification accuracy of 95% for the calibration set and 98% for the prediction set. The KNN model had a classification accuracy of 92% for the calibration set and 94% for prediction set. The non-linear classification method was superior to the linear ones. Generally, the results demonstrated that the crude drugs from different geographical origins and the crude drugs and prepared slices of Trichosanthis Fructus could be distinguished by NIR spectroscopy coupled with SVM-DA model rapidly, nondestructively, and reliably.

The differences in metabolites in male and female individuals of dioecious Morus alba L. (Moraceae) are usually ignored and lack study. In the present study, 58 leaves and 61 stem barks from male and female individuals were analyzed by untargeted metabolomics via headspace solid-phase microextraction gas chromatography-mass spectrometry (HS-SPME-GC-MS) coupled with chemometrics, including principal component analysis (PCA) and orthogonal partial least squares-discriminant analysis (OPLS-DA). A total of 66 and 44 metabolites were identified from leaves and stem barks, respectively. Four and eight differential metabolites among candidate metabolites in leaves and stem barks from male and female individuals were identified. Moreover, females possessed stronger antioxidant activity than males. This is the first report where untargeted metabolomics coupled with chemometrics was used to analyze the different metabolites and to discriminate the gender of leaves and stem barks of dioecious M. alba. It provided the basis for further study of M. alba and reference value for researching dioecious plants.

To comprehensively evaluate the quality of medicinal and edible Ziziphi Spinosae Semen (ZSS, the dried ripe seeds of Ziziphus jujuba var. spinosa) before and after rancidity during storage, some indicators including traditional sensory properties, physicochemical characteristics, and volatile compounds were analyzed. As a result, compared with the normal samples, the rancid samples of ZSS produced a darker color, a bitter taste, and an irritating odor, increased moisture content, electrical conductivity, fatty oil content, and acid value, and decreased water- and alcohol-soluble extract contents and pH value. Among them, the acid value had significant difference (p < 0.01) from 3.90 of normal ZSS to 18.68 mg/g of rancid ZSS. A total of 39 volatile compounds were identified in samples, including 20 in normal ZSS and 38 compounds in rancid ZSS. Nineteen common compounds were identified in normal and rancid samples. Among them, the content of 10 compounds such as δ-limonene, (R,R)-2,3-butanediol, and (R,S)-2,3-butanediol was decreased but that of nine compounds such as acetic acid, n-octanoic acid, and n-nonanoic acid was increased in rancid ZSS. Nineteen unique compounds such as β-phellandrene, α-pinene, and 3-carene were detected and only one compound, δ-cadinene, was not detected in rancid ZSS. In addition, eight short-chain organic acids, acetic, propanoic, butanoic, pentanoic, hexanoic, heptanoic, octanoic, and nonanoic acids, were new products in rancid ZSS, and it was speculated that the production of a series of organic acids might be the material basis of irritating odor after normal ZSS became rancid. This is the first report that a series of short-chain organic acids have been found in a rancid substance. In conclusion, there was a significant difference between normal and rancid ZSS. These indicators could be used as an early warning for judging the rancidity phenomenon of medicinal and edible ZSS. In addition, this is the first comprehensive evaluation about the rancidity process of a medicinal and edible substance.

Qingpi, the dried immature pericarp of Citrus reticulata Blanco, is a commonly used medicinal food with some health-promoting benefits. In general, it is essential that Qingpi be stored for a period of time, but there are no reports about the number of storage years needed to obtain the best quality of Qingpi. Our aim was to determine the best storage time of Qingpi by studying the physicochemical properties and metabolite changes in product stored from 1 to 5 years. As a result, the color of Qingpi became darker during storage. Both the levels of three flavonoids (hesperidin, nobiletin, and tangeretin) and total flavonoids (TFs) and the antioxidant activity decreased during storage and the total phenolics (TPs) content fluctuated during storage. Cluster analysis was performed on the color parameters measured using a color difference meter, revealing that the color of Qingpi differed before and after 3 years of storage. A total of 9 special differential metabolites were identified that could be used to distinguish the storage years of Qingpi. This is the first study to report the quality changes of Qingpi during storage. The optimized results of the quality evaluation indicated that Qingpi should be stored for no more than 3 years.

Herpetospermum pedunculosum (Ser.) C. B. Clarke (Family Cucurbitaceae) is a dioecious plant and has been used as a traditional Tibetan medicine for the treatment of hepatobiliary diseases. The component, content, and difference in volatile compounds in the female and male buds of H. pedunculosum were explored by using headspace solid-phase microextraction-gas chromatography-mass spectrometry (HS-SPME-GC-MS) technology and multivariate statistical analysis. The results showed that isoamyl alcohol was the main compound in both female and male buds and its content in males was higher than that in females; 18 compounds were identified in female buds including 6 unique compounds such as (E)-4-hexenol and isoamyl acetate, and 32 compounds were identified in male buds, including 20 unique compounds such as (Z)-3-methylbutyraldehyde oxime and benzyl alcohol. (Z)-3-methylbutyraldehyde oxime and (E)-3-methylbutyraldehyde oxime were found in male buds, which only occurred in night-flowering plants. In total, 9 differential volatile compounds between female and male buds were screened out, including isoamyl alcohol, (Z)-3-methylbutanal oxime, and 1-nitropentane based on multivariate statistical analysis such as principal component analysis (PCA) and orthogonal partial least squares discrimination analysis (OPLS-DA). This is the first time to report the volatile components of H. pedunculosum, which not only find characteristic difference between female and male buds, but also point out the correlation between volatile compounds, floral odor, and plant physiology. This study enriches the basic theory of dioecious plants and has guiding significance for the production and development of H. pedunculosum germplasm resources.

¹H Nuclear Magnetic Resonance (¹H NMR) combined with multivariate statistics was adopted to discriminate female and male flower buds of Populus tomentosa in the study. Samples of 11 female and 16 male flower buds of P. tomentosa were collected in Beijing, China. ¹H NMR spectra were acquired on a 400 MHz spectrometer. In total, 30 chemical compounds were identified with standards and literature according to chemical shifts, peak areas, and multiplicity. Principal component analysis (PCA), hierarchical clustering analysis (HCA), and supervised orthogonal partial least squares-discriminant analysis (OPLS-DA) were applied to discriminate female and male flower buds. An apparent grouping trend (R²X, 0.809; Q², 0.903) between female and male groups was exhibited with PCA and HCA. The two groups were also well discriminated with OPLS-DA (R²X, 0.808; R²Y, 0.976; Q², 0.960). Combined with variable importance in projection (VIP) > 1.0 and p < 0.05 of OPLS-DA, it was found that the content of daucosterol, β-sitosterol, ursolic acid, and betulonic acid in male group was higher than that in female, which should be the key differences of chemical constituents in female and male flower buds of P. tomentosa. The study demonstrated that ¹H NMR combined with multivariate statistics could be used to discriminate female and male plants and clarify differences, which provided a novel method to identify the gender of dioecious plants.