Chemical Fingerprint Research Articles

Egyptian Opuntia ficus-indica (OFI) Residues: Recovery and Characterization of Fresh Mucilage from Cladodes

The utilization of biopolymers gained recent attention worldwide due to their effective role in producing eco-friendly and economical products. Mucilage from Opuntia ficus-indica (OFI, and other succulent plants) has the capacity to absorb huge amounts of water, forming a viscous colloid with interesting rheological properties. It also had the potential ability for use as food additives or food technological products. We, therefore, aimed at extracting and characterizing pure liquid mucilage from the cladodes of OFI (Egyptian variety) using multidimensional approaches including HPLC-RID, FTIR, XRD, NMR, DSC, and TGA assays. The chemical composition, total polyphenols, total flavonoids, total flavonols, and antioxidant capacity by DPPH and ABTS assays were also measured. HPLC-RID analysis showed that the mucilage’s sugars are composed of glucose, xylose, rhamnose, galacturonic acid, arabinose, galactose, and fucose with total sugars of 0.375 mg/mL, which were subsequently confirmed by FTIR and NMR results. The specific signals of these sugars were also observed in 13C and 1H NMR spectra and their chemical fingerprint was obtained by FTIR. XRD patterns showed that mucilage has high calcium content, and the glass transition temperature was observed at 85.9 °C. Meanwhile, total phenolic content, flavonoids, and flavonols were about 7.96 mg GAE/g FW, 3.61 mg QE/g FW, and 1.47 mg QE/g FW, respectively. The antioxidant capacity of mucilage was around 26.15 and 22.5 µmol TE/g FW for DPPH and ABTS methods, respectively. It can be concluded that OFI cladode mucilage showed promising properties that would improve and open new opportunities and trends in the food, pharmaceutical, cosmetic, and other industries. The use of pure liquid mucilage could also be economically profitable due to its low cost, availability, and effectiveness for many edible applications.

Detection of pyridine derivatives by SABRE hyperpolarization at zero field

Nuclear magnetic resonance (NMR) spectroscopy is a powerful analytical tool used in modern science and technology. Its novel incarnation, based on measurements of NMR signals without external magnetic fields, provides direct access to intramolecular interactions based on heteronuclear scalar J-coupling. The uniqueness of these interactions makes each zero-field NMR spectrum distinct and useful in chemical fingerprinting. However, the necessity of heteronuclear coupling often results in weak signals due to the low abundance of certain nuclei (e.g., 15N). Hyperpolarization of such compounds may solve the problem. In this work, we investigate molecules with natural isotopic abundance that are polarized using non-hydrogenative parahydrogen-induced polarization. We demonstrate that spectra of hyperpolarized naturally abundant pyridine derivatives can be observed and uniquely identified whether the same substituent is placed at a different position of the pyridine ring or different constituents are placed at the same position. To do so, we constructed an experimental system using a home-built nitrogen vapor condenser, which allows for consistent long-term measurements, crucial for identifying naturally abundant hyperpolarized molecules at a concentration level of ~1 mM. This opens avenues for future chemical detection of naturally abundant compounds using zero-field NMR.

Discrimination of Polygonati Rhizoma Species: An Investigation Utilizing High-Performance Liquid Chromatography Fingerprints and Chemometrics.

Polygonati Rhizoma has been a famous traditional Chinese medicine (TCM) for two thousand years. It is increasingly being used not just as a traditional herbal medicine but also as a popular functional food. In this study, qualitative and quantitative analysis of PR from three different origins were initially performed using chemical fingerprint and chemometrics methods. Hierarchical cluster analysis (HCA) and Principal component analysis (PCA) were used to classify 60 PR samples from three different origins. The results revealed that the PR samples fell into three clusters related to the origins. In addition, pairwise comparison of varying PR and obtaining chemical markers between different species through the establishment of partial least squares discriminant analysis. Finally, chemical markers 9,13 and 17 were identified by LC/MS as disporopsin, 5,7-dihydroxy-3-(4'-hydroxybenzyl)-6,8-dimethylchroman-4-one and (3R)-5,7-dihydroxy-3-(4'-hydroxybenzyl)-6-methylchroman-4-one or isomer, respectively. In conclusion, these methods can be applied to identify and distinguish the quality of PR with other original plants and provide novel ideas for evaluating herbal products used in TCM.

GC-MS analysis of honeybee products derived from medicinal plants

BackgroundHoneybees provide a wealth of valuable natural products containing health-promoting bioactive compounds, including honey, bee bread, bee venom, bee pollen, propolis, and royal jelly. In the present study, we investigated the chemical composition of four honeybee products (bees, honey, royal jelly, and bee bread) derived from three medicinal plants (marjoram, trifolium, and citrus) using headspace GC-MS.ResultsGC-MS analysis coupled with the headspace method resulted in identification of 24 volatile compounds in marjoram honey, 14 volatile compounds in trifolium honey, and 25 volatile compounds in citrus honey, e.g., some of these compounds appeared in all three types of honey aroma, which are 2,3-dihydro-3,5-dihydroxy-6-methyl-4H-pyran-4-one, 2-furancarboxaldehyde, 5-(hydroxymethyl) and other unique compounds specific for each type where 23 compounds were from marjoram bees, 38 compounds from trifolium bees, and about 37 compounds were identified in citrus bees where 2,4-decadienal, (E, E) and methyl N-methyl anthranilate were common in all. Furthermore, the volatile compounds of all three types of royal jelly aroma were acetic acid, 2,3-dihydro-3,5-dihydroxy-6-methyl-4H-pyran-4-one, 8-nonen-2-one and furfural where one compound appeared in both marjoram and trifolium royal jelly that is 2-furancarboxaldehyde,5-(Hydroxymethyl) and the volatile compounds in marjoram and citrus are 2,3-butanediol and 5-methylfurfural also only one volatile compound appear in both trifolium and citrus royal jelly that is furfur alcohol, Finally, 3 compounds from marjoram bee bread, 30 volatile compounds from trifolium bee bread, and 3 volatile compounds in citrus bee bread were identified.ConclusionsA detailed metabolomic analysis of the four honey product groups revealed an intriguing chemical diversity, with each sample exhibiting its own chemical fingerprint.

Metabolomics-guided identification of compounds with antibacterial and antioxidant activities from Polygonatum sibiricum-derived endophytic fungi

BackgroundInfections caused by multidrug resistant bacterial pathogens have been recognized as major global healthcare threat to medicinal, agricultural and pharmaceutical industries by World Health Organization. In this regard, the present study was aimed to isolate endophytes from medicinal plant Polygonatum sibiricum (P. sibiricum) and to investigate their antibacterial efficacy, radical scavenging ability and chemical fingerprinting using Gas Chromatography–Mass Spectrum (GC–MS) analysis.ResultsTwo endophytic fungi Talaromyces assiutensis HJ.14 (T. assiutensis) and Fusarium oxysporum HJ.15 (F. oxysporum) were isolated and identified from the rhizomes of P. sibiricum. Among the extracts screened, ethyl acetate extract of F. oxysporum HJ.15 showed maximum antibacterial activity with the zones of inhibition ranging from 10.98 ± 0.19 to 15.66 ± 1.49 mm and the MIC values ranging from 0.24 to 1.88 µg/mL against the tested bacterial pathogens. In addition, it showed significant antioxidant activity with EC50 values of 6.21–17.97 µg/mL. Further, GC–MS analysis revealed the presence of propanoic acid ethyl ester, hexadecanoic acid methyl ester, hexadecanoic acid ethyl ester, 9-Octadecenoic acid (Z)-methyl ester, 1-Octanol, 2-Undecenal, butanoic acid, 3-hydroxy- and hexanoic acid were the most abundant compounds in the active crude extract which was responsible for the significant antibacterial and antioxidant properties.ConclusionsIn summary, our results clearly suggest that the F. oxysporum HJ.15 will be a promising starting point for the isolation of active antibacterial compounds with antioxidant properties.

Fine aerosol sources at an urban background site in the Eastern Mediterranean (Nicosia; Cyprus): Insights from offline versus online source apportionment comparison for carbonaceous aerosols

A total of 348 daily PM2.5 samples were collected at an urban background site of Nicosia, capital of Cyprus, for one-year period (October 2018–October 2019) to assess the origin and sources of fine PM at the Eastern Mediterranean, a poorly characterized area of the world.The samples were analysed for water soluble ionic species, elemental and organic carbon, carbohydrates and trace metals, the combination of which were utilized to identify pollution sources by applying Positive Matrix Factorization (PMF). Six PM2.5 sources, namely long-range transport (LRT; 38 %), traffic (20 %), biomass burning (16 %), dust (10 %), sea salt (9 %) and heavy oil combustion (7 %), were identified.Despite sampling in an urban agglomeration, the chemical fingerprint of the aerosol is largely dictated by air mass origin rather than local sources. Springtime is characterized by the most elevated particulate levels due to the southerly air masses carrying particles from the Sahara Desert. Northerlies are observed throughout the year but are predominant during summer allowing the LRT source to peak (54 % during summer). Only during winter, due to extensive use of biomass combustion for domestic heating (36.6 % during winter), local sources dominate.A co-located online PMF source apportionment of submicron carbonaceous aerosols (Organic Aerosols, OA; Black Carbon) was performed by the means of an Aerosol Chemical Speciation Monitor (for OA) and an Aethalometer (for BC) for a four-month period. The comparison between the two methodologies allowed to better assess the robustness and limitations of the two methodologies. More specifically, LRT OA and biomass burning BC apportioned by the offline PMF showed a strong consistency with the online apportioned more oxidized oxygenated OA and BCwb, respectively; cross validating these sources. On the other hand, our traffic factor may contain additional hydrocarbon-like OA and BC from fossil fuel sources other than just vehicular emissions. Finally, the offline biomass burning OA source is likely to contain both primary and secondary OA.

Holistically assessing the quality consistency of compound liquorice tablets from similarities of both all chemical fingerprints and the integrated dissolution curves by systematically quantified fingerprint method

In recent years, traditional analytical methods have failed to meet the widespread use of multi-component Chinese pharmaceutical formulations. To solve this problem, this study proposed a comprehensive analytical strategy using compound liquorice tablets (CLTs) as an example, both in terms of chemical quality and dissolution curve consistency. Firstly, the peak purity of the two wavelengths was checked using dual-wavelength absorbance coefficient ratio spectra (DARS) to avoid the fingerprint bias caused by peak purity. Secondly, liquid-phase dual-wavelength tandem fingerprint (DWTF) of 38 batches of CLTs was established for the first time. The two analytical methods were also evaluated using the systematically quantified fingerprint method (SQFM), and the 38 batches of samples were classified into two grades with good quality consistency. Quantitative analysis of the five markers of CLTs was performed simultaneously using the standard curve method (SCM) and the quantitative analysis of multiple components by single marker (QAMS). The results showed no significant differences between the two analytical methods (p > 0.5). In addition, the in vitro dissolution of CLTs in two media (pure water and pH = 4.5 medium) was determined by the total UV fingerprint dissolution assay. The similarity of the dissolution curves was also analyzed by combining the f2 factor and the dissolution-systematically quantified fingerprint method (DSQFM). The result showed that most of the samples had f2 > 50 and Pm satisfied the range of 70–130%. Finally, a principal component analysis (PCA) model was developed to combine the evaluation parameters of chemical fingerprint and dissolution curves for comprehensive analysis of the samples. In this study, a chromatographic and dissolution-based quality analysis method was proposed, which effectively overcomes the shortcomings of previous analytical methods and provides a scientific analytical method for the quality control of natural drugs.

Early Islamic glass (7th- 10th centuries AD) in Unguja Ukuu, Zanzibar: A microcosm of a globalised industry in the early 'Abbasid period.

Eighty-two glass vessels, recovered from the excavations at the ancient Swahili settlement and port of Unguja Ukuu in Zanzibar, Eastern Africa, were analysed using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). The results show that all of the glass samples are soda-lime-silica glass. Fifteen glass vessels belong to the natron glass type and are characterised by low MgO and K2O (<1.50%), suggesting they were made from natron, a mineral flux that was widely used during the Roman period and Late Antiquity. Sixty-seven glass vessels belong to the plant ash glass type, characterised by high magnesia and potash levels (>1.50%), suggesting plant ash was the main alkali flux. Based on the major, minor and trace elements, three different compositional groups were identified for the natron glass and three were identified for the plant ash glass: (1) UU Natron Type 1, (2) UU Natron Type 2, (3) UU Natron Type 3, (4) UU Plant ash Type 1, (5) UU Plant ash Type 2 and (6) UU Plan ash Type 3. Comparison with contemporary Middle Eastern glass groups shows that UU Natron Types 1, 2 and 3 correspond to Egypt II high Na2O, Levantine I and Levantine II respectively, while UU Plant ash Type 1 matches closely with Samarra Group 2. UU Plant ash Types 2 and 3 have unique chemical fingerprints that do not match any of the contemporary plant ash glass groups, but their chemical compositions show some affinity with the old Sassanian plant ash glass, suggesting a possible Mesopotamian provenance. Combined with existing research on early Islamic glass, the authors reveal a complex trading network in the globalisation of Islamic glass, particularly involving glass corresponding to modern Iraq and Syria, in the 7th- 9th centuries AD.

Tracing the origin of Taiping Houkui green tea using 1H NMR and HS-SPME-GC–MS chemical fingerprints, data fusion and chemometrics

The narrow geographical traceability of green tea is both important and challenging. This study aimed to establish multi-technology metabolomic and chemometric approaches to finely discriminate the geographic origins of green teas. Taiping Houkui green tea samples were analyzed by headspace solid-phase microextraction coupled with gas chromatography-mass spectrometry and 1H NMR of polar (D2O) and non-polar (CDCl3). Common dimension, low-level and mid-level data fusion approaches were tested to verify if the combination of several analytical sources can improve the classification ability of samples from different origins. In assessments of tea from six origins, the single instrument data test set results in 40.00% to 80.00% accuracy. Data fusion improved single-instrument performance classification with mid-level data fusion to obtain 93.33% accuracy in the test set. These results provide comprehensive metabolomic insights into the origin of TPHK fingerprinting and open up new metabolomic approaches for quality control in the tea industry.

Merging bioactivity predictions from cell morphology and chemical fingerprint models using similarity to training data

The applicability domain of machine learning models trained on structural fingerprints for the prediction of biological endpoints is often limited by the lack of diversity of chemical space of the training data. In this work, we developed similarity-based merger models which combined the outputs of individual models trained on cell morphology (based on Cell Painting) and chemical structure (based on chemical fingerprints) and the structural and morphological similarities of the compounds in the test dataset to compounds in the training dataset. We applied these similarity-based merger models using logistic regression models on the predictions and similarities as features and predicted assay hit calls of 177 assays from ChEMBL, PubChem and the Broad Institute (where the required Cell Painting annotations were available). We found that the similarity-based merger models outperformed other models with an additional 20% assays (79 out of 177 assays) with an AUC > 0.70 compared with 65 out of 177 assays using structural models and 50 out of 177 assays using Cell Painting models. Our results demonstrated that similarity-based merger models combining structure and cell morphology models can more accurately predict a wide range of biological assay outcomes and further expanded the applicability domain by better extrapolating to new structural and morphology spaces.Graphical

UPLC-QTOF-MS/MS-based metabolomic approach and gastroprotective effect of two chemotypes of Egletes viscosa (L.) less. against ethanol-induced gastric ulcer in mice.

Egletes viscosa (L.) (macela) is a native wild herb that can be found in different states of northeastern Brazil. The infusions of its flower buds are traditionally used for the treatment of gastrointestinal disorders. E. viscosa possesses two chemotypes (named A and B), distinguishable by the composition of the essential oil from the flower buds. Although there are previous studies of the gastroprotective effect of the isolated constituents of E. viscosa, its infusions have not been investigated yet. The present study aimed to evaluate and compare the chemical composition and the gastroprotective effect of flower bud infusions of E. viscosa from chemotype A (EVCA) and chemotype B (EVCB). Sixteen infusions were brewed with flower buds according to the traditional preparation mode and were analyzed through a UPLC-QTOF-MS/MS based metabolomic approach for determination of their metabolic fingerprints and quantification of bioactive compounds. Afterward, these data were analyzed by chemometric methods (OPLS-DA) for discrimination of the two chemotypes. Additionally, infusions of EVCA and EVCB (50, 100 and 200mg/kg, p.o.) were evaluated on gastric ulcers induced by absolute ethanol (96%, 0.2mL, p.o.) in mice. To elucidate the gastroprotective mechanisms, the effect of EVCA and EVCB on gastric acid secretion and gastric wall mucus was determined and the role of TRPV1 channels, prostaglandins, nitric oxide and KATP channels were assessed. Moreover, the oxidative stress-related parameters and the histological aspects of the stomach tissue were analyzed. The chemotypes can be discriminated from each other using UPLC-QTOF-MS/MS chemical fingerprints. Both chemotypes presented similar chemical compositions, consisting basically of caffeic acid derivatives, flavonoids and diterpenes. The quantification of bioactive compounds demonstrated that chemotype A possesses more ternatin, tanabalin and centipedic than chemotype B. EVCA and EVCB (50, 100 and 200mg/kg, p.o.) significantly decreased the severity of ethanol-induced gastric lesions, as shown by a reduction in histological alterations and leucocyte infiltration in gastric tissue. The gastroprotective mechanism of both infusions involves an antioxidant effect, maintenance of gastric mucus and reduction gastric secretion. Stimulation of endogenous prostaglandins and nitric oxide release, activation of TRPV1 channels, and KATP channels are also involved in the gastroprotection of the infusions. The gastroprotective effect of EVCA and EVCB was equivalent and mediated through antioxidant and antisecretory actions, including the activation of TRPV1 receptors, stimulation of endogenous prostaglandins and nitric oxide, and opening of KATP channels. The presence of caffeic acid derivatives, flavonoids and diterpenes in both infusions is involved in mediating this protective effect. Our findings support the traditional use of infusions of E. viscosa for gastric disorders regardless of the chemotype.

Quality evaluation of Huocao based on UPLC fingerprint and multi-component content determination

Huocao(a traditional Chinese herbal medicine) moxibustion is a characteristic technology in Yi medicine suitable for cold-dampness diseases. Huocao, as the moxibustion material, is confusedly used in clinical practice and little is known about its quality control. In this study, UPLC method was used to establish the chemical fingerprint of non-volatile components in Huocao, and the contents of eight phenolic acids such as chlorogenic acid were determined. Multivariate statistical analysis was performed to obtain the indicator components of Huocao for quality evaluation, and thus a comprehensive evaluation system for the quality of Huocao was built. The UPLC fingerprints of 49 batches of Huocao were established, and there were 20 common peaks, of which eight phenolic acids including neochlorogenic acid and chlorogenic acid were identified. Except for three batches of Huocao, the similarity of the other 46 batches was higher than 0.89, suggesting that the established fingerprint method could be used for quality control of the medicinal herb. The correlation coefficient between entropy weight score of the eight phenolic acids and comprehensive fingerprint score in Huocao was 0.875(P&lt;0.01), which indicated that the eight phenolic acids could be used as indicator components for the quality evaluation of Huocao. Furthermore, in multivariate statistical analysis on the common peaks of fingerprint and the contents of the eight phenolic acids, chlorogenic acid, isochlorogenic acid A and isochlorogenic acid C were screened to be the indicator components. The results revealed that the proposed method achieved a simple and accurate quality control of Huocao based on UPLC fingerprint and multi-component content determination, which provided useful data for establishing the quality standard of Huocao.

Machine learning applications for identify the geographical origin, variety and processing of black tea using 1H NMR chemical fingerprinting

Machine learning applications for identify the geographical origin, variety and processing of black tea using 1H NMR chemical fingerprinting

Application of Chemometrics and HPLC Fingerprint for Species Differentiation and Authentication of the Genus Pterocarpus

Pterocarpus species are well known for their nutritional and medicinal values, in order to examine the similarities or differences in the chemical profile of some common Pterocarpus species, four species of the genus namely; Pterocarpus erinaceus, P. mildbraedii, P. osun and P. santalinoides were analyzed using HPLC combined with Principal component analysis (PCA) and Hierarchical clustering analysis (HCA). This study aims to investigate the chemical fingerprints of the species and compare them in order to highlight the similarities in their chemical constituents. The ethanol extract of each sample was taken and filtered through a 0.45 μm millipore membrane filter and then transferred into the HPLC vial before injecting it into the HPLC machine. PCA and HCA were performed on the relative retention times and percentage peak composition. The species were chemically similar with nine (9) peaks in common, the most prominent peaks in all samples appeared at 3.26 min which corresponds to gallic acid (a known compound). Cluster analysis revealed some similar chemical variables with Gallic acid being the major compound in the Pterocarpus species and could be used as a marker compound for taxonomic purposes.

High-Precision Trace Hydrogen Sensing by Multipass Raman Scattering.

Despite its growing importance in the energy generation and storage industry, the detection of hydrogen in trace concentrations remains challenging, as established optical absorption methods are ineffective in probing homonuclear diatomics. Besides indirect detection approaches using, e.g., chemically sensitized microdevices, Raman scattering has shown promise as an alternative direct method of unambiguous hydrogen chemical fingerprinting. We investigated the suitability of feedback-assisted multipass spontaneous Raman scattering for this task and examined the precision with which hydrogen can be sensed at concentrations below 2 parts per million. A limit of detection of 60, 30, and 20 parts per billion was obtained at a pressure of 0.2 MPa in a 10-min-long, 120-min-long, and 720-min-long measurement, respectively, with the lowest concentration probed being 75 parts per billion. Various methods of signal extraction were compared, including asymmetric multi-peak fitting, which allowed the resolution of concentration steps of 50 parts per billion, determining the ambient air hydrogen concentration with an uncertainty level of 20 parts per billion.

Comprehensive Quality Evaluation of Polygonatum cyrtonema and Its Processed Product: Chemical Fingerprinting, Determination and Bioactivity.

Processing of Chinese herbal medicines (CHMs) is a traditional pharmaceutical technology in Chinese medicine. Traditionally, proper processing of CHMs is necessary to meet the specific clinical requirements of different syndromes. Processing with black bean juice is considered one of the most important techniques in traditional Chinese pharmaceutical technology. Despite the long-standing practice of processing Polygonatum cyrtonema Hua (PCH), there is little research on the changes in chemical constituents and bioactivity before and after processing. This study investigated the influence of black bean juice processing on the chemical composition and bioactivity of PCH. The results revealed significant changes in both composition and contents during processing. Saccharide and saponin content significantly increased after processing. Moreover, the processed samples exhibited considerably stronger DPPH and ABTS radical scavenging capacity, as well as FRAP-reducing capacity, compared to the raw samples. The IC50 values for DPPH were 1.0 ± 0.12 mg/mL and 0.65 ± 0.10 mg/mL for the raw and processed samples, respectively. For ABTS, the IC50 values were 0.65 ± 0.07 mg/mL and 0.25 ± 0.04 mg/mL, respectively. Additionally, the processed sample demonstrated significantly higher inhibitory activity against α-glucosidase and α-amylase (IC50 = 1.29 ± 0.12 mg/mL and 0.48 ± 0.04 mg/mL) compared to the raw sample (IC50 = 5.58 ± 0.22 mg/mL and 0.80 ± 0.09 mg/mL). These findings underscore the significance of black bean processing in enhancing the properties of PCH and lay the foundation for its further development as a functional food. The study elucidates the role of black bean processing in PCH and offers valuable insights for its application.

Integration of Per- and Polyfluoroalkyl Substance (PFAS) Fingerprints in Fish with Machine Learning for PFAS Source Tracking in Surface Water

Per- and polyfluoroalkyl substances (PFASs) are a class of environmental contaminants that originate from various sources. The unique chemical fingerprints associated with many commercial products and industrial applications make PFASs ideal candidates for machine learning (ML)-assisted environmental forensics. Here, we propose a novel use of PFAS fingerprints in fish tissue from surface water systems to classify exposure from multiple sources of PFASs using a proof-of-concept demonstration. Three supervised ML classification techniques (k-nearest neighbors (KNN), decision trees, support vector machines) implementing two predictive features are used to classify literature-reported PFAS fingerprints in fish (n = 1057). The importance of additional predictive features was explored using brute force optimization of a multifeature KNN algorithm. The multiclass classification considered exposure to aqueous film-forming foam-impacted water, paper industry wastewater, diffuse sources, or PFASs undergoing long-range transport. The optimized classifiers demonstrated 85%–94% classification accuracy for this first known multiclass classification of PFASs for environmental forensics. The optimized classifiers also demonstrated 79%–92% classification accuracy with a set of independent external validation data (n = 192). Our results demonstrate that PFAS fingerprints in fish tissue may be an effective means of PFAS source tracking in surface water systems. The source code is provided for guidance on best practices for ML-assisted environmental forensics.

Discrimination of Green Coffee (Coffea arabica and Coffea canephora) of Different Geographical Origin Based on Antioxidant Activity, High-Throughput Metabolomics, and DNA RFLP Fingerprinting.

The genus Coffea is known for the two species C. arabica (CA) and C. canephora (CC), which are used to prepare the beverage coffee. Proper identification of green beans of coffee varieties is based on phenotypic and phytochemical/molecular characteristics. In this work, a combination of chemical (UV/Vis, HPLC-DAD-MS/MS, GC-MS, and GC-FID) and molecular (PCR-RFLP) fingerprinting was used to discriminate commercial green coffee accessions from different geographical origin. The highest content of polyphenols and flavonoids was always found in CC accessions, whereas CA showed lower values. ABTS and FRAP assays showed a significant correlation between phenolic content and antioxidant activity in most CC accessions. We identified 32 different compounds, including 28 flavonoids and four N-containing compounds. The highest contents of caffeine and melatonin were detected in CC accessions, whereas the highest levels of quercetin and kaempferol derivatives were found in CA accessions. Fatty acids of CC accessions were characterized by low levels of linoleic and cis octadecenoic acid and high amounts of elaidic acid and myristic acid. Discrimination of species according to their geographical origin was achieved using high-throughput data analysis, combining all measured parameters. Lastly, PCR-RFLP analysis was instrumental for the identification of recognition markers for the majority of accessions. Using the restriction enzyme AluI on the trnL-trnF region, we clearly discriminated C. canephora from C. arabica, whereas the cleavage performed by the restriction enzymes MseI and XholI on the 5S-rRNA-NTS region produced specific discrimination patterns useful for the correct identification of the different coffee accessions. This work extends our previous studies and provides new information on the complete flavonoid profile, combining high-throughput data with DNA fingerprinting to assess the geographical discrimination of green coffee.

Improving Chuanxiong Rhizoma quality standards using an effect-constituent index based bioassay

Chuanxiong Rhizoma is a traditional Chinese medicine (TCM) that is used to promote blood circulation. We set out to improve Chuanxiong Rhizoma quality standards using a bioassay-based Effect-constituent Index (ECI). We performed high performance liquid chromatography (HPLC) analysis to determine the chemical constituents of 10 Chuanxiong Rhizoma samples from different locations. We then constructed a direct bioassay method to investigate each sample’s antiplatelet aggregation effects. To screen for active ingredients that promote antiplatelet aggregation, we carried out Pearson correlation analyses between biopotency and compounds identified in the HPLC data. We developed an ECI of platelet aggregation inhibition using a multi-indicator synthetic evaluation method based on the integration of biopotency and active constituents. To further assess the biopotency-based Chuanxiong Rhizoma quality evaluation result accuracy, we compared the ECI with the chemical indicator’ method. Eight common chemical fingerprints peaks indicated notable content variation among samples. Biological evaluation showed that all 10 samples could inhibit platelet aggregation, although they had significantly different biological potencies. Using spectrum-effect relationships, we determined that Ligustilide was the significant active constituent responsible for antiplatelet aggregation. Using correlation analysis, we found that ECI correlated with the Chuanxiong Rhizoma extract’s platelet aggregation inhibitory effect. Additionally, ECI proved to be a good indicator of Chuanxiong Rhizoma quality, whereas chemical indicators failed to distinguish and predict the biopotency-based quality grade. This work indicates that ECI is a useful tool for associating sample quality with chemical markers linked to TCM clinical effects. ECI also provides a paradigm for improving the quality control of other TCMs that invigorate blood circulation.

Rapid Characterization of Hops (Humulus lupulus) Using DART-MS and Chemometrics

Hops represent a key ingredient in beer and are often utilized to impart specific flavors. The popularity of hoppy beers (e.g., India Pale Ales) is raising expectations for stability, quality, and unique organoleptic properties of hops. Evaluation of hops is typically performed by sensory evaluation, requiring a trained human panel, and often yielding subjective results with limited throughput. Here, we present the use of ambient mass spectrometry (AMS) as an alternative approach to enable objective and rapid chemical fingerprinting of hops for quality screening reflective of sensory. Twelve hop samples were sourced from three different suppliers across four different farms located in Washington and Oregon (U.S.A.) over two growing seasons. The samples included three commercial cultivars, Cascade, Centennial, and Strata. The hop samples were extracted using an 80% ethanol solution and chemical fingerprints were acquired by Direct Analysis in Real Time Mass Spectrometry (DART-MS). The resulting data were used to train and validate predictive multivariate statistical models. Additionally, authentic standards of important hop compounds (hop α-acids, terpenes) were used to putatively annotate DART-MS signals and traditional sensory analysis was performed to support that the DART-MS data is reflective of sensory attributes. The results demonstrate the potential of this approach for rapid evaluation of hops quality. Ultimately, implementation of this tool could have applications for quality assurance programs and rapid phenotyping of hops by producers.