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A validated UHPLC-PDA with an ESI-MS/MS method has been developed for simultaneous estimation of six bioactive alkaloids (magnoflorine, berbamine, columbamine, jatrorrhizine, palmatine and berberine) in the different extracts of the roots of Berberis aristata DC (Family:Berberdiaceae). It is an important medicinal herb native to Northern Himalaya and commonly known as ‘daruharidra’, ‘daruhaldi’, ‘Indian barberry’ or ‘tree turmeric’. An insight into the research literature uncovered reports on isoquinoline alkaloids like magnoflorine, berbamine, columbamine, jatrorrhizine, palmatine, and berberine as major bioactives in B. aristata roots, possessing different pharmacological and therapeutic effects. In the present study, these aforementioned alkaloids were separated on Phenomenex Luna®, 5 µm-C8 analytical column. The HPLC-MS analysis was performed at a flow rate of 0.90 mL min−1. Each alkaloid that is resolved was characterized by precursor ions and fragment ions with electrospray ionization (ESI) source in both positive and negative ionization using scan mode. The limit of detections (LODs) were 0.087, 0.727, 0.035, 0.124, 0.782 and 0.794 μg mL−1 for magnoflorine, berbamine, columbamine, jatrorrhizine, palmatine and berberine, respectively. The proposed UHPLC-PDA method was fully validated according to international (ICH) guidelines and was found to be selective, sensitive and highly accurate for the concomitant estimation of the aforementioned symbolic bio-markers of B. aristata roots.

An analytical method based on UHPLC-PDA and LC–ESI–MS/MS was developed for the simultaneous and reliable determination of 22 antidepressant and anti-anxiety pharmaceutical compounds in adulterated functional foods. The method was validated in terms of specificity, linearity, limit of detection (LOD), limit of quantification (LOQ), method detection limit (MDL), method quantitation limit (MQL), precision, accuracy, recovery, stability, and matrix effect. For solid and liquid blank samples, the developed method had LOD = 0.10–1.01 μg/mL for UHPLC and 0.01–5.05 ng/mL for LC–ESI–MS/MS, respectively, LOQ = 0.30–3.02 μg/mL and 0.03–15.15 ng/mL, and R2 > 0.999 and R2 > 0.99. Recoveries from spiked blank samples in powder, liquid, tablet, and capsule forms were determined to be 80.13–113.76%. The precision, accuracy, and stability were acceptable, and the matrix effect was insignificant. A total of 118 real samples were successfully analysed using the proposed rapid screening method.

Xanthones and polyisoprenylated benzophenones found in Garcinia species are groups of secondary metabolites with a wide range of bioactivities. Three xanthones namely α-mangostin, β-mangostin, γ-mangostin and two polyisoprenylated benzophenone namely xanthochymol and isoxanthochymol were identified and quantified in the extracts prepared from fruit rinds of G. lanceifolia using a validated UHPLC-PDA method. Total phenolic content of extracts prepared from G. lanceifolia fruit rinds with solvents of varying polarity was determined by the Folin-Ciocalteu method. These extracts were also evaluated for their antioxidant potential using three different in vitro assays namely DPPH free radical, ABTS cation radical and reducing power. α-mangostin was not quantified in hexane and chloroform extracts. β-mangostin could not get quantified in hexane extract. γ-mangostin was not detected in any of the six extracts. The maximum content of xanthochymol (289.26 ± 0.31 mg/g) was detected in hexane extract. Isoxanthochymol content (9.91 ± 0.01 mg/g) was maximum in hexane extract and it was followed by chloroform extract (2.67 ± 0.01 mg/g). The highest total phenolic content was recorded for hexane extract (18.60 ± 1.95 mg/g GAE). In vitro assays established that G. lanceifolia extracts exhibited significant antioxidant activity.

Moringa oleifera is known as a drumstick tree and is cultivated in the subtropics and tropics. It exhibits antihypertensive and antidiabetic effects. An ultra-high-performance liquid chromatography method was developed for the determination of 9 phytochemicals in M. oleifera leaves and marketed products. The efficient separation was achieved within 7 min with a temperature of 45 °C by using a C-18 column as the stationary phase and water/acetonitrile with 0.05% formic acid as the mobile phase. The method was validated for linearity, repeatability, limits of detection, and limits of quantification. The limits of detections of phenolic compounds 1 – 9 were as low as 0.2 µg/mL. The photodiode array detector at 220 and 255 nm wavelengths was recruited for quantification. The key phytochemicals were detected in the range of 0.42 to 2.57 mg/100 mg sample weight in 13 dietary supplements. This study considers the quantitative analysis for lignans in M. oleifera for the first time. Isoquercitrin (5) and quercetin 3-O-(6-O-malonyl)-β−D-glucopyranoside (6) predominates the leaves of M. oleifera with inherent degradable nature detected for compound 6. Niazirin (2) was detected in amounts between 0.010 – 0.049 mg/100 mg while compound 1 was undetectable and potentially an artifact because of the fractionation process. The characterization and confirmation of components were achieved by liquid chromatography-electrospray ionization-mass spectrometry with extractive ion monitoring for the positive and negative ion modes. The developed and validated method is robust and rapid in the conclusive quantification of phytochemicals and authentication of the Moringa samples for quality assurance.

Xanthones are well recognized as chemotaxonomic markers for the plants belonging to the genus Garcinia. Xanthones have many interesting pharmacological properties. Efficient extraction and rapid liquid chromatography methods are essentially required for qualitative and quantitative determination of xanthones in their natural sources. In the present investigation, fruit rinds extracts of 8 Garcinia species from India, were prepared with solvents of varying polarity. Identification and quantification of 3 xanthones, namely, α-mangostin, β-mangostin, and γ-mangostin in these extracts were carried out using a rapid and validated ultra-high-performance liquid chromatography–photodiode array detection (UHPLC–PDA) method at 254 nm. γ-Mangostin (3.97 ± 0.05 min) was first eluted, and it was followed by α-mangostin (4.68 ± 0.03 min) and β-mangostin (5.60 ± 0.04 min). The calibration curve for α-mangostin, β-mangostin, and γ- mangostin was linear in the concentration range 0.781–100 μg/mL. α-Mangostin was quantified in all 4 extracts of Garcinia mangostana. Its content (%) in hexane, chloroform, ethyl acetate, and methanol extracts of G. mangostana was 10.36 ± 0.10, 4.88 ± 0.01, 3.98 ± 0.004, and 0.044 ± 0.002, respectively. However, the content of α-mangostin was below the limit of detection or limit of quantification in the extracts of other Garcinia species. Similarly, β-mangostin was quantified only in hexane (1.17 ± 0.01%), chloroform (0.39 ± 0.07%), and ethyl acetate (0.28 ± 0.03%) extracts of G. mangostana. γ-Mangostin was quantified in all 4 extracts of G. mangostana. Its content (%) in hexane, chloroform, ethyl acetate, and methanol extracts of G. mangostana was 0.84 ± 0.01, 1.04 ± 0.01, 0.63 ± 0.04, and 0.15 ± 0.01, respectively. γ-Mangostin was also quantified in hexane (0.09 ± 0.01), chloroform (0.05 ± 0.01), and ethyl acetate (0.03 ± 0.01) extracts of G. cowa, ethyl acetate extract of G. cambogia (0.02 ± 0.01), G. indica (0.03 ± 0.01), and G. loniceroides (0.07 ± 0.01). Similarly, γ-mangostin was quantified in 3 extracts of G. morella, namely, hexane (0.03 ± 0.01), chloroform (0.04 ± 0.01), and methanol (0.03 ± 0.01). In the case of G. xanthochymus, γ-mangostin was quantified in chloroform (0.03 ± 0.001) extract only. α-Mangostin and β-mangostin were not detected in any of 4 extracts of G. pedunculata.

Cocona fruits are a popular food and medicinal fruit used mainly in the Amazon and several countries of South America for the preparation of several food products such as drinks, jams and milk shakes. In this study five ecotypes of cocona native to Peru have been studied regarding their nutritional and antioxidants values plus antihyperlipidemic activities. Seventy bioactive compounds have been detected in Peruvian cocona ecotypes including several phenolic acids, aminoacids and flavonoids; of those six were spermidines, (peaks 1, 2, 25, 26, 38 and 39), thirteen were aminoacids, (peaks 3,‐9, 11‐13, 16, 17, 22‐24), eighteen flavonoids (peaks 28, 30‐32 45,46, 48‐53 56, 57, 61 and 64‐66), twelve were phenolics (peaks 19, 21, 27, 29, 34, 35, 36, 42, 43, 44, 54, and 59), two carotenoids, (peak 62 and 63), eight were lipid derivatives (peaks 37, 55, 58, 60 and 67‐70), one sugar (peak 47), four terpenes (peaks 33, 40, 41 and 47), two amides, (peaks 10 and 18), one aldehyde, (peak 15), and three saturated organic acids, (peaks 4, 5 and 20). Hypercholesterolemic rats administered with pulp of the ecotypes CTR and SRN9 showed the lowest cholesterol and triglyceride levels after treatment (126.74 ± 6.63; 102.11 ± 9.47; 58.16 ± 6.64; 61.05 ± 4.00 mg/dL, for cholesterol, triglycerides, high‐density lipoprotein and low‐density lipoprotein respectively, for the group treated with SRN9 pulp, and 130.09 ± 8.55; 108.51 ± 10.04; 57.30 ± 5.72; and 65.41 ± 7.68 mg/dL, for cholesterol, triglycerides, HDL and LDL lipoproteins respectively for the group treated with CTR pulp). The ecotypes proved to be good sources of natural antioxidants and their consumption represent an alternative for the prevention of atherosclerosis. © 2021 by the authors. Licensee MDPI, Basel, Switzerland. Funding: This research was funded by the Project Concytec – Banco Mundial “Mejoramiento y Ampliación de los Servicios del Sistema Nacional de Ciencia Tecnología e Innovación Tecnológica” 8682, through its executing unit Fondecyt [Contrato N° 119‐2018‐FONDECYT‐BM‐IADT‐MU]. M. J. S acknowledge fondecyt 1180059.

In this study, a method using ultrahigh-performance liquid chromatography with photodiode array (UHPLC-PDA) was established and validated for the simultaneous quantification of 10 active components, including eight macamides and two glucosinolates, in Lepidium meyenii (maca). A gas chromatographic mass spectroscopy (GC-MS) method was used to determine the levels of three benzyl isothiocyanates and two sterols in maca. Liquid chromatographic separation was achieved on a Waters Acquity UHPLC HSS T3 column (2.1 mm × 100 mm, 1.8 μm) with gradient elution over 15 min. The mobile phase was (B) acetonitrile-(A) 10 mM aqueous ammonium phosphate, and the detection wavelength was 210 nm. The gas chromatographic separation was performed on an SH-Rxi-1 MS column, and the ionization mode was electron ionization (EI). Two methods were confirmed to have desirable precision (RSD

Round and ring-shaped abrasions and whitish islands were observed with a digital microscope in a degraded area of blue paint in Jan de Bray’s (1626/7–1697) Judith and Holofernes, 1659, a Dutch pane...

Ziziphus plants are well recognized for their nutritive and medicinal value worldwide, albeit their chemical profile has yet to be fully reported. The secondary metabolites profile of three traditionally used Ziziphus leaf accessions was investigated via ultra-high performance liquid chromatography coupled to photodiode array and electrospray ionization mass detectors (UHPLC/PDA/ESI-MS). A total of 102 metabolites were characterized revealing the first holistic approach onto Ziziphus leaf metabolome and to include the first report of several novel flavonoids and cyclopeptide alkaloids. Fragmentation pattern for cyclopeptide alkaloids was proposed via ESI-MS. Principal component analysis (PCA) revealed close metabolite resemblance among Z. spina-christi and Z. mauritiana leaf specimens found enriched in saponins and distinct from that of Z. jujuba in which quercetin-3-O-(2-pentosyl)-rhamnoside was most abundant. Further, in-vitro antioxidant, anti-inflammatory and antidiabetic assays revealed for Z. spina-christi and Z. mauritiana strong effects compared to Z. jujuba and in correlation with their metabolites repertoire.

Background: Xanthones and polyisoprenylated benzophenones (PIBs) are two important classes of plant secondary metabolites with a wide range of bioactivities. Garcinia species synthesize numerous xanthones and PIBs. As per the literature, no data claiming simultaneous identification and quantification of three xanthones, α-mangostin, β-mangostin, γ-mangostin, and two PIBs, xanthochymol, isoxanthochymol, were found. Methods: A validated ultra-HPLC (UHPLC)-photodiode array (PDA) method for the simultaneous identification and quantification of five compounds in different extracts of eight Indian Garcinia species was developed. The compounds were separated on a Waters ACQUITY™ UPLC H-Class column using a mobile phase consisting of solvents 0.1% formic acid in water (A) and methanol (B) in gradient elution mode. The total run time was 9 min. Results: From fruit rinds of eight Indian Garcinia species, namely Garcinia cambogia, G. cowa, G. indica, G. loniceroides, G. mangostana, G. morella, G. pedunculata, and G. xanthochymus, extracts were prepared using solvents of varying polarity. These extracts were analyzed for five biologically important compounds, namely α-mangostin, β-mangostin, γ-mangostin, xanthochymol, and isoxanthochymol. The results revealed that there is a wide variation in concentration of these compounds in extracts of Garcinia species. Conclusions: The developed and validated UHPLC-PDA method could be used for simultaneous identification and quantification of these five compounds for bioprospection of other Garcinia species.

With the recent development of hand-held and miniature mass spectrometers, low cost and compact mass detectors have become more available and accessible for on-site and routine laboratory use. Here we present a rapid ultra-high performance liquid chromatography-photodiode array/mass spectrometry (UHPLC-PDA/MS) method for the routine screening of a wide variety of illicit drugs using a small and cost effective single quadrupole MS (SQD) with electron spray ionization (ESI). Two libraries for common drugs of forensic interest, a PDA library including retention time (RT) and PDA spectra and a MS library including RT and [M+H]+/[M-H]-, were developed. Using a BEH phenyl column and gradient elution of acetonitrile and 0.1% formic acid, drugs of forensic interest were detected within 8.5min and identified based on their RT/RRT to an internal standard (Codeine-d6), UV spectrum, and/or MS spectrum/(de)protonated molecular mass. The method proved to be efficient, reproducible, and sensitive with a limit of detection (LOD) ≤0.5μg/mL for untargeted screening using PDA and MS in full scan mode and ≤0.1μg/mL for targeted screening by MS in select ion recording (SIR) mode. Improved isomer discrimination was achieved, when a second injection and separation by a charged column (CSH C18) was incorporated into the same acquisition sequence. The method was applied to 20 seized drugs with similar detection limits and identifications by GC-MS. Using an orthogonal separation technique and dual detection systems, the UHPLC-PDA/SQD method serves as an attractive technique for a direct and fast screening of illicit drugs with excellent discrimination power and detection capacity. The developed method can be an alternative screening method to GC-FID and complementary technique to GC-MS for routine forensic drug screening.

Radix Dipsaci (RD), the dried root of Dipsacus asper, is used in traditional Chinese medicine as a remedy for bone fractures, traumatic hematoma, threatened abortion, and uterine bleeding. A novel ultra high-performance liquid chromatography coupled with quadrupole-time-of-flight tanderm mass spectrometry (UHPLC-Q-TOF/MS) approach was performed to rapidly characterize the chemical constituents of RD. Consequently, 21 compounds, including 12 iridoid glycosides (IGs), 4 furofuran lignans (FLs), and 5 phenolic acids (PAs) were discovered and identified from RD. Among these compounds, 3 IGs were previously unreported. Furthermore, a rapid and reliable UHPLC-DAD-based method was developed. The linearity (R2 > 0.999), repeatability (RSDs

This work reports the development and validation of an ultra-high-performance liquid chromatography method to separate 11 different cardiovascular drugs: acenocoumarol, amiloride, bisoprolol, fluvastatin, furosemide, glibenclamide, hydrochlorothiazide, rosiglitazone (internal standard), valsartan, verapamil and warfarin. Detection of the analytes was carried out by means of photodiode array and fluorescence detection. Initially, the most significant variables in liquid chromatography (pH of the mobile phase, nature of the organic modifier and stationary phase type) were studied simultaneously in a systematic way. Taking into account the resolution obtained for the different chromatographic separations, pH 4.5, methanol and C18 were chosen as mobile phase pH, organic modifier and stationary phase, respectively. The method was validated and applied to the analysis of real human plasma samples using a solid phase extraction sample treatment, and the robustness of the chromatographic separation was studied by experimental design. The reported method allows the separation of all the analytes and the IS in less than 6 min, and, furthermore, it simplifies the analysis of drugs used in combined cardiovascular therapy by applying a fast and simple methodology.

Grapes are a great source of phenolic compounds, which have excellent antioxidant properties. Efficient analytical methods are necessary to selectively and precisely determine these compounds content in grapes. In this study, a reverse-phase ultra-high performance liquid chromatography (UHPLC) method with fluorescence and photodiode array detection has been developed to determine and quantify 27 of the main phenolic compounds present in grapes. An ACQUITY UPLC® BEH C18 (50 mm × 2.1 mm i.d., 1.7 mm particle size) column was employed. A gradient method was developed and column temperature (25–55 °C), as well as flow rate (0.6–0.75 mL min−1), were optimized. The optimum conditions allowed the separation of all the compounds in less than 9 min. The method was validated and demonstrated excellent detection and quantification limits, precision, and selectivity. Finally, several grape varieties were studied in order to demonstrate the applicability of the method to the analysis of real matrix samples.

Background Methyl xanthines (MX), known for its psychostimulant effect, occurs mostly in tea and coffee samples. However most of the market available products does not mention the proper amount and quality of MX present where, its consumption in high amount may pose health risks. Aim of the study To develop and validate a fast, efficient and reliable method of MX extraction along with a sensitive, rapid and precise method for simultaneous analysis of MX i.e. Theobromine (TB), Theophylline (TH) and Caffeine (C), with application in commercial tea and coffee samples. Materials and methods Accelerated Solvent Extraction (ASE) was utilized for the first time to extract MX, whereas UHPLC-DAD was applied in order to quantify MX. Results ASE resulted a high extract yield (940.22 ± 192.28 mg/g) with optimized conditions of temperature (100 °C) and solvent (MeOH). UHPLC-DAD showed retention time (min) of 1.51 (TB), 1.81 (TH), 2.30 (C) with r2 values (0.980–0.988). Average MX (μg/mL) was as; TB (14.73 ± 20.9), TH (32.05 ± 55.5), C (121.87 ± 32.3). The method application in commercial samples showed a high extract yield with MX concentration (mg/g) as; TB (0.13–0.38), TH (0–0.55), C (7.14–11.20). Temperature and solvent variation showed important correlation with samples in terms of extraction yield. Conclusion ASE-UHPLC/DAD revealed a fast and sensitive method of MX extraction, quantification and quality determination in market available tea and coffee samples.

Asimina triloba, commonly known as paw paw, is one of approximately 2100 species in the Annonaceae family, scores of which are known to biosynthesize bioactive secondary metabolites, termed Annonaceous acetogenins. Even with over 400 acetogenins identified, a high-throughput screening protocol for these compounds does not exist. Advances in direct ambient ionization mass spectrometry have opened the door to many metabolite profiling methodologies, but for acetogenins, this is often complicated by the abundance of isomers that are present. A droplet-liquid microjunction-surface sampling probe coupled to UPLC-PDA-HRMS/MS system was employed to detect acetogenins in situ from A. triloba. The seeds, fruit pulp, twigs, leaves, and flowers of A. triloba were all examined for acetogenins. Additionally, lithium was infused post-column to increase the sensitivity of the fragments, thus allowing for characterization of the structural classes, and mass defect filtering was used to mine the data for the various acetogenin analogues. This surface sampling system allowed for the rapid identification and differentiation of Annonaceous acetogenins directly from the various organs of A. triloba, including the never before studied flowers.

Anthocyanins from black carrots ( Daucus carota ssp. sativus var. atrorubens Alef.) are widely applied to impart bright red hues to foods such as beverages, fruit preparations, and confectionary. Highly efficient methods for their analyses may be instrumental for manufacturers of coloring foodstuff and for plant breeders to select highly pigmented black carrot varieties. For this purpose, a rapid and exhaustive ultrasound-assisted extraction procedure for anthocyanins was developed and validated. Thereby, deteriorative enzymes like polyphenol oxidase and peroxidase were inactivated. Extraction required only 60 s, yielding coefficients of variation (CVs) for intra-day and inter-day repeatability of ≤4.4 and 4.7%, respectively. For post-extractive quantitation of black carrot anthocyanins, a rapid UHPLC-PDA method was developed and validated. Compared to HPLC separation on a core-shell-column, UHPLC separation time (4.5 min) was 8.2 times faster and solvent consumption 92% less. Limits of detection and quantitation were fully satisfactory. Moreover, stability of non-acylated pigments used as reference compounds was acceptable for 24 h at room temperature, and within 4.5 months of storage time at −20 °C and −80 °C, pigment concentration remained unchanged. Two black carrot varieties were analyzed applying the proposed method, and the results were compared to previously published data.

Vinpocetine and picamilon are drugs prescribed in many countries to treat a variety of cerebrovascular disorders. In the United States, vinpocetine and picamilon have never been approved by the US Food and Drug Administration, but they are both available for sale directly to consumers as dietary supplements. We designed our study to determine the accuracy of supplement labels with regard to the presence and quantity of vinpocetine and picamilon. A validated ultra-high performance liquid chromatography-photodiode-array method was developed for the quantification of vinpocetine and picamilon. The separation was achieved using a reversed phase (C-18) column, photodiode array detection, and water/acetonitrile as the mobile phase. Vinpocetine and picamilon were detected at concentrations as low as 10 and 50 ng/mL, respectively. The presence of vinpocetine and picamilon was confirmed using reference standards. Twenty-three supplements labelled as containing vinpocetine were available for sale at two large supplement retail chains; 17 contained vinpocetine with quantities ranging from 0.3 to 32 mg per recommended daily serving. No vinpocetine was detected in six of the sampled supplements. The supplement label implied that vinpocetine was a constituent of lesser periwinkle in three of the supplements. Of the 31 picamilon supplements available for sale from a variety of retailers: 30 contained picamilon in quantities ranging from 2.7 to 721.5 mg per recommended daily serving. We found that consumers cannot obtain accurate information from supplement labels regarding the presence or quantity of vinpocetine and picamilon. Copyright © 2015 John Wiley & Sons, Ltd.

Sugarcane honey (SCH) is a black syrup recognized by its excellent quality, being produced in Madeira Island using the regional sugarcane cultivars and following a traditional and peculiar manufacturing and storage processes. However, some low-quality commercial products have been labeled as SCH but do not respect its criteria, revealing the need of develop powerful strategies in order to detect and prevent adulterations. The knowledge of furanic derivatives (FDs) profile, produced during browning reactions that occurs during food processing and storage, emerged as a promising strategy in food quality and fraud prevention. Therefore, the aim of this study was to establish the FDs profiling of typical SCH produced by certified and non-certified producers, in different geographical regions (Madeira and Brazil), based on microextraction by packed sorbent (MEPS) combined with ultra-high performance liquid chromatography (UHPLC) as a useful approach to define its typicality and authenticity. These parameters are defined through the differentiation and discrimination of FDs profiles among other sugarcane-derived products using multivariate statistical analysis (ANOVA with post-hoc Tukey, principal components analysis, partial least square, linear discriminant analysis and hierarchical clustering). The results demonstrated that SCH samples from non-certified producers present the highest levels of FDs. In addition, SCH samples from Brazil present higher levels of FDs than samples from Madeira region. The obtained results revealed that the proposed approach is a valuable strategy to establish the typicality of SCH, ensuring its quality, authenticity, safety control and a useful support regarding the application of SCH from Madeira Island to EU certification.

The marketing of new argan-based products is greatly increased in the last few years and consequently, it has enhanced the number of control analysis aimed at detecting counterfeit products claiming argan oil as a major ingredient. Argan oil is produced in Morocco and it is quite expensive. Two simple methods for the rapid screening of pure oil and argan-oil based products, focused on the analysis of the triacylglycerol profile, have been developed. A three-minute-run by UHPLC-PDA allows the identification of a pure argan oil, while the same run with the MS detector allows also the analysis of products containing the oil down to 0.03%. On the other hand, by HPTLC the simultaneous analysis of twenty samples, containing argan oil down to 0.5%, can be carried out in a forty-five-minute run. The triglyceride profile of the most common vegetable fats such as almond, coconut, linseed, wheat germ, sunflower, peanut, olive, soybean, rapeseed, hemp oils as well as shea butter used either in cosmetics or commonly added for the counterfeiting of argan oil, has been also investigated. Over sixty products with different formulations and use have been successfully analyzed and argan oil in the 2.4-0.06% concentration range has been quantified. The methods are suitable either for a rapid screening or for quantifying argan oil in different formulations.

A deeper knowledge of the chemical composition of coffee silverskin (CS) is needed due to the growing interest in its use as a food additive or an ingredient of dietary supplements. Accordingly, the aim of this paper was to investigate the metabolic profile of aqueous extracts of two varieties of CS, Coffee arabica (CS-A), Coffee canephora var. robusta (CS-R) and of a blend of the two (CS-b) and to compare it to the profile of Coffee arabica green coffee (GC). Chlorogenic acids, caffeine, furokauranes, and atractyligenins, phytotoxins not previously detected in CS, were either identified or tentatively assigned. An unknown compound, presumably a carboxyatractyligenin glycoside was detected only in GC. Caffeine and chlorogenic acids were quantified while the content of furokauranes and atractyligens was estimated. GC and CS were also characterized in terms of total polyphenols and antioxidant capacity. Differences in the metabolites distribution, polyphenols and antioxidant capacity in GC and CS were detailed.

An UHPLC method was developed for the determination of 15 prenylflavonoids from aerial parts of Epimedium grandiflorum and related species (Berberidaceae). The separation was achieved using a reverse phased column and water/acetonitrile gradient as a mobile phase at a temperature of 40°C. The developed analytical method was validated for linearity, limits of detection (LOD) and limits of quantification (LOQ), stability and repeatability. The LOD and LOQ were found to be in the range from 0.1-0.5 μg/mL and 0.3–1 μg/mL, respectively. The wavelength used for quantification with the photodiode array detector was 269 nm. The total content of 15 prenylflavonoids was 9.1–20.6 mg/g for E. grandiflorum (except for sample #2899 and #20862), 5.6–35.4 mg/g for E. brevicornu and 10.8–30.5 mg/g for E. sagittatum. Twenty dietary supplements contained in the range from 0.1 to 81.7 mg/day. The developed method is simple, rapid and especially suitable for quality assessment of E. grandiflorum and dietary supplements containing E. grandiflorum. Liquid chromatography quadrupole time-of-flight-mass spectrometry (LC-QToF) is described for the identification and confirmation of compounds in plant samples and dietary supplements. This technique is also used for chemical profiling of Epimedium samples. This method involved the use of protonated ions in the positive ion mode and deprotonated ions in the negative ion mode with extracted ion chromatogram (EIC). Chemometric analytical tools for visualizing the plant and commercial samples quality were used for discriminating between Epimedium species and dietary supplements with regards to the relative content or presence of components. A HPTLC method was also developed for the fast chemical fingerprint analysis of Epimedium species.

Oligomeric proanthocyanidins were successfully identified by UHPLC-PDA-HRMS(n) in a selection of plant-derived materials (jujube fruit, Fuji apple, fruit pericarps of litchi and mangosteen, dark chocolate, and grape seed and cranberry extracts). The identities of 247 proanthocyanidins were theoretically predicted by computing high-accuracy masses based on the degree of polymerization, flavan-3-ol components, and the number of A type linkages and galloyls. MS(n) fragments allowed characterization on flavan-3-ol based on the monomer, connectivity, and location of A-type bonds. Identification of doubly or triply charged ions of 50 PAs was made on the basis of theoretical calculations. A single catechin standard and molar relative response factors (MRRFs) were used to quantify the well-separated PAs. The ratios of the SIM peak counts were used to quantify each of the unseparated isomers. This is the first report of direct determination of each of the proanthocyanidins in plant-derived foods and proanthocyanidins containing an epifisetinidol unit in grape seeds.

The toxicity of the sea mango (Cerbera manghas L.) is well known. The plant is ranked as one of the deadliest of the southern Asian coastline. Cardenolidic heterosides are responsible for the cardiotoxicity of trees of the Cerbera genus. We have identified and determined the concentration of the principal glycosidic steroids present in the seeds of sea mangos (Thailand). Drug screening of an extract of the seeds was carried out using ultra-high performance liquid chromatography coupled to photodiode array detection and mass spectrometry (UHPLC–PDA-MS) with quantification at 219 nm. Identification was confirmed by UHPLC–HRMS. Deacetyltanghinin (m/z 549.3055 ± 2 ppm), neriifolin (m/z 535.3259 ± 2 ppm), tanghinin (m/z 591.3169 ± 2 ppm) and cerberin (577.3375 ± 2 ppm) were the most abundant glycosidic steroids present in the sea mango seeds. A seed of the dried ripe fruit had concentrations of 1209.1, 804.2, 621.4 and 285.9 μg/g, respectively. A seed of the fresh unripe fruit had concentrations of 49.4, 47.0, 3.5 and 2.3 μg/g.

In the present study, pollen-identical pure manuka and kanuka honeys and an Australian jelly bush honey were analyzed for the nonvolatiles by UHPLC-PDA-MS/MS and for the volatiles by HS-SPME-GC/MS. A chromatographic profile matchup by means of characteristic marker compounds achieved a clear discrimination between manuka, kanuka, and jelly bush honey. UHPLC-PDA profiles of manuka honey show leptosin, acetyl-2-hydroxy-4-(2-methoxyphenyl)-4-oxobutanate, 3-hydroxy-1-(2-methoxyphenyl)-penta-1,4-dione, kojic acid, 5-methyl-3-furancarboxylic acid, and two unknown compounds as prominent, kanuka honey was characterized by 4-methoxyphenyllactic acid, methyl syringate, p-anisic acid, and lumichrome. 2-Methylbenzofuran, 2'-hydroxyacetophenone, and 2'-methoxyacetophenone were markant volatiles for manuka honey, whereas kanuka honey was characterized by 2,6,6-trimethyl-2-cyclohexene-1,4-dione, phenethyl alcohol, p-anisaldehyde, and an unknown compound in HS-SPME-GC/MS. The jelly bush honey differed from the manuka honey by higher contents of 2-methoxybenzoic acid and an individual unknown substance in the PDA profile and by lower intensities of 2'-methoxyacetophenone, higher concentrations of cis-linalool oxide, and 3,4,5-trimethylphenol in the HS-SPME-GC/MS profile.

Food products enriched with fatty acid-esterified xanthophylls may result in deviating dietary apo-carotenoids. Therefore, free astaxanthin and its mono- and dipalmitate esters were subjected to two degradation processes in a methanolic model system: light-accelerated autoxidation and hypochlorous acid/hypochlorite (HOCl/OCl(-)) bleaching. Reversed phase ultrahigh-performance liquid chromatography photodiode array with in-line electrospray ionization mass spectrometry (RP-UHPLC-PDA-ESI-MS) was used for assessment of degradation products. Apo-astaxanthinals and -astaxanthinones containing 3 (apo-9) to 10 (apo-8') conjugated double bonds were found upon autoxidation for all three types of astaxanthin (except free apo-8'-astaxanthinal). Fragmentation of [M + H](+) and [M + Na](+) parent masses of apo-astaxanthins from dipalmitate astaxanthin indicated palmitate esterification. Astaxanthin monopalmitate degradation resulted in a mixture of free and palmitate apo-astaxanthins. HOCl/OCl(-) rapidly converted the astaxanthins into a mixture of epoxy-apo-9- and epoxy-apo-13-astaxanthinones. The palmitate ester bond was hardly affected by autoxidation, whereas for HOCl/OCl(-) the ester bond of the apo-astaxanthin palmitoyl esters was degraded.

Potential toxic effects in mice of an infusion prepared from the stem bark of Exostema caribaeum was assessed by means of the Lorke procedure. The preparation was not found to be toxic, with the LD50 value estimated to be more than 5 g/kg. This preparation at 100, 300, and 500 mg/kg also caused a significant hypoglycemic effect and a reduction in the postprandial glycemia peak in both normal and nicotinamide/streptozotocin (NA/STZ)-diabetic mice in an oral sucrose tolerance test. Phytochemical analysis of the infusion revealed that the major active principles are 4-phenylcoumarins (2-8) and chlorogenic acid (1). During this process, a new 4-phenylcoumarin was isolated along with several known analogues. The structure of the new compound was established as 5-O-[β-D-xylopyranosyl-(1→6)-β-D-glucopyranosyl]-7,3',4'-trihydroxy-4-phenylcoumarin (2) by spectroscopic means. A simple, efficient, fast, and reliable UHPLC-PDA analytical method for quantifying 4-phenylcoumarins and chlorogenic acid (1) was developed and validated. Parameters assessed for the method validation were selectivity, linearity, the limits of detection (LOD) and quantification (LOQ), precision, and accuracy. It was found that all calibration curves showed good linearity (R(2)0.9931), within the range of concentrations tested.

A fast and reliable method for the quantification of patulin using ultra high performance liquid chromatography coupled to a photodiode array detector was developed and validated for the analysis of several apple-based foodstuffs. Sample preparation was based on the QuEChERS procedure. Samples were extracted with acetonitrile and partitioned with a mixture of sodium citrate, NaCl, and Mg2SO4. The cleanup step was performed using dispersive SPE mixed with Mg2SO4 and PSA. This step was carried out twice in order to improve chromatographic results. The method was validated in spiked cloudy apple juice, apple puree, apple yogurt, beer with apple juice, and cider and applied to 24 commercial samples. The limits of detection and limits of quantification were ≥0.4 and ≥2 ng/g, respectively. Both were below the maximum legal limit established by the European Union. Recoveries for all the matrices were between 78.4 and 94.7 % while relative standard deviations were between 3.8 and 10.4 %. Patulin was detected on four apple juices from concentrate, one cloudy apple juice from an eco-store, and one beer. Nevertheless, the highest concentration found was 25.4 ng/g.

Several fruits and vegetables from Madeira Island (Portugal) were evaluated by two analytical methods for their total vitamin C content ( l -ascorbic acid, l -AA and dehydroascorbic acid, DHAA). DHAA was determined indirectly with DL-1,4-dithiotreitol (DTT) applied as a pre-column reductant. Ultra high performance liquid chromatography coupled to photodiode array (UHPLC-PDA) determinations were compared with l -AA content obtained by a classic iodometric titration method. The stability of vitamin C in horticultural extracts stored at different temperatures was also investigated. Red peppers represented the better source of vitamin C followed by green peppers and papayas. Passion fruits and cherimoyas were the analyzed foodstuffs with lowest vitamin C content. Both analytical methods were suitable for l -AA analysis in various food commodities, the UHPLC-PDA technique being preferred due to its advantages of selectivity, speed and accuracy. The degradation study showed that horticultural extracts were stable at least 24 h at 4 °C and during 4 weeks when stored at −80 °C.

Objectifs : Une methode semi-quantitative en toxicologie clinique a ete developpee utilisant une extraction par micro-elution en phase solide suivie d’une analyse par un systeme de chromatographie liquide ultra-haute performance couplee a une spectrometrie UV-visible a barrettes de diodes (PDA) (UHPLC-PDA). Cette etude a ete realisee sur 122 molecules medicamenteuses en respectant les recommandations de la norme NF EN ISO 15189. Methodes : Parmi differentes cartouches SPE (Solid-Phase Extraction ) testees, la cartouche Strata®-X a ete selectionnee pour ses meilleurs rendements d’extraction. Un protocole d’extraction manuelle a partir de plasma sanguin a ete mis en place pour 3 concentrations (0,1 mg/L, 1 mg/L et 10 mg/L) avec le methanol comme solvant d’elution. La separation sur UHPLC a ete realisee avec un gradient de phase mobile acetate d’ammonium 5 mM/acetonitrile (ACN) (85/15; V/V) a pH 3,8 ± 0,05 et d’ACN sur une colonne BEH C18 1,7 μ m, 2,1 mm × 150 mm avec un debit de 0,45 mL/min. Les analytes ont ete detectes par PDA (190–400 nm). Resultats : Les rendements d’extraction etaient satisfaisants de meme que la precision (CV% repetabilite 15 % pour certaines molecules) mais diminuaient lorsqu’ils etaient rapportes aux 2 etalons internes (flurazepam et prazepam). La semi-quantification s’est faite a l’aide de 2 facteurs de reponses et les LOD et LOQ ont ete comparees aux valeurs therapeutiques ou toxiques. Conclusion : La methode decrite est simple et rapide. Les resultats ont montre la capacite de la cartouche Strata®-X a extraire des molecules appartenant a plusieurs classes pharmacologiques avec des proprietes physico-chimiques differentes.

The aim of this study was to investigate the possibility of using the non-official species Scutellaria indica L. as the substitute for the official species Scutellaria barbata D. Don. A sensitive, precise and accurate method was developed to identify their chemical compositions from the crude extracts using UHPLC–PDA–QTOF–MS/MS. 36 peaks were detected and 28 peaks have been tentatively and structurally characterized by comparing their retention times, UV spectra and HR-MS data with those of the reference substances and/or the data of the literatures. Additionally, 5 flavonoids have been quantified by multiple reaction monitoring (MRM) in the negative ionization mode. The results demonstrated that there were 23 common peaks between these two species. However, the other 13 peaks from S. barbata could not be detected in S. indica . Furthermore, the content of 5 flavonoids is significantly different. Scutellarein cannot be detected in S. indica , which was considered as the characteristic component for distinguishing the two species. Our data, therefore, clearly demonstrate that S. indica may not be used as the substitute for S. barbata and further investigation is needed to determine through investigation of their therapeutic efficacy.

An UHPLC-PDA-ESI/HRMS(n) profiling method was used to identify the glucosinolates and flavonoids of Rorippa indica (Cruciferae), a wild vegetable and Chinese herb used to treat cough, diarrhea, and rheumatoid arthritis. Thirty-three glucosinolates, more than 40 flavonol glycosides, and 18 other phenolic and common organic compounds were identified. The glucosinolates and polyphenols were separated by UHPLC. High-resolution deprotonated molecules provided high accuracy mass values that were used to determine formulas and provide putative identification of the glucosinolates and flavonoids. The fragments from multistage mass spectrometry were used to elucidate the structures. The concentrations of the main components were based on UV peak areas and molar relative response factors with a single calibration standard. This study found this plant to be a rich source for glucosinolates, containing 24 new glucosinolates, including 14 glucosylated glucosinolates that were previously unidentified.

The global metabolic profile of Laurencia crude red algal extracts was addressed by applying high-throughput analytical techniques, namely UHPLC–PDA–HRMS and 2D HSQC NMR. An integrated platform including software tools and databases, such as Xcalibur, ToxID, ACD/Labs and MarinLit, has been developed to mine the complex analytical data towards the accelerated identification of known metabolites and the detection of new natural products at the early stages of phytochemical analysis. In parallel, a searchable ‘in-house’ Laurencia-focused NMR database incorporating chemical structures, NMR spectroscopic data and reported biological activities has been generated. The screening strategy has been developed as a tool to prioritize the crude extracts to be further subjected to phytochemical analysis by tracing the presence of new natural products among the pool of known compounds. The successful application of this integrated methodology in the crude extract of Laurencia chondrioides led to the rapid detection of two new C15 bromoallene acetogenins (1 and 2), which were subsequently isolated and characterized.