Chemometric analysis of Tunisian durum wheat metabolites using UPLC-ESI-QTOF-MS/MS.

Bioactive compounds in wheat have received a great interest in the last few years due to their nutritional and health benefits. Various analytical procedures were used to identify these compounds in wheat kernels. An ultra-performance liquid chromatography coupled to electrospray ionization quadrupole-time-of-flight mass spectrometry (UPLC-ESI-QTOF-MS/MS) was used for the screening of bioactive compounds in seven Tunisian durum wheat extracts. The aim of this study was to realize a screening of several classes of bioactive compounds in the same analysis and to identify specific metabolite markers for discriminating the durum wheat varieties. The UPLC-ESI-QTOF-MS/MS allows the detection of 81 metabolites, belonging to different chemical families such as sugars, organic acids, amino acids, fatty acids, and phenolic compounds represented by benzoic and cinnamic acid derivatives, phenolic alcohols, flavones, lignans, and condensed tannins. Chemical profiles identified varied greatly between different wheat genotypes. As far as the authors know, this is the first time that different chemical classes were detected at the same time in durum wheat kernels using UPLC-ESI-QTOF-MS/MS. This study gives the most complete map of metabolites in Tunisian durum wheat and proves that UPLC-QTOF-MS/MS coupled with chemometric analysis is a great tool for discrimination between durum wheat cultivars.

A Review on Fully Bio-Based Materials Development from Polylactide and Cellulose Nanowhiskers.

This review covers the development of eco-friendly, bio-based materials based on polylactide (PLA) and cellulose nanowhiskers (CNWs). As a biodegradable polymer, PLA is one of the promising materials to replace petroleum-based polymers. In the field of nanocomposites, CNWs offer many advantages; they are made from renewable resources and exhibit beneficial mechanical and thermal properties in combination with polymer matrix. A wide range of surface modifications has been done to improve the miscibility of CNW with the PLA homopolymer, which generally gives rise to hydrophobic properties. PLA-CNW nanocomposite materials are fully degradable and sustainable and also offer improved mechanical and thermal properties. Limitations pertaining to the miscibility of CNWs with PLA were solved through surface modification and chemical grafting on the CNW surfaces. Further development has been done by combining PLA-based material via stereocomplexation approaches in the presence of CNW particles, known as bio-stereo-nanocomposite PLA-CNW. The combination of stereocomplex crystalline structures in the presence of well-distributed CNW particles produces synergetic effects that enhance the mechanical and thermal properties, including stereocomplex memory (melt stability). The bio-based materials from PLA and CNWs may serve as eco-friendly materials owing to their sustainability (obtained from renewable resources), biodegradability, and tunability properties.

The Effect of Stereocomplex Polylactide Particles on the Stereocomplexation of High Molecular Weight Polylactide Blends.

Stereocomplexation is one of several approaches for improving polylactide (PLA) properties. The high molecular weight of poly L-lactide (PLLA) and poly D-lactide (PDLA) homopolymers are a constraint during the formation of stereocomplex PLAs (s-PLAs). The presence of s-PLA particles in PLA PLLA/PDLA blends can initiate the formation of s-PLA crystalline structures. We used the solution casting method to study the utilization of s-PLA materials from high molecular weight PLLA/PDLA blends for increasing s-PLA formation. The s-PLA particles initiated the formation of high molecular weight PLLA/PDLA blends, obtaining 49.13% s-PLA and 44.34% of the total crystalline fraction. In addition, the mechanical properties were enhanced through s-PLA crystalline formation and the increasing of total crystallinity of the PLLA/PDLA blends. The s-PLA particles supported initiation for s-PLA formation and acted as a nucleating agent for PLA homopolymers. These unique characteristics of s-PLA particles show potential to overcome the molecular weight limitation for stereocomplexation of PLLA/PDLA blends.

Properties Enhancement of High Molecular Weight Polylactide Using Stereocomplex Polylactide as a Nucleating Agent.

As one of the most attractive biopolymers nowadays in terms of their sustainability, degradability, and material tune-ability, the improvement of polylactide (PLA) homopolymer properties by studying the utilization of stereocomplex polylactide (s-PLA) effectively and efficiently is needed. In this sense, we have studied the utilization of s-PLA compared to poly D-lactide (PDLA) homopolymers as a nucleating agent for PLA homopolymers. The mechanical and thermal properties and crystallization behavior of PLA homopolymers in the presence of nucleating agents have been evaluated using a universal testing machine, differential scanning calorimeter, and X-ray diffractometer instruments, respectively. PDLA and s-PLA materials can be used to increase the thermal and mechanical properties of poly L-lactide (PLLA) homopolymers. The s-PLA materials increased the mechanical properties by increasing crystallinity of the PLLA homopolymers. PLLA/s-PLA enhanced mechanical properties to a certain level (5% s-PLA content), then decreased them due to higher s-PLA materials affecting the brittleness of the blends. PDLA homopolymers increased mechanical properties by forming stereocomplex PLA with PLLA homopolymers. Non-isothermal and isothermal evaluation showed that s-PLA materials were more effective at enhancing PLLA homopolymer properties through nucleating agent mechanism.

LC-MS-based metabolite profiling of methanolic extracts from the medicinal and aromatic species Mentha pulegium and Origanum majorana.

INTRODUCTION: There has been increasing interest dedicated to the phenolic compounds with a view to their antioxidant and healthy properties. Recent studies have focused on plants from the Lamiaceae family with special interest in phenolic compounds antioxidant potential. OBJECTIVE: The metabolite profile of methanolic extracts from two Lamiacea medicinal plants was investigated. MATERIALS AND METHODS: Mentha pulegium and Origanum majorana methanolic extracts were analysed using reversed-phase ultra-high-performance liquid chromatography (RP-UHPLC) coupled to electrospray ionisation quadrupole time-of-flight mass spectrometry (ESI-QTOF-MS) detection in the negative ion mode. RESULTS: A total of 85 metabolites were characterised from different families, such as organic acids and derivatives, amino acids and derivatives, nucleosides, phenolic compounds as well as other polar metabolites, by using the MS and MS/MS information provided by the QTOF-MS. However, the total phenols and flavonoids were also quantified spectrophotometrically and they registered higher amounts in Mentha pulegium than in Origanum majorana extract. Gallocatechin was the major compound in M. pulegium extract whereas quercetin dimethyl ether, jaceidin and dihydrokaempferide were the major ones in O. majorana extract. CONCLUSION: The distribution of phenolic compounds in the methanolic extract showed a variation among studied plants. Mentha pulegium can be considered as a source of gallocatechin.

UPLC-QTOF/MS for a rapid characterisation of phenolic compounds from leaves of Myrtus communis L.

INTRODUCTION: Although continuous research has been conducted on the biological activities of myrtle and the characterisation of its essential oil, few studies have focused on its phenolic composition despite major beneficial properties. OBJECTIVE: To carry out a comprehensive characterisation of infusion and methanolic extract from myrtle leaves by UPLC-QTOF/MS. METHODS: Myrtle-leaf infusions, prepared using deionised water, and the methanolic extracts were analysed by reversed-phase ultra-performance liquid chromatography (UPLC) coupled to electrospray ionisation quadrupole time-of-flight mass spectrometry (ESI/QTOF/MS). The MS and MS/MS experiments were conducted using the negative-ionisation mode, in order to provide molecular-mass information and production spectra of the compounds for structural elucidation. RESULTS: The analytical method applied enabled the characterisation of several compounds such as gallic acid and galloyl derivatives, ellagic acid and derivatives, hexahydroxydiphenolyl and derivatives, flavonoids, lignans and gallomyrtucommulones. Flavonoids, ellagic acid and its derivatives and gallic acid and its derivatives formed the major fractions. CONCLUSION: UPLC combined with QTOF/MS is a powerful analytical method for characterising infusions and alcoholic extracts from myrtle leaves.

Identification of polyphenols and their metabolites in human urine after cranberry-syrup consumption.

As the beneficial effects of American cranberry (Vaccinium macrocarpon) can be partly attributed to its phenolic composition, the evaluation of the physiological behaviour of this fraction is crucial. A rapid and sensitive method by ultra-performance liquid chromatography coupled to quadrupole-time-of-flight mass spectrometry (UPLC-Q-TOF-MS) has been used to identify phenolic metabolites in human urine after a single dose of cranberry syrup. Prior to the analysis, metabolites were extracted using an optimised solid-phase extraction procedure. All possible metabolites were investigated based on retention time, accurate mass data and isotope and fragmentation patterns. Free coumaroyl hexose (isomer 1 and 2), dihydroxybenzoic acid, caffeoyl glucose, dihydroferulic acid 4-O-ß-d-glucuronide, methoxyquercetin 3-O-galactoside, scopoletin, myricetin and quercetin, together with other 23 phase-I and phase-II metabolites, including various isomers, could be tentatively identified in the urine. Afterwards, the metabolites were simultaneously screened in the urine of different subjects at 0, 2, 4, and 6h after the ingestion of cranberry syrup by Target Analysis(TM) software.

Characterization by high-performance liquid chromatography with diode-array detection coupled to time-of-flight mass spectrometry of the phenolic fraction in a cranberry syrup used to prevent urinary tract diseases, together with a study of its antibacterial activity.

The phenolic fraction of a commercial cranberry syrup, which is purported to have good properties for the prevention of urinary diseases, has been thoroughly characterized using HPLC-DAD-TOF-MS. A study of its antibacterial activity has also been carried out. For this purpose a new HPLC-DAD-TOF-MS method using negative and positive ionization modes was developed and it was thus possible to identify 34 different compounds, nine of which have been tentatively characterized for the first time in cranberry syrup. It is also important to highlight that different coumarins in this matrix were also determined, which, to our knowledge, have not been found previously in the cranberry. The phenolic fraction obtained by HPLC-DAD was found to be 5.47 mg/mL. Catechin and procyanidins belonging to flavanols were the family of compounds found at the highest concentrations (2.37 mg/mL); flavonols were at a concentration of 1.91 mg/mL and phenolic-acid derivatives were found at the lowest concentration (0.15 mg/mL). With regard to antibacterial activity, the incubation of Escherichia coli with cranberry syrup was found to reduce surface hydrophobicity as a function of the concentration of the extract.

Identification of phenolic compounds in aqueous and ethanolic rooibos extracts (Aspalathus linearis) by HPLC-ESI-MS (TOF/IT).

Rooibos (Aspalathus linearis) is a rich source of polyphenols and used to make a mild-tasting tea containing no caffeine, is low in tannins compared to green or black teas, and has antioxidant and antimutagenic/antitumoral properties. In vivo results show that rooibos has beneficial effects upon the lipid profile by decreasing serum triglycerides and cholesterol. In this sense, we have developed a simple and rapid method to separate and characterize simultaneously the polyphenolic compounds in aqueous and ethanolic rooibos extracts using high-performance liquid chromatography coupled to electrospray ionization time-of-flight mass spectrometry (HPLC-ESI-TOF-MS) and ion trap multiple mass spectrometry (HPLC-ESI-IT-MS(2)). The phenolic compounds were separated on a C(18) column (4.6 × 150 mm, 1.8 µm) with 1% formic acid in water/acetonitrile 90:10 v/v and acetonitrile as mobile phases. The accuracy mass data generated by TOF-MS together with the fragmentation pattern obtained by IT-MS(2) experiments confirmed the presence of 25 and 30 phenolic compounds in the aqueous and ethanolic extracts, respectively.