The metabolic profile of lemon juice by proton HR-MAS NMR: the case of the PGI Interdonato Lemon of Messina

We have studied by means of High Resolution Magic Angle Spinning Nuclear Magnetic Resonance (HR-MAS NMR) the metabolic profile of the famous Sicilian lemon known as 'Interdonato Lemon of Messina PGI’. The PGI Interdonato Lemon of Messina possesses high organoleptic and healthy properties and is recognised as one of the most nutrient fruits. In particular, some of its constituents are actively studied for their chemo-preventive and therapeutic properties. In this paper, we have determined by means of HR-MAS NMR spectroscopy the molar concentration of the main metabolites constituent the juice of PGI Interdonato Lemon of Messina in comparison with that of the not-PGI Interdonato Lemon of Turkey. Our aim is to develop an analytical technique, in order to determine a metabolic fingerprint able to reveal commercial frauds in national and international markets.     

Influence of drying methods on chemical compositions,antioxidant and antibacterial activity of essential oil from lemon peel

The influence of natural, hot-air and infrared drying on chemical composition and bioactivity of lemon peel essential oil are investigated in this study. The results showed that drying resulted in losses or increases of some components or production of some new substances, but the d-limonene (59.52–70.01%) was found as the main component of essential oil. Drying brought about decreases in the yield, antioxidant and antibacterial activity of essential oil. However, the natural drying had little effect, while the hot-air and infrared drying resulted in significant decreases in these parameters, especially at the higher temperature. The yield was the lowest under hot-air drying (60 °C) and decreased by 78%, while infrared drying (60 °C) sample exhibited the lowest antioxidant and antibacterial activities. Infrared drying was easier to lead to the decrease in bioactivity than hot-air drying at the same temperature. These results provided the theoretical basis for drying lemon peel.     

Composition of essential oil of lemon thyme (Thymus × citriodorus) at different hydrodistillation times

Distillation time can both to optimise the production and to engineer the composition of essential oil in essential oil bearing plants. Purpose of this study was to evaluate the effect of duration of hydrodistillation on composition of essential oil of Thymus × citriodorus, the natural source of commercially important geraniol and citral, a component with valuable biological properties. Essential oils were isolated by hydrodistillation at different distillation times and analysed by GC/MS analytical methods. Increase in percentage of essential oil during all hydrodistillation time gradient was uneven. Elongation of hydrodistillation time decreased percentages of monoterpenes but increased percentages of sesquiterpenes in essential oil. Results showed that the hydrodistillation of essential oil from lemon thyme longer than 60 min is useless.     

Accumulation of PCBs,PAHs, plasticizers and inorganic elements in Hexanchus griseus from the strait of Messina (Central Mediterranean sea)

Abstract

This study investigates the inorganic elements and the persistent organic pollutants (POPs) accumulated in liver of a sexually mature Hexanchus griseus living in the Mediterranean Sea. The casual finding of a specimen in the Strait of Messina (April 2018) allowed us to carefully analyse its liver which can be considered a very important biological indicator. The determination of inorganic elements was carried out by ICP-MS technique. Quantitative determination of polycyclic aromatic hydrocarbons (PAH) and poly-chloro-biphenyl compounds (PCB), distinguished in dioxine-like (DL) and not-dioxine-like (NDL) derivates, has been carried out by HRGC/MS and HRGC-MS/MS respectively. Worrying levels of PCB-DL (TEQ?=?Σ(PCB-DL)*TEF?=?5.96?ng g^?1), PCB-NDL (Σ(PCB-NDL)?=?1390.4?ng g^?1) together with the presence of pesticides and plasticizers were found in the shark liver oil. The levels of heavy metals were below the legal limits.     

Limonene concentration in lemon (Citrus volkameriana) peel oil as a function of ripeness

The dependence of the limonene content of lemon (Citrus volkameriana) peel oil on the degree of ripeness of the fruit has been studied by using steam distillation and cold pressing to extract the oils from lemon fruit peel at different stages of maturation (green, greenish-yellow, and yellow-orange peel coloration). Samples of essential oils were analyzed by high resolution GC and GC-MS, using tetradecane as internal standard for quantitation. Forty components were detected; thirty eight were positively identified by comparison of their mass spectra (El, 70 eV) and Kováts retention indexes (determined using a non-logarithmic scale on capillary columns coated with both polar (DB-Wax) and non-polar (DB-1) stationary phases) with those of standards and with data reported in the literature. The limonene concentration reached a maximum level of 79.4% when the fruit was in the intermediate maturation stage characterized by greenish-yellow coloration.     

Characterization of Pygeum africanum bark extracts by HRGC with computer assistance

The components of Pygeum africanum bark extracts, used for the treatment of benign prostatic hypertrophy, were characterized by high resolution gas chromatography (HRGC) and mass spectrometry (MS). Among various compounds n-docosyl trans-ferulate was identified and quantitated by HRGC as a derivative of n-docosanol, which is considered to be one of the active components of the extract. The origin of different Pygeum a. extracts can be studied by eigenvector projection of HRGC profiles with computer assistance.     

Fractionation of lemon essential oil by solvent extraction: Phase equilibrium for model systems at T = 298.2 K

The fractioning of lemon essential oil can be performed by liquid–liquid extraction using hydrous ethanol as a solvent. A quaternary mixture composed of limonene, γ-terpinene, β-pinene, and citral was used to simulate lemon essential oil. In this paper, we present (liquid + liquid) equilibrium data that were experimentally determined for systems containing essential oil compounds, ethanol, and water at T = 298.2 K.The experimental data were correlated using the NRTL and UNIQUAC models, and the mean deviations between calculated and experimental data were less than 0.0053 in all systems, indicating the accuracy of these molecular models in describing our systems.The results show that as the water content in the solvent phase increased, the values of the distribution coefficients decreased, regardless of the type of compound studied. However, the oxygenated compound always showed the highest distribution coefficient among the components of the essential oil, thus making deterpenation of the lemon essential oil a feasible process.     

Essential oil composition of Citrus medica L. Cv. Diamante (Diamante citron) determined after using different extraction methods

In this paper, we report the qualitative and quantitative composition of the volatile and the oxygenated heterocyclic fraction of citron (Citrus medica L. cv. Diamante (Diamante citron)). The fruits selected for the extraction were of three types: green citron of little size, green citron of big size, and yellow citron after 1 month from the harvest. The essential oils were extracted using three different methods. The nine samples of oil thus obtained were analyzed by high resolution GC (HRGC)‐flame ionization detection (FID), HRGC‐MS, and RP‐HPLC. They differ only in the quantitative composition, while the qualitative profile was the same. The volatile fraction of every sample of oil is characterized by a high content of limonene, γ‐terpinene, and monoterpene aldehydes and a lower content of α‐ and β‐pinene and myrcene, sesquiterpenes, and aliphatic aldehydes. Enantioselective (Es)‐GC analysis of the extracts allowed the determination of the enantiomeric distribution of five terpenoid compounds; a prevalence of four dextrorotatory isomers was observed. Oxypeucedanin was the main component of the oxygenated heterocyclic fraction in the extracts of green fruits, while citropten was the major oxygenated compound in the oil obtained from yellow citron.     

Determination of petitgrain oils landmark parameters by using gas chromatography–combustion–isotope ratio mass spectrometry and enantioselective multidimensional gas chromatography

Gas chromatography–combustion–isotope mass spectrometry was employed for the assessment of the Carbon isotope ratios of volatiles in Italian mandarin and lemon petitgrain oils. In addition, the composition of the whole oil and the enantiomeric distribution of selected chiral compounds were determined for all the samples by using gas chromatography and by multidimensional and conventional enantioselective gas chromatography. The composition of the oils was compared with previous studies. The enantiomeric distribution of lemon petitgrain oils is here reported for the first time. On the composition of mandarin petitgrain oil, the information available in literature, to date, is relative only to one sample from Egypt. Carbon isotope ratio of several terpene hydrocarbons and of their oxygenated derivatives contained in petitgrains was compared with the δ ¹³C_VPDB values of the same compounds present in the corresponding genuine Italian Citrus peel oil. The results prove that the isotopic values obtained for lemon and mandarin petitgrain oils are very close to those relative to the corresponding peel oils determined in previous studies.     

Green synthesis of some new thiopyrano[2,3-d][1,3]thiazoles using lemon juice and their antibacterial activity

A simple green method has been developed for the synthesis of a series of new 3-phenyl-6-(substituted)-thiopyrano[2,3-d]thiazole-2,5,7(6H)-triones, 6-cyano-2-oxo-3-phenyl-thiopyrano[2,3-d]thiazoles, 3-phenyl-3,5,5a,11b-tetrahydro-2H,6H-chromeno-[4′,3′:4,5]thiopyrano[2,3-d]thiazole-2,6-dione and 5-amino-6-cyano-2-oxo-3-phenyl-3,7-dihydro-2H-thiopyrano[2,3-d]thiazoles via hetero-Diels–Alder reaction by conventional method and green method using lemon juice as natural acid. The structure of all the newly synthesized compounds was interpreted by elemental analyses and spectral data. The synthesized compounds were evaluated for their in vitro antibacterial activity against some pathogenic bacteria. This study is a platform for the future design of more potent antimicrobial agents.     

HRGC and GC–MS analysis of essential oil from colombian ylang-ylang (Cananga odorata Hook fil. et Thomson,forma genuina)

Samples of essential oil from Colombian ylang-ylang trees were analyzed by means of HRGC, HRGC–MS, IR and ¹H- and ¹³C-NMR. 57 components were detected, 51 of which were positively identified. Camphene and anethol were identified in ylang-ylang essential oil for the first time. Among the composition-determining variables studied (extraction time, part of the flower, and flower freshness), the extraction time and the flower condition (fresh versus dry) were found to have the largest incidence in the quality of the essential oil.     

Effects of PAR and UV‐B Radiation on Herbal Yield,Bioactive Compounds and Their Antioxidant Capacity of Some Medicinal Plants Under Controlled Environmental Conditions

Photosynthetically active radiation (PAR) and Ultraviolet B (UV‐B) radiation are among the main environmental factors acting on herbal yield and biosynthesis of bioactive compounds in medicinal plants. The objective of this study was to evaluate the influence of biologically effective UV‐B light (280–315 nm) and PAR (400–700 nm) on herbal yield, content and composition, as well as antioxidant capacity of essential oils and polyphenols of lemon catmint (Nepeta cataria L. f. citriodora), lemon balm (Melissa officinalis L.) and sage (Salvia officinalis L.) under controlled greenhouse cultivation. Intensive UV‐B radiation (2.5 kJ m^?2 d^?1) influenced positively the herbal yield. The essential oil content and composition of studied herbs were mainly affected by PAR and UV‐B radiation. In general, additional low‐dose UV‐B radiation (1 kJ m^?2d^?1) was most effective for biosynthesis of polyphenols in herbs. Analysis of major polyphenolic compounds provided differences in sensitivity of main polyphenols to PAR and UV‐B radiation. Essential oils and polyphenol‐rich extracts of radiated herbs showed essential differences in antioxidant capacity by the ABTS system. Information from this study can be useful for herbal biomass and secondary metabolite production with superior quality under controlled environment conditions.     

Study of immobilized and extracellular invertase of lemon balm

Cell suspensions of lemon balm (Melissa officinalis L.) were permeabilized by Tween 20, Tween 80, ethanol, hexadecyltrimethylammonium bromide, and hexadecylpyridinium chloride, and immobilized by glutaraldehyde. The invertase pH optimum was 4.5 at temperature 50°C. The hydrolysis of substrate was linear for 4 h, reaching 60% conversion. The cells had high invertase activity and good stability, and in longterm storage they showed good physicomechanical properties. The culture medium (without cells) was used for the identification and determination of extracellular enzyme activity. Intracellular activity was estimated from the cell suspension. For the lemon balm cell suspension, the intracellular activity accounted for 83.7% of the total activity, and the extracellular one for 12.7%. The intracellular specific activity is 4.2 times higher. Our method permits the rapid, simple, and specific identification and determination of plant invertase. Published in Khimiya Prirodnykh Soedinenii, No. 6, pp. 611-615, November-December, 2008.     

Authenticity control of essential oils containing citronellal and citral by chiral and stable-isotope gas-chromatographic analysis

Enantioselective capillary GC on a Supelco β-DEX 225 column (heptakis(2,3-di-O-acetyl-6-O-tert-butyldimethylsilyl)-β-cyclodextrin SPB 20poly—20% diphenyl, 80% dimethylsiloxane) and isotope-ratio mass spectrometry, coupled online with capillary GC on an HP5 column have been used for origin-specific analysis and authenticity control of essential oils, for example lemon (Citrus limon), lemongrass (Cymbopogon citratus and Cymbopogon flexuosus), citronella (Cymbopogon nardus L.—Ceylon type and Cymbopogon winterianus—Java type), Litsea cubeba, Lippia citriodora, lemon myrtle (Backhousia citriodora), lemon gum (Eucalyptus citriodora), and, especially, precious lemon balm oil (Melissa officinalis L.). Isotope data (δ¹³C_PDB and δ²H_V-SMOW) for citral (neral + geranial) and citronellal from on-line GC–C/Py–IRMS and chiral data for citronellal in these essential oils are reported. The possibility of using these data to determine the origin of these essential oils and to detect adulteration is discussed. Principal-components analysis (PCA) of specific compounds in two essential oils of lemongrass and Litsea cubeba was performed as a practical statistical method for distinguishing between these two types of oil.     

Establishing the chromatographic fingerprints of flavan‐3‐ols and proanthocyanidins from rose hip (Rosa sp.) species

The profile of flavan‐3‐ols and proanthocyanidins in five different Rosa species (R. canina, R. glutinosa, R. rubiginosa, R. multiflora, and R. spinosissima) was estimated on high performance thin layer chromatography cellulose plates. Differences in flavanol and proanthocyanidin profiles of the extracts were evident, among which Rosa spinosissima stood out with catechin as the only detected flavanol and red zones as indication of anthocyanins. Furthermore, the elution solvent for thin layer chromatography with mass spectrometry analyses of glycosylated flavan‐3‐ols and proanthocyanidins was optimized, enabling identification of catechin, (epi)catechin hexoside, proanthocyanidin dimer, and proanthocyanidin dimers and trimers hexosides. A total of 15 flavanols and their derivatives were identified using ultra‐high‐performance liquid chromatography with linear trap quadrupole‐Orbitrap mass analyzer and epicatechin, gallocatechin, and proanthocyanidin trimer were identified only using this technique. However, proanthocyanidin trimer trihexoside was identified only by thin‐layer chromatography with mass spectrometry. To establish the relationships between the flavanols and proanthocyanidins composition of rose hip and their origin, principal component analysis was performed on the entire set of liquid chromatography/mass spectrometry data. Both principal components’ scores plots showed that Rosa spinosissima could be considered as an outlier. Our study demonstrated that flavanol and proanthocyanidin profiles of different rose hips depend on the geographical origin rather than on the cultivar and genotype.     

Multiple analytical approaches for the organic and inorganic characterization of Origanum vulgare L. samples

Origanum vulgare L. samples, marketed in different geographic locations, were characterized by their organic and inorganic chemical composition. A total of 35 commercial samples were collected from various sites and analyzed to determine the qualitative and quantitative profile of essential oils, phenolic compounds and some inorganic elements. The variation in the content and composition of the essential oil was assessed by GC and GC-MS analyses, the phenolic fraction was investigated by UPLC^®/PDA, and the inorganic elements were determined by ICP-MS. The Principal Component Analysis (PCA) was applied with the aim to sort out the Origanum vulgare L. samples with different composition according to the different belonging origins. The results showed appreciable qualitative and quantitative differences among samples from different geographic origin.     

Fatty acid,tocopherol, and sterol content of three <Emphasis Type="Italic">Teucrium</Emphasis> species from Tunisia

In the present study analyses concerning the composition of vitamin E, sterols, triglycerides, and fatty acids of three Teucrium species (Teucrium alopecurus, T. nabli, and T. polium) seed oil were performed. Linoleic, linolenic, and palmitic were the major fatty acids. The oil was characterized by a high amount of phytosterol, wherein clerosterol, sitosterol, and stigmasterol are the main constituents. The amount of tocopherol is nearly 550 mg/kg of oil, with α-tocopherol as the major isomer. Information concerning the composition of Teucrium seed oil is very important for evaluating the therapeutic effect of this oil. Published in Khimiya Prirodnykh Soedinenii, No. 3, pp. 261–264, May–June, 2009.     

Study of quantitative and qualitative variations in essential oils of Sicilian Rosmarinus officinalis L.

In this study the chemical characterisation of 10 Sicilian Rosmarinus officinalis L. biotypes essential oils is reported. The main goal of this work was to analyse the relationship between the essential oils yield and the geographical distribution of the species plants. The essential oils were analysed by GC-FID and GC-MS. Hierarchical cluster analysis and principal component analysis statistical methods were used to cluster biotypes according to the essential oils chemical composition. The essential oil yield ranged from 0.8 to 2.3 (v/w). In total 82 compounds have been identified, these represent 96.7–99.9% of the essential oil. The most represented compounds in the essential oils were 1.8-cineole, linalool, α-terpineol, verbenone, α-pinene, limonene, bornyl acetate and terpinolene. The results show that the essential oil yield of the 10 biotypes is affected by the environmental characteristics of the sampling sites while the chemical composition is linked to the genetic characteristics of different biotypes.     

Development of a voltammetric electronic tongue for discrimination of edible oils

In this paper, we propose a novel strategy to perform cyclic voltammetric measurements with a platinum microelectrode directly in edible oil samples. The microelectrode was employed as an electronic tongue that, along with the application of chemometrics to the current–potential responses, proved useful for discriminating oils on the basis of their quality and geographical origin. The method proposed here is based on the use of suitable room temperature ionic liquids, added to oils as supporting electrolytes to provide conductivity to the low-polarity samples. The entire voltammograms, recorded directly on the oil/RTIL mixtures, were processed via principal component analysis and a classification technique (K nearest neighbors), to extract information on samples characteristics. Data processing showed that oils having different nature (i.e. maize and olive) or geographical origin (i.e. olive oils coming from different regions) can be distinguished.     

Characterization and classification of Western Greek olive oils according to cultivar and geographical origin based on volatile compounds

The aim of the present study was to characterize and classify olive oils from Western Greece according to cultivar and geographical origin, based on volatile compound composition, by means of Linear Discriminant Analysis. A total of 51 olive oil samples were collected during the harvesting period 2007-2008 from six regions of Western Greece and from six local cultivars. Forty-five of the samples were characterized as extra virgin olive oils. The analysis of volatile compounds was performed by Headspace Solid Phase Microextraction-Gas Chromatography/Mass Spectrometry (HS-SPME-GC/MS). Fifty-three (53) different volatile compounds were tentatively identified and semi-quantified. Using selected volatile compound composition data (selection was based on the application of ANOVA to total volatiles to determine those variables showing substantial differences among samples of different geographical origin/cultivar), the olive oil samples were satisfactorily classified according to geographical origin (87.2%) and cultivar (74%).