No full-text available
To read the full-text of this research,
you can request a copy directly from the authors.
Isolation and identification of cyclitols in carob pods (Ceratonia siliqua L.)
Abstract
In the food industry, carob powder is used as a cocoa substitute. It consists primarily of sugars (sucrose, glucose, fructose) in addition to tannins, fibers, etc. D-(+)-Pinitol (3-O-methyl-D-chiro-inositol), myo-inositol, and D-(+)-chiro-inositol were isolated from a fermented water extract of carob powder. The concentration of pinitol ranged from 5 to 7.5% of the dry weight of the powder as determined by GC. myo-Inositol and chiro-inositol were minor components with concentrations of 0.5 to 1% and 0.1%, respectively. As pinitol is not present in cocoa powder, it can be used as a natural marker of carob adulteration of cocoa powder. Further investigations, including GC-MS, revealed traces of ononitol (4-O-methyl-myo-mositol), sequoyitol (5-O-methyl-myo-inositol), and bornesitol (1-O-methyl-myo-inositol) to be present in a fermented water extract of carob powder in addition to sorbitol.
... Polyols differ from cyclic sugars in being of low-calorie intake due to their low bioavailability which favors their use for diabetic patients or in slimming products. D-pinitol is specifically present in Outgoing and Potential Trends… family Fabaceae dominantly in soy beans and carob pods (Baumgartner et al. 1986). A previous study suggested that 10 mg/kg body weight of pure D-pinitol efficiently present in 10 g of carob syrup quiet sufficient to lower elevated blood glucose levels from ½-2 hours post administration (Narayanan et al. 1987) asides from other health benefits to include anti-inflammatory, anti-asthmatic, anti-hyperlipidemic and antioxidant effects (Loullis and Pinakoulaki 2018). ...
... It's worth to mention that the highest content of D-pinitol is present in Turkish samples of carob pods ranging between 65-95 g/kg dry weight in contrast to soy beans recording 5-20 g/kg dry weight. D-pinitol as a unique and rich component of carob pods can be employed as a biomarker for detection of carob adulteration or admixture (Baumgartner et al. 1986;Tetik et al. 2011). D-pinitol content was found higher in wild Anatolian carob than cultivated one (Goulas et al. 2016;Turhan 2014), however that has yet to be reported from other origin. ...
... Dietary fibers exert a variety of pharmacological actions throughout the GIT including regulating intestinal capacity, reduction of blood pressure and reducing blood glucose and cholesterol levels (Anderson et al. 2009). Cyclitols, on the other hand are cyclic polyols synthesized in considerable amounts by several plants in the Fabaceae family, including carob (Baumgartner et al. 1986;Phillips et al. 1982). D-pinitol (1D-3-O-methyl-chiro-inositol), the principle cyclitol identified in carob pods, is a compound of considerable merit for its established role in regulating blood glucose levels by increasing insulin sensitivity in type II diabetic patients (Bates et al. 2000;Kim et al. 2007;Sivakumar et al. 2010). ...
Ceratonia siliqua (Carob); is a Mediterranean legume globally recognized for its commercial value, being used as a cold beverage, in bakery and confectionary products. It is widely used as a Cocoa substitute not only due to its richness in sugar but rather the absence of caffeine and theobromine stimulant action. Both fruit pulp and seeds are of potential nutritive and medicinal values. The pulp comprises a high sugar content dominantly sucrose as well as polyphenols viz. phenolic acids, flavonoids and tannins. Seeds potential usage is attributed to its locust bean gum (LBG), commercially and pharmaceutically used as gelling and stiffening agent. Carob syrup is a traditional product native to the Mediterranean region, enriched in D-pinitol sugar of anti-diabetic effect. Considering the diversity of carob active constituents’ classes, a myriad of biological effects is recorded to include antioxidant, anticancer, antimicrobial and anti-hyperlipidemic effects. This book chapter presents up to date information on carob usage and chemistry while providing insight on research questions or applications yet to be addressed.
... It was first isolated in the sugar pine (Pinus Lambertiana) (Anderson et al., 1952). D-pinitol is a naturally occurring compound present in peanut (Lee and Morris, 1963), Bougainvillea spectabilis (Jawla et al., 2013;Narayanan et al., 1987;Vidhate et al., 2015), and Argyrolobium roseum (Ram et al., 2007;Sharma et al., 2016), but for manufacturing purposes it is generally extracted from soybean (Kawai and Kumazawa, 1982;Phillips et al., 1982;Streeter et al., 2001) and also from carob (Baumgartner et al., 1986;Cháfer and Berna, 2014;Tetik and Yüksel, 2014). ...
... Although ethanol and methanol are common extraction solvents used to extract cyclitols from plant material (Kawai and Kumazawa, 1982;McDonald et al., 2012;Narayanan et al., 1987;Sharma et al., 2016), water is quite often used to extract these high polar compounds (Baumgartner et al., 1986;Rodríguez-Sa'nchez et al., 2010). Presently ethanol is preferred to methanol due to its lower toxicity. ...
... TLC, GC, GC-MS, melting point and optical rotation. Baumgartner et al. (1986) Argyrolobium roseum D-pinitol À Extraction with 95% ethanol (15 h). À Washing with petroleum ether to remove non-polar material, then with chloroform. ...
Cyclitols are cycloalkanes with one hydroxyl group on each of three or more ring atoms, also called cycloalkane polyols or sugar alcohol which attract attention since they have numerous pharmaceutical properties and are widespread in the plants. Inositols are important cyclitols, which constitute a group of naturally occurring polyhydric alcohols and some isomers of this group can be commonly found in most plants, provided adequate methods of detection are employed. This review presents plant containing cyclitols, with emphasis put on their pharmaceutical properties. The text focuses on sample preparation, extraction and purification and on analysis of cyclitols in plants. In addition, it addresses the application of different methodologies utilized in the analysis of cyclitol compounds in plant.
... Recently, ultrasound-assisted extraction and supercritical fluid extraction have been proposed for the isolation of D-pinitol from carob [23,41]. Finally, myo-inositol, D-(+)-chiro-inositol, ononitol (4-O-methyl-myo-inositol), sequoyitol (5-O-methyl-myo-inositol) and bornesitol (1-O-methyl-myo-inositol) have been detected only at trace levels [39]. great diversity (1.0-8.5 g 100 g −1 ·d.m.) (Figure 2a). ...
... The concentration of D-pinitol is influenced by genetic and environmental factors; especially the mean D-pinitol content of wild carob cultivars is higher than mean D-pinitol content of cultivated ones [35]. The presence of D-pinitol is of high importance as it can be used as a marker of carob adulteration by cocoa [39]. In addition, carob bean can be considered as an excellent reservoir of D-pinitol and its isolation procedure has been patented [40]. ...
... Recently, ultrasound-assisted extraction and supercritical fluid extraction have been proposed for the isolation of D-pinitol from carob [23,41]. Finally, myo-inositol, D-(+)-chiro-inositol, ononitol (4-O-methyl-myo-inositol), sequoyitol (5-O-methyl-myo-inositol) and bornesitol (1-O-methyl-myoinositol) have been detected only at trace levels [39]. ...
The contribution of natural products to the drug-discovery pipeline has been remarkable since they have served as a rich source for drug development and discovery. Natural products have adapted, during the course of evolution, optimum chemical scaffolds against a wide variety of diseases, including cancer and diabetes. Advances in high-throughput screening assays, assisted by the continuous development on the instrumentation’s capabilities and omics, have resulted in charting a large chemical and biological space of drug-like compounds, originating from natural sources. Herein, we attempt to integrate the information on the chemical composition and the associated biological impact of carob fruit in regards to human health. The beneficial and health-promoting effects of carob along with the clinical trials and the drug formulations derived from carob’s natural components are presented in this review.
... Because of the high commercial value of LBG, carob seeds have primarily been used for LBG production. Crushed and deseeded carob pods have been evaluated as a cacao substitute after a powdering process (Baumgartner et al. 1986), feed for livestock (Khair et al. 2001), feedstock for the production of bioethanol (Roukas 1995, Turhan et al. 2010) and as a substrate for citric acid production (Roukas 1995). Most carob pods have been used for pekmez production, a traditional concentrated syrup native to Turkey, after a liquid-solid extraction process with water (Petit and Pinilla 1995, Batu 2005, Turhan et al. 2006. ...
... One of the important bioactive components of carob is (3-Omethyl-D-chiro-inositol) (Figure 1), a cyclitol that is highly soluble in water (Dowd andStevens 2002, Dozois et al. 1938). D-initol is the most dominant component of the low molecular weight carbohydrate fraction of legumes (Baumgartner et al. 1986, and approximately 99% of total chiroinositol (40.0 g/kg) in carob pod exists as D-pinitol ). D-Pinitol has an insulin-like effect (Bates et al. 2000) and dietary intake of D-pinitol represents the major metabolic source for being a precursor of D-chiro-inositol in vivo (Davis et al. 2000. ...
... The study showed that carob syrup was the richest source of D-pinitol compared with other food legumes. Baumgartner et al. (1986) reported that D-pinitol in cacao powder could be used as a marker to indicate adulteration by addition of carob pulp powder. On the contrary, carob syrup could be sometimes adulterated with low-quality sugar-containing products. ...
... While the seeds of carob fruits are generally used for locust bean gum production, carob pods, which are industrially less valuable, have mainly been used in carob syrup [6,7], as feedstock for ethanol [8], in production of lactic [9] and citric acid [10], as feed for livestock [11] and as a cacao substitute after a powdering process [12]. ...
... Carob pods, known to be rich in sugars (mainly sucrose, glucose and fructose) and phenolics [13], have recently increased in value due to their high D-pinitol (1D-3-O-methyl-chiro-inositol) content. D-Pinitol is a kind of functional cyclitol which is highly soluble in water [12,14,15]. D-Chiro inositol and its derivatives (especially D-pinitol) have been reported in different studies to regulate blood sugar level in patients with Type II diabetes mellitus by increasing insulin sensitivity [16][17][18], protect susceptible organs such as the liver and kidney [19][20][21], prevent cataract formation [22], and reduce hyperlipidemia [23], inflammation [24] and polycystic ovary syndrome [25]. ...
... D-Chiro inositol and its derivatives (especially D-pinitol) have been reported in different studies to regulate blood sugar level in patients with Type II diabetes mellitus by increasing insulin sensitivity [16][17][18], protect susceptible organs such as the liver and kidney [19][20][21], prevent cataract formation [22], and reduce hyperlipidemia [23], inflammation [24] and polycystic ovary syndrome [25]. D-Pinitol is specially extracted and purified from rich sources including carob [12] and soy bean [26] commercially. In the extraction of D-pinitol at high concentration, it is necessary to optimize the conditions to increase the transition from material matrix to the extract. ...
... Yeasts have been commonly used for the purification and removal of mono-and disaccharide by-products in carbohydrate preparations. 16,17 They have also been applied to remove major sugars present in complex mixtures thereby allowing the analysis and identification of minor carbohydrates 18,19 or the in vitro evaluation of their bioactivity. 20,21 Among yeast strains, Saccharomyces cerevisiae, considered as a safe organism, 22 has been extensively used in the field of food processing. ...
... As previously reported by other authors, pinitol (I T = 1742) was detected in soy beans, 9 chickpeas, 9 lentils 12,24 and carob extracts; 18 its highest concentration (112.7 mg g −1 of sample) was found in this latter legume. A methyl-inositol, identified as ononitol according to Yasui et al., 11 and with the same I T of the first isomer of the trimethylsilyl oxime of glucose (I T = 1896), was detected in black-eyed peas (Fig. 1A, solid line, peak 5). ...
... Chromatographic profile of black-eyed peas extract before (control; solid line) and after 3h (dashed line) and 24 h (dotted line) of yeast treatment. Peak identification: (1) unidentified monosaccharide, (2) fructose, (3) galactose, (4) glucose, (5) ononitol, (6) glucuronic acid, (7) myo-inositol, (8) sucrose, (9) unidentified disaccharide, (10) trehalose, (11) unidentified disaccharide, (12) maltose,(13) galactosyl-ononitol,(14) melibiose, (15) galactinol, (16) raffinose,(17) galactopyranosyl-(1 → 6)-α-galactopyranosyl-(1 → 6)-α-glucopyranoside,(18) stachyose,(19) galactopyranosyl-(1 → 6)-α-galactopyranosyl-(1 → 6)-α-galactopyranosyl-(1 → 6)-α-glucopyranoside,(20) verbascose, *interference. ...
Background:
Currently, disorders such as diabetes mellitus, obesity or atherosclerosis are recognised as major global health problems. The use of inositols for treating these illnesses has attracted considerable attention and their extraction from natural sources presents added value as they are considered bioactive ingredients in the food industry. Legumes are natural and rich sources of inositols; however, the co-existence of other low molecular weight carbohydrates (LMWCs) in their extracts, which interfere in their bioactivity, might constitute an important drawback, thereby making their removal essential.
Results:
LMWCs, including inositols, methyl-inositols and glycosyl-inositols of different legume extracts, were determined by GC-MS; the presence of bornesitol (2.35 mg g(-1) ) and lathyritol (0.27 mg g(-1) ) were reported for the first time in grass peas. The use of Saccharomyces cerevisiae for the selective removal of interfering carbohydrates was optimised. Incubation time (3-40 h) was highly dependent on the composition of the legume considered; inositol contents were generally stable along the treatment.
Conclusion:
Removal of interfering LMWCs from inositol-enriched extracts was successfully achieved using a clean and easily scalable fractionation methodology. This biotechnological procedure not only represents high interest for the production of bioactive food ingredients but for applications in other research areas.
... A number of studies investigating the presence of D-pinitol and other cyclitols have been previously performed using high performance liquid chromatography (HPLC) [7] and gas chromatography (GC) in combination with mass spectrometry (MS) [9]. Furthermore, spectroscopic techniques like nuclear magnetic resonance (NMR) and infrared spectroscopy (IR) were also employed [5]. ...
... In the same content, TLC, GC and GC-MS were applied for the isolation and identification of sugars and cyclitols in carob powder. The major compounds identified were sucrose, fructose, glucose, D-pinitol, myo-inositol and D-chiro-inositol, along with traces of ononitol (4-O-methyl-myo-inositol), sequoyitol (5-O-methyl-myo-inositol), bornesitol (1-O-methyl-myo-inositol) and sorbitol [9]. In carob seed samples, the concentrations of D-pinitol were determined under the LOD of the method (≤1.93 mg/g). ...
D-pinitol (3-O-methyl-D-chiro-inositol) is a well-known bioactive compound with anti-diabetic and anti-oxidant biological functions. A gas chromatography–mass spectrometry (GC–MS) method was developed for its quantitation in carob syrup, flesh and seed samples originated from Cyprus. The analysis was performed after derivatization of carbohydrates and polyols into trimethylsilyl ether derivatives. D-pinitol was determined in 13 carob syrup samples, in concentrations ranging 65.71 ± 4.60 – 77.72 ± 5.44 mg/g (mean: 68.58 ± 4.80 mg/g, n = 13). In two commercial samples, it was determined in relative medium-low concentrations (21.96 ± 1.54 and 44.71 ± 3.13 mg/g), revealing possible adulteration; however, this needs further investigation. Similarly, it was determined in high concentrations in carob flesh samples, in concentrations ranging 53.20 ± 3.72 – 54.58 ± 3.82 mg/g (mean: 53.81 ± 3.76 mg/g, n = 3). On the other hand, seed samples proved very poor in D-pinitol (<LOD). Therefore, bioprospecting of carob fruit and syrup is highlighted. Compared to other plants or legumes, carob appears to be the richest source of D-pinitol, highlighting carobs role as a functional organic food. The historical and cultural association of Cyprus with carobs is linked with traditional foods and habits.
... This is likely to account for a sweet taste of unripe pod, in which sucrose is present at lower levels (12-26%). D-pinitol (Fig. 6d), a sugar polyol, reported in legume seeds (e.g. in soybean and Carob) was proposed to exhibit an anti-diabetic effect (Baumgartner, Genner-Ritzmann, Haas, Amado, & Neukom, 1986;Tetik, Turhan, Oziyci, & Karhan, 2011). In this study, D-pinitol (Fig. 6d) could be detected at high relative intensity (11-13% of the most intense chromatographic peak) in the most of the unripe and mid ripe samples. ...
... However, these relative intensities further decreased to 5% upon roasting. This observation is contrary to previous reports as major sugar forms in carob which highlights that geographical origin can impact functional foods metabolites composition (Ayaz et al., 2007;Baumgartner et al., 1986). ...
Ceratonia siliqua is a legume tree of a considerable commercial importance for the flavor and sweet industry. In this context, it is cultivated mostly for its pods, which are known for their nutritive value and multiple health benefits. However, metabolite patterns, underlying these properties are still mostly uncharacterized. In this study, the role of geographical origin, ontogenetic changes and thermal processing on Ceratonia siliqua pod
metabolome was assessed by mass spectrometry (MS)-based metabolomics. Thereby, a total of 70 fruit primary metabolites, represented mainly by carbohydrates, organic and amino acids were detected. Analysis of secondary bioactive metabolites assessed by ultra-high-performance liquid chromatography-electrospray ionization high resolution mass spectrometry (UHPLC-ESI-HR-MS) revealed in total 83 signals. The major signals, most significantly contributing in discrimination of C. siliqua specimens were assigned to tannins and flavonoids. PCA models derived from either UHPLC-MS or GC-MS proved to be powerful tools for discrimination of C. siliqua specimens
... Compounds 10-12 have previously been identified in various parts of C. siliqua. This includes the isolation, [27] as well as identification of D-pinitol (pods), [4,10,12] myricitrin (leaves), [20] and sucrose (pods). [12,28] The 1 H, 13 C, and heteronuclear single quantum correlation (HSQC) NMR spectroscopic data associated with siliquapyranone 9 were consistent with the high-resolution electrospray ionisation mass spectrometry (HR-ESI-MS) data (m/z 595.1301; calcd for [ , and a methyl resonance at d H 1.28 (d, J 6.3, 3H, C-6), which were consistent with the presence of a 3-hydroxy-5-hexanolide structure. ...
... It is well established that D-pinitol is the most dominant component of the low molecular weight carbohydrate fraction of legumes. [27,31] More specifically, D-pinitol represents ,99 % of the total chiroinositol content of the carob pod (40.0 g kg À1 ). [31] Gallic acid has shown antioxidant and anticancer activity. ...
Studies of the phytochemistry of carob (Ceratonia siliqua) leaf material are extremely limited. This report features the second natural product isolation study of carob leaves and the first such investigation of C. siliqua grown in Australia. Investigation of leaf material from seven carob cultivars using pressurised hot water extraction (PHWE) revealed the presence of high levels of myricitrin, d-pinitol, and sucrose in addition to the previously unreported natural product siliquapyranone {(2R,3R,4S,5R,6R)-5-hydroxy-6-(hydroxymethyl)-2-(((2S,4S)-2-methyl-6-oxotetrahydro-2H-pyran-4-yl)oxy)tetrahydro-2H-pyran-3,4-diyl bis(3,4,5-trihydroxybenzoate)}. Siliquapyranone represents a biosynthetic fusion of conventional 2,3-gallate esters on a β-glucose tannin with a hydroxytetrahydro-2H-pyran-2-one-related non-tannin tetrahydropyran-2-one, parasorboside. Preliminary biological testing indicates that siliquapyranone exhibits weak activity against both tumour and normal cell lines. This suggests that, like most tannins and parasorboside, siliquapyranone may act as an antifeedant.
... El nombre "pinitol" deriva de "pine" (pino) debido a que este compuesto fue aislado por primera vez de la madera de este árbol. El pinitol se ha detectado en leguminosas, siendo especialmente abundante en la algarroba (50-75 mg/g peso seco) y en la soja (6-9 mg/g peso seco) (12,20,23,24). No obstante, también se encuentra en cantidades relativamente altas en otras legumbres como garbanzos, lentejas o judías (4,5-12,6 mg/g peso seco) (20,25,26). ...
... Son muchos los estudios llevados a cabo para la determinación de ciclitoles en alimentos mediante GC (3,8,(14)(15)(16)23,28,36). Los inositoles, debido a su alta polaridad, hidrofilidad y baja volatilidad, tienen que ser convertidos a sus derivados volátiles antes de poder ser analizados adecuadamente por GC. ...
ENE.-MAR. VOL.19,N.º1. Inositoles en alimentos: estructura, propiedades y funcionalidad L. Ruiz-Aceituno, L. Ramos Rivero, M. L.
En este trabajo se detallan las características y propiedades de los inositoles, discutiendo también su presencia en alimentos, así como los métodos de extracción y análisis más habituales para su determinación en estas matrices
... The known compounds (2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15) were identified by comparison of their NMR spectral data (Supplementary Figs. 12-55) with the literature [15][16][17][18][19][20][21][22][23][24][25][26][27][28]. However, the fragmentation pattern of isoflavones have drawn great attention, especially for large-scale metabolite profiling studies [13,29,30]. ...
The genus Poiretia belongs to the Fabaceae (Leguminosae) family and it encompasses twelve species of flowering plants. The chemistry of this genus is scarcely investigated, although some studies have demonstrated the potential of Poiretia species to produce important bioactive compounds. Herein, we describe the phytochemical investigation of P. bahiana C. Mueller leaves. A new isoflavone glucoside named as 2',4',5'-trimethoxyisoflavone-7-O-β-D-glucopyranoside (1), along with six known isoflavones (2-7), two rotenones (8-9), cyclitol 3-O-methyl-chiro-inositol (10), the amino acid proline (11), a mixture of sitosterol (12) and stigmasterol (13), and a mixture of the triterpenes lupeol (14) and β-amirine (15) were obtained from P. bahiana leaves. The structures were established by extensive analysis of their spectroscopic data, which included 1H NMR, 13C NMR, DEPT, and 2D-NMR (13C1H HETCOR and 13C1H COLOC). Two isoflavones (3 and 5) and two rotenones (8-9) exhibited antifungal activity against the plant pathogenic fungus Cladosporium sphaerospermum. Furthermore, the biogenetic implications of the oxygenation pattern of the B-ring of the isoflavones, and the chemophenetics and fragmentation pattern of the isoflavones and rotenones are discussed.
... This methyl-inositol is the most common in foods. It has been reported in legumes (mainly in soybeans, chickpeas, lentils, peanuts or beans) [27][28][29][30] , and also in alfalfa [31] , carob [32,33] , pine nuts [34] and honey [35] , but it has not previously been described in artichoke. The presence of this methyl-inositol in FS16, together with a methyl-glucopyranose ( t R = 5.89 min) and two non-identified compounds ( t R : 9.94 and 10.26 min), not detected in reference extracts and in other FSOC, could be indicative of the non-declared addition of plants other than artichoke for its manufacturing. ...
Despite the widespread use of artichoke-based food supplements for obesity control (FSOC), studies on evaluation of the quality/authenticity of these commercial products are scarce. To that aim, a new multi-analytical strategy, based on the use of gas chromatography coupled to mass spectrometry (GC-MS) and high performance liquid chromatography coupled to ultraviolet and mass spectrometry detection (HPLC-UV-MS), in combination with chemometrics, has been developed. Twenty-one artichoke FSOC and different bract and leaf extracts (used as reference samples) were analysed. Sugars, inositols, caffeoylquinic acids, dicaffeoylquinic acids, flavonoids and their glycosides were detected in reference samples and in most artichoke FSOC. Low concentrations of bioactives, and the presence of other compounds probably related to heat treatment during manufacturing (difructosyl anhydrides, 3-deoxyglucosone), or to the addition of caloric additives (maltose, maltotriose) or non-declared plants (e.g. pinitol, disaccharides, silybin derivatives) were also detected in some FSOC by either GC-MS or HPLC-UV-MS. Application of Principal Component Analysis to the combined GC-MS + HPLC-UV data matrix, proved that this multi-analytical strategy provides advantages over single analytical techniques for the detection of the wide variety of fraudulent practices affecting authenticity of artichoke FSOC and for assessment of their quality.
... Moreover, grain bread was found to contain more myo-inositol than white bread, while from the cereals, oats and bran contained more myo-inositol than did cereals derived from other grains (Clements and Darnell 1980). Besides the sources mentioned above, myo-inositol (Baumgartner et al. 1986) and more than 10% as detected in some Spanish varieties (Nasar-Abbas et al. 2016). Other important sources of D-pinitol are chickpea, lentil, soybean, jojoba seed, alfalfa, enological tannins from gall plant, chestnut, and quebracho (Al-Suod et al. 2017;Lein et al. 2002;Murakeözy et al. 2002;Sanz et al. 2008). ...
In food and biological systems, the main function of tocochromanols is antioxidant action – they deactivate free radicals and protect lipids from peroxidation (autoxidation). In addition to the antioxidant role of vitamin E and protection against oxidative stress, the “non-antioxidant” functions of vitamin E, including cell signaling and antiproliferation, is also described. Tocopherols and tocotrienols are not the only compounds classified as tocol derivatives. This chapter also includes an overview of the properties and occurrence of other forms of tocols (including: tocomonoenols, tocodienols, and plastochromanol-8). Content of tocochromanols in food may be determined using a wide range of analytical techniques. Capillary gas chromatography and high performance liquid chromatography coupled with various detection systems and mass spectrometers enable identification of individual compounds. In the analysis of these compounds, spectroscopic methods are also being developed. The principles of these techniques are discussed in the chapter and examples of their applications are also provided.
... Sucrose content 75% or more of the sugar content (more than 50%) of carob shells. Because of its taste similar to chocolate, carob flour is frequently used as a substitute for chocolate and cocoa (Baumgartner, Genner-Ritzmann, Haas, Amado, & Neukom, 1986;Bengoechea et al., 2008;Yousif & Alghzawi, 2000). Yousif and Alghzawi (2000) found that the color values of heated carob flour and cocoa are close to each other; therefore, in many foods, the contribution of up to 25% of cocoa flour may not be noticeable in many foods. ...
Antioxidant activity values of cookie samples were determined between 2.32% (0.0% (carob) and 76.75% (50% carob) while total phenolic contents of cookies vary between 36.59 (0.0% carob) and 123.61 mgGAE/100g (100% carob). The brightness (L*) of the cookies with carob flour decreased. While palmitic acid contents of cookie samples change between 32.58 (50% carob) and 35.86% (100% carob), oleic acid contents of cookies were determined between 28.84 (50% carob) and 29.59% (60% carob). Gallic acid, 3,4‐dihydroxybenzoic acid,(+)‐ catechin and 1,2‐dihydroxybenzene were the most common phenolic components in the cookie samples. 1,2‐Dihydroxybenzene contents of cookie samples varied between 10.69 (control) and 32.27 mg/100g (50% carob).While Ca contents of cookie samples change between 1189.10 (control) and 3286.82 mg/kg (100% carob),K contents of cookies were determined between 554.65 (control) and 7402.83 mg/kg (100% carob).Taste, crispness, color and fragrance values of cookies were partially decreased with the increase in carob flour concentration.
... Interestingly we demonstrated that liquorice leaves extract as well as D-pinitol possess insulin sensitising effects since GGLME or D-pinitol pre-treatment induced insulin-PI3K/ Akt/eNOS pathway also under basal conditions. D-Pinitol has been isolated mainly in plants belonging to Leguminosae family, including Ceratonia siliqua L. (carob), whose pods can contain up to 5-10% of this product (Baumgartner et al. 1986, Lopez-Sanchez et al. 2018. Recently, the consumption of a D-pinitol-enriched carob pod beverage was demonstrated to down-regulate the inflammatory pathway in obese subjects (L opez-Dom enech et al. 2018). ...
Background: Glycyrrhyza glabra L. is one of the most popular medicinal plant in the world, its roots having been used since ancient times in many traditional medicines. On the contrary, scarce attention has been dedicated to liquorice aerial parts. Previous studies showed the presence of a large group of polyphenols and a consistent amount of d-pinitol in the leaf extract.
Methods: The methanolic extract from G. glabra leaves was profiled for its content in polyphenols; the amount of d-pinitol was also measured with two independent methods (HPLC-ELSD and NMR). The extract was tested for its in vitro protective effects against insulin resistance-related endothelial dysfunction in human umbilical vein endothelial cells exposed to palmitic acid, which is the most prevalent saturated free fatty acid in circulation.
Results: Methanolic extract from liquorice leaves has a protective effect against the lipotoxicity-associated alterations of insulin pathway in human endothelial cells, similarly to what observed with pure d-pinitol.
Conclusions: Liquorice leaves are to be considered a waste product which gives a phytocomplex endowed with interesting potential therapeutic properties, moreover the use of a liquorice leaves phytocomplex rather than a pure compound allows avoiding a series of isolation/purification procedures and can be easily scaled up for industrial applications.
... 5) L-(+)-Bornesitol is a methyl myo-inositol found in several plant species. 6) It has been identified by gas chromatography in decaffeinated and non-decaffeinated coffee beverages, 7) chickpeas, lentils, 8) and legumes such as carob beans 9) and grass peas. 10) Bornesitol has also been reported as responsible for the sweet taste of Drypetes floribunda stem and Sapindus rarak pericarp. ...
The cyclitol bornesitol is the main constituent of the leaves from the antihypertensive medicinal plant Hancornia speciosa. This study aimed to investigate the ability of bornesitol to reduce blood pressure and its mechanism of action. Normotensive Wistar rats were divided into control group and bornesitol groups treated intravenously with bornesitol (0.1, 1.0 and 3.0 mg/kg). Systolic blood pressure (SBP) and diastolic blood pressure (DBP) were recorded in non-anesthetized awake animals. Nitric oxide (NO) and angiotensin-converting enzyme (ACE) were measured in plasma by using colorimetric methods. Vascular reactivity study was performed in rat aorta rings and the involvement of nitric oxide synthase (NOS), calcium-calmodulin complex and phosphatidylinositol-3-kinase (PI3K)/Akt pathway in the vasodilator effect was investigated. Administration of bornesitol significantly reduced the SBP, increased the plasmatic level of nitrite, and decreased ACE activity in normotensive rats. In the rat aorta, bornesitol induced endothelium-dependent vasodilatation, which was abolished by NOS blockade. While calcium-calmodulin complex inhibition decreased the vasodilator effect of bornesitol, the inhibition of PI3K/Akt pathway did not alter it. Bornesitol reduced the blood pressure by a mechanism involving an increased production or bioavailability of NO, inhibition of ACE, and by an endothelium- and NO-dependent vasodilator effect. The present results support the use of bornesitol as an active marker for the cardiovascular activity of Hancornia speciosa.
Graphical Abstract Fullsize Image
... The improvement in the metabolic parameters observed after the use of inositols in polycystic ovary syndrome, and type 2 diabetes mellitus suggests that they may have a protective effect on the cardiovascular system (Cussons et al., 2006). D-pinitol (3-O-methyl-D-chiro-inositol) is a cyclitol present in several edible plants, including soybean and carob (Kawai and Kumazawa, 1982;Baumgartner et al., 1986). The chemical similarity suggests that pinitol is a natural source of D-chiro-inositol in vivo (Davis et al., 2000). ...
D-pinitol is a cyclitol present in several edible plant species and extensively investigated for the treatment of metabolic diseases in humans, as food supplement, and demonstrated protective effects in the cardiovascular system. For these reasons, the present work aimed at investigating the mechanisms involved in the vascular effects of D-pinitol in mouse mesenteric artery. Mesenteric arteries from male C57BL/6 mice were mounted in a wire myograph. Nitrite was measured by the 2,3-diaminonaphthalene (DAN) method. Protein expression and phosphorylation were measured by Western blot. The systolic blood pressure (SBP) was measured by tail-cuff plethysmography. D-pinitol induced a concentration-dependent vasodilatation in endothelium-intact, but not in endothelium-denuded arteries. Nω-Nitro-L-arginine methyl ester (300 µM) abolished the effect of D-pinitol, while 1H-[1,2,4]oxadiazolo[4,3-a]quinoxalin-1-one (ODQ; 10 µM) shifted the concentration-response curve to the right. KN-93 (1 µM) blunted the vasodilator effect of D-pinitol, but H-89 (0.1 µM) did not change it. 1-[2-(Trifluoromethyl) phenyl]imidazole (300 µM), indomethacin (10 µM), celecoxib (5 µM), wortmannin (1 µM), ruthenium red (10 µM), tiron (10 µM), MnTMPyP (30 µM), MPP (0.1 µM), PHTPP (0.1 µM), and atropine (1 µM) did not change the effect of D-pinitol. D-pinitol increased the concentration of nitrite, which was inhibited by L-NAME and calmidazolium (10 µM). D-pinitol increased the phosphorylation level of eNOS activation site at Ser1177 and reduced the phosphorylation level of its inactivation site at Thr495. In normotensive mice, the intraperitoneal administration of D-pinitol (10 mg/kg) induced a significant reduction of the SBP after 30 minutes. The present results led us to conclude that D-pinitol has an endothelium- and NO-dependent vasodilator effect in mouse mesenteric artery through a mechanism dependent on the activation of eNOS by the calcium-calmodulin complex, which can explain its hypotensive effect in mice.
... 202 It is important to indicate here that in this review article we tried to focus our attention on major natural products found in Carob, despite the fact that some compounds that are found in trace amounts, might be of some interest. 203 But these compounds are found in other plants in higher amounts and were studied in that context. 204 ...
... Although analysis can be carried out directly, a simultaneous derivatization of Py products is usually recommended to avoid the presence of OH groups which could give rise to co-elution problems of pyrolitic fragments (Baumgartner et al. 1986); this procedure is usually referred to as thermochemolysis. ...
Sample preparation, equipment, and several outstanding applications using gas chromatography (GC) to analyze bioactive food oligosaccharides are described and discussed. In addition to basic operations for sample pretreatment, chemical procedures such as derivatization (for the direct analysis of oligosaccharides) and hydrolysis and methylation (for their structural characterization) are described in detail. Simultaneous pyrolysis and derivatization (thermochemolysis) are also reported for GC characterization of oligosaccharides. Advances in GC such as the use of high-temperature columns to analyse oligosaccharides with a degree of polymerization of up to 11 and mass spectrometry detectors for better identification/characterization of unidentified compounds are also described. Finally, the potential of the recently developed Comprehensive Two-Dimensional Gas Chromatography technique to separate complex carbohydrate mixtures is discussed.
... d-(+)-Pinitol (3-O-methyl-d- chiro-inositol), myo-inositol, and d-(+)-chiro-inositol were isolated from carob powder. The concentration of d-pinitol ranged from 5% to 7.5% (dry weight of the powder) whereas myo-inositol and chiro-inositol were minor components with concentrations of 0.5% to 1% and 0.1%, respectively (Baumgartner and others 1986). Higher d-pinitol (methyl-inositols) contents (113 mg/g) in carob has been reported in a recent study from Spain which was much higher than those in other legumes such as soybean (3.5 mg/g), chickpea (2.0 mg/g), and lentil (2.0 mg/g) (Ruiz-Aceituno and others 2013). ...
Carob (Ceratonia siliqua L.) is well known for its valuable locust bean gum obtained from the carob seeds. Separation of seeds from the pod leaves behind the carob kibble which is a good source of dietary fiber, sugars, and a range of bioactive compounds such as polyphenols and pinitol. Bioactive compounds present in carob kibble have been found to be beneficial in the control of many health problems such as diabetes, heart diseases, and colon cancer due to their antidiabetic, antioxidant, and anti-inflammatory activities. Carob kibble has substantial potential to be used as a food ingredient. This article focuses on the composition, health benefits, and food applications of carob kibble.
... soybean) of Leguminosae family. Among these, D-pinitol concentration is very high (5-8 g/100 g DW) (6,7). D-pinitol, 3-O-methyl-D-chiro-inositol, is a water soluble, bioactive cyclitol and mainly found in the plants of Leguminosae family (8). ...
... However, decomposition of the sugars in the alkaline medium can occur, and carbohydrates can be strongly adsorbed in the resin, resulting its regeneration difficult and expensive in terms of eluent and time consumption (Macias Camero & Sanjuan Merino, 2004). Saccharomyces cerevisiae has been used to remove monosaccharides from mixtures of carbohydrates (Baumgartner, Genner-Ritzmann, Haas, Amado, & Neukom, 1986;Ruiz-Matute, Soria, Martínez-Castro, & Sanz, 2007) and recently this method has been suggested to be effective for the production of inositol extracts free from interfering sugars from legumes (Ruiz-Aceituno, Rodríguez-Sánchez, Ruiz-Matute, Ramos, Soria, & Sanz, 2013). ...
Pressurized liquid extraction (PLE) has been used for the first time to extract bioactive inositols from pine nuts. The influence of extraction time, temperature and cycles of extraction in the yield and composition of the extract was studied. A quadratic lineal model using multiple linear regression in the stepwise mode was used to evaluate possible trends in the process. Under optimised PLE conditions (50°C, 18min, 3 cycles of 1.5mL water each one) at 10MPa, a noticeable reduction in extraction time and solvent volume, compared with solid-liquid extraction (SLE; room temperature, 2h, 2cycles of 5mL water each one) was achieved; 5.7mg/g inositols were extracted by PLE, whereas yields of only 3.7mg/g were obtained by SLE. Subsequent incubation of PLE extracts with Saccharomyces cerevisiae (37°C, 5h) allowed the removal of other co-extracted low molecular weight carbohydrates which may interfere in the bioactivity of inositols.
... The carob bean (Ceratonia siliqua L.) tree, which belongs to the Caesalpinaceae sub-family of the family Leguminoseae, has been widely cultivated in the Mediterranean region (Batlle and Tous, 1997;Yousif and Alghzawi, 2000;Zohary, 2002). The fruit of the carob tree has recently become a valuable commodity and has been evaluated for multipurpose uses such as gum, syrup, powder, biofertilizer, d-pinitol, ethanol, mannitol, lactic and citric acid (Batu, 2005;Baumgartner et al., 1986;Carvalheiro et al., 2011;El-Shatnawi and Ereifej, 2001;Medeiros and Lannes, 2009;Parrado et al., 2008;Petit and Pinilla, 1995;Roukas, 1998;Tetik et al., 2011b;Turhan et al., 2010aTurhan et al., ,b, 2006. Turkey has a significant annual production capacity of this fruit (14,000 t) and is one of the main carob-producing and exporting countries (Anonymous, 2013). ...
Wild and grafted carob fruits (61 different carob trees in the selected locations in total) grown in 2009 and 2010 in Antalya province of Turkey were evaluated for their mineral composition of different fruit parts, including the pods and seeds of wild (PW, SW) and grafted types (PG, SG). The highest mean values of total ash content (3.85%) and total nitrogen (%) were observed in the seeds of grafted carob fruits (SG). Among the macro minerals analyzed, the potassium content was very high in all samples (1.01–1.19%). Although the fruit type (wild or grafted) was not a significant parameter on mineral concentration of the samples (P > 0.05), the seeds generally contained higher macro and micro minerals than the pods in both carob types.
... Both compounds are in the D-configuration. D-chiro-Inositol (7) and D-pinitol (1D-3-O-methyl-chiro-inositol) (8) are optically active (dextrorotation) (Schweizer et al., 1978;Baumgartner et al., 1986). ...
Mature dry legume seeds may contain up to 30 different soluble carbohydrates. Sucrose is a major component of the total soluble carbohydrates; others include the raffinose family oligosaccharides (RFOs; raffinose, stachyose, verbascose) that are mono-, di- and tri-α-galactosyl derivatives of sucrose. Other galactosides may include α-galactosyl derivatives of the cyclitols myo-inositol (galactinol, digalactosyl myo-inositol and trigalactosyl myo-inositol), d-pinitol (galactopinitol A, digalactosyl pinitol A (ciceritol) and trigalactosyl pinitol A; and galactopinitol B; higher galactosyl oligomers of galactopintiol B have rarely been detected), d-chiro-inositol (fagopyritol B1, fagopyritol B2 and fagopyritol B3) and d-ononitol (galactosyl d-ononitol and digalactosyl d-ononitol). Small amounts of myo-inositol, d-pinitol and d-chiro-inositol may also be present. Raffinose, stachyose and verbascose increase late in seed maturation, with 70% of RFOs accumulating after maximum seed dry weight is attained. RFOs are mostly degraded during germination. Sucrose, myo-inositol, d-pinitol and d-chiro-inositol are synthesized in maternal tissues of some legumes and are transported to and unloaded by seed coats into the apoplastic space surrounding developing seed embryos. Free cyclitols may be 60% of total soluble carbohydrates in leaves and 20% in seed coat cup exudates. Increasing the supply of free cyclitols may increase the accumulation of their respective α-galactosides in mature seeds. Seeds with reduced RFO accumulation, but with normal to elevated concentrations of galactosyl cyclitols (including fagopyritols), have normal field emergence and are also tolerant to imbibitional chilling under laboratory conditions. Molecular structures, biosynthetic pathways, accumulation of soluble carbohydrates in response to seed-expressed mutations and the physiological role of galactosides are reviewed.
... 20−25 With regard to inositols, papers 26,27 describe their purification using ion-exchange resins (Amberjet 4200, Dowex 50, or Dowex 1). Microbiological treatments such as yeast (Saccharomyces bayanus and Saccharomyces cerevisiae, among others) incubation have also been described to separate interfering carbohydrates (sucrose, fructose, and glucose) from cyclitols present in powdered carob 28 and legume 29 extracts. S. cerevisiae has also been used for the selective separation of monosaccharides and disaccharides with different glycosidic linkages. ...
Pressurized liquid extraction (PLE) was applied for the first time to extract bioactive low molecular weight carbohydrates (iminosugars and inositols) from mulberry (Morus alba) leaves. Under optimized conditions, PLE provided a similar yield to the conventional process used to extract these bioactives, but in less time (5 min vs. 90 min). To remove carbohydrates that interfere with the bioactivity of iminosugars from PLE extracts, two fractionation treatments were evaluated: yeast (Saccharomyces cerevisiae) incubation and cation exchange chromatography (CEC). Both methods allowed complete removal of major soluble carbohydrates (fructose, glucose, galactose and sucrose), without affecting the content of mulberry bioactives. As an advantage over CEC, the yeast treatment preserves bioactive inositols and it is an affordable methodology which employs food grade solvents. This work found PLE followed by yeast treatment to be an easily scalable and automatizable procedure that can be implemented in the food industry.
S. sesban is mainly used as economical purpose and S. grandiflora is known for medicinal as well as economical. Chemical characterization and antidiabetic activity of seed extracts were not explored yet. Seeds of S. sesban and S. grandiflora were separated in seed coat, germ, and endosperm by domestic grinder mixer. Successive soxhlet extraction of separated parts of Sesbania seed were carried out. Chemical profiling of methanolic extract was carried out by GC-MS, HPLC, and in vitro alpha amylase inhibitory assay. D-pinitol was found to be maximum (48.39%) in seed coat and minimum in seed (8.35%) of methanolic extracts of Sesbania seed. Alpha-amylase inhibitory activity of methanolic extracts of different parts were also studied in which DSSh, DSSp, & DSSe showed similar IC50 to acarbose, antidiabetic drugs. The result showed that S. sesban and S. grandiflora seed and endosperm is rich in health promoting mineral like Na (241 mg/100 gm and 238 mg/100 gm), K (103.1 mg/100 gm) and (60.2 mg/100 gm), Ca (525 mg/100 gm) and (500 mg/100 gm) and Fe (67.5 and 91.9 mg/100 gm). Hence, it is similar to some edible legumes which possess bioactive compound with therapeutic value and can be efficiently explored for the development of new functional or nutraceutically valued food products.
Cyclitols are high polarity polyols, belonging to secondary metabolites, which are easily isolable from plant material. These compounds are biosynthetically derived from glucose, and occur in all living cells. They form a group of biologically active compounds and participate in many cellular processes such as: membrane biogenesis, signal transduction, ion channel physiology, osmoregulation, antioxidation, and others. The methods for the separation and determination of cyclitols include: preliminary sample preparation (drying, grinding, freezing, homogenization), sample extraction (optional: maceration, Soxhlet, ASE, MAE, SFE, UAE), isolation and purification (LLE, SPE, and others), analysis (GC-MS, HPLC, MALDI), and interpretation (identification, quantification, statistical analysis). Some other additional steps may be required, which are specific for the method chosen for the analysis. For example GC-MS analysis requires a derivatization step, while MALDI involves a laborious procedure for sample preparation. Cyclitols shows several health-promoting and therapeutic properties as follows: improving lipid profile in decreasing of serum triglycerides and total cholesterol, as well as having an insulin-mimetic effect. The beneficial properties of cyclitols are that they can be used for therapeutic purposes, particularly in neutralization of the results of chronic inflammation, which leads to increased risk of developing such metabolic disorders as diabetes, hypertension, atherosclerosis, etc. A notable factor is also good tolerance of cyclitols and their low toxicity, due to which they can be successfully used in treating pregnant women and children. Many benefits of cyclitols properties offer the possibility that these polyols may be candidates for discovery of novel drugs, food supplements and they can be used as well in cosmetic industry.
In this study, it was aimed to enrich D-pinitol in carob extract using nanofilters in the range of 1-5 kDa molecular weight cut-off (MWCO). Enrichment stages were extraction, clarification, adsorbent application and nanofiltration applications. The Box-Behnken Response Surface Methodology (RSM) was used to optimize nanofiltration application. D-pinitol content, sugar composition, total phenolic matters (TPC), total dry matters (TDM) and total minerals were determined for the purity control of the product obtained in the final stage. The highest D-pinitol concentration in extracts was achieved in nanofiltration at the 5 kDa MWCO under the condition of 3 bar feed pressure, 25°C feed temperature and 83.3% permeate rate, in which the extract contained 10.48 g/L of D-pinitol. In the study, an optimization model based on pressure, temperature and permeate/retentate ratio variables were created for the nanofiltration process. Thus, the change in the D-pinitol concentration of the extracts depending on different conditions was mathematically modelled with a high accuracy (R2=0.91). Depending on this model, the highest amount of sucrose, TPC and TDM in carob extracts was determined under the condition that the D-pinitol concentration was 8.7%.
This study investigates the effects of temperature (50–80 °C), time (10–60 min), carob-to-solvent ratio (2–8 g/40 mL), and solvent concentration (0–50 ethanol/water%, v/v) on microwave-assisted extraction of d-pinitol compound from carob fruit with optimization using Box–Behnken design. The optimal conditions for maximum d-pinitol yield (64.16 g/kg dry sample) include 50 °C temperature, 5.6 g carob/40 mL solvent, water used as a solvent, and an extraction time of 10 min. The fitness of the model was determined by ANOVA analysis with a high coefficient (R2 = 0.9057). Extraction was performed under optimum conditions for model validation, and 63.89 g/kg dry sample of d-pinitol extraction was achieved. In addition, the effects of the same variables on the total phenolic (TP) content of MEA extraction of carob were also investigated. Extraction efficiency of 426 g/kg was obtained under the optimum conditions determined for TP (80 °C, 8 g of carob, 50% ethanol, and 10 min), but it was observed that TP content decreased to 49.7 g/kg under optimum conditions determined for d-pinitol. Sucrose, glucose, and fructose sugar contents of the extract were determined only for optimum conditions for d-pinitol, and the fructose content was found to be the lowest. Determining the d-pinitol, TP, and sugar contents of the extract in optimum condition confirms the direct usability of the extract, because only water is used as a solvent. Conventional extraction method was carried out at 50 °C for control purposes, yielding 42.83 g/kg of d-pinitol, thereby supporting the effect of the microwave on extraction.
Gas chromatography is widely used in applications involving food analysis. Typical applications pertain to the quantitative and/or qualitative analysis of food composition, natural products, food additives, and flavour and aroma components. Providing an up-to-date look at the significant advances in the technology, this book includes details on novel sample preparation processes; conventional, high-speed multidimensional gas chromatography systems, including preparative instrumentation; gas chromatography–olfactometry principles; and, finally, chemometrics principles and applications in food analysis.
Aimed at providing the food researcher or analyst with detailed analytical information related to advanced gas chromatography technologies, this book is suitable for professionals and postgraduate students learning about the technique in the food industry and research.
Based on the bioactive properties of certain compounds, such as antioxidant and anti‐inflammatory activities, an interesting subject of research are natural substances present in various parts of plants. The choice of the most appropriate method for separation and quantification of biologically active compounds from plants and natural products is a crucial step of any analytical procedure. The aim of this review article is to present an overview of a comprehensive literature study from the last ten years (2007‐2017), where relevant articles exposed the latest trends and the most appropriate methods applicable for separation and quantification of biologically active compounds from plant material and natural products. Consequently, various extraction methods have been discussed, together with the available procedures for purification and pre‐concentration and dedicated methods used for analysis.
This article is protected by copyright. All rights reserved
Cyclitols are phytochemicals naturally occurring in plant material which attracted an increasing interest due to multiple medicinal attributes, amongst the most important are the anti-diabetic, antioxidant and anti-cancer properties. Due to their valuable properties, sugars are used in food industry as sweeteners, preservatives, texture modifiers, fermentation substrates, flavoring and coloring agents. In this study we report for the first time the quantitative analysis of sugars and cyclitols isolated from Solidago virgaurea L. (S. virgaurea) which was used for the selection of the optimal solvent and extraction technique that can provide the best possible yield. Moreover, the quantities of sugars and cyclitols extracted from other two species, Solidago canadensis (S. canadensis) and Solidago gigantea (S. gigantea) were investigated using the best extraction method and the most appropriate solvent. Comparative analysis of natural plant extracts obtained using five different techniques – maceration, Soxhlet extraction, pressurized liquid extraction (PLE), ultrasound assisted extraction (UAE), and supercritical fluid extraction (SFE) – was performed in order to decide the most suitable, efficient and economically convenient extraction method. Three different solvents were used. Analysis of samples has been performed by solid phase extraction (SPE) for purification and pre-concentration, followed by derivation and GC-MS analysis. The highest efficiency for the total amount of obtained compounds has been reached by PLE, when water was used as a solvent. D-pinitol amount was almost similar for every solvent and for all extraction technique involved.
D-pinitol is a natural compound related to the important family of inositols. It can be found and isolated from many plants, being the active component of ayurvedic remedies such as Talisa patra (Abies webbiana, A. pindrow) or antidiabetic as Bougainvillea (Bougainvillea spectabilis). Although many synthetic and semi-synthetic methods have been reported for D-pinitol and its derivatives, through chemical and biochemical transformations, Ceratonia siliqua L. (Carob), a Mediterranean tree now in decline, known because of its environmental advantages, is the only raw material from which D-pinitol can be isolated in quantities enough for a viable commercial exploitation. Fortunately, the pharmacological interest in this compound has risen enormously in the last years owing to their established multifunctional properties through a variety of signalling pathways: i) anti-cancer, through inhibition of TNF-ᾳ and suppression of NF-ⱪB pathway; ii) insulinomimetic and metabolic regulator in type 2 diabetes mellitus, via a post-receptor pathway of insulin action; iii) antioxidant; iv) hepatoprotective; v) immuno-modulator, balancing Th1/Th2 cytokines; vi) osteoporosis preventive, through p38/JNK and NF-ⱪB pathways; vii) anti-aging, via reduction of the insulin/IGF-1 signaling (IIS) pathway; viii) improver of creatine retention; ix) preventive and ameliorative of Alzheimer’s disease through selective g-secretase modulation.
Thus, the present review compress the literature reported to date in relation to the health-promoting effects and metabolic pathways of this naturally occurring super-food ingredient and its derivatives, providing an extensive guide for a future utilization of all of its potentialities, aiming a positive impact in the promotion and recovery of carob crops.
Development of efficient methods for isolation and separation of biologically active compounds remains an important challenge for researchers. Designing systems such as organomineral composite materials that allow extraction of a wide range of biologically active compounds, acting as broad-utility solid-phase extraction agents, remains an important and necessary task. Selective sorbents can be easily used for highly selective and reliable extraction of specific components present in complex matrices. Herein, state-of-the-art approaches for selective isolation, preconcentration, and separation of biologically active compounds from a range of matrices are discussed. Primary focus is given to novel extraction methods for some biologically active compounds including cyclic polyols, flavonoids, and oligosaccharides from plants. In addition, application of silica-, carbon-, and polymer-based solid-phase extraction adsorbents and membrane extraction for selective separation of these compounds is discussed. Potential separation process interactions are recommended; their understanding is of utmost importance for the creation of optimal conditions to extract biologically active compounds including those with estrogenic properties.
D-pinitol, a cyclic sugar alcohol, is claimed to be a potential therapeutic compound related to the
illnesses arising from insulin mechanism. Carob is a rich source of this compound and has recently
begun to be used in different separation and purification studies for obtaining D-pinitol. In this study,
different enrichment processes were applied to concentrate the D-pinitol content of the carob extract.
To determine the effectiveness of the processes applied for concentration of the target compound in
carob extract, removal of other impurities (mainly sugars) was used as an important indicator. According
to the results; the highest increase in D-pinitol concentration was observed in the enrichment process
combining the techniques such as ethanol fermentation, membrane filtration and solvent extraction. At
the end of this multi-stage process, D-pinitol concentration increased approximately four-fold (37.53
g/100 mL dry weight) when compared to its initial level (9.38 g/100 mL dry weight) in carob extract.
Carob (Ceratonia Siliqua) is an evergreen tree that has the ability to adapt to harsh environmental conditions, and has become aplant of economic multipurpose. This study was conducted to assess a few biological and morphological characteristics of racemes andthe impact of different insect visitors that pollinate Carob flowers. A group of male, female and hermaphrodite trees were randomlyselected to measure the initiation and cessation of flowers, raceme length, and number of flowers per racemes. Flowers of dioeciouslyCeratonia Siliqua trees were subjected to three pollination treatments; open pollination, supplementary hand pollination with insects, andsupplementary hand pollination without insects. These pollination treatments were conducted to identify whether low fruit production perraceme was due to pollination limitation. Pod length and weight, seed number per pod, 10 seed weight, and seed viability were measured.Supplementary hand pollination increased pod production and seed number per pod compared to non-supplemented flowers. Pod lengthand weight were not affected by Supplementary hand pollination treatments. Open pollinated flowers produced heavy seeds with higherseed germination rates.
Keywords: Ceratonia Siliqua, Jordan, Pollination, Pod set, Seed set, Seed viability
Yield instability is a common problem in Ceratonia Siliqua grown in Jordan. This study was conducted to evaluate the responsibility of the plant itself on pollination failure and to assess the compatibility of hermaphrodite flowers. Flowers of Ceratonia Siliqua were subjected to three flower removal treatments: 1) Removal of late flowers and 2) Removal of late and intermediate flowers and 3) Non-removed flowers (control). To assess self-compatibility of Ceratonia Siliqua pollen grains; self, cross and geitonogamy pollination treatments were conducted on Ceratonia Siliqua trees producing hermaphrodite flowers. Results of non-removal treatment indicated that the average number of matured pods of late flowers was significantly higher than that of center and base flowers. The removal of the apical flowers significantly improved the fruit set of both the intermediate and late flowers. Removal of the late flowers (Remove of the apex) did not significantly increase in both pod length, weight but increased the average seed number per pod. Removal of the late and intermediate flowers significantly increased 10 seeds weight and improved seed germination percentage. Hermaphrodite trees showed a complete self-compatible. There were no significant differences in average number of matured pods between bagged self-pollinated flowers, cross pollinated flowers, Geitonogamy and open pollinated hermaphrodite flowers. Cross and open pollinated flowers produced significantly higher pod length, weight, seed number per pod and seed germination rate.
Pinitol is a very common cyclitol present in many leguminous plants and it is the mono methyl ether of d - inositol. The present study was designed to identify Pinitol, a proven anti-diabetic insulommetic drug in plants extracts by High Performance Thin Layer Chromatography (HPTLC). The TLC procedure was optimized with mobile phase chloroform: methanol: water (6:3.5:0.5) and ammoniacal silver nitrate as a derivatizing agent. The proposed HPTLC method was found to be simple, faster and specific laboratory method of identification of pinitol in plants extracts.
Locust (Ceratonia siliqua L.) is an evergreen tree which is widely cultivated or naturally grown in the Mediterranean area. The species belongs to the Cesalpinaceae subfamily of the family Leguminoseae (syn Fabaceae). The fruits are normally used after crushing to separate seed and pulp, and the seed endosperm is processed to obtain a mucilaginous gum, which is then used in a wide range of commercial food products as a thickener and stabilizer. Contrary to other traditional crops, there is now an increasing demand for the carob dérivâtes produced in the Sicilian province of Ragusa and Siracusa, which represents a potential benefit to farmers and a diversification of farm incomes. Cesalpinia Food preserves and enhances locust crop in Sicily, giving several carob products and byproducts obtained industrially from its beans (pulp, flour from pulp, seed gum, natural carob) and interesting for several purposes, particularly in confectionery, as thickeners and alternative to cacao. This study presents a detailed description of carob processing and its role in product formulation, with particular attention to the traceability system applied to food safety by Cesalpinia Food.
Nine compounds were isolated from the roots of Cassia tora. Their structures were elucidated as α-amyrin octacosanoate, palmitic acid, chrysophanol, β-sitosterol, physcion, chrysophanol-8-methyl ether, betulone, β-sitosterol-β-D-glucoside and ononitol. All of these, except β-sitosterol were isolated for the first time from the roots of this plant and betulone is being reported for the first time from this genus.
D-Pinitol, the major constituent of soybean plant is known as an insulin mimicker. There is a growing interest in the use of D-Pinitol as a food supplement because of its reported efficacy in lowering blood glucose levels with no side effects and nil toxicity. Pinitol was first isolated from pine tree and later from many plants of the Leguminosae family. DPinitol has been recently reported from Pisonia alba (synonym- Pisonia grandis) of the Nyctaginaceae family (Patent Pending 385/CHE/2010). As the demand for pinitol as a food supplement and as a pharmaceutical increased, any attempt to isolate it from natural sources including plants is considered highly worthy. This review covers literature reported on isolation of D-Pinitol from plants during the period 1940 to May 2011.
The carob pod, an important fruit of the food industry in the production of concentrated syrup, is rich in potentially health-promoting phenolic compounds and sugars. Moreover, one of the important bioactive components of carob is D-pinitol, and it has some beneficial effects on human metabolism. The optimum conditions for extraction of D-pinitol and total phenolic compounds (TPC) from cultivated and wild types of carob pods were determined using response surface methodology (RSM). The Box-Behnken Design (BBD) was used to investigate the effects of three independent variables; extraction temperature (degrees C), dilution rate (w/v), and extraction time (h) on the response, D-pinitol and the total phenolic compounds. The optimum extraction conditions obtained using the response optimizer were an extraction temperature of 80 degrees C, a dilution rate of 1:4, and an extraction time of 2h. Under the mentioned above conditions, the maximum D-pinitol and TPC concentrations were 9.67 g/L and 5916.55 mg/L in wild carob pod extract, respectively.
The reports have been written in the context of the EU project Public Information Tobacco Control (PITOC) and aim to inform on the contribution of selected tobacco additives , Carob Bean Extract, Cellulose Fibre, Guar Gum, Liquorice, Menthol, Prune Juice Concentrate and Vanillin to attractiveness, addictiveness and toxicity of tobacco smoking.
The Robinia pseudoacacia plant extract has been reported to have protective effect against cucumber powdery mildew (Sphaerotheca fuliginea). In this study, the active compound of R. pseudoacacia was isolated from the plant extract, and the structure was identified to be d-Pinitol by nuclear magnetic resonance. d-Pinitol, as a known compound, has important physiological activity on plant osmotic tolerance and medicinal activities on human health. This study is the first to report the antifungal activity of d-pinitol on an obligate parasite S. fuliginea and tried to develop a phytochemical fungicide. The evaluation in the growth chamber showed that the control effect of d-pinitol and its formulation against cucumber powdery mildew disease was 80.7% and 94.4%, at a concentration of 0.5 mg/ml. This formulation was further tested in a greenhouse to evaluate its control effect against cucumber (S. fuliginea) and tobacco (Erysiphe cichoracearum) powdery mildew under natural condition. The efficacy of d-pinitol in both trials was better than that of positive control at the recommended concentration. The content of d-pinitol in this plant was 25 mg/g (w/w, dry leaves weight) as determined by gas chromatography. The abundant biomass of d-pinitol in R. pseudoacacia plant extract makes it more economical in practical use. Our study provides a base for the future exploitation of d-pinitol as a natural phytochemical fungicide.
d-pinitol is a bioactive compound with an important application in both food and nonfood industries. In the present study, the leaves of twelve vegetable soybean cultivars that are usually treated as agricultural waste were screened for the presence of d-pinitol. The results showed that the d-pinitol content in these 12 cultivars ranged from 1.32 to 3.04% (w/w) of dry weight, and the cultivar Z98002 was found to contain the highest amount of d-pinitol. Response surface methodology (RSM) was used for optimization of d-pinitol extraction conditions by the Box–Behnken design. The predicted extraction efficiency, which is at least 1.3-fold that of the previously reported typical method, reached to 3.27% under the following optimal conditions: temperature of 65.5 °C, extraction time of 86.8 min, and dilution rate of 1:10. The test in the growth chamber showed that the efficacy of soybean extracts in cucumber powdery mildew control was dose-dependent on the d-pinitol concentration, and the formulated extracts clearly increased the control compared to the crude extract. This effect of the d-pinitol formulation in a greenhouse was confirmed in four provinces of China over a period of two years. Our present study provides the optimized extraction conditions for a selected agricultural waste—vegetable soybean—to obtain a high yield of d-pinitol. Results from the growth chamber test and the greenhouse bioassay will be useful in exploring a low-cost phytochemical fungicide for cucumber powdery mildew control.
Chemical investigation of the stem bark of
Bauhinia rufescens resulted in the isolation of a new cyanoglucoside and menisdaurin from methanol extract and oxepin from petroleum ether extract. The isolated compounds
were tested for their anti-inflammatory potentials based on the cyclooxygenase-2 enzyme (COX-2) model. Cyanoglucoside exhibited the highest activity among the compounds with an inhibition activity of 49.34 % at 100 μM (IC50 0.46 μM) compared to the positive control, indomethacin (79.20 %, IC50 0.24 μM).
Volatile components of carob beans were analysed using established procedures. In all, 169 components (ca 97.4% of the total isolate) were positively identified, of which 163 are reported as carob bean volatiles for the first time. A further eight components (ca 0.5 %) were partially characterized. Seven aliphatic acids represented an extraordinarily high level (77.5%) of the isolate, the major contributors being methylpropanoic acid (45.0%) and hexanoic acid (19.0%). The non-acid volatiles contained 25 aliphatic esters (10.52%), most of which derived from the above acids, together with a range of classic volatile products deriving largely from the high sugar content and the lower protein and lipid content of mature carobs.
Three α-d-galactopyranosylcyclitols previously isolated from soya bean are shown to be 1d-2-O-(α-d-galactopyranosyl)-4-O-methyl-chiro-inositol, 1d-5-O-(α-d-galactopyranosyl)-4-O-methyl-chiro-inositol, and 1d-2-O-(α-d-galactopyranosyl)-chiro-inositol. Assignments of the 13C-n.m.r. spectra of these compounds and of ll-1-O-(α-d-galactopyranosyl)-myo-inositol (galactinol) are presented. The mass spectra of derivatives prepared by permethylation or perdeuteriomethylation, followed by hydrolysis and acetylation or methylation, are discussed.
Ethyl α-D-galactopyranpside and pinitol were isolated during an investigation of the flavor components extracted from dehulled, full-fat, soybean flakes with an azeotropic mixture of hexane:ethanol 81:19. These two compounds were identified by carbon-hydrogen analysis, chromatographic behavior, spectroscopy, optical rotation, and melting point. Full-fat and defatted flakes contain about 0.6 and 0.3 % pinitol, respectively. Nearly 0.2 % ethyl galactoside was formed in full-fat flakes during extraction with the hexane-ethanol azeotrope; only 0.03 % was formed during extraction of de-fatted flakes. Ethyl α-D-galactopyranoside is bitter, and pinitol is somewhat sweet. Taste panel tests indicated that the bitter threshold of the galactoside is 0.5 % in a water solution, which level indicates that it would not contribute to the bitterness of soy products. L-Tryptophan, also present in soy flakes in its free state at less than threshold levels, is more bitter than the galactoside. The addition of ethyl α-D-galactopyranoside had an additive rather than potentiating effect on the bitterness threshold of either a tryptophan or a soy protein isolate solution.
The soluble carbohydrates in leguminous and nodulated nonleguminous plants were compared to determine if there were differences or similarities that might relate to the ability of microsymbionts to fix nitrogen. Gas-liquid chromatography of the trimethylsilyl derivatives was used to quantitate the 80% ethanol soluble carbohydrates and the identities of component peaks were verified by mass spectrometry. The sugars glucose, fructose, and sucrose and the cyclitols myo-inositol and chiro-inositol were present in varying quantities in all tissues of all species. Trehalose was present only in nodules of all species. Pinitol (1D-3-O-methyl-chiro-inositol) was a major component in all legumes but was not detected in the nodulated nonlegumes. (-)-Viburnitol (1L-1,2,4/3,5-cyclohexanepentol) was a major component in the nodulated nonlegumes but was not detected in the legumes.
Samples of cambial sap from each of the three coniferous species Pinus sylvestris L., Picea Abies Karst. and Abies alba Mill. were taken at the time the trees were coming into bud and analysed for low molecular weight carbohydrates, cyclitols and organic acids. They all contained the same free sugars and cyclitols, but in markedly different proportions. Quantitative analyses were carried out for glucose, fructose, sucrose, raffinose, myo-inositol, D-inositol, pinitol, sequoyitol and coniferin.The three main components of the organic acid fractions-quinic acid, shikimic acid and malic acid—were determined quantitatively. The amount of quinic acid greatly exceeded the amount of all the other acids in all three species.
14C-labelled quinic acid applied to the cut ends of Pinus sylvestris needles was transported to the twig. There was no conversion of quinic acid to shikimic acid over short periods of time.
A new trisaccharide was isolated from an aqueous ethanolic extract of chick pea (Cicer arietinum) cotyledons by preparative PC. The trimethylsilyl derivative of this sugar had the same GC retention time as manninotriose previously wrongly reported in seeds of chickpea and lentil. HPLC analysis allowed a good separation between the new trisaccharide and manninotriose showing that the latter was absent in chickpea and in the other legume seeds under study. The composition and structure of the new sugar were determined by enzymatic hydrolysis assays, GC analysis of alditol acetate derivatives obtained after complete acid hydrolysis, GC analysis of by-products from dilute acid hydrolysis and GC/MS analysis of partially methylated or trideuteriomethylated alditol acetates. The new trisaccharide is an α-d-digalactoside of pinitol and is O-α-d-galactopyranosyl-(1–6)-O-α-d-galactopyranosyl-(1–2)-1d-4-O-methyl-chiro-inositol. As originating mainly from chickpea the name ciceritol is proposed. The seeds of seven commercially important legumes were analysed by HPLC and GC for cyclitols, cyclitol-derived oligosaccharides and sucrose α-d-galactosides. Ciceritol was detected in chickpea (2.80% per dehulled seed), lentil (1.60%), white lupin (0.65%), soya bean (0.08%) and bean (traces). The contribution of ciceritol and other α-d-galactosides to flatus is discussed on the basis of α-d-galactosidase sensitivity.
A procedure for identifying natural O-methylinositols by g.l.c.-m.s. analysis is described. Chromatographic retention-index values for these compounds and commonly co-occurring compounds are given. The procedure is illustrated by analyses of clover and peanut cyclitols.
Chase experiments with 14CO2 and feeding experiments with labelled inositols showed that d-pinitol in leaves of Simmondsia chinensis arises via epimerization of d-ononitol. This finding represents an alternative pathway, since d-pinitol is formed in gymnosperms and other plants by epimerization of sequoyitol.
The free cyclitols present in soybean plants were pinitol (1D-3-O-methyl-chiro-inositol), D-chiro-inositol, myo-inositol, and sequoyitol (5-O-methyl-myo-inositol). Pinitol was a major component of all plant parts and was found in large quantities in all soybean cultivars examined. D-chiro-Inositol, myo-inositol, and sequoyitol were minor components. Root nodules contained the same cyclitols found in other plant parts but the relative abundance differed considerably. In soybean seed pinitol was the only monosaccharide of significance. The use of a simple procedure to separate sugars from cyclitols is discussed.
- W N L Davies
- P I Orphanos
- J Papaconstantinou
Davies, W. N. L.; Orphanos, P. I.; Papaconstantinou, J. J. Sci.
Dittrich, P.; Korak, A. Phytochemistry 1984, 23, 65-66.
- T F Schweizer
- I Horman
- P Wursch
Schweizer, T. F.; Horman, I.; Wursch, P. J. Sci. Food Agric. 1978,
Tinner, H. Mitt. Gebiete Lebensm. Hyg. 1960,51, 366-372.
- K Wallenfels
- J Lehmann
Wallenfels, K.; Lehmann, J. Chem. Ber. 1957, 90, 1000-1007.
- M C Charaux
Charaux, M. C. Bull. SOC. Chim. Biol. 1922, 597-600.
- P Nicolas
- I Gertsch
- C Parisod
Nicolas, P.; Gertsch, I.; Parisod, C. Carbohydr. Res. 1984, 131,
Phillips, D. V.; Dougherty, D. E.; Smith, A. E. J. Agric. Food
Phillips, D. V.; Smith, A. E. Can. J. Bot. 1974, 52, 2447-2452.
Food Plouvier, V. In Chemical Plant Taxonomy
- D V Phillips
- D Wilson
- D E J Dougherty
- F Swain
Phillips, D. V.; Wilson, D. 0.; Dougherty, D. E. J. Agric. Food
Plouvier, V. In Chemical Plant Taxonomy; Swain, F., Ed.; Ac-
Quemener, B.; Brillouet, J. M. Phytochemistry 1983, 22,
Saura Calixto, F.; Canellas, J. J. Sci. Food Agric. 1982, 33,
Schweizer, T. F.; Horman, I. Carbohydr. Res. 1981, 95, 61-71.
- R J Beveridge
- C W Ford
- G N Richards
- R J Binder
- J E Coit
- K T Williams
- J E Brekke
- R G Binder
- W F Haddon
Beveridge, R. J.; Ford, C. W.; Richards, G. N. Aust. J. Chem. 1977,
Binder, R. J.; Coit, J. E.; Williams, K. T.; Brekke, J. E. Food
Binder, R. G.; Haddon, W. F. J. Agric. Food Chem. 1984a, 32,
Binder, R. G.; Haddon, W. F. Carbohydr. Res. 198413,129,21-32.
- D H Honig
- J J Rackis
- D J Sessa
Honig, D. H.; Rackis, J. J.; Sessa, D. J. J. Agric. Food Chem. 1971,
Kindl, H.; Hoffmann-Ostenhof, 0. Prog. Chem. Org. Nut. Prod.
Saura Calixto, F.; Canellas
- B Quemener
- J M Brillouet
- T F Schweizer
- I Horman
Quemener, B.; Brillouet, J. M. Phytochemistry 1983, 22,
Saura Calixto, F.; Canellas, J. J. Sci. Food Agric. 1982, 33,
Schweizer, T. F.; Horman, I. Carbohydr. Res. 1981, 95, 61-71.