RESUMO
This study aims at investigating p-menthane, a novel bio-based solvent resulting from the hydrogenation of d-limonene, as a green alternative to n-hexane or toluene for the extraction and solubilization of natural substances. First, conductor-like combination of quantum chemistry (COSMO) coupled with statistical thermodynamics (RS) calculations show a comparable solubilization profile of p-menthane and n-hexane for carotene, volatile monoterpenes such as carvone and limonene, and model triglycerides. Other data obtained experimentally in solid/liquid extraction conditions further indicate that p-menthane showed similar performances to n-hexane for extracting carotenes from carrots, aromas from caraway seeds, and oils from rapeseeds, as these products showed a comparable composition. p-Menthane was also tested using common analytical extraction procedures such as Soxhlet for determination of oil content via multiple extraction stages, and Dean-Stark for determination of water content via azeotropic distillation. For both systems, yields were comparable, but for Dean-Stark, the distillation curve slope was higher when using p-menthane, and the time needed to attain 100% water recovery was 55% shorter than for toluene. Taken together, these results reveal the potential of p-menthane as a green replacer for petroleum-based solvents such as n-hexane or toluene.
Assuntos
Produtos Biológicos/química , Citrus sinensis/química , Química Verde/métodos , Mentol/química , Solventes/química , Carotenoides/isolamento & purificação , Carum/química , Daucus carota/química , Destilação , Ácidos Graxos/análise , Cinética , Odorantes/análise , Óleo de Brassica napus , Sementes/química , Solubilidade , Tolueno/química , Água/químicaRESUMO
Carnosic acid, a phenolic diterpene specific to the Lamiaceae family, is highly abundant in rosemary (Rosmarinus officinalis). Despite numerous industrial and medicinal/pharmaceutical applications of its antioxidative features, this compound in planta and its antioxidant mechanism have received little attention, except a few studies of rosemary plants under natural conditions. In vitro analyses, using high-performance liquid chromatography-ultraviolet and luminescence imaging, revealed that carnosic acid and its major oxidized derivative, carnosol, protect lipids from oxidation. Both compounds preserved linolenic acid and monogalactosyldiacylglycerol from singlet oxygen and from hydroxyl radical. When applied exogenously, they were both able to protect thylakoid membranes prepared from Arabidopsis (Arabidopsis thaliana) leaves against lipid peroxidation. Different levels of carnosic acid and carnosol in two contrasting rosemary varieties correlated with tolerance to lipid peroxidation. Upon reactive oxygen species (ROS) oxidation of lipids, carnosic acid was consumed and oxidized into various derivatives, including into carnosol, while carnosol resisted, suggesting that carnosic acid is a chemical quencher of ROS. The antioxidative function of carnosol relies on another mechanism, occurring directly in the lipid oxidation process. Under oxidative conditions that did not involve ROS generation, carnosol inhibited lipid peroxidation, contrary to carnosic acid. Using spin probes and electron paramagnetic resonance detection, we confirmed that carnosic acid, rather than carnosol, is a ROS quencher. Various oxidized derivatives of carnosic acid were detected in rosemary leaves in low light, indicating chronic oxidation of this compound, and accumulated in plants exposed to stress conditions, in parallel with a loss of carnosic acid, confirming that chemical quenching of ROS by carnosic acid takes place in planta.
Assuntos
Abietanos/farmacologia , Antioxidantes/farmacologia , Rosmarinus/metabolismo , Membranas Intracelulares/efeitos dos fármacos , Membranas Intracelulares/metabolismo , Peroxidação de Lipídeos/efeitos dos fármacos , Lipídeos/química , Oxirredução , Folhas de Planta/efeitos dos fármacos , Folhas de Planta/metabolismo , Folhas de Planta/ultraestrutura , Espécies Reativas de Oxigênio/metabolismo , Tilacoides/efeitos dos fármacos , Tilacoides/metabolismo , Tilacoides/ultraestrutura , Fatores de Tempo , alfa-Tocoferol/farmacologiaRESUMO
Extracts rich in antioxidants, such as rosemary extracts, are currently obtained by extraction of the plant material using hydro-alcoholic mixtures with high ethanol content. As this ratio is generally chosen by default and scarcely optimized, we intended to investigate the impact of the hydro-alcoholic composition on extract characteristics such as extraction yield, composition profile in selected compounds, and antioxidant/reducing activity such as Folin-Ciocalteu, DPPH, and ORAC. A theoretical determination of rosmarinic (RA) and carnosic (CA) acid solubilities in ethanol:water mixtures was also performed using COSMO-RS and was confronted to experiments. While the best solubilizing solvent (100% ethanol) was also the best extracting solvent for CA, it was not the case with RA since pure ethanol appeared as a poor solvent compared to 30% ethanol which was optimal. Finally, the best antioxidant activities were obtained with 30% ethanol.
RESUMO
The beneficial health effects of chlorogenic acids (CGAs), major components of coffee beans, are well known and have been attributed to multiple mechanisms of action. However, the lipolytic activity of CGAs does not appear to have been reported. We studied the effects of varying concentrations of Svetol®, a decaffeinated green coffee bean extract enriched in CGAs, on the liberation of free fatty acids from human adipocytes following short-term (2 h) and long-term (192 h) exposure. The results showed that although lipolytic activity observed following short-term incubation could be tentatively linked to residual caffeine traces in the sample, longer-term exposure clearly showed the effects of Svetol® on release of free fatty acids, and this effect was not due to caffeine. The results of this study provide a further mechanism by which to explain the long-term health benefits of CGAs and Svetol®.
Assuntos
Adipócitos/efeitos dos fármacos , Ácido Clorogênico/farmacologia , Café/química , Ácidos Graxos/metabolismo , Lipólise/efeitos dos fármacos , Adulto , Cafeína , Células Cultivadas , Feminino , HumanosRESUMO
Two new secoiridoid glucosides, excelsides A (1) and B (2), were isolated from the seeds of Fraxinus excelsior. Their structures were elucidated as (2S,4S,3E)-methyl 3-ethylidene-4-(2-methoxy-2-oxoethyl)-2-[(6-O-beta-D-glucopyranosyl-beta-d-glucopyranosyl)oxy]-3,4-dihydro-2H-pyran-5-carboxylate and (2S,4S,3E)-methyl 3-ethylidene-4-{2-[2-(4-hydroxyphenyl)ethyl]oxy-2-oxoethyl}-2-[(6-O-beta-d-glucopyranosyl-beta-d-glucopyranosyl)oxy]-3,4-dihydro-2H-pyran-5-carboxylate, respectively, on the basis of NMR and MS data. Eight known compounds were identified as nuzhenide (3), GI3 (4), GI5 (5), ligstroside (6), oleoside 11-methyl ester (7), oleoside dimethyl ester (8), 1'''-O-beta-D-glucosylformoside (9), and salidroside (10). Compounds 1-9 inhibited adipocyte differentiation in 3T3-L1 cells. Dilutions of the aqueous extract of F. excelsior (1:10,000) as well as compounds 2, 3, 4, 5, and 8 activated the peroxisome proliferator-mediated receptor-alpha (PPARalpha) reporter cell system in the range of 10(-4) M, compared to 10(-7)-10(-8) M for the synthetic PPARalpha activator, WY14,643. Both biological activity profiles support the hypothesis that inhibition of adipocyte differentiation and PPARalpha-mediated mechanisms might be relevant pathways for the antidiabetic activity of F. excelsior extract.
Assuntos
Fraxinus/química , Iridoides/isolamento & purificação , Iridoides/farmacologia , PPAR alfa/efeitos dos fármacos , Plantas Medicinais/química , Adipócitos/efeitos dos fármacos , Animais , Glucosídeos Iridoides , Glicosídeos Iridoides , Iridoides/química , Camundongos , Estrutura Molecular , Sementes/química , EstereoisomerismoRESUMO
Nowadays, "green analytical chemistry" challenges are to develop techniques which reduce the environmental impact not only in term of analysis but also in the sample preparation step. Within this objective, pressurized liquid extraction (PLE) was investigated to determine the initial composition of key antioxidants contained in rosemary leaves: Rosmarinic acid (RA), carnosic acid (CA), and carnosol (CO). An experimental design was applied to identify an optimized PLE set of extraction parameters: A temperature of 183 °C, a pressure of 130 bar, and an extraction duration of 3 min enabled recovering rosemary antioxidants. PLE was further compared to conventional Soxhlet extraction (CSE) in term of global processing time, energy used, solvent recovery, raw material used, accuracy, reproducibility, and robustness to extract quantitatively RA, CA, and CO from rosemary leaves. A statistical comparison of the two extraction procedure (PLE and CSE) was achieved and showed no significant difference between the two procedures in terms of RA, CA, and CO extraction. To complete the study showing that the use of PLE is an advantageous alternative to CSE, the eco-footprint of the PLE process was evaluated. Results demonstrate that it is a rapid, clean, and environmentally friendly extraction technique.
RESUMO
In lipid dispersions, the ability of reactants to move from one lipid particle to another is an important, yet often ignored, determinant of lipid oxidation and its inhibition by antioxidants. This review describes three putative interparticle transfer mechanisms for oxidants and antioxidants: (a) diffusion, (b) collision-exchange-separation, and (c) micelle-assisted transfer. Mechanism a involves the diffusion of molecules from one particle to another through the intervening aqueous phase. Mechanism b involves the transfer of molecules from one particle to another when the particles collide with each other. Mechanism c involves the solubilization of molecules in micelles within the aqueous phase and then their transfer between particles. During lipid oxidation, the accumulation of surface-active lipid hydroperoxides (LOOHs) beyond their critical micelle concentration may shift their mass transport from the collision-exchange-separation pathway (slow transfer) to the micelle-assisted mechanism (fast transfer), which may account for the transition from the initiation to the propagation phase. Similarly, the cut-off effect governing antioxidant activity in lipid dispersions may be due to the fact that above a certain hydrophobicity, the transfer mechanism for antioxidants changes from diffusion to collision-exchange-separation. This hypothesis provides a simple model to rationalize the design and formulation of antioxidants and dispersed lipids.
Assuntos
Antioxidantes/química , Lipídeos/química , Difusão , Peróxidos Lipídicos/química , Micelas , Modelos Químicos , Oxirredução , Tensoativos/químicaRESUMO
Carnosic acid (salvin), which possesses antioxidative and antimicrobial properties, is increasingly exploited within the food, nutritional health and cosmetics industries. Since its first extraction from a Salvia species (â¼70 years ago) and its identification (â¼50 years ago), numerous articles and patents (â¼400) have been published on specific food and medicinal applications of Rosmarinus and Salvia plant extracts abundant in carnosic acid. In contrast, relevant biochemical, physiological or molecular studies in planta have remained rare. In this overview, recent advances in understanding of carnosic acid distribution, biosynthesis, accumulation and role in planta, and its applications are summarised. We also discuss the deficiencies in our understanding of the relevant biochemical processes, and suggest the molecular targets of carnosic acid. Finally, future perspectives and studies related to its potential roles are highlighted.
Assuntos
Abietanos/química , Abietanos/farmacologia , Anti-Infecciosos/química , Anti-Infecciosos/farmacologia , Antioxidantes/química , Antioxidantes/farmacologia , Rosmarinus/química , Salvia/química , Abietanos/isolamento & purificação , Animais , Anti-Infecciosos/isolamento & purificação , Antioxidantes/isolamento & purificação , Cromatografia Líquida de Alta Pressão , Humanos , Camundongos , Estrutura Molecular , Folhas de Planta/química , Ratos , Rosmarinus/classificação , OvinosRESUMO
Four trichothecene-producing strains of Fusarium graminearum were grown on three maize grain fractions, whole grain, degermed grain, and the germ, to determine the effect of natural substrates on mycotoxin production. Monitoring the ergosterol content after 25 days of incubation indicated that fungal growth on all grain fractions was comparable. Trichothecene (TCT) production was highest on degermed grain, less on whole grain, and very low or nondetectable on the germ; similar results were found with four different strains. It was concluded that inhibitor(s) of TCT biosynthesis were present in maize germ. The presence of phenolic compounds was investigated in the different fractions. The hydroxamate 4-acetylbenzoxazolin-2-one (4-ABOA), a known inhibitor of mycotoxin production, was found in the degermed and whole grain fractions but not in the germ. Therefore, the TCT inhibition observed on the maize germ fraction used in our study is clearly not linked to 4-ABOA. Other soluble phenolic compounds were found at a much higher concentration in the germ than in the two other fractions. The inhibition property of the soluble ester-bound extracts was tested in liquid culture. A possible role for these compounds is discussed.
Assuntos
Fusarium/metabolismo , Fenóis/metabolismo , Tricotecenos/biossíntese , Zea mays/microbiologia , Zea mays/químicaRESUMO
PURPOSE: The aim of this study was to determine whether a Fraxinus excelsior L. seed extract, FraxiPure™ (0.5% in the diet), limits weight gain and hyperglycemia in mice. In a previous report, we identified several secoiridoids in FraxiPure™, some of which activated peroxisome proliferator-activated receptor alpha (PPARα) in vitro and inhibited the differentiation of 3T3-L1 preadipocyte cells. In a separate study, FraxiPure™ reduced glycemia in healthy volunteers, following an oral glucose tolerance test. These findings suggest that FraxiPure™ has antiobesity and antihyperglycemia effects. MATERIALS AND METHODS: FraxiPure™ was tested in mice that were fed a high-fat diet over 16 weeks and compared with low-fat and high-fat diet controls. Weight gain, omental and retroperitoneal fat, fasting blood glucose, and fasting blood insulin were measured. RESULTS: FraxiPure™ reduced gains in body weight by 32.30% (p < 0.05), omental fat by 17.92%, and retroperitoneal fat by 17.78%. FraxiPure™ also lowered fasting blood glucose levels by 76.52% (p < 0.001) and plasma insulin levels by 53.43% (p < 0.05) after 16 weeks. Moreover, FraxiPure™ lowered liver weight gains by 63.62% (p < 0.05) and the incidence of fatty livers by 66.67%. CONCLUSIONS: Our novel results demonstrate the antiobesity effects of chronic administration of an F. excelsior seed extract and confirm its ability to regulate glycemia and insulinemia. In addition, this extract, which is rich in secoiridoid glucosides, protects against obesity-related liver steatosis.
Assuntos
Tecido Adiposo/efeitos dos fármacos , Fraxinus , Hiperglicemia/tratamento farmacológico , Hipoglicemiantes/uso terapêutico , Obesidade/prevenção & controle , Fitoterapia , Aumento de Peso/efeitos dos fármacos , Tecido Adiposo/metabolismo , Animais , Fármacos Antiobesidade/farmacologia , Fármacos Antiobesidade/uso terapêutico , Glicemia/metabolismo , Gorduras na Dieta/efeitos adversos , Fígado Gorduroso/epidemiologia , Fígado Gorduroso/prevenção & controle , Hiperglicemia/metabolismo , Hipoglicemiantes/farmacologia , Incidência , Insulina/sangue , Fígado/efeitos dos fármacos , Masculino , Camundongos , Camundongos Endogâmicos C57BL , Camundongos Obesos , Obesidade/induzido quimicamente , Obesidade/metabolismo , Tamanho do Órgão/efeitos dos fármacos , PPAR alfa , Extratos Vegetais/farmacologia , Extratos Vegetais/uso terapêutico , SementesRESUMO
Two new 5-O-glucosylflavones, 5-O-ß-D-glucopyranosyl cirsimaritin (1) and 5, 4'-O-ß-D-diglucopyranosyl cirsimaritin (2), four known flavonoids, cirsimarin (3), cirsimaritin (4), salvigenin (5), 4', 5-dihydroxy-7-methoxyflavone (6), and a norisoprenoid, vomifoliol (7), have been isolated from the aerial parts of Microtea debilis. All isolates were tested for cytotoxicity in human cancer cell lines (Hep G2, COLO 205, and HL-60) and anti-inflammatory activities in LPS-treated RAW264.7 macrophages. Compound 6 was found to be a potent inhibitor to nitrite production in macrophages. Compounds 2, 4, 6, and 7 showed moderate anti-proliferative activity against COLO-205 cells with IC(50) values of 7.1, 13.1, 6.1, and 6.8 µM, respectively.
Assuntos
Anti-Inflamatórios/farmacologia , Antineoplásicos Fitogênicos/farmacologia , Flavonas/farmacologia , Glucosídeos/farmacologia , Phytolaccaceae/química , Fitoterapia , Extratos Vegetais/farmacologia , Animais , Anti-Inflamatórios/isolamento & purificação , Anti-Inflamatórios/uso terapêutico , Antineoplásicos Fitogênicos/isolamento & purificação , Antineoplásicos Fitogênicos/uso terapêutico , Linhagem Celular Tumoral , Proliferação de Células/efeitos dos fármacos , Flavonas/isolamento & purificação , Flavonas/uso terapêutico , Glucosídeos/isolamento & purificação , Glucosídeos/uso terapêutico , Células Hep G2 , Humanos , Lipopolissacarídeos , Macrófagos/efeitos dos fármacos , Macrófagos/metabolismo , Camundongos , Neoplasias/tratamento farmacológico , Nitritos/metabolismo , Componentes Aéreos da Planta , Extratos Vegetais/química , Extratos Vegetais/uso terapêuticoRESUMO
The overproduction of free radicals and oxygen reactive species is suspected to be implicated in a wide range of metabolic reactions that can have pernicious consequences in the development of a variety of human diseases. Botanical extracts are sources of antioxidants that counteract both free radicals and oxygen reactive species. The processing conditions used in the botanical extraction may influence the antioxidant composition; therefore, different extracts from the same plant may have different antioxidant properties. To illustrate this fact, we conducted a study using three commercial rosemary (Rosmarinus officinalis L.) leaf extracts. The three extracts were standardized to contain, respectively, 20% carnosic acid, 40% ursolic acid, or 20% rosmarinic acid. They were evaluated for their total (hydrophilic + lipophilic) antioxidant effects on oxygen radical absorbance capacity (ORAC), their ferric reducing/antioxidant power (FRAP), and their capacity to inhibit Cu(2+)-induced low-density lipoprotein (LDL) oxidation ex vivo. The ursolic acid extract showed the lowest antioxidant capacity on all models. The rosmarinic acid extract had an antioxidant capacity 1.5 times higher on ORAC and four times higher on FRAP than the carnosic acid extract. However, the carnosic acid extract was better than the rosmarinic acid extract in inhibiting the oxidation of LDL ex vivo. These results encourage conducting further studies to evaluate the carnosic acid and rosmarinic acid extracts in vivo. Our study offers an example of the importance of the extraction procedures, on which depends the nature of the antioxidant composition, and highlights interest to proceed with in vitro/ex vivo assay selection for the evaluation of the antioxidant properties of botanical extracts.
Assuntos
Antioxidantes/análise , Extratos Vegetais/normas , Folhas de Planta/química , Rosmarinus/química , Abietanos/análise , Antioxidantes/farmacologia , Cinamatos/análise , Sulfato de Cobre/química , Depsídeos/análise , Compostos Férricos/química , Lipoproteínas LDL/química , Oxirredução , Extratos Vegetais/análise , Extratos Vegetais/química , Extratos Vegetais/farmacologia , Espécies Reativas de Oxigênio/química , Triterpenos/análise , Ácido Rosmarínico , Ácido UrsólicoRESUMO
AIM OF THE STUDY: Fraxinus excelsior L. (Family: Oleaceae) seeds are consumed as a food, condiment, and folk medicine. The seeds are traditionally used as a potent hypoglycemic agent, but no clinical evidence exists in as to this regard. We assessed the clinical efficacy and safety of the seed extract (FraxiPure, Naturex), containing 6.8% of nuzhenide and 5.8% of GI3 (w/w), on plasma glucose and insulin levels against glucose (50 g) induced postprandial glycemia. MATERIALS AND METHODS: Preselected dose (1.0 g) was used in a double blind, randomized, crossover, placebo (wheat bran) controlled study on 16 healthy volunteers. Each treatment was given immediately after a fasting blood glucose sample (0 min). Postprandial plasma glucose levels were estimated at 0, 15, 30, 45, 60, 90 and 120 min; and postprandial plasma insulin at 0, 30, 60, 90 and 120 min. RESULTS: The extract lowered the incremental postprandial plasma glucose concentration as compared to placebo at 45 min (P = 0.06) and 120 min (P = 0.07). It statistically (P = 0.02) reduced the glycemic area under the blood glucose curve. The seed, also, induced a significant (P = 0.002) secretion of insulin at 90 min after glucose administration. However, the insulinemic area under the blood insulin curve was not different than the placebo. No adverse events were reported. CONCLUSIONS: Our findings confirm the hypoglycemic action of Fraxinus excelsior L. seed extract. These promising results, thus, encourage conducting long-term clinical studies to further evaluate the efficacy and safety of Fraxinus excelsior L. seed extract in healthy and diabetic volunteers and also to explore the possible mechanism(s) of action.
Assuntos
Glicemia/metabolismo , Fraxinus , Hipoglicemiantes/farmacologia , Insulina/metabolismo , Extratos Vegetais/farmacologia , Adulto , Área Sob a Curva , Método Duplo-Cego , Feminino , Humanos , Insulina/sangue , Secreção de Insulina , Masculino , Pessoa de Meia-Idade , Período Pós-Prandial , Valores de Referência , Sementes , Adulto JovemRESUMO
A new, rapid HPLC-PAD-APCI/MS assay has been developed in order to measure accurately the amount of p-coumaric, E- and Z-ferulic acid and the dehydrodimers of ferulic acid in cereal grain. In the positive ionisation mode, MS patterns gave additional information for the identification of the dimers. The time required and the quantities of solvents employed in the developed analytical method are much lower than those involved in previously available assays of these compounds, thus making the method suitable for the screening of cereal genotypes. Application of the method to accessions of maize, wheat and sorghum showed that E-ferulic was the most abundant phenylpropanoid, whilst the major dimer was 8-O-4' dehydrodimer of ferulic acid followed by the 5-5' and then the 8-5' forms. Maize grains, especially of the Mexican landraces, contained the highest levels of these dimers.