Use of spinning band distillation equipment for fractionation of volatile compounds of Copaifera oleoresins for developing a validated gas chromatographic method and evaluating antimicrobial activity

Copaifera is a tree that produces an oleoresin that has great historical and economic importance. These oleoresins display several pharmacological properties, such as anti‐inflammatory and antimicrobial, among others. The commercialization of Copaifera oleoresin occurs, in many cases, without any quality control, which facilitates its adulteration. Validated analytical methods can provide a safe quality control. In this work, the 800 Automatic Spinning Band Distillation equipment was used to perform the fractionation of the volatile oils obtained by hydrodistillation of Copaifera multijuga, C. paupera, C. Publifora and C. langsdorffii, aiming to isolate and purify the major compounds present in these oils. For purification, classical column chromatography was used, furnishing six isolated sesquiterpenes. The sesquiterpenes were used as standards in the development and validation of the method by GC–FID. The evaluated parameters were selectivity, linearity, precision, accuracy and robustness and they are all in accordance with ANVISA and International Conference on Harmonization guidelines. The developed method is reliable for the quantification of sesquiterpenes in Copaifera oleoresins. Both volatile oils and isolated sesquiterpenes had their minimum inhibitory concentration determined against strains of Gram‐negative and Gram‐positive bacteria and yeasts. Copaifera langsdorffi oleoresin was the only one active against all of the evaluated microorganisms, displaying good antimicrobial potential.     

Antimicrobial evaluation of diterpenes from Copaifera langsdorffii oleoresin against periodontal anaerobic bacteria

The antimicrobial activity of four labdane-type diterpenes isolated from the oleoresin of Copaifera langsdorffii as well as of two commercially available diterpenes (sclareol and manool) was investigated against a representative panel of microorganisms responsible for periodontitis. Among all the evaluated compounds, (-)-copalic acid (CA) was the most active, displaying a very promising MIC value (3.1 μg mL-1; 10.2 μM) against the key pathogen (Porphyromonas gingivalis) involved in this infectious disease. Moreover, CA did not exhibit cytotoxicity when tested in human fibroblasts. Time-kill curve assays performed with CA against P. gingivalis revealed that this compound only inhibited the growth of the inoculums in the first 12 h (bacteriostatic effect). However, its bactericidal effect was clearly noted thereafter (between 12 and 24 h). It was also possible to verify an additive effect when CA and chlorhexidine dihydrochloride (CHD, positive control) were associated at their MBC values. The time curve profile resulting from this combination showed that this association needed only six hours for the bactericidal effect to be noted. In summary, CA has shown to be an important metabolite for the control of periodontal diseases. Moreover, the use of standardized extracts based on copaiba oleoresin with high CA contents can be an important strategy in the development of novel oral care products.     

Evaluation of cytoprotective effects of compounds isolated from Copaifera langsdorffii Desf. against induced cytotoxicity by exposure to methylmercury and lead

Abstract

Copaifera langsdorffii L. is one of the most known medicinal species in Brazil. Its leaves are rich in phenolic compounds with potential biological activities as an antioxidant and chelating agent. This paper reports the isolation of four compounds from the hydroalcoholic extract of the leaves of C. langsdorffii and the investigation of their possible cytoprotective effects against heavy metal poisoning. Quercitrin (1), afzelin (2), 3,5-di-O-(3-O-methyl galloyl) quinic acid (3) and 4,5-di-O-(3-O-methyl galloyl) quinic acid (4), were associated with toxic doses of methylmercury and lead and evaluated by Alamar blue cell viability assays in HepG2 and PC12. The compounds displayed significant cytoprotective effect for the HepG2 cell line against both metals. Compounds 1–4 did not protect PC12 cells against methylmercury induced-cytotoxicity, but at lower concentrations, they protected against lead induced-cytotoxicity. The evaluated compounds showed a promising cytoprotection effect against exposure to heavy metals and should be further investigated as protective agents.     

Terpenoids of the oleoresin ofPinus kochiana

The chemical composition of the oleoresin of Koch's pine growing in the Caucasus has been studied. It has been shown that, with respect to the composition of the monoterpenes and the resin acids, the oleoresin of this species does not differ from oleoresins of the subgenusDiploxylon studied previously. Predominating among the sesquiterpenes is germacrene D, which has not previously been found in the resins of the conifers of the USSR. The diterpenoids are represented by tricyclic compounds (pimarinol, isopimarinol, and methyl 15-hydroxydehydroabietate and the hydrocarbons corresponding to them).     

Triterpenoids of plants of the genus Abies Hill

A review is given for the first time of the results of investigations of Soviet and foreign authors on the isolation of triterpenoids from the bark, needles, oleoresin, and seeds of various species ofAbies (fir) and the determination of their structures and properties. Features of the PMR, mass, UV, and CD spectra of the compounds under consideration are discussed specially and information is given on their classification, distribution in firs, and biological activities.Novosibirsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 443–455, July–August, 1990.     

Terpenoids of the oleoresins ofPicea orientalis andAbies normanniana growing in the Caucasus

The terpenoid compositions of the oleoresins of the oriental spruce and of the Nordmann fir growing in the Caucasus have been studied. From the oleoresin ofPicea orientalis (L.) Link, which belongs to the sectionOmorica, 32 mono-, sesqui-, and diterpene compounds have been identified, and fromAbies nordmanniana Stev. 37 mono-, sesqui, and diterpene compounds. Together with other diterpenoids that are characteristic for the oleoresins of all species of fir, methyl dehydroabietate and methyl 15-hydroxy dehydroabietate have been found in the oleoresin of the Nordmann fir. Three new sesquiterpene hydrocarbons have been isolated.     

New diterpenoid components of the oleoresin ofPinus pumila

Summary 1. Five new diterpenoid components have been isolated from the oleoresin of the Japanese stone pine — (+)-dehydroabietane, (–)-abietadine, 13E-labda-8(20), 13-dien-15-al, 13Z-labda-8(20), 13-dien-15-al, and pumiloxide, which is probably an enantiomer of deoxyafricenol. The presence of methyl anticopalate (copaiferate) and of the methyl esters of abietic, dehydroabietic, isopimaric, and isopimara-8, 15-dien-18-oic acids has been established in this resin.2. From the components of its oleoresin, the Japanese stone pine differs from other species ofPinus present in the section Cembrae by its low content of cembrane diterpenoids, the absence of lambertianic acid and its methyl ester, and the specific biosynthesis of labdane diterpenoids consisting in the accumulation in the oleoresin of 13E-labda-8(20), 13-dien-15-ol and its subsequent oxidation predominantly at C₁₅.Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Academy of Sciences of the USSR. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 345–349, May–June, 1978.     

Mono- and sesquiterpenoids of the oleoresin ofPinus koraiensis andP. pumila. crystal structure of 1β,4αH,7αH,10βH-Guaiane-5α,14-diol

The composition of the mono- and sesquiterpenoids of the oleoresin of two species of conifers of thePinaceae family has been studied. In the oleoresin ofPinus koraiensis Sieb. et Zucc. 10 oxidized monoterpenoids, 18 sesquiterpene hydrocarbons, and six sesquiterpene alcohols have been identified. In theoleoresin ofPinus pumila (Pall.) Rg1. 10 monoterpene hydrocarbons, six oxidized monoterpenoids, 14 sesquiterpene hydrocarbons, and four sesquiterpene alcohols have been found. The structure of 1β,4αH,7αH,10βH-guaiane-5α,14-diol, one of the hydroboration-oxidation products of an unidentified sesquiterpene alcohol isolated from both oleoresins, has been determined by x-ray structural analysis.     

Diols from the oleoresin ofPicea ajanensis

Oplodiol, 3β-hydroxyepimanool, and epitorulosol have been isolated for the first time from the oleoresin ofPicea ajanensis. On the basis of the results obtained, it may be assumed that the species studied is possibly a hybrid of Yeddo spruce and Siberian spruce.     

Determination of Monoterpenes in Oleoresin: A Chemosystematic Study of the Interaction between Fraser Fir (Abies fraseri) and Balsam Woolly Adelgid (Adelges piceae)

The Fraser fir (Abies fraseri), a conifer native to high elevation sites in the southern Appalachians, has suffered severe mortality attributed to an exotic insect, the balsam woolly adelgid (BWA) (Adelges piceae). Fraser fir, like many other plants, produce volatile organic compounds called monoterpenes in a variety of tissues, including the cortical oleoresin found in blisters on the bark. The purpose of this study was to perform a chemosystematic study to evaluate whether differences in monoterpene composition of Fraser fir oleoresin were observed as a function of the season sampled, the presence or absence of BWA infestation, the health of a tree, and the susceptibility of trees to BWA, based on geographic location. Oleoresin was collected in September and December, 1994, at two mountains, Mount Rogers, where the fir were relatively healthy, and Roan Mountain, where heavy to moderate mortality has been observed. The oleoresin samples were dissolved in methylene chloride, and the monoterpenes were determined by gas chromatography. This method was shown to have acceptable precision for chemosystematic studies for five monoterpenes and the total of all monoterpenes. The levels of monoterpenes in oleoresin were statistically the same for most compounds in September and December, although the total monoterpenes were higher in September at Mount Rogers and α-pinene was higher in December at Roan Mountain. Infested and uninfested fir had the same levels of oleoresin monoterpenes at both mountains. No differences in monoterpene levels were observed at Mount Rogers with healthy and unhealthy fir, but at Roan Mountain, the total monoterpene concentrations were different in these categories. A comparison of monoterpene concentrations in oleoresin from Mount Rogers and Roan Mountain showed statistically significant differences for 3-carene, β-phellandrene, and total monoterpenes.     

气相色谱-质谱技术分析姜油树脂中的挥发性及非挥发性成分

用超临界CO2萃取生姜根茎中的姜油树脂,并用气相色谱-质谱联用技术对其进行了成分分析。从姜油树脂中分析出77种化合物,其中挥发油成分50种,主要是α-姜烯(22.29%)、 β-倍半水芹烯(8.58%)、α-法尼烯(3.93%)、 β-没药烯(3.87%)和α-姜黄烯(2.63%)等倍半萜类化合物;姜辣素成分27种,主要成分为6-姜酚(9.38%)、6-姜烯酚(7.59%)和分析过程中由姜酚类或姜烯酚类化合物受热分解而形成的姜油酮(9.24%)。在姜辣素成分中,6-异姜酚、(Z)-10-异姜烯酚和(E)-10-异姜烯酚3种化合物是新发现的未见报道的化合物。实验中对这3种新化合物进行了质谱裂解分析。     

Terpenoids ofPinus funebris

The complete chemical composition of the oleoresin of the Chinese pine growing in the Far East has been studied. It has been shown that the main components of the monoterpenes are α-pinene, β-phellandrene, and α-terpineol. The sesquiterpenes contain longifolene and compounds related to it. The oleoresin of the Chinese pine is distinguished by a high content of diterpene cembrane compounds. Among the resin acids, dehydroabietic acid predominates (42.4%).     

Oriental Lacquer. 10. The South East Asian Lacquer

Abstract

The family Anacardiaceae consists of 76 genera and about 600 species. A comparison of the species of Anacardiaceae is discussed with special emphasis on the importance of the exudates, the so-called sap, for their importance as lacquer to produce lacquer ware. Many exudates are poisonous. The individual chemical compounds which constitute the active ingredients of the oleoresin part of the sap and their function are described based on space-filling molecular models. Emphasis is also given to the organic components of lacquer trees of the South East Asian region, which is compared to other species of the Anacardiaceae family.     

Higher isoprenoids—VIII: Diterpenoids from the oleoresin of hardwickia pinnata part 1: hardwickiic acid

The oleoresin from Hardwickia pinnata Roxb. is shown to be a complex blend of sesquiterpenes and diterpenes. (?)-Copaene, (?)-caryophyllene and humulene account for over 90% of the sesquiterpenes present. The diterpenes, which constitute some 60% of the oleoresin, have been found to consist of a series of closely related new diterpenoids of ent-clerodane type. Evidence leading to the elucidation of the absolute stereostructure of the main diterpenoid-hardwickiic acid—is presented.     

Liquid chromatographic-mass spectrometric analysis of supercritical-fluid extracts of rosemary plants

A two-step supercritical fluid extraction process of rosemary leaves, on a pilot plant scale, is proposed to divide the oleoresin into two fractions with different antioxidant activities and essential oil composition. Rosemary leaves were extracted by using different conditions of pressure and temperature as well as different conditions for fractionation of the extracts. Conditions can be tuned to selectively extract one antioxidant fraction with almost no residual aroma. In the present investigation, the antioxidant fraction was exhaustively studied in terms of antioxidant activity measurements as well as of chemical composition. An LC–MS method was adapted to perform the analysis and identification of the compounds responsible for the antioxidant activity of the extracts. Different extraction and fractionation conditions were studied in order to correlate the process conditions with the antioxidant activities obtained.     

New diterpenoid components of the oleoresin ofPinus koraiensis

Summary 1. The following compounds have been isolated from the oleoresin ofPinus koraiensis Sieb. et Zucc., in addition to those described previously: cis-abienol, labd-8(20),13-dien-15-ol, (+)-manoyl oxide, epimanoyl oxide, and 7-hydroxydehydroabietinol (in the form of the diacetate). The structure of the last-mentioned, previously unknown, diterpenoid has been shown by chemical transformations and by spectroscopy.2. It has been established that the cembrene, isocembrene, pinacenes, neoabienol isolated previously and the 18-norcembra-2,7,11-trien-4-one now isolated for the first time are secondary products formed in the storage and treatment of the oleoresin.Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Academy of Sciences of the USSR. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 174–179. March–April, 1976.     

Steroid glycosides from the seeds ofPetunia hybrida. Structures of petuniosides B,D, and F

Oplodiol, 3-hydroxyepimanool, and epitorulosol have been isolated for the first time from the oleoresin ofPicea ajanensis. On the basis of the results obtained, it may be assumed that the species studied is possibly a hybrid of Yeddo spruce and Siberian spruce.Novosibirsk Institute of Organic Chemistry, Siberian Division of the Russian Academy of Sciences. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 359–363, May–June, 1994.     

Resin acids of the oleoresins of conifers growing in Transcarpathia

The chemical composition of the resin acids of the oleoresins of five species of the conifers of Transcarpathia has been studied. The oleoresins contain eight resin acids. ^8,9-Isopimaric and anticopalic acids have been found in the acid part of the oleoresin of the Weymouth pine.Novosibirsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 212–214, March–April, 1987.     

GC-MS Analysis of the Essential Oil from the Oleoresin of Pistacia atlantica var. mutica

The oleoresin of Pistacia atlantica var. mutica, growing in different regions of Iran, is a popular naturally occurring chewing gum and has been used traditionally in the treatment of peptic ulcer. The GC-MS analysis of the essential oil, obtained from steam distillation of the oleoresin of P. Atlantica var. mutica, has led to the identification and quantification of eleven terpenoids, -pinene (70%), -pinene (1.94%), 3-carene (0.2%), carveol (2.18%), epoxypinene (2.15%), limonene oxide (9%), myrtenol (5.31%), limonene (0.62%), citral (5.72%), -phellandrene (0.2%), and -myrcene (0.3%). The total amount of essential oil obtained was 22% v/w which is higher than any other species of the genus Pestacia.     

Can Extracts from the Leaves and Fruits of the Cotoneaster Species Be Considered Promising Anti-Acne Agents?

This study aimed to evaluate the phenolic profile and biological activity of the extracts from the leaves and fruits of Cotoneaster nebrodensis and Cotoneaster roseus. Considering that miscellaneous species of Cotoneaster are thought to be healing in traditional Asian medicine, we assumed that this uninvestigated species may reveal significant therapeutic properties. Here, we report the simultaneous assessment of chemical composition as well as biological activities (antioxidant, anti-inflammatory, antibacterial, and cytotoxic properties) of tested species. Complementary LC-MS analysis revealed that polyphenols (especially flavonoids and proanthocyanidins) are the overriding phytochemicals with the greatest significance in tested biological activities. In vitro chemical tests considering biological activities revealed that obtained results showed different values depending on concentration, extraction solvent as well as phenolic content. Biological assays demonstrated that the investigated extracts possessed antibacterial properties and were not cytotoxic toward normal skin fibroblasts. Given the obtained results, we concluded that knowledge of the chemical composition and biological activities of investigated species are important to achieve a better understanding of the utilization of these plants in traditional medicine and be useful for further research in their application to treat various diseases, such as skin disorders.