Citrus essential oil of Nigeria. Part V: Volatile constituents of sweet orange leaf oil (Citrus sinensis)

The volatile oils extracted from leaves of eight cultivars of Citrus sinensis (L) Osbeck were comprehensively analysed by a combination of GC and GC-MS. Fifty four constituents accounting for 82.3-98.2% were identified. Sabinene (20.9-49.1%), delta-3-carene (0.3-14.3%), (E)-beta-ocimene (4.4-12.6%), linalool (3.7-11.1%) and terpinen-4-ol (1.7-12.5%) were the major constituents that are common to all the volatile oils. In addition, a cluster analysis was carried out and indicated at least four different chemotypes for the C. sinensis cultivars.     

Characterization of aroma active compounds in fruit juice and peel oil of Jinchen sweet orange fruit (Citrus sinensis (L.) Osbeck) by GC-MS and GC-O

Gas chromatography-mass spectrometry (GC-MS) and gas chromatography-olfactometry (GC-O) were used to determine the aromatic composition and aroma active compounds of fruit juice and peel oil of Jinchen sweet orange fruit. Totals of 49 and 32 compounds were identified in fruit juice and peel oil, respectively. GC-O was performed to study the aromatic profile of Jinchen fruit juice and peel oil. A total of 41 components appeared to contribute to the aroma of fruit juice and peel oil. Twelve components were the odorants perceived in both samples. The aromatic compositions of fruit juice were more complex than that of peel oil. Ethyl butanoate, beta-myrcene, octanal, linalool, alpha-pinene, and decanal were found to be responsible for the aromatic notes in fruit juice and peel oil. Nineteen components have been perceived only in the juice and ten compounds were described as aromatic components of only the peel oil by the panelists. These differences lead to the different overall aroma between fruit juice and peel oil.     

The phytochemical analysis and antioxidant activity assessment of orange peel (Citrus sinensis) cultivated in Greece-Crete indicates a new commercial source of hesperidin

The flavonoid content of several methanolic extract fractions of Navel orange peel (flavedo and albedo of Citrus sinensis) cultivated in Crete (Greece) was first analysed phytochemically and then assessed for its antioxidant activity in vitro. The chemical structures of the constituents fractionated were originally determined by comparing their retention times and the obtained UV spectral data with the available bibliographic data and further verified by detailed LC-DAD-MS (ESI+) analysis. The main flavonoid groups found within the fractions examined were polymethoxylated flavones, O-glycosylated flavones, C-glycosylated flavones, O-glycosylated flavonols, O-glycosylated flavanones and phenolic acids along with their ester derivatives. In addition, the quantitative HPLC analysis confirmed that hesperidin is the major flavonoid glycoside found in the orange peel. Interestingly enough, its quantity at 48 mg/g of dry peel permits the commercial use of orange peel as a source for the production of hesperidin. The antioxidant activity of the orange peel methanolic extract fractions was evaluated by applying two complementary methodologies, DPPH(*) assay and the Co(II)/EDTA-induced luminol chemiluminescence approach. Overall, the results have shown that orange peel methanolic extracts possess moderate antioxidant activity as compared with the activity seen in tests where the corresponding aglycones, diosmetin and hesperetin were assessed in different ratios.     

Clinical evaluation of Moro (Citrus sinensis (L.) Osbeck) orange juice supplementation for the weight management

In the last years, several studies have recently evaluated the beneficial effects of red orange juice (Citrus sinensis (L.) Osbeck) and its active components in weight management and obesity. Moro orange is a cultivar of red orange, particularly rich in active compounds such as anthocyanins, hydroxycinnamic acids, flavone glycosides and ascorbic acid, which displays anti-obesity effects in in vitro and in vivo studies. In this clinical study, the effect of a Moro juice extract (Morosil^®, 400 mg/die) supplementation was evaluated in overweight healthy human volunteers for 12 weeks. Results showed that Moro juice extract intake was able to induce a significant reduction in body mass index (BMI) after 4 weeks of treatment (p < 0.05). Moreover, in subjects treated with Moro extract, body weight, BMI, waist and hip circumference were significantly different from the placebo group (p < 0.05). In conclusion, it could be suggested that the active compounds contained in Moro juice have a synergistic effect on fat accumulation in humans and Moro juice extract can be used in weight management and in the prevention of human obesity.     

Analysis of antioxidant compounds in sweet orange peel by HPLC-diode array detection-electrospray ionization mass spectrometry

HPLC-diode array detection-electrospray ionization mass spectrometry was used to determine qualitatively and quantitatively the flavonoid content of several fractions and residues of extracts of Greek navel sweet orange peel (Citrus sinensis) from the region of southern Greece (Leonidi-Tripoli). The main groups of flavonoids found according to HPLC retention times, spectral data and literature references were polymethoxylated flavones, C-glycosylated flavones, O-glycosylated flavones, O-glycosylated flavanones, flavonols and phenolic acids and their derivatives. The ethyl acetate fraction which has been shown in previous work to possess the best radical scavenging activity among the others was found to contain C-glycosylated flavones, polymethoxylated flavones, O-glycosylated flavones, O-glycosylated flavanones, two phenolic acid derivatives and two unknown compounds, all in low concentrations. The group of C-glycosylated flavones was reported for the first time in the peel of Navel sweet orange. The C-glycosylated flavones found according to their spectral characteristics and literature were 6-C-beta-glucosyldiosmin, 6,8-di-C-glucopyranosylapigenin, 6,8-di-C-beta-glucosyldiosmin and two unknown. The results suggest that the ethyl acetate fraction of navel Citrus sinensis peel consists of significant antioxidant compounds and can be used as a food additive of natural origin or a pharmaceutical supplement using as a source of peel the byproducts of the orange juice industry.     

Thermo-kinetics study of orange peel in air

Thermal degradation of orange peel was studied in dynamic air atmosphere by means of simultaneous TG-DSC and TG-FTIR analysis. According to the obtained thermal profiles, the orange peel degradation occurred in at least three steps associated with its three main components (hemicellulose, cellulose and lignin). The volatiles compounds evolved out at 150–400 °C and the gas products were mainly CO₂, CO, and CH₄. A mixture of acids, aldehydes or ketones C=O, alkanes C–C, ethers C–O–C and H₂O was also detected. The E _α on α dependence reveled the existence of different and simultaneous processes suggesting that the combustion reaction is controlled by oxygen accessibility, motivated by the high evolution low-molecular-mass gases and volatile organic compounds. These results could explain the non-autocatalytic character of the reactions during the decomposition process.     

Insecticidal activity against Bemisia tabaci biotype B of peel essential oil of Citrus sinensis var. pear and Citrus aurantium cultivated in northeast Brazil

The fumigant action of peel essential oils of Citrus sinensis var. pear (pear orange = PO) and C. aurantium (bitter orange = BO) from the northeast of Brazil were evaluated against Bemisia tabaci biotype B and compared with eugenol as a positive control. The oil concentration in the PO at 8.5 microL/L of air caused 97% mortality, while the oil concentration of BO at 9.5 microL/L of air caused 99% mortality. However, the LC50 estimates for both oils (LC50 = 3.80 microL/L of air for PO and LC50 = 5.80 microL/L of air for BO) did not differ from each other, but they did when compared with eugenol (LC50 = 0.20 microL/L of air). Regarding their effects on oviposition, the Citrus oils showed concentration-response dependence, reducing the number of eggs as the concentration increased, which was not observed for eugenol. The minimum concentrations of the oils that caused a significant reduction in the egg lay were 3.5 and 7.0 microL/L of air for BO and PO, respectively. These results suggest that oils from PO and BO peels may be promising as models to develop new insecticides that might be applied into the integrated management of whiteflies.     

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

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

Cyanex272功能化的橘子皮对Cd(Ⅱ)的吸附动力学和热力学

本文采用橘皮(OP)吸附剂从水介质中去除Cd(Ⅱ).用萃取剂Cyanex272对生物质进行预处理活化,找到了去除Cd(Ⅱ)的最佳操作条件.通过用几种模型拟合实验数据后,发现最佳拟合模型为Langmuir模型和准二级动力学模型.不同吸附剂对Cd(Ⅱ)的吸附量顺序依次为272SCO>SCO>272CO>272OP>CO>OP.272SCO的最大吸附量为0.8663mol·g^-1,Cd(Ⅱ)的吸附量严格依赖于pH,所有吸附剂的最适合pH范围为5.5~6.0.对于吸附剂的再生,以0.1mol·L^-1 HCl为最佳解吸剂,解吸率接近100%.萃取剂Cyanex 272预处理后的橘皮可作为一种高效、低成本的吸附剂,用于去除水溶液中的镉.     

Biomimetic preparation of polymer-supported free radical scavenging, cytocompatible and antimicrobial "green" silver nanoparticles using aqueous extract of Citrus sinensis peel

In the pursuit of making the nanoscale-research greener, the utilization of the reductive potency of a common byproduct of food processing industry i.e. orange peel is reported here to prepare biopolymer-templated "green" silver nanoparticles. Aqueous extract of orange peel at basic pH was exploited to prepare starch supported nanoparticles under ambient conditions. The compositional abundance of pectins, flavonoids, ascorbic acid, sugars, carotenoids and myriad other flavones may be envisaged for the effective reductive potential of orange peel to generate silver nanoparticles. The nanoparticles were distributed within a narrow size spectrum of (3-12 nm) with characteristic Bragg's reflection planes of fcc structure, and surface plasmon resonance peak at 404 nm. Anti-lipid peroxidation assay using goat liver homogenate and DPPH scavenging test established the anti-oxidant potency of the silver nanoparticles. Their synergy with rifampicin against Bacillus subtilis MTCC 736 and cytocompatibility with the human leukemic monocytic cell line, THP-1 were also investigated. Thus, the present work deals with the preparation of starch assisted anti-microbial, cytocompatible and free radical scavenging "green" silver nanoparticles.     

Effects of Citrus aurantium (bitter orange) fruit extracts and p-synephrine on metabolic fluxes in the rat liver

The fruit extracts of Citrus aurantium (bitter orange) are traditionally used as weight-loss products and as appetite supressants. An important fruit component is p-synephrine, which is structurally similar to the adrenergic agents. Weight-loss and adrenergic actions are always related to metabolic changes and this work was designed to investigate a possible action of the C. aurantium extract on liver metabolism. The isolated perfused rat liver was used to measure catabolic and anabolic pathways, including oxygen uptake and perfusion pressure. The C. aurantium extract and p-synephrine increased glycogenolysis, glycolysis, oxygen uptake and perfusion pressure. These changes were partly sensitive to α- and β-adrenergic antagonists. p-Synephrine (200 μM) produced an increase in glucose output that was only 15% smaller than the increment caused by the extract containing 196 μM p-synephrine. At low concentrations the C. aurantium extract tended to increase gluconeogenesis, but at high concentrations it was inhibitory, opposite to what happened with p-synephrine. The action of the C. aurantium extract on liver metabolism is similar to the well known actions of adrenergic agents and can be partly attributed to its content in p-synephrine. Many of these actions are catabolic and compatible with the weight-loss effects usually attributed to C. aurantium.     

Adsorption/desorption of Cd(II), Cu(II) and Pb(II) using chemically modified orange peel: Equilibrium and kinetic studies

Waste materials from industries such as food processing may act as cost effective and efficient biosorbents to remove toxic contaminants from wastewater. This study aimed to establish an optimized condition and closed loop application of processed orange peel for metals removal. A comparative study of the adsorption capacity of the chemically modified orange peel was performed against environmentally problematic metal ions, namely, Cd²⁺, Cu²⁺ and Pb²⁺, from aqueous solutions. Chemically modified orange peel (MOP) showed a significantly higher metal uptake capacity compared to original orange peel (OP). Fourier Transform Infrared (FTIR) Spectra of peel showed that the carboxylic group peak shifted from 1637 to 1644 cm⁻¹ after Pb (II) ions binding, indicated the involvement of carboxyl groups in Pb(II) ions binding. The metals uptake by MOP was rapid and the equilibrium time was 30 min at constant temperature and pH. Sorption kinetics followed a second-order model. The mechanism of metal sorption by MOP gave good fits for Freundlich and Langmuir models. Desorption of metals and regeneration of the biosorbent was attained simultaneously by acid elution. Even after four cycles of adsorption-elution, the adsorption capacity was regained completely and adsorption efficiency of metal was maintained at around 90%.     

Discrimination of Genetically Very Close Accessions of Sweet Orange (Citrus sinensis L. Osbeck) by Laser-Induced Breakdown Spectroscopy (LIBS)

The correct recognition of sweet orange (Citrus sinensis L. Osbeck) variety accessions at the nursery stage of growth is a challenge for the productive sector as they do not show any difference in phenotype traits. Furthermore, there is no DNA marker able to distinguish orange accessions within a variety due to their narrow genetic trace. As different combinations of canopy and rootstock affect the uptake of elements from soil, each accession features a typical elemental concentration in the leaves. Thus, the main aim of this work was to analyze two sets of ten different accessions of very close genetic characters of three varieties of fresh citrus leaves at the nursery stage of growth by measuring the differences in elemental concentration by laser-induced breakdown spectroscopy (LIBS). The accessions were discriminated by both principal component analysis (PCA) and a classifier based on the combination of classification via regression (CVR) and partial least square regression (PLSR) models, which used the elemental concentrations measured by LIBS as input data. A correct classification of 95.1% and 80.96% was achieved, respectively, for set 1 and set 2. These results showed that LIBS is a valuable technique to discriminate among citrus accessions, which can be applied in the productive sector as an excellent cost–benefit tool in citrus breeding programs.     

Production of ethanol from enzymatically hydrolyzed orange peel by the yeastSaccharomyces cerevisiae

Applied Biochemistry and Biotechnology - We extended our previous investigations of enzymatic hydrolysis of polysaccharides in orange peel by commercial cellulase and pectinase enzymes to higher,...     

Pyrolysis of poly(vinyl chloride)

A pyrolysis–gas chromatography–mass spectrometric technique has been developed to study the thermal degradation of poly(vinyl chlorides) polymerized at different temperatures. Hydrogen chloride and benzene evolution during successive stages of pyrolysis have been quantitatively determined and correlated to the tacticity and molecular weight of the polymer. It was found that lowering the temperature of polymerization and molecular weight depresses benzene evolution and increases char weight but does not affect the HCl yield. It is suggested that the syndiotactic trans microstructure favored at low temperature of polymerization yields polyenes which cannot cyclize to form benzene. As the molecular weight decreases, the increase in number of vinyl chain ends facilitates pyrolytic crosslinking and char formation.     

High-performance liquid chromatography for the characterization of carotenoids in the new sweet orange (Earlygold) grown in Florida, USA

High-performance liquid chromatography with photodiode array detection was developed for the separation and identification of carotenoids from a new sweet orange, Earlygold. Carotenoid pigments were extracted using hexane-acetone-ethanol and saponified using 10% methanolic potassium hydroxide. More than 25 carotenoid pigments were separated within 40 min using a ternary gradient (acetonitrile-methanol, methyl tert-butyl ether and water) elution on a C30 reversed-phase column. The carotenoid pattern of Earlygold was generally similar to the early season Hamlin but with some quantitative differences, especially with violaxanthin. Major carotenoids including violaxanthin, lutein, beta-cryptoxanthin, antheraxanthin, luteoxanthin, zeaxanthin, beta-carotene, and alpha-carotene were identified based on on-line spectral data obtained by a photodiode array detector, and comparison to the spectra of the standards and reported values. A numerical notation, the ratio of the peak heights between absorption bands, was also calculated to compare to the literature values.     

An improved microwave Clevenger apparatus for distillation of essential oils from orange peel

Microwave Clevenger or microwave accelerated distillation (MAD) is a combination of microwave heating and distillation, performed at atmospheric pressure without added any solvent or water. Isolation and concentration of volatile compounds are performed by a single stage. MAD extraction of orange essential oil was studied using fresh orange peel from Valencia late cultivar oranges as the raw material. MAD has been compared with a conventional technique, which used a Clevenger apparatus with hydro-distillation (HD). MAD and HD were compared in term of extraction time, yields, chemical composition and quality of the essential oil, efficiency and costs of the process. Extraction of essential oils from orange peels with MAD was better in terms of energy saving, extraction time (30 min versus 3 h), oxygenated fraction (11.7% versus 7.9%), product yield (0.42% versus 0.39%) and product quality. Orange peels treated by MAD and HD were observed by scanning electronic microscopy (SEM). Micrographs provide evidence of more rapid opening of essential oil glands treated by MAD, in contrast to conventional hydro-distillation.     

Preparative separation of six coumarins from the pummelo (Citrus maxima (Burm.) Merr. Cv. Shatian Yu) peel by high-speed countercurrent chromatography

In this work, six coumarins, including two new ones, 8-(3-hydroxy-2,2-dimethylpropyl)-7-methoxy-2H-chromen-2-one (2) and 5-[(7′,8′-dihydroxy-3′,8′-dimethyl-2-nonadienyl)oxy] psoralen (4), as well as four known ones, 5-[(6′,7′-dihydroxy-3′,7′-dimethyl-2-octenyl) oxy] psoralen (1), marmin (3), epoxybergamottin (5), and aurapten (6) were successfully separated from the crude extract of pummelo (Citrus maxima (Burm.) Merr. Cv. Shatian Yu) peel by high-speed countercurrent chromatography in a single run with petroleum-ether–ethyl acetate–methanol–water (4:6:6:4, v/v). The structures of these six coumarins were elucidated by ESI-MS, extensive 1D and 2D NMR spectroscopy.