Colour stability of anthocyanins in aqueous solutions at various pH values

This study focuses on the impact of anthocyanin structures such as 5-glucosidic substitution and aromatic acylation on anthocyanin, colour and stability at various pH values. Two concentrations (0.05 and 0.15 mM) of cyanidin 3-glucoside (1), cyanidin 3-(2″-glucosylglucoside)-5-glucoside (2), and cyanidin 3-(2″-(2^′′′-sinapoylglucosyl)-6″-sinapoylglucoside)-5-glucoside (3) in aqueous solutions were studied at fourteen pH levels between 1.1 and 10.5 during a 98 day period at 10 °C. The three pigments represent the structural variation of many anthocyanins isolated from fruits and vegetables. Colours were expressed by the CIELAB coordinates h_ab, (hue angle), C^* (chroma=saturation), and L^* (lightness), as well as by visible absorption maxima (λ_max) and molar absorption coefficients (ε). Limitations of using only spectral parameters, such as λ_max and ε, to express colour variations, were revealed. Pigment 2 was more unstable than 1 at most pH values, showing lower C^* and higher L^* values after storage for only hours in neutral and weakly acid solutions. Pigment 3 showed higher colour stability than the nonacylated forms at all pH values but pH 1.1, where all pigments retained their colours in the storage period, and in the most alkaline solutions, where all pigments experienced dramatic colour changes. Of potential importance for some food products, in solutions with pH 4.1 and 5.1, 3 maintained nearly the same h_ab, C^*, and L^* values during the whole measuring period (98 days), in contrast to pigments 1 and 2. The hue angle shift towards bluish tones in freshly made samples of anthocyanins with 5-glucosidic substitution, were amplified with aromatic acylation (3) throughout the entire pH range except pH 10.5. The variations in the results emphasizes the importance of structure for anthocyanin properties in fresh and processed fruits and vegetables.     

Isolation,characterization, and neuroprotective activities of sesquiterpenes from Petasites japonicus

Neuroprotective reagents to protect the nerve cells against oxidative stress and other damages are potentially effective for the medical treatment of Parkinson’s disease. Petasites japonicus, a wild vegetable, belongs to the family Compositae and its extract has shown the neuroprotective effects. A further phytochemical investigation of P. japonicus for neuroprotective substances led to the isolation of eight new (1–8) and two known (9 and 10) sesquiterpenes. Their structures were elucidated on the basis of extensive 1D and 2D NMR (HMQC, HMBC, ¹H–¹H COSY, and NOESY) spectroscopic data analyses, and the structure of 1 was confirmed by X-ray crystallography. The neuroprotective activities of these sesquiterpenes were evaluated against cobalt chloride (CoCl₂)-induced neuronal cell death in human dopaminergic SH-SY5Y cells. Five compounds showed a neuroprotective activity.     

Phenolic antioxidants from Chinese toon (fresh young leaves and shoots of Toona sinensis)

Chinese toon (the fresh young leaves and shoots of Toona sinensis), known as a tree vegetable, belongs to the family of Meliaceae. It is one of the most popular vegetables in China. The 80% acetone extract of Chinese toon exhibited considerable antioxidant activity in the 1,1-diphenyl-2-picryldydrazyl (DPPH) radical-scavenging assay. Bioassay-guided purification of the extract led to the isolation of 12 phenolic compounds (1–12), whose structures were determined by detailed spectroscopic analyses, including UV, IR, MS, 1D and 2D NMR techniques. Of them, compounds 3–8 and 11 were isolated from T. sinensis for the first time. All of the isolated compounds were examined for their antioxidant activities by the DPPH method, and the results showed that gallic acid and its derivatives, gallotannins and flavonoids were the main constituents contributing to the antioxidant activity of Chinese toon. From the health point of view, Chinese toon is an ideal dietary vegetable with natural antioxidants.     

Isolation and identification of 5-carboxy-pyranoanthocyanins in beverages from cherry (Prunus cerasus L.)

Novel pyranoanthocyanins were identified by HPLC–ESI-MSⁿ in fermented and unfermented fruit juices from cherry (Prunus cerasus L.). The two major compounds, namely 5-carboxy-pyranocyanidin 3-O-(2^G-glucosylrutinoside) and 5-carboxy-pyranocyanidin 3-O-rutinoside were isolated by a combination of high-speed countercurrent chromatography with semi-preparative HPLC. Their structures were fully elucidated by means of NMR spectroscopy and mass spectrometry. As minor compounds 5-carboxy-pyranocyanidin 3-glucoside, 5-carboxy-pyranopeonidin-3-glucoside, and 5-carboxy-pyranopeonidin 3-rutinoside could be identified.These compounds are formed during storage of the juice through the reaction of pyruvic acid with the respective genuine anthocyanins.Industrial relevanceFor the consumers the color of fruit juices is one of the most important quality markers. However due to a fast degradation of anthocyanins, changes in color from purple/red hues to orange/brown hues can be observed during storage. The main objective of this study was the isolation, structural characterization and evaluation of pigments that are formed during aging of fruit juices. Pyranoanthocyanins were reported to possess a color stabilizing effect. In the present study it could be demonstrated that the color contribution of these newly formed pigments to the overall color of fruit juice was overestimated. Instead, the formation of polymeric pigments yields the highest impact (> 80%) on the color of aged fruit juices.     

New phragmalin-type limonoids from Swietenia macrophylla King

The fruit of Swietenia macrophylla is commonly known as “sky fruit”. The fruit, which contains flavonoids and saponins, is processed commercially into a wide range of health foods and healthcare products. The fruit concentrate is used traditionally to improve blood circulation and impart a healthy skin. In this paper, we describe the isolation and structure elucidation of three new phragmalin ortho esters, named swietephragmin H-J (1–3), and a new polyhydroxylated phragmalin, named swietemacrophine (4), from the leaves of S. macrophylla. The structures of the compounds were elucidated by spectroscopic methods, including HRESIMS, ¹H NMR, ¹³C NMR, DEPT, ¹H–¹H COSY, HMQC, HMBC and NOESY spectra. This is the first report of phragmalin ortho esters and a polyhydroxylated phragmalin from this plant.     

TLC bioautography-guided isolation of antioxidants from fruit of Perilla frutescens var. acuta

Guided isolation through bioautography on TLC using 1,1-diphenyl-2-picryl-hydrazyl radical (DPPH) as a detection reagent led to the isolation of four antioxidant compounds from fruit of Perilla frutescens var. acuta. These compounds were identified as rosmarinic acid (1), luteolin (2), apigenin (3), and chrysoeriol (4), by means of UV, NMR, and ESI MS. All the compounds were isolated for the first time from the fruit of the plant. Compounds 1 and 2 showed significant DPPH scavenging capacities, with IC₅₀ values of 8.61 and 7.50 μM, respectively. Further quantitative HPLC analysis confirmed that compounds 1-4 are the predominant contributors to the free radical scavenging activity of the extract of P. frutescens var. acuta.     

Antioxidant polyketide phenolic metabolites from the edible mushroom Cortinarius purpurascens

Phytochemical investigation of the ethyl acetate extract of the edible macrofungus, Cortinarius purpurascens, led to the isolation of nine anthraquinone-related pigments, citreorosein 6,8-dimethyl ether (1), physcione (2), rufoolivacin (3), rufoolivacin C (4), rufoolivacin D (5), leucorufoolivacin (6), verbindung cr11 (7), verbindung cr60 (8) and 1-Hydroxy-3-methyl-2-isopropanyl-6,8-dimethoxyanthraquinone (9). The structures of these isolated compounds were characterised by spectroscopic methods and comparison with published data. Among the tested compounds, 3–6 exhibited potent DPPH radical-scavenging activity with IC₅₀ values in the range of 3–8 μg/ml. The results indicated that the fungus is a possible source of natural products with potential antioxidant activity.     

Studies on the antioxidant potential of flavones of Allium vineale isolated from its water-soluble fraction

The aim of this work was to examine the chemical constituents and antioxidant potential of water-soluble fractions from the commonly consumed vegetable, Allium vineale. The water-soluble fraction, containing phenolic compounds, was extracted with ethyl acetate to obtain flavonoids which were separated and purified by repeated column chromatography over Sephadex LH-20, RP C18 and silica gel. The isolated compounds were identified according to their physicochemical properties and spectral data (UV, HPLC–TOF/MS, ¹H NMR, ¹³C NMR and 2D NMR). Three flavonoids were isolated and identified as chrysoeriol-7-O-[2″-O-E-feruloyl]-β-d-glucoside (1), chrysoeriol (2), and isorhamnetin-3-β-d-glucoside (3). Antioxidant studies of the aqueous extract and three isolated compounds, 1, 2, 3, were undertaken and they were found to have significant antioxidant activity. Antioxidant activities were evaluated for total antioxidant activity by the ferric thiocyanate method, ferric ion (Fe³⁺) reducing antioxidant power assay (FRAP), ferrous ion (Fe²⁺) metal chelating activity, and DPPH free radical-scavenging activity. The water-soluble ethyl acetate and methanol extraction methods were also compared using HPLC–TOF/MS.     

Two flavanone compounds from litchi (Litchi chinensis Sonn.) seeds,one previously unreported,and appraisal of their α-glucosidase inhibitory activities

Using a bioactivity-guided method, a new and a previously reported flavanone glycoside were isolated from 50% ethanol extract of litchi (Litchi chinensis Sonn.) seeds. Column chromatography using macroporous resin, silica gel and Sephadex LH-20 was applied during the isolation, and the method of PMP derivatisation was performed to investigate the component sugar of the compounds. The structures of the compounds were elucidated by ¹H, ¹³C, and 2D NMR (HMQC, HMBC) spectroscopy and HR-ESIMS. Compound 1 was identified as (2R)-naringenin-7-O-(3-O-α-l-rhamnopyranosyl-β-d-glucopyranoside), a new, natural product that had been synthesised previously. Compound 2 was (2S)-pinocembrin-7-O-(6-O-α-l-rhamnopyranosyl-β-d-glucopyranoside). The two isolated compounds showed activity in the α-glucosidase inhibition assay.     

Biguaiascorzolides A and B: Two novel dimeric guaianolides with a rare skeleton,from Scorzonera austriaca

The root of Scorzonera austriaca has been used in indigenous cuisines as a delicious food and in the Tibetan traditional medicine in northwestern China. Two novel dimeric guaianolides linked by a carbon–carbon bond with a rare carbon skeleton, termed biguaiascorzolides A (1) and B (2), respectively, have been isolated from roots of S. austriaca. Acetylation of 1 gave 1a. The structures of 1, 1a and 2 were characterised by HR-ESI-MS, EI-MS, UV, IR, and 1D- and 2D-NMR techniques (¹H and ¹³C NMR, ¹H-¹H COSY, HMQC, HMBC, and NOESY experiments). The cytotoxicity of 1a was assayed against selected cancer cell lines, including the human erythroleukaemia adriamycin-resistant subline (K562/ADM) and human stomach carcinoma (MGC-803) cell lines. Compound 1a exhibits a moderate activity against K562/ADM cell lines (IC₅₀ 39.8 μm) and is inactive towards MGC-803 cell lines.     

Evaluation of Asian salted noodles in the presence of Amaranthus betacyanin pigments

The effect of betacyanin pigments from Amaranthus tricolor on the functional properties and colour of wheat flour in relation to the quality of Asian salted noodles was studied. Addition of Amaranthus pigments significantly decreased the viscosity of wheat flour pastes as well as hardness and adhesiveness of the gels. Low levels of Amaranthus pigments (0.1% and 0.5%) imparted a more pink shade to flour gels, dried raw noodles, and cooked noodles, whereas higher levels (1.0% and 2.0%) gave a more red shade with decreased brightness. Pigment addition at low levels had no significant effect on the cooking and textural properties of noodles, whereas high level (2.0%) did have a significant influence. Several RVA and textural parameters of wheat flour pastes and gels were highly correlated to quality of cooked noodles and may be used in predicting actual noodle quality in the presence of Amaranthus pigments.     

Antioxidant activity of a new phenolic glycoside from Lagenaria siceraria Stand. fruits

The antioxidant properties of different extracts of Lagenaria siceraria (bottle gourd) fruit were evaluated. In the process, a new phenolic glycoside (E)-4-hydroxymethyl-phenyl-6-O-caffeoyl-β-d-glucopyranoside (1) was isolated and identified together with 1-(2-hydroxy-4-hydroxymethyl)-phenyl-6-O-caffeoyl-β-d-gluco-pyranoside (2), protocatechuic acid (3), gallic acid (4), caffeic acid (5) and 3,4-dimethoxy cinnamic acid (6). Their structures were elucidated by extensive NMR experiments including ¹H-¹H (COSY) and ¹H-¹³C (HMQC and HMBC) spectroscopy and chemical evidences. The antioxidant potential of the compound 1 and 2 was tested in different in vitro assay systems such as free radical scavenging assay, 3-(4,5-dimethylthiazole-2-yl)-2,5-diphenyltetrazolium bromide (MTT) reduction assay, superoxide scavenging activity, reducing power assay and linoleic acid peroxidation assay.     

Authenticity assessment of 2- and 3-methylbutanol using enantioselective and/or 13C/12C isotope ratio analysis

Enantioselective gas chromatography and/or ¹³C/¹²C isotope ratio analysis are suitable tools for the authenticity assessment of the fusel alcohols, 2- and 3-methylbutanol (1 and 2, respectively). The chiral compound, 1 is biosynthesised almost completely as the (S)-enantiomer, regardless of which carbohydrate source is used for fermentation. The type of CO₂ fixation and some plant-specific influences were of prime importance to the ¹³C/¹²C isotope ratios of the starting materials in alcoholic fermentation, and the δ¹³C values of 1 and 2 differed significantly. In general, the δ¹³C values of 2 were about 4–5ö lower than those of 1 produced via the same fermentation process. ¹³C/¹²C isotope ratio analysis results can be used to determine between fusel alcohols produced from different sources, and provides a new and valuable method of authenticity assessment.     

Studies on cytotoxic triterpene saponins from the leaves of Aralia elata

Aralia elata has long been used as a tonic, anticancer and antidiabetic agent in China and Japan, and is widely consumed as food. Phytochemical investigation of the leaves of A. elata has led to the isolation of four new compounds, 3-O-[β-d-glucopyranosyl(1 → 3)-β-d-glucopyranosyl] echinocystic acid 28-O-β-d-glucopyranosyl ester (congmuyenoside I, 1), 3-O-[β-d-glucopyranosyl(1 → 2)-β-d-glucopyranosyl] hederagenin 28-O-β-d-glucopyranosyl ester (congmuyenoside II, 2), 3-O-{[β-d-glucopyranosyl(1 → 2)]-[β-d-glucopyranosyl(1 → 3)-β-d-glucopyranosyl(1 → 3)]-β-d-glucopyranosyl} echinocystic acid 28-O-β-d-glucopyranosyl ester (congmuyenoside III, 3) and 3-O-β-d-glucopyranosyl caulophyllogenin 28-O-β-d-glucopyranosyl ester (congmuyenoside IV, 4), and eight known triterpene saponins (5–12). The structural determination was accomplished with spectroscopic analysis, in particularly ¹³C NMR, 2D NMR and HR-ESI-MS techniques. In addition, compounds 5–10 were found for the first time in the genus Aralia. Compounds 1–12 were tested for their inhibition of the growth of HL60, A549 and DU145 cancer cells. In addition, compound 8 showed significant cytotoxic activities against HL60, A549 and DU145 cancer cells with IC₅₀ values of 15.62, 11.25 and 7.59 μM, respectively.     

Terpenoids from Stinking toe (Hymneae courbaril) fruits with cyclooxygenase and lipid peroxidation inhibitory activities

Stinking toe (Hymenaea courbaril), also called Jatoba and Kerosene tree, is a medicinal plant commonly found in the central and South American countries. In the Caribbean, Mexico and Brazil, the powdery sweet dust of its fruit is consumed for energy. The chemical examination of the yellowish sweet powder of the fruit yielded sucrose and linolenic acid as major compounds. The pods yielded the labdane diterpenoids crotomachlin (1), labd-13E-en-8-ol-15-oic acid (2), labdanolic acid (4), (13E)-labda 7, 13 dien-15-oic acid (5) and labd-8 (17), 13E- dien-15-oic acid (6), along with the sesquiterpene, spathulenol (7), as confirmed by ¹H and ¹³C NMR spectral studies. The methyl ester of labd-13E-en-8-ol-15-oic acid (3) was also characterized during the purification of compound 5. The total amount of these terpenoids in the fruit was about 0.1% (w/w) of the dried fruit. Compounds 1–5 and 7 were assayed for anti-inflammatory activity using cyclooxygenase-1 (COX-1) and -2 (COX-2) enzymes. At 100 ppm, compounds 3 and 4 showed selective COX-2 enzyme inhibition. Also, compounds 1, 2 and 5 inhibited lipid peroxidation by 46%, 48% and 75%, respectively, at 100 ppm. These compounds were isolated from this fruit and their COX and lipid peroxidation inhibitory activities are reported for the first time in this paper.     

Application of high resolution NMR,FTIR, and GC–MS to a comparative study of some indigenous seed oils from Botswana

Spectroscopic techniques utilizing FTIR, ¹H and ¹³C NMR spectral fingerprints of the neat oils, as well as standard titrimetric and GC–MS analyses were all employed to determine the quality parameters and fatty acid (FA) profiles for Soxhlet-extracted seed oils of four indigenous plants from Botswana: Tylosema esculentum (morama), Schinziophyton rautanenii (mungongo), Citrullus lanatus (kgengwe) and Bauhinia petersiana (mogose). The physicochemical parameters and FA composition obtained from spectroscopic methods were found to be similar to those obtained from classical procedures indicating that oil quality parameters can reliably be obtained from spectroscopic data. The FA analysis showed the presence of 73–84% unsaturated FAs in the four seed oils. In addition, spectroscopic data clearly established the presence of the uncommon tri-unsaturated FA, α-eleostearic acid (α-ESA) in mungongo seed oil which was quantified as 25% by ¹³C NMR. Generally, the high levels of unsaturated FAs in the oils indicate their suitability in health food supplements.Industrial relevanceThe four plants studied are highly treasured in the areas where they grow due to the fact that they have for centuries provided food security, and means of livelihood for populations living in the Kalahari Desert and other marginal regions of the southern Africa region. Currently, there is a drive to add value to such often underutilized plants to aid in poverty alleviation by processing and marketing the products as healthy food supplements or cosmetic formulations. To this end, reliable methods for characterization and comparison of the FA composition of the seed oils from different geographical locations is required. The development of rapid, non-destructive spectroscopic techniques that can be applied directly on the neat oils is therefore an important venture.     

Effect of pulsed electric fields (PEFs) on the pigments extracted from spinach (Spinacia oleracea L.)

In order to investigate the effect of PEF on the pigments of spinach, pigments were extracted and were treated by different electric field strength at different temperatures (20, 35 and 45 °C). Results showed that with the increasing temperature, the degradation of chlorophyll content was appeared for pigments without PEF treatment. However, the concentrations of chlorophyll a, b and carotenoids were increased by the PEF treatment, especially for the higher electric field strength. Moreover, the structure of spinach pigments treated by PEF also was determined by UV–Vis, FT-IR and XRD. From the structural information, it was indicated that the effect of PEF treatment mainly focused on the hydrogen bonds and the pyrrole ring of chlorophyll, as well as the crystal structure of the compound was modified. In addition, the PEF treatment also significantly increased the antioxidation activity of pigments over the series of temperatures.Industrial relevanceThis study provide evidences that the PEF treatment can inhibit the degradation of chlorophyll and carotenoids, and can increase the antioxidation activity of extraction solution compared to the thermal treatment. From the structural information, it was indicated that PEF can promote the crosslink reaction with other chlorophyll moleculars, and formed the chlorophyll-aggregated structures, such as dimers and oligomers chlorophyll. Therefore, the PEF treatment is an efficient food processing method, especially foods rich in pigment.     

Different postharvest strategies to preserve broccoli quality during storage and shelf life: Controlled atmosphere and 1-MCP

Broccoli (Brassica oleracea var. italica) is a vegetable that requires the application of postharvest techniques to extend its marketability. Controlled atmosphere and 1-MCP treatments are most used to extend the shelf life of broccoli and reduce post-harvest deterioration. The aim of this study was to evaluate the visual, physicochemical and functional changes of broccoli head samples stored at 1–2 °C and 85–90% relative humidity (RH) in air (Control samples), under controlled atmospheres (10% O₂ and 5% CO₂) (CA samples) and treated with 1-MCP (0.6 μL/L). After storage all samples were maintained at 20 °C for 2 and 4 days, in order to assess their shelf life. The most suitable postharvest treatment to extend broccoli quality during storage and shelf life, in terms of maintaining the visual quality and reducing loss of health-promoting compounds, was achieved by storage under controlled atmosphere conditions. The use of 1-MCP reduced the loss of green colour and chlorophyll pigments, but only during cold storage not during shelf life at 20 °C.     

Microbial adherence to cosmetic contact lenses

AimTo investigate whether cosmetic contact lenses (CCL) with surface pigments affect microbial adherence.MethodFifteen brands of CCL were purchased from optical, non-optical retail outlets, and via the Internet. A standardized rub-off test was performed on each CCL (five lenses per brand) to confirm the location of the pigments. The rub-off test comprised gentle rubbing on the surfaces of each CCL with wetted cotton buds for a maximum of 20 rubs per surface. A new set of CCL (five lenses per brand) were incubated in Pseudomonas aeruginosa overnight. Viable counts of adhered bacteria were determined by the number of colony-forming units (CFU) on agar media on each lens. The adherence of P. aeruginosa as well as Staphylococcus aureus and Serratia marcescens to three brands of CCL (A–C) (five lenses per brand) were also compared to their adherences on their clear counterparts.ResultsOnly two of the 15 brands of CCL tested (brands B and C) had pigments that did not detach with the rub-off test. The remaining 13 brands of CCL all failed the rub-off test and these lenses showed higher P. aeruginosa adherence (8.7 × 10⁵–1.9 × 10⁶ CFU/lens). Brands B and C lenses showed at least six times less bacterial adhesion than the other 13 brands. Compared to their clear counterparts, bacterial adherence to brands B and C lenses did not differ significantly, whereas brand A lenses showed significantly higher adherence.ConclusionSurface pigments on CCL resulted in significantly higher bacterial adherence.     

Effects of senofilcon A and lotrafilcon B bandage contact lenses on epithelial healing and pain management after bilateral photorefractive keratectomy

PurposeThe purpose of this study was to compare postoperative epithelial healing time and ocular discomfort score in patients wearing two types of silicon hydrogel bandage contact lenses (BCLs) following bilateral photorefractive keratectomy (PRK).MethodsFor the study’s contralateral eye comparison, 43 patients who underwent bilateral PRK were randomized to be fitted for a senofilcon a lens in one eye and a lotrafilcon B lens in the other. The patients were masked to the specific BCL in each eye. On the first 3 days after PRK, the epithelial defect size was calculated, and patients reported their level of ocular discomfort, including pain, epiphora, and photophobia, on a visual analog scale (0 = no pain or discomfort, 10 = highest level of pain and discomfort).ResultsEpithelial defect size (mm²) did not differ significantly between the BCLs on Day 1 (senofilcon A vs. lotrafilcon B: 14.15 ± 5.59 vs. 14.93 ± 5.72, p = .327), Day 2 (senofilcon A vs. lotrafilcon B: 7.43 ± 4.67 vs. 7.04 ± 3.82, p = .586), or Day 3 (senofilcon A vs. lotrafilcon B: 0.59 ± 1.44 vs. 0.38 ± 1.08, p = .348) postoperation. By Day 3, re-epithelialization was complete in 35 eyes (81.3%) with senofilcon A lenses and 36 eyes (83.7%) with lotrafilcon B lenses. Patients reported less pain in eyes with senofilcon A lenses during the first 3 days postoperation (for all, p < .001) and less epiphora during the first 2 days postoperation (Day 1: p = .008, Day 2: p < .001, Day 3: p = .267) than in eyes with lotrafilcon B lenses. No significant difference in photophobia emerged between the BCLs postoperatively (for all, p > .05).ConclusionsAlthough duration of corneal re-epithelialization after PRK between the two BCLs did not differ significantly, senofilcon A lenses caused significantly less pain and epiphora after PRK.