Pigment

In last few decades, there has been an increasing trend towards replacement of synthetic colorants with natural pigments because of the strong consumer demand for more natural products. Natural pigments and synthetic dyes have been extensively used in various fields of everyday life such as food production, textile industries, paper production, agricultural practices and researches, water science and technology. Natural pigments not only have the capacity to increase the marketability of products, they also display advantageous biological activities as antioxidants and anticancer agents. On the other hand, synthetic pigments cause considerably environmental pollution and adverse toxicological side effects. It is therefore, essential to explore various natural sources of food grade colorants and their use potentials. Use of microbial pigments in processed food is an area of promise with large economic potential. However, microbial pigments offer challenges due to high cost, lower stability and variation in shades due to changes in pH.

Human beings have had an inherent urge to leave their mark in the form of works of art since prehistoric times. This has driven the quest for new and better pigments with which to make paints. This paper describes the origins and composition of earliest earth pigments used by primitive man to decorate the walls of caves through to the synthetic pigments developed in more recent times. Despite modern technology, the artist's palette remains a mixture of the pigments used by cave artists, natural pigments used in the middle ages, and modern organic compounds.

Powerful categories of evidence for symbolically mediated behaviour, variously described as 'modern' or 'cognitively modern' human behaviour, are geometric or iconographic representations. After 40,000 years ago such evidence is well documented in much of the Old World and is widely considered as typifying 'modern human culture,' but earlier evidence is rare. In Africa, this includes two deliberately engraved ochre pieces from c. 75,000 year old levels at Blombos Cave, Western Cape, South Africa and the greater than 55,000 year old incised ostrich egg shell from the Diepkloof shelter, located in the same province. Here we report on thirteen additional pieces of incised ochre recovered from c. 75,000-100,000 year old levels at Blombos Cave. These finds, taken together with other engraved objects reported from other southern African sites, suggest that symbolic intent and tradition were present in this region at an earlier date than previously thought.

The date (Phoenix dactylifera L.), a high-energy fruit, is regarded as a popular food commodity for thousands of years in Egypt, the Arabian Gulf peninsula and its neighboring region. The aim of present study is to characterize the biochemical and nutritional values of constituents of the Egyptian date fruits. Date palm fruits contain a variety of B-complex vitamins B1, B2, Nicotinic acid and vitamin A. the date palm extracts contains 13.80 % moisture and 86.50 % total solid. Ash and Crud fibers contents were 2.13 and 5.20 respectively. Protein, carbohydrates and lipids contents were 3.00%, 73.00% and 2.90 % respectively. The low level of lipids content 2.90% compared with its content of sugars means that, the date palm is save to heart and blood patients because its containing a very low level of fatty acids and cholesterol. HPLC analysis of sugars content showed that, the carbohydrate content consists of a large amount of glucose, fructose and sucrose, The protein pattern on SDS-PAGE showed that, most of proteins in the date palm are a high molecular weight proteins between 80 and 135 KD and contained a minimum levels of the LMW proteins less than 55 KD. Date Palm contained high concentration of Aspartic acid, Proline, Glycine, Histidine, Valine, Leucine and Arginine, but low concentration of Threonine, Serine, Methionine, Isoleucine, Tyrosine, Phenylalanine and Lysine and very low concentration of Alanine. The date palm fruits provide unique functional and nutritional values. Numerous health benefits beyond its nutritional value have been associated with consuming date palm fruits to enrich nutrition values of different kinds of food.

This study characterizes biologically active compounds of berry fruits, including non-nutritive compounds such as phenolic compounds, including anthocyanins, phenolic acids, stilbens and tannins, as well as nutritive compounds such as carotenoids and vitamin C. It discusses the biological activity of those compounds, in particular their antioxidant properties and the resulting health benefits.

Clay minerals and iron oxides are intimately related in the process of their natural formation. Their mineralogical composition and physical properties correspond to the physical -chemical conditions of weathering, sedimentation and alteration processes by means of which these minerals are associated giving different types of laterites, ferrolites, ochres, and coloured clays and soils. Very early in human history, these and other clay materials were adopted as mineral pigments. Their structural and mineralogical features are directly related with their natural genesis and provenance and help us in the study of historical painting techniques and materials. This paper gives general information about geological sources and their characteristics, the literary evidence of use of different forms of earthy pigments on historical paintings, about analytical methods suitable in their identification within the ground and colour layers of the painting, and handling with the samples of works of art. The examples focused preferentially on the period of European mediaeval and baroque painting. D

Pomegranate (Punica granatum) bioactive compounds (polyphenols and anthocyanins) of juice (PJ) and ethanolic extracts (PE) were encapsulated with maltodextrin (MD) or soybean protein isolates (SPI) by spray drying using a 2 2 statistical factorial design for each systems studied (PJ-MD, PJ-SPI, PE-MD and PE-SPI) considering the proportion of coating material and the inlet temperature as independent variables. The stability of the bioactive compounds microcapsules powders obtained under optimal conditions for each system was studied at 60°C in oven for 56 days. The polyphenols encapsulating efficiency was significantly better in SPI matrix whereas for anthocyanins was in MD matrix. By the other hand, during the storage, the MD microcapsules provided a significant greater protective effect on the polyphenols and anthocyanins than SPI, as was shown by the lower degradation rate constants. When the microcapsules were added to yogurt the stability of the bioactive compounds followed a similar behaviour to those without encapsulation, except for PE-MD.

Fig fruit has been a typical component in the health-promoting Mediterranean diet for millennia. To study the potential health-promoting constituents of fig fruits, six commercial fig varieties differing in color (black, red, yellow, and green) were analyzed for total polyphenols, total flavonoids, antioxidant capacity, and amount and profile of anthocyanins. Using reversed-phase liquid chromatography (RP-LC), various concentrations of anthocyanins but a similar profile was found in all varieties studied. Hydrolysis revealed cyanidin as the major aglycon. Proton and carbon NMR confirmed cyanidin-3-O-rhamnoglucoside (cyanidin-3-O-rutinoside; C3R) as the main anthocyanin in all fruits. Color appearance of fig extract correlated well with total polyphenols, flavonoids, anthocyanins, and antioxidant capacity. Extracts of darker varieties showed higher contents of phytochemicals compared to lighter colored varieties. Fruit skins contributed most of the above phytochemicals and antioxidant activity compared to the fruit pulp. Antioxidant capacity correlated well with the amounts of polyphenols and anthocyanins (R 2 ) 0.985 and 0.992, respectively). In the dark-colored Mission and the red Brown-Turkey varieties, the anthocyanin fraction contributed 36 and 28% of the total antioxidant capacity, respectively. C3R contributed 92% of the total antioxidant capacity of the anthocyanin fraction. Fruits of the Mission variety contained the highest levels of polyphenols, flavonoids, and anthocyanins and exhibited the highest antioxidant capacity.

Tea is a complex mixture containing a range of compounds from simple phenolics to complex thearubigins, many of which have well-recognized antioxidant properties. This paper describes the application of high-performance liquid chromatography-mass spectrometry (HPLC-MS n ) methods for the rapid and routine analysis of more than 30 phenolics in tea. Green and black tea infusions were injected directly onto a reversed phase HPLC column, and the phenolics eluted using two different mobile phase gradients, one optimized to resolve catechin derivatives and the other, flavonols and theaflavins. Compounds, identified on the basis of their retention time, absorbance spectrum, and MS fragmentation pattern, included (+)-catechin, (-)-epicatechin, theaflavin and their various gallate derivatives, quercetin and kaempferol mono-, di-, and triglycosides, quinic acid esters of gallic acid and hydroxycinnamates, and the purine alkaloids, caffeine and theobromine.

Gac fruit aril has an attractive orange red colour and very high level of carotenoids, giving it exceptional antioxidant properties. However, spray drying of this material has not been successful and malto dextrin is considered as a suitable drying aid to preserve its colour and antioxidant properties. This paper reports the effects of inlet drying air temperature (120, 140, 160, 180 and 200 °C) and maltodextrin addition (10%, 20% and 30%) on the physicochemical and antioxidant properties of the Gac aril powder. Moisture content and bulk density, colour characteristics, total carotenoid content (TCC), encapsulation efficiency and total antioxidant activity (TAA) were significantly affected by maltodextrin concentration and the inlet air temperatures. However, pH, aw and water solubility index were not significantly influenced by the spray drying conditions. Overall, a good quality Gac powder in terms of colour, TCC and TAA can be produced by spray-drying at inlet temperature of 120 °C and adding maltodextrin concentration at 10% w/v. Crown

Detachment of the retinal pigment epithelium is a prominent feature of many chorioretinal disease processes, the most prevalent of which is age-related macular degeneration (AMD). Detachment of the retinal pigment epithelium may or may not be associated with choroidal neovascularization and may be caused by different types of pathogenesis, each associated with distinct angiographic features, natural course, visual prognosis, and response to treatment. The phrase ''detachment of the retinal pigment epithelium'' is used quite often, not always in the correct association and with no clear differentiation between its various types. It is important to identify the specific nature of detachment of the retinal pigment epithelium, and to establish an accurate diagnosis and treatment plan. Therefore, we present a review of the existing types of detachment of the retinal pigment epithelium with what we propose as being appropriate nomenclature and classification, and potential treatment recommendations. (Surv Ophthalmol 52:227--243, 2007. Ó 2007 Elsevier Inc. All rights reserved.)

A photosynthesizing microorganism culture, like Spirulina platensis, can be an alternative source of protein for human food and feed purposes, with the possibility of obtaining other products like pigments (carotenoids, phycocyanin and chlorophyll), vitamins and lipids. The biomass obtained can be introduced directly in the diet and it can also be used in cases of malnutrition. This type of biomass has been used as a food since ancient times in some regions of Africa and Mexico, from where Spirulina sp. originated. In this work, the influence of inoculum age in S. platensis cultivation in Erlenmeyer's flasks and in mini-tanks was studied. After the determination of the best inoculum age, a study of the influence of inoculum concentration in mini-tanks cultivation was performed. Assays with four different inocula ages: 3, 6, 10 and 14 days and four different concentrations: 50, 100, 150 and 200 mg l À1 were made. The biomass obtained was analyzed in terms of their chemical composition and chlorophyll contents. The results showed that the best inoculum age was six days with 50 mg l À1 of concentration.

Pepper fruits (Capsicum annuum) contain a wide array of phytochemicals with well-known antioxidant properties. Since bioactive compounds depend on their bioavailability to exert beneficial effects, it was crucial to estimate the extent of release from the food matrix and thus their bioaccessibility. Accordingly, we determined the individual carotenoid and phenolic content as well as the antioxidant properties of four red hot dried cultivars (Capsicum annuum L.) of high consumption in Mexico and estimated the extent of intestinal bioaccessibility of carotenoids with significance in human health, β-carotene, β-cryptoxanthin, and zeaxanthin, using an in vitro gastrointestinal model. Hot dried peppers at ripe stage had a high content of bioactive compounds that exhibited significant antioxidant properties (26-80 μmol trolox equivalents/g of dry matter), such as polyphenols (>2000 mg/100 g of dry matter) and carotenoids (95-437 mg/100 g of dry matter), which were partially bioaccessible. The amount released from the food matrix by the action of digestive enzymes was about 75% for total polyphenols, up to 49% for both β-carotene and zeaxanthin, and up to 41% for β-cryptoxanthin. The results suggest that from 50 to 80% of these carotenoids could reach the colon to be potentially fermented or could remain unavailable.

It is generally accepted that abstract and iconographic representations are reflections of symbolic material culture. Here we describe a fragmented ocherous pebble bearing a sequence of sub-parallel linear incisions. These were produced by a lithic point and may represent one of the oldest instances of a deliberate engraving. The object was recovered from Middle Stone Age II levels of Klasies River Cave 1, South Africa, and is dated to between 100,000 and 85,000 years ago. Microscopic analysis reveals that the surface of the object was ground until smooth before being engraved with a sequence of sub-parallel lines made by single and multiple strokes. X-ray fluorescence and colorimetric analysis of the object and a sample of twelve additional ochre pieces from the same level reveals that the brown colour and Manganese-rich composition renders the engraved piece distinct. This suggests that a particular type of raw material may have been selected for engraving purposes. Although the purpose of marking this object remains uncertain, its detailed analysis adds relevant information to previously published occurrences of Middle Stone Age engraved objects and contributes to clarify their distribution through time and space.

The origins of raw glass used to fashion Mycenaean beads were explored using trace elements analyzed by laser ablation ICP-TOFMS. The use of this minimally destructive technique for the in-situ analysis of these beads was ideal given that the material is exceedingly rare and thus too sensitive to make use of traditional micro-sampling (e.g., by scalpel). A wide range of trace elements were measured to compare these Greek glasses to other Late Bronze Age glass coming from Egypt and Mesopotamia. Of the eleven beads analyzed, four blue glasses colored with cobalt and two blue/green glasses colored with copper have trace element compositions consistent with an Egyptian origin of manufacture. The other five of the glasses, all colored with copper, were found to conform to the composition of Mesopotamian glass. These data are the first to demonstrate direct and clear evidence for the trade of raw glass to the Mycenaean states.

Four wild fruits, Diospyros mespiliformis, Flacourtia indica, Uapaca kirkiana and Ziziphus mauritiana, were extracted with methanol and analysed for radical-scavenging effect of 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical, reducing power and anion radical effect on superoxide anion using colorimetric method. There was an increase in the radical-scavenging effect, reducing power and superoxide anion radical-scavenging effect as the concentration of sample increased. Diospyros mespiliformis had high DPPH radical-scavenging capacity. The peels of F. indica and U. kirkiana had higher DPPH radical-scavenging effects, reducing power and superoxide-scavenging effects compared with the pulp while the pulp of Z. mauritiana had high DPPH radical-scavenging effects, reducing power and superoxide-scavenging effects compared with the peel.

This paper proposes an HPLC method for analysing a great variety of phenolic compounds from vine and wine products with UV-Vis photodiode array (DAD) and fluorescence detection. In order to obtain a good chromatographic separation, a ternary solvent gradient that combines changes in polarity and pH was used. The pH changes from 2.6 to 1.5 to promote the elution of anthocyanins in their flavylium cationic form. The fluorescence detector enables the limit of quantification of flavan-3-ols to be reduced, and also prevents interferences caused by other phenolics that force the use of time-consuming fractionating protocols. With this method, it was possible to separate and quantify up to 48 phenolic compounds in a single, direct injection: 2 benzoic acids (DAD set at 280 nm), 9 hydroxycinnamic acids and GRP (DAD set at 320 nm), 7 flavan-3-ols (5 with fluorescence detector set at excitation/emission of 280/320 nm, and 2 with DAD set at 280 nm), 12 flavonols (DAD set at 360 nm), 15 anthocyanins (DAD set at 520 nm), and 2 stilbens (DAD set at 320 nm). Studies were performed to determine the precision, accuracy, and detection limits and data are provided on the concentration of the phenolics found in grape seed and skin extracts, as well as in wines prepared from the Vitis vinifera cultivar Cencibel. r

Carotenoids are involved in the nutritional and sensory characteristics of dairy products, and are potential biomarkers for traceability of cows' feeding management. We review general and recent knowledge on carotenoids from forage to milk and dairy products in ruminants. Nearly 10 carotenoids (i.e., xanthophylls and carotene) have been quantified in forages, and their concentrations vary highly according to development stage and length of conservation. Sensitivity of ␤-carotene to ruminal degradation varies among studies, depending on its dietary source. Data suggest that carotenoid digestion would be linked to dietary lipids for transit, and to specific transporters of lipophilic molecules for absorption. Among ruminants, only bovines accumulate high concentrations of carotenoids, mainly ␤-carotene, possibly due to lower Vitamin A synthesis efficiencies in enterocytes. Carotenoid flows in plasma and tissues in dairy cows remain to be investigated, especially the ability of adipose tissue to release ␤-carotene in depleted or underfed animals. Carotenoids in cows' milk mainly consist of all-trans-␤-carotene and, to a lesser extent, lutein. In milk, concentration is more variable for ␤carotene than for retinol, for which the plasma concentration is well regulated. Milk concentration of ␤-carotene depends on its dietary supply. Both animal and feeding factors that affect milk yield (i.e., breed, parity, physiological stage, level of intake) generally also control milk ␤-carotene concentration by concentration/dilution mechanisms, and by efficiency of extraction from plasma. The ␤-carotene concentration in cheese is highly linked to milk concentration, whereas high losses of retinol occur during cheese-making. The color of dairy products highly depends on their carotenoid concentration, 419 suggesting that color may be a promising rapid measurement tool for traceability of feeding conditions. Feeding management of dairy cows allows efficient control of carotenoid concentration and color in dairy products.

Four betacyanin pigments were analysed by LC NMR and subjected to extensive NMR characterisation after isolation. Previously, low pH values were applied for NMR investigations of betalains resulting in rapid degradation of the purified substances thus preventing extensive NMR studies. Consequently, up to now only one single (13)C NMR spectrum of a betalain pigment, namely that of neobetanin (=14,15-dehydrobetanin), was available. Because of its sufficient stability under highly acidic conditions otherwise detrimental for betacyanins, this pigment remained an exemption. Since betalains are most stable in the pH range of 5-7, a new solvent system has been developed allowing improved data acquisition through improved pigment stability at near neutral pH. Thus, not only (1)H, but for the first time also partial (13)C data of betanin, isobetanin, phyllocactin and hylocerenin isolated from red-purple pitaya [Hylocereus polyrhizus (Weber) Britton & Rose, Cactaceae] could be indirectly obta...

A procedure for the production, extraction, and puri®cation of violacein was developed using Chromobacterium violaceum (CCT 3496) cultivated on cotton, in modi®ed 1 litre Roux bottles. A surface tray bioreactor was built to perform these experiments. Violacein was extracted with commercial ethanol, and puri®ed by ®ltration, Soxhlet extraction, crystallization and high performance liquid chromatography. The violacein was analysed and identi®ed by proton and carbon-13 NMR spectroscopies, thermogravimetric analysis, mass spectrometry, UV-VIS spectroscopy and infrared spectroscopy. It was concluded that the product was highly puri®ed violacein.

BACKGROUND: Chlorella vulgaris is a green microalgae that contains various pigment components of carotenoids and chlorophylls. Supercritical CO 2 is widely used for extraction of pharmaceutical compounds because it is non-oxic and easily separated from extracted material by simply depressurizing. In this work, pharmaceutical compounds from Chlorella vulgaris have been extracted using supercritical CO 2 with or without entrainer at various extraction conditions. RESULTS: Based on high performance liquid chromatography (HPLC) analysis, the extracts contained pigment components, such as lutein, β-carotene, chlorophyll a and b. Higher extraction pressure and temperature promoted higher lutein extraction by supercritical CO 2 . The optimum pressure and temperature for extraction were obtained as 50 MPa and 80 • C. Ethanol as an entrainer was more effective than acetone for the extraction of pigment components. Pigment components in the extract obtained by supercritical CO 2 with and without entrainer were compared with the extract obtained by a conventional extraction method.

BACKROUND:Spirulina platensis (Toliara, Madagascar) provides a food supplement which can fight against malnutrition and food insufficiency in Madagascar. In this country, the current production from three open basins is not sufficient to cover needs, and presents drawbacks such as low productivity and possible contamination. Thus cultivation of S. platensis in a closed photobioreactor opens the possibility of extending this microalga production. In this study, the influence of colour and intensity of the light on S. platensis growth and protein content was investigated in a bubble column.RESULTS: Growth kinetics were obtained for four colours (green, white, red and blue) and four intensities (400, 800, 1000 and 1200 lux) of light. The influence of light colour on Spirulina growth was discussed. The highest productivity (183.6 mg L−1 d−1) and concentration (2643 mg L−1) were obtained for green light at 1200 lux. The protein content was 58%.CONCLUSION: Using green light allows improvement of S. platensis growth. Performance obtained with the closed system was higher than that reported in the literature. Copyright © 2008 Society of Chemical Industry

Dietary change in Micronesia has led to serious problems of vitamin A deficiency and other nutritionally-related health problems. It is essential to identify nutrient-rich indigenous foods that may be promoted for health improvements. Giant swamp taro (Cyrtosperma merkusii) is important for food and culture on atoll and mountainous islands of Micronesia. There are many Cyrtosperma cultivars, but few have been analyzed for nutrient content. Samples were collected in the Federated States of Micronesia (Pohnpei, Chuuk and Yap) and the Republic of Palau, assessed for corm flesh color and other attributes, and analyzed for carotenoids (b-and a-carotene, b-cryptoxanthin, lutein, zeaxanthin, and lycopene) and minerals (including iron, zinc, and calcium). Of 34 cultivars analyzed, b-carotene concentrations varied from 50 to 4486 mg/100 g. Yellow-fleshed cultivars generally contained higher carotenoid concentrations. Of the ten cultivars analyzed for mineral content (wet weight basis), substantial concentrations of zinc (5.4-46.1 mg/100 g), iron (0.3-0.8 mg/100 g) and calcium (121-305 mg/100 g) were found. All cultivars were acceptable for taste and production factors. These carotenoid-and mineral-rich cultivars should be considered for promotion in Micronesia and other areas for potential health benefits. r

The antioxidant capacity of pomegranate juices (PJs) obtained from eight cultivars were determined by the scavenging activity against 1,1-diphenyl-2-picrylhydrazyl (DPPH), 2,2 0 -azino-bis(3-ethyl-benzothiazoline-6-sulfonic acid) (ABTS) and b-carotene-linoleate model system. Total phenolic content (TPC) and total anthocyanin content (TAC) were also determined and found to vary between the range of 208.3-343.6 mg catechin equivalents and 8.1-36.9 mg cyanidine-3-glucoside equivalents per 100 ml of PJ, respectively. Cultivar Izmir 8 showed the highest scores for trolox equivalent antioxidant capacity (TEAC) as 418.3 ± 5.2 mg/100 ml of PJ, anti-lipid peroxidative activity (ALPA) as 93.5 ± 1.8% and efficient concentration (EC 50 ) as 29.8 ± 2.9 ml of PJ/g of DPPH. The hierarchy of PJs for antioxidant capacity with respect to their TEAC and ALPA values was I8 > I1499 > I10 > I1264 > I1479 > I26 > I23 > Zivzik. Interrelationships among the analyzed parameters and PJs obtained from eight cultivars were investigated by principal component analysis (PCA). Dimension of data set was reduced to two components by PCA accounting for the 93% of the total variance. Eight PJs were classified into three groups by cluster analysis (CA).

Process waters in deinking mills often feature a strong coloration, due to dyes and pigments released from the recovered paper. This can usually be remediated by pulp bleaching treatment with appropriate chemicals. However, the red shade (from rhodamine dye) is resistant to conventional bleaching treatments. This largely limits the use of deinked pulp in white paper grades. In this review, the available technologies for process water decolorization are discussed (chemical methods, physicochemical methods and biological treatments). Ozonation of the process water appears to be the most promising technique for decolorization of process water in deinking mills. Other emerging technologies such as photo-catalytic treatment or mineralization by white-rot fungi (after adsorption on low-cost agricultural residues) should be considered as well.

A procedure for the production, extraction, and puri®cation of violacein was developed using Chromobacterium violaceum (CCT 3496) cultivated on cotton, in modi®ed 1 litre Roux bottles. A surface tray bioreactor was built to perform these experiments. Violacein was extracted with commercial ethanol, and puri®ed by ®ltration, Soxhlet extraction, crystallization and high performance liquid chromatography. The violacein was analysed and identi®ed by proton and carbon-13 NMR spectroscopies, thermogravimetric analysis, mass spectrometry, UV-VIS spectroscopy and infrared spectroscopy. It was concluded that the product was highly puri®ed violacein.

The effects of postharvest irradiation with visible light and UV-B radiation on several health and sensory related properties, including antioxidant capacity (ORAC assay), phenolic compounds, total phenols, ascorbic acid, skin colour, soluble solids and titratable acidity, were measured in 'Aroma' apples and the relationships between these properties were evaluated. The kinetics of flavonoid accumulation during irradiation were measured with a non-destructive method based on chlorophyll fluorescence. The response to irradiation was compared between peel and flesh of apples harvested from the inner (shade-grown) and outer (sun-exposed) canopy of the tree. The antioxidant capacity, the sum of phenols (HPLC) and the content of anthocyanins, quercetin glycosides, chlorogenic acid and ascorbic acid increased upon postharvest irradiation. The accumulation of flavonols started earlier and increased to a higher level than that of anthocyanins. A combination of visible light and UV-B radiation was the most effective irradiation treatment and the response was greatest for the peel of the shade-grown apples. The apple flesh showed no response to any of the irradiation treatments. Postharvest irradiation improved the apple skin colour, but did not influence the level of soluble solids or titratable acidity in the apples. No visible damage or substantial weight loss was found in the apples after the irradiation treatments. The results suggest that postharvest irradiation can be utilised to improve the health value and colour appearance of apples without changing important taste-related parameters or causing damage to the fruit. Principal component analysis of the data showed that principal component 1 explained 72% of the total variation and was closely related to the skin colour, sum of the phenols, total phenols, the content of ascorbic acid and also the level of soluble solids and antioxidant capacity. Principal component 2 explained 12% of the total variation and was primarily related to titratable acidity. The antioxidant capacity in the peel was better correlated with the sum of the phenols (r = 0.70, P < 0.001) than with the content of ascorbic acid (r = 0.54, P < 0.001). The red to green colour values (a * ) of the apple skin were closely correlated with the sum of the phenols (r = 0.91, P < 0.001) and ascorbic acid content (r = 0.83, P < 0.001) in the apple peel.

On several paintings of James Ensor (1860-1949), a gradual fading of originally bright yellow areas, painted with the pigment cadmium yellow (CdS), is observed. Additionally, in some areas exposed to light, the formation of small white-colored globules on top of the original paint surface is observed. In this paper the chemical transformation leading to the color change and to the formation of the globules is elucidated. Microscopic X-ray absorption near-edge spectroscopy (µ-XANES) experiments show that sulfur, originally present in sulfidic form (S 2-), is oxidized during the transformation to the sulfate form (S 6+ ). Upon formation (at or immediately below the surface), the highly soluble cadmium sulfate is assumed to be transported to the surface in solution and reprecipitates there, forming the whitish globules. The presence of cadmium sulfate (CdSO 4 · 2H 2 O) and ammonium cadmium sulfate [(NH 4 ) 2 Cd(SO 4 ) 2 ] at the surface is confirmed by microscopic X-ray diffraction measurements, where the latter salt is suspected to result from a secondary reaction of cadmium sulfate with ammonia. Measurements performed on cross sections reveal that the oxidation front has penetrated into the yellow paint down to ca. 1-2 µm. The morphology and elemental distribution of the paint and degradation product were examined by means of scanning electron microscopy equipped with an energy-dispersive spectrometer (SEM-EDS) and synchrotron radiation based micro-X-ray fluorescence spectrometry (SR µ-XRF). In addition, ultraviolet-induced visible fluorescence photography (UIVFP) revealed itself to be a straightforward technique for documenting the occurrence of this specific kind of degradation on a macroscale by painting conservators. Figure 7. (A) Optical micrograph of the area (OM ×100) of a type 2 sample analyzed by scanning µ-XRD; µ-XRD maps of (B) CdSO 4 · H 2 O, (C) otavite (CdCO 3 ), (D) greenockite (CdS), and (E) anglesite (PbSO 4 )

The effect of different parameters such as high hydrostatic pressure (HHP) (200, 400, 600 MPa), ethanol concentration (20-100%), time (30-90 min) and temperature (20-70°C) was studied for the optimal anthocyanin extraction from red grape skins. Extracts obtained at an ethanol concentration of 50%, at 70°C and 600 MPa possessed the highest antioxidant capacity ðlmol TROLOX equivalents ðTEÞ g À1 DM Þ and the extraction yields were three-fold greater than control extractions. The antioxidant capacity of the extracts was not directly correlated to the highest amount of anthocyanins, which were optimal extracted with the set of conditions -100% ethanol, 50°C and 600 MPa -achieving extraction yields about 23% higher than under control conditions. Anthocyanin recovery under HHP was selective and increased according to the glucoside moiety linked to the flavylium nucleus; p-coumaroylglucoside anthocyanins were more favourably extracted than mono-and acetylglucosides. Therefore, a higher extraction rate was related to the higher number of methoxyl and hydroxyl groups linked to the C 3 and C 5 of the flavylium nucleus, hence extraction of malvidin > peonidin > petunidin > delphinidin > cyanidin.

Edible berries, a potential source of natural anthocyanin antioxidants, have demonstrated a broad spectrum of biomedical functions. These include cardiovascular disorders, advancing age-induced oxidative stress, inflammatory responses, and diverse degenerative diseases. Berry anthocyanins also improve neuronal and cognitive brain functions, ocular health as well as protect genomic DNA integrity. This chapter demonstrates the beneficial effects of wild blueberry, bilberry, cranberry, elderberry, raspberry seeds, and strawberry in human health and disease prevention. Furthermore, this chapter will discuss the pharmacological benefits of a novel combination of selected berry extracts known as OptiBerry, a combination of wild blueberry, wild bilberry, cranberry, elderberry, raspberry seeds, and strawberry, and its potential benefit over individual berries. Recent studies in our laboratories have demonstrated that OptiBerry exhibits high antioxidant efficacy as shown by its high oxygen radical absorbance capacity (ORAC) values, novel antiangiogenic and antiatherosclerotic activities, and potential cytotoxicity towards Helicobacter pylori, a noxious pathogen responsible for various gastrointestinal disorders including duodenal ulcer and gastric cancer, as compared to individual berry extracts. OptiBerry also significantly inhibited basal MCP-1 and inducible NF-κβ transcriptions as well as the inflammatory biomarker IL-8, and significantly reduced the ability to form hemangioma and markedly decreased EOMA cell-induced tumor growth in an in vivo model. Overall, berry anthocyanins trigger genetic signaling in promoting human health and disease prevention.

The antioxidant activities of crude methanolic extract (CME) and its fractions using ethyl acetate (EAF), hexane (HF) and water (WF) of black cumin seedcake were investigated. DPPH radical scavenging activity, b-carotene-linoleate bleaching, and inhibition of corn oil oxidation were used to evaluate the antioxidant capacity. The total phenolics were found to be 78.8, 27.8, 32.1 and 12.1 mg gallic acid equivalents (GAE)/g in EAF, CME, WF and HF, respectively. The CME and EAF exhibited the highest DPPH followed by WF and HF. The extract/fractions showed high effect on reducing the oxidation of b-carotene. The effect of extract/fractions on the oxidative stability of corn oil at 70°C was tested in the dark and compared with butylated hydroxyanisole (BHA). The oil peroxide and anisidine values were generally lower with addition of PRFs in comparison to a control. The predominant phenolic compounds identified by HPLC-DAD in CME and WF of black cumin seedcake were hydroxybenzoic, syringic and p-cumaric acids.

Changes in colour and stability of anthocyanins have been evaluated over pH range 2.0-8.7. The study was made on crude extract (XAD-7 Amberlite-retained fraction) as well as on the following pure pigments isolated from tamarillo fruit (Solanum betaceum Cav.):

The chemical composition of redspotted shrimp (Penaeus paulensis) waste was investigated. The shrimp waste (freeze-dried heads, shells and tails) was found to have high protein (49% d.w.) and ash (27% d.w.) contents, but a low lipid content (4.9% d.w.) although the latter was higher than those found in other kinds of shrimp captured in Brazil. The fatty acid compositions showed that the lipids had a high content of unsaturated fatty acids, mainly EPA (C20:5; n-3) and DHA (C22:6; n-3). In order to establish an efficient and environmentally friendly recovery process for the astaxanthin (principal carotenoid and antioxidant present in the waste), the following processes were examined: traditional solvent extraction (TSE), super-critical fluid extraction (SC-CO2) and super-critical fluid extraction with co-solvent (SC-CO2 + ethanol). The temperature and pressure conditions for all the SC-CO2 extractions were 50 °C and 30.0 MPa. The results showed that the mixture of 60% (v/v) n-hexane:isopropyl alcohol gave the highest (53 mg/kg waste) carotenoid extraction yield as compared to acetone, SC-CO2 and SC-CO2 + ethanol. The SC-CO2 showed the lowest extraction yield of astaxanthin, but the addition of the entrainer (10% w/w) produced an important effect, increasing the astaxanthin extraction to values of 57.9%, similar to extraction with acetone (63.3%).

The present case study concerns the technology of Byzantine wall paintings from the Mani Peninsula, Greece. An assemblage of 12 Byzantine churches, constructed in the tenth to fifteenth century, was included in an initial analytical survey. Two random samples of wall paintings were taken in each monument in order to study their micro stratigraphy and the composition of pigment and plaster layers. Polished sections were fabricated for examination with optical microscopy and scanning electron microscopy (SEM). Furthermore, selected samples were powdered and analysed with Fourier-transformed infrared spectroscopy (FTIR) and X-ray diffraction (XRD). The analytical results achieved in this case study provided general conclusions concerning painting techniques for wall paintings in a rather provincial area of the Byzantine Empire. The palette comprised mainly earthen pigments like ochres and carbon black but occasionally also other pigments like cinnabar, minium and ultramarine. In view of future studies, a portable X-ray fluorescence analysis (XRF) set-up was tested.

1. Pigment analysis by high-performance liquid chromatography (HPLC) combined with data analysis using the CHEMTAX program has proven to be a fast and precise method for determining the abundance of phytoplankton groups in marine environments. To determine whether CHEMTAX is applicable also to freshwater phytoplankton, 20 different species of freshwater algae were cultured and their pigment/chlorophyll a (Chl a) ratios determined for exponential growth at three different light intensities and for stationary growth at one light intensity.2. The different treatments had a relatively insignificant impact on the absolute values of the diagnostic pigment/Chl a ratios, with the exception of cyanobacteria and cryptophytes for which the zeaxanthin/Chl a and alloxanthin/Chl a ratios varied considerably.3. The pigment ratios were tested on samples collected in six different eutrophic Danish lakes during two summer periods using the CHEMTAX program to calculate the biomass of the phytoplankton groups as Chl a. The CHEMTAX-derived seasonal changes in Chl a biomass corresponded well with the volume of the microscopically determined phytoplankton groups. More phytoplankton groups were detected by the pigment method than by the microscopic method.4. Applying the pigment ratios developed in this study, the pigment method can be used to determine the abundance of the individual phytoplankton groups, which are useful as biological water quality indicators when determining the ecological status of freshwater lakes.

The origins of raw glass used to fashion Mycenaean beads were explored using trace elements analyzed by laser ablation ICP-TOFMS. The use of this minimally destructive technique for the in-situ analysis of these beads was ideal given that the material is exceedingly rare and thus too sensitive to make use of traditional micro-sampling (e.g., by scalpel). A wide range of trace elements were measured to compare these Greek glasses to other Late Bronze Age glass coming from Egypt and Mesopotamia. Of the eleven beads analyzed, four blue glasses colored with cobalt and two blue/green glasses colored with copper have trace element compositions consistent with an Egyptian origin of manufacture. The other five of the glasses, all colored with copper, were found to conform to the composition of Mesopotamian glass. These data are the first to demonstrate direct and clear evidence for the trade of raw glass to the Mycenaean states.

The relationships between grapevine (Vitis vinifera) vigor variation and resulting wine anthocyanin concentration and composition and pigmented polymer formation were investigated. The study was conducted in a commercial vineyard consisting of the same clone, rootstock, age, and vineyard management practices. Vine vigor parameters were used to designate vigor zones within two vineyard sites (A and B) to produce research wines (2003 and 2004) and conduct a model extraction experiment (2004 only) to investigate the vine-fruit-wine continuum. Wines and model extracts were analyzed by HPLC and UV-vis spectrophotometry. For the model extractions, there were no differences between sites for pomace weight, whereas juice volume was higher for site A. This was not related to a larger berry size. Site A had a higher anthocyanin concentration (milligrams per liter) in the model extracts than site B specifically for the medium-and low-vigor zones. For anthocyanin composition in the model extraction, site B had a greater proportion of malvidin-3-O-glucoside and less of the remaining anthocyanin glucosides (delphinidin, cyanidin, petunidin, and peonidin) compared to site A. In the wines, there was a vintage effect, with the 2003 wines having a higher anthocyanin concentration (milligrams per liter) than the 2004 wines. This appears to have been primarily due to a greater accumulation of anthocyanins in the fruit. In general, the medium-vigor zone wines had higher anthocyanin concentrations than either the high-or low-vigor zone wines. There was also vintage variation related to anthocyanin composition, with the 2003 wines having a higher proportion of delphinidin and petunidin glucosides and lower malvidin-3-O-glucoside compared to 2004. In both years, there were higher proportions of delphinidin and petunidin glucosides in wines made from low-vigor-zone fruit. Wines made from low-vigor zones showed a greater propensity to form vitisin A as well as pigmented polymers. Low-vigor-zone wines had a ∼2-fold increase in pigmented polymer concentration (milligrams per liter) over high-vigor-zones wines. There was a strong positive relationship between pigmented polymer concentration, bisulfite bleaching resistant pigments, proanthocyanidin concentration, and color density in wines. Overall, differences found in the wines magnified variation in the fruit.

In the present study, the betaxanthin (bx) and betacyanin patterns of differently coloured inflorescences from Gomphrena globosa L. and Bougainvillea sp. have been investigated in detail by applying reversed phase high-performance liquid chromatography-diode array detection (HPLC-DAD) coupled with positive ion electrospray mass spectrometry. Histidine-bx was found to be the predominant betaxanthin of Gomphrena globosa inflorescences. Furthermore, arginine-bx was detected as a novel betaxanthin, which to the best of our knowledge has not been reported as a pigment that occurs naturally so far. Dopa-bx was the major betaxanthin of Bougainvillea sp., although several minor betaxanthins were also present, including lysine-bx and putrescine-bx, novel betaxanthins hitherto not observed naturally. Remarkable differences in the betacyanin patterns between the purple, red and orange varieties were observed for both Gomphrena and Bougainvillea inflorescences. Hence, both the betacyanin profiles and the relative betaxanthin:betacyanin ratios determine the broad colour palette of Gomphrena petals and Bougainvillea bracts.

Anthocyanin stability was assessed over temperatures ranging from 30 to 90°C for seven products: blood orange juice [Citrus sinensis (L.) Osbeck]; two tropical highland blackberry juices (Rubus adenotrichus Schlech.), one with high content and the other with low content of suspended insoluble solids (SIS); and four roselle extracts (Hibiscus sabdariffa L.). The blackberry juice showed the highest content of anthocyanins with 1.2 g/L (two times less in the roselle extracts and 12 times less in the blood orange juice). The rate constant for anthocyanin degradation and isothermal kinetic parameters were calculated according to three models: Arrhenius, Eyring, and Ball. Anthocyanins in blood orange juice presented the highest rate constant for degradation, followed by the blackberry juices and roselle extracts. Values of activation energies were 66 and 37 kJ/mol, respectively, for blood orange and blackberry and 47-61 kJ/mol for roselle extracts. For the blackberry juices, a high SIS content provided only slight protection for the anthocyanins. The increasing content of dissolved oxygen, from 0.5 to 8.5 g/L, did not significantly increase the rate constant. For both isothermal and nonisothermal treatments, all three models accurately predicted anthocyanin losses from different food matrices.

The King George III copy of the Gutenberg Bible, held at the British Library, has been analyzed using Raman spectroscopy to determine the palette of pigments used in the illuminations on this work. The palette is found to comprise cinnabar/vermilion, lead tin yellow (type 1), carbon-based black, azurite, malachite, an organo-copper complex (a "verdigris"), calcium carbonate (chalk), gypsum, gold leaf, and basic lead carbonate ("lead white"). This is in agreement with contemporary descriptions of the pigments used for the illuminations. One pigment could not be identified, specifically the organic dark red/ purple color used for the foliage. The palette of this copy of the Gutenberg Bible has been compared with those used for six other copies, held at Eton College and Lambeth Palace, England, the Bibliothè que Mazarine and the Bibliothè que nationale de France, and the Staatsbibliothek zu Berlin and the Niedersa 1chsische Staats-und Universita 1tsbibliothek (SUB) Go 1 ttingen, Germany. The palettes are shown to be similar to one another, even though the styles of the primary illuminations differ. The two Gutenberg Bibles held in Germany, printed on vellum, have the more expensive palettes, which include lazurite. The SUB Go 1 ttingen copy has the most extensive palette with 16 pigment-related materials having been identified.