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PubMed2002

Analytical study of the chemical and physical changes induced by KrF laser cleaning of tempera paints.

The cleaning of paintings using UV lasers is a growing field of interest in the practice of conservation. In this work, we have studied the chemical and physical changes induced by KrF excimer laser at 248 nm of tempera paint dosimeter systems. The changes have been evaluated by using a range of analytical techniques. These include profilometry; colorimetry; optical and vibrational spectroscopies, such as laser-induced fluorescence (LIF), laser-induced breakdown spectroscopy (LIBS), Fourier transform Raman (FTR), and infrared (FT-IR); and analytical mass spectrometric techniques, such as direct-temperature-resolved mass spectrometry (DTMS) and matrix-assisted laser desorption and ionization mass spectrometry (MALDI-MS). Integration of the results obtained by these techniques allowed the investigation of the nature and degree of change of the irradiated paint systems. Direct laser irradiation induces various degrees of discoloration that depend strongly on the nature of the pigment. This effect takes place mainly on the surface layer of the sample. Degradation of the binding medium occurs in the presence of inorganic pigments, and in some cases, evidence of alterations in the molecular composition of the pigment has been obtained. Varnished systems do not display this discoloration when a thin protective layer is left on the paint. A laser cleaning strategy for varnished paintings should be based on the partial removal of the varnish, leaving a residual layer that shields the underlying pigments from direct laser exposure.

Journal Article↗

PubMed2002

Lonophore-based lithium ion film optode realizing multiple color variations utilizing digital color analysis.

Digital color analysis (DCA), utilizing colors themselves or digital information of colors, can not only be applied to various quantitative analysis using chromaticity coordinates but can also be used to develop suitable sensors for visual colorimetry based on the characteristics of human visual perception by virtual simulations based on digital color information. To achieve a clear visual color variation for lithium ion determination, we designed and prepared a color-changeable film sensor (film optode) by the use of two kinds of lipophilic dyes, KD-C4 and KD-M11, whose colors and pKa values are different. This film sensor is a plasticized PVC membrane containing the mixture of two kinds of dyes with the lithium ionophore TTD14C4 and the lipophilic anionic additive tetrakis-[3,5-bis(trisfluoromethyl)phenyl]borate sodium salt dihydrate. The simulation of the color variation using the mixed dyes was evaluated by plotting the values on a uniform chromaticity scale diagram in a*b* coordinates, after converting the tristimulus values of each dye into its L*a*b* values. When the lithium ion concentration was actually determined by the PVC film optode containing the mixed dyes whose molecular ratio of KD-C4/KD-Ml 1 was 3:1, the hues of red --> orange --> yellow --> green --> blue could be realized in the range of 10(-6)-1 M. This observed color variation was similar to the result of the virtual simulation based on DCA.

Journal Article↗

PubMed2005

On-chip transformation of bacteria.

On-chip transformation of Escherichia coli cells was accomplished for the first time using a microbial array chip. The continuous E. coli transformation procedures were performed on a chip in which the microcompartment was composed of PDMS microfluidic channels and a silicon substrate predeposited with different plasmid DNAs. The PDMS microfluidic device enabled the parallel transformation of E. coli cells with various plasmid DNAs by separating each transformation area. The phenotypic differences reflecting different plasmid DNAs were identified by various approaches such as colorimetry, fluorometry, and electrochemical methods. This microbial array chip could become a versatile tool for many cell biological applications.

DNA, Bacterial↗

PubMed1999

Amperometric determination of total cholesterol at gold electrodes covalently modified with cholesterol oxidase and cholesterol esterase with use of thionin as an electron mediator.

Immobilization of cholesterol oxidase (EC 1.1.3.6) (ChOx) on a gold electrode was attempted by cross-linking using glutaraldehyde between ChOx molecules and a self-assembled monolayer of 2-aminoethanethiolate. The resulting electrode (ChOx/Au) exhibits an amperometric response to free cholesterol in the presence of thionin as an electron mediator, and a steady-state response is obtained approximately 60 s after injection of cholesterol into the electrolyte solution. Coimmobilization of cholesterol esterase (EC 3.1.1.13) (ChE) and ChOx (ChE/ChOx/Au) allows the amperometric determination of both esterified cholesterol and free cholesterol. Cyclic voltammetry of the ChE/ChOx/Au and the dependence of the amperometric response to cholesterol on the concentration of thionin suggest that thionin is encapsulated in the enzyme film on the electrode surface. Apparent Michaelis constants of the ChOx/Au and the ChE/ChOx/Au electrodes suggest that the amperometric response was controlled by penetration of the reaction substrate into the films of the enzyme(s). The concentration of total (free and esterified) cholesterol in human serum samples, determined by using the techniques developed in the present study, is in good agreement with that determined by the well-established technique using colorimetry.

Cholesterol↗

PubMed1994

Role of the strictly conserved tryptophan-25 residue in the stabilization of the structure and in the ligand binding properties of the kringle 2 domain of tissue-type plasminogen activator.

The involvement of the strictly conserved tryptophan-25 (W25) residue in the structural stability and omega-amino acid ligand binding properties of the recombinant (r) kringle 2 (K2) domain of tissue-type plasminogen activator (tPA) has been investigated. Two conservative mutants were constructed and expressed that contained W25-->F and W25-->Y substitutions. The binding (dissociation) constants (Kd) for three ligands, viz., 6-aminohexanoic acid (EACA), 7-aminoheptanoic acid (7-AHpA), and L-lysine (Lys), to these polypeptides were determined by intrinsic fluorescence titrations. In the case of r-[K2tPA/W25F], the Kd values for these ligands were found to be 37, 16, and 89 microM for EACA, 7-AHpA, and Lys, respectively. For r-[K2tPA/W25Y], the Kd values for these same ligands were 64, 9, and 115 microM, respectively. The wild-type (wt) kringle domain possessed Kd values of 43, 6, and 85 microM for EACA, 7-AHpA, and Lys, respectively. The effect of these mutations on the stability of the r-[K2tPA] domain has been examined by differential scanning colorimetry. The temperature of maximum heat capacity (Tm) of wt-r-[K2tPA] (75.6 degrees C) was dramatically reduced to 50.8 and 58.0 degrees C for r-[K2tPA/W25F] and r-[K2tPA/W25Y], respectively. In the presence of EACA, the Tm values were increased to 86.1, 61.7, and 68.7 degrees C, respectively, indicating that EACA does interact with the r-[K2tPA] mutants and stabilizes their native conformations, similar to the case with wt-r-[K2tPA].(ABSTRACT TRUNCATED AT 250 WORDS)

Base Sequence↗

PubMed2003

Disposable indicators for monitoring lighting conditions in museums.

Photoinduced alterations of light-sensitive artifacts represent one of the main problems that conservators and curators have to face for environmental control in museums and galleries. Therefore, increasing attention has been recently devoted to developing strategies of indoor light monitoring, especially aimed at minimizing the cumulated light exposure for the objects on exhibit. In this work a prototype of a light dosimeter, constituted by a photosensitive dyes/polymer mixture applied on a paper substrate, is presented. This indicator, specially designed for a preventive assessment of the risk of damage for highly light-sensitive objects, undergoes a progressive color variation as its exposure to the light increases. Different, easily distinguishable color steps are exhibited depending on the light dose received, so that the dosimeter can be used straightforwardly to have a first, instrumentation-free estimation of the total light exposure. A reflectance spectroscopy study in the 350-860 nm range was carried out on prototype dosimeters exposed to light emitted from a tungsten-halogen lamp to investigate the response of the dosimeter to the light and to study the fading mechanism. Two different approaches were evaluated for the calibration of the prototype: colorimetry and principal component analysis of the reflectance spectra. The usefulness of the two methods in providing a quantitative indication of the light dose received was evaluated.

Art↗

PubMed2003

Determination of strongly reducing substances in sediment.

Reducing substances in sediments play an important role in regulating the chemical and biological status of the sediment. Strongly reducing substances are the most active part of them, and are difficult to measure directly. In this work, we have developed a method for their determination based on the oxidation by Fe(III). Then, the produced Fe(II) was determined by colorimetry, using 2,2'-bipyridine as the chelating agent. Prior to determination, these substances were extracted from the sediment by M acetic acid. The whole process was carried out in a closed system, so that oxidation of Fe(II) and reducing substances by atmospheric oxygen could be avoided. The calibration curve between absorbance and Fe(II)-chelate concentration in extract was linear. When ascorbic acid was added to the extract, the recovery was larger than 94.0%. The effect of surplus Fe(III) on the result was discussed. With the proposed method, the concentration of strongly reducing substances in sediment samples from Dianchi Lake of China was measured with good reproducibility.

Chelating Agents↗

PubMed2004

Effects of commercial anthocyanin-rich extracts on colonic cancer and nontumorigenic colonic cell growth.

Commercially prepared grape (Vitis vinifera), bilberry (Vaccinium myrtillus L.), and chokeberry (Aronia meloncarpa E.) anthocyanin-rich extracts (AREs) were investigated for their potential chemopreventive activity against colon cancer. The growth of colon-cancer-derived HT-29 and nontumorigenic colonic NCM460 cells exposed to semipurified AREs (10-75 microg of monomeric anthocyanin/mL) was monitored for up to 72 h using a sulforhodamine B assay. All extracts inhibited the growth of HT-29 cells, with chokeberry ARE being the most potent inhibitor. HT-29 cell growth was inhibited approximately 50% after 48 h of exposure to 25 microg/mL chokeberry ARE. Most importantly, the growth of NCM460 cells was not inhibited at lower concentrations of all three AREs, illustrating greater growth inhibition of colon cancer, as compared to nontumorigenic colon cells. Extracts were semipurified and characterized by high-pressure liquid chromatography, spectrophotometry, and colorimetry. Grape anthocyanins were the glucosylated derivatives of five different anthocyanidin molecules, with or without p-coumaric acid acylation. Bilberry contained five different anthocyanidins glycosylated with galactose, glucose, and arabinose. Chokeberry anthocyanins were cyanidin derivatives, monoglycosylated mostly with galactose and arabinose. The varying compositions and degrees of growth inhibition suggest that the anthocyanin chemical structure may play an important role in the growth inhibitory activity of commercially available AREs.

Anthocyanins↗

PubMed2004

Effect of the maceration technique on the relationships between anthocyanin composition and objective color of Syrah wines.

The effects of two different vinification techniques, traditional fermentation and carbonic maceration, on the anthocyanin composition and color of young red wines, made with Syrah grapes grown in a warm climate, were compared. Tristimulus colorimetry was applied to study the color of wines during the vinification, and a high-performance liquid chromatography (HPLC) procedure was used for the analysis of anthocyanins. Carbonic maceration led to wines with lower anthocyanin content, mainly monoglucosides, and total phenols. This was related to lighter wines, less saturated, but more colorful (higher chroma C*ab values), and hues hab similar to those of the Syrah wines made by traditional vinification. Thus, the lightness L* had much more influence on the saturation s*uv of the wines obtained by carbonic maceration than the chroma (s*uv = C*uv/L*). From a study of the color-composition relationships using linear and multiple regression, better relationships were found for the wines from traditional vinification, where the chromatic parameters L*, hab, and s*uv could be predicted from the 3-monoglucosides of delphinidin, petunidin, peonidin, and malvidin concentrations (R > 0.9). However, a good prediction of the chroma C*ab from the anthocyanin composition was not possible. On the contrary, C*ab was the best predicted parameter from the anthocyanins monoglucosides (R > 0.9) in the carbonic maceration wines.

Anthocyanins↗

PubMed2006

Influence of different phenolic copigments on the color of malvidin 3-glucoside.

The effectiveness of seven phenolic compounds (catechin, epicatechin, procyanidin B2, caffeic acid, p-coumaric acid, myricitrin, and quercitrin) as copigments of malvidin 3-glucoside, the major anthocyanin in red wines from Vitis vinifera, using a copigment/pigment molar ratio of 1:1 was assayed in model wine solutions under the same conditions (pH=3.6, 12% ethanol). The stability of the copigment-pigment complexes formed was studied during a storage period of 60 days at 25 degrees C. Tristimulus colorimetry was applied for color characterization of the copigmentation process, and HPLC-DAD-MS was used to monitor changes in the composition of the samples. Copigmentation has been found to occur in all cases despite the low copigment/pigment molar ratio used, although the effect was different depending on the compound. Flavan-3-ols appeared as the less effective copigments, procyanidin B2 being even worse than monomeric flavanols, whereas flavonols behaved as the best ones. These latter copigments also induced the most statistically significant bathochromic shift in lambdamax. In the colorimetric analysis, it was observed that the lightness L* of the copigmented solutions increased with time, chroma C*ab decreased, and the hue hab increased. The copigments that produced a greater increase in the hue angle were the monomeric flavan-3-ols, which therefore showed to be the least protective cofactors against browning of the anthocyanin solution during the storage. With the time of storage, the formation of new pigments was observed in the solutions containing flavanols (xanthylium structures) and hydroxycinnamic acids (pyranoanthocyanins), which explains some of the color modifications produced in these solutions. Another relevant observation was that the stability of the anthocyanin was not much improved by most of the assayed copigments, since quite similar degradation rates were observed in the presence and absence of those cofactors.

Anthocyanins↗

PubMed1998

Effects of Sunlight Illumination of Marigold Flower Meals on Egg Yolk Pigmentation.

The effect of sunlight illumination of marigold flower meal on the pigmentation of feed for laying hens and of their resulting egg yolks was evaluated by high-performance liquid chromatography and by subjective and light reflectance colorimetry techniques. Illumination did not have an effect on the identity of carotenoids in the flower meal. Interestingly, illuminated marigold flower meals yielded an oleoresin with a higher all-trans-zeaxanthin level, with respect to meals kept in darkness. A higher level of all-trans-zeaxanthin was also present in feed pigmented with that oleoresin. Additionally, this pigmented feed showed the best color values and resulted in egg yolks with good color; remarkably, these egg yolks had a low pigment content with respect to control treatments. Thus, sunlight illumination of marigold flower meal showed a positive effect on egg yolk color; the main factors contributing to this effect were not the identity or quantity of carotenoids in laying hen feed or egg yolks, but rather other as yet unidentified marigold component(s) which was (were) somehow influenced by sunlight illumination.

Journal Article↗

PubMed1999

Sialic acids in fungi: a minireview.

The increasing number of reports on the presence of sialic acids in fungi (N-acetyl-, N-glycolyl- and 5,9-N,O-diacetylneuraminic acids) based on direct and indirect evidence warrants the present review. Formerly suggested as sialidase-sensitive sources of anionic groups at the cell surface of fungal species grown in chemically defined media (e.g., Fonsecaea pedrosoi), sialic acids have also been found in Sporothrix schenckii, Paracoccidioides brasiliensis, Cryptococcus neoformans and recently, in Candida albicans. Methods used involved adequate hydrolysis and extraction procedures, HPTLC, gas-chromatography, colorimetry, mass spectroscopy, lectin and influenza virus binding. Apart from protecting fungal cells against phagocytosis (S. schenckii, C. neoformans) and playing a cellular structural role (F. pedrosoi), other biological functions of sialic acids are still being investigated.

Fungi↗

PubMed2000

Effect of skin-penetrating enhancers on the thermophysical properties of cholesteryl oleyl carbonate embedded in a thermo-responsive membrane.

The effect of skin-penetrating enhancers such as propylene glycol (PG), Azone and ethanol on the thermophysical properties of cholesteryl oleyl carbonate (COC) was investigated using differential scanning colorimetry (DSC) and microscopic Fourier-transform infrared (FT-IR) spectroscopy. The results indicate that PG did not influence the DSC thermograms and IR spectra of COC in the different ratios of COC and PG mixture; whereas Azone interacted with COC not only to lower the semectic-cholesteric phase transition temperature of COC but also to induce a new IR spectral peak at 1653 cm(-1) which shifted from the carbonyl stretching band (1636 cm(-1)) of Azone. Ethanol did not interact with COC, but it influenced the IR spectral peak intensity of COC at 1253 cm(-1). The peak intensity at 1253 cm(-1) gradually rose with the time of ethanol evaporation and was similar to that of the temperature effect. The solubility parameter was also used to explain the miscibility and interaction between COC and PG, Azone or ethanol.

Journal Article↗

PubMed2003

Factors affecting the optical properties of Pd-free Au-Pt-based dental alloys.

The optical properties of experimental Au-Pt-based alloys containing a small amount of In, Sn, and Zn were investigated by spectrophotometric colorimetry to extract factors affecting color of Au-Pt-based high-karat dental alloys. It was found that the optical properties of Au-Pt-based alloys are strongly affected by the number of valence electrons per atom in an alloy, namely, the electron:atom ratio, e/a. That is, by increasing the e/a-value, activities of reflection in the long-wavelength range and absorption in the short-wavelength range in the visible spectrum apparently increased. As a result, the maximum slope of the spectral reflectance curve at the absorption edge, which is located near 515 nm (approximately 2.4 eV), apparently increased with e/a-value. Due to this effect, the b*-coordinate (yellow-blue) in the CIELAB color space considerably increased and the a*-coordinate (red-green) slightly increased with e/a-value. The addition of a third element with a higher number of valence electrons to the binary Au-Pt alloy is, therefore, effective in giving a gold tinge to the parent Au-Pt alloy. This information may be useful in controlling the color of Au-Pt-based dental alloys.

Journal Article↗

PubMed2003

The relationship between constitutive pigmentation and sensitivity to ultraviolet radiation induced erythema is dose-dependent.

The relationship between skin colour and experimental exposure to ultraviolet radiation (UVR) B, with response measured as erythema was studied. Two reflectance methods were used to measure skin colour--tristimulus colorimetry using a Minolta instrument (summarized as the alpha characteristic angle) and the melanin index based on the Diastron reflectance instrument. As expected both measures are highly correlated (0.91). A dose-dependent relationship between skin colour measured as the alpha characteristic angle and UVR was established, with the gradient increasing from 0.99 at 119 mJ to 2.7 at 300 mJ, with the relevant standard errors being 0.39 and 0.47, respectively. Similarly, for the melanin index (where the scale goes in the opposite direction) the gradient differs between -0.49 for 119 mJ and -0.91 for 300 mJ, with the standard errors being 0.14 and 0.17 respectively. The proportion of variation explained is also greater at higher UVR challenge doses. Studies relating UVR sensitivity and pigmentation need to take account of the dose of UVR administered.

Dose-Response Relationship, Radiation↗

PubMed2005

Potential role of interleukin-18 in liver disease associated with insulin resistance.

OBJECTIVE: Interleukin (IL)-18 has been associated with obesity and insulin resistance, both risk factors for the development of liver disease, but the role of IL-18 in liver disease associated with insulin resistance is presently unknown. We hypothesized that circulating IL-18 would be related to serum concentrations of liver chemistry tests (LCTs) in apparently healthy subjects and wished to study whether this correlation was dependent on insulin sensitivity (S(I)). RESEARCH METHODS AND PROCEDURES: One hundred six apparently healthy white men consecutively enrolled in a cross-sectional, population-based study dealing with S(I) in men were studied, and S(I) (minimal model analysis), LCTs (colorimetry), and IL-18 serum concentrations (immunoassay) were assessed. RESULTS: Compared with subjects in the lowest quartile for serum IL-18, subjects in the highest quartile exhibited increased serum triglycerides and decreased S(I), in addition to higher serum alanine aminotransferase (ALT) and aspartate aminotransferase (AST) (all p < 0.05). The direct association between both ALT and AST and IL-18 was further confirmed by examining the distribution of serum IL-18 by quartiles of ALT and AST. Subjects in the highest quartile for serum ALT and AST had higher IL-18 concentrations compared with subjects in the lowest quartile for these LCTs (both p = 0.01). In multiple regression analysis, IL-18, but not S(I), was an independent predictor of serum concentrations of ALT and AST, explaining 7% and 4% of their variance, respectively. DISCUSSION: In summary, IL-18 serum concentrations are associated in apparently healthy humans with plasma concentrations of various LCTs. IL-18 could contribute to the development of liver disease associated with insulin resistance.

Adult↗

PubMed1992

Determination of dietary fibre as non-starch polysaccharides by gas-liquid chromatography.

An improved method is described for the measurement of total, soluble and insoluble dietary fibre as non-starch polysaccharides (NSP). An established procedure is modified to allow more rapid removal of starch and hydrolysis of NSP. In its present form the procedure is simpler and more robust than those previously published. In the modified method starch is removed enzymically within 50 min and NSP is precipitated with ethanol and then hydrolysed by treatment with sulfuric acid for 2 h. The constituent sugars can in turn be measured by gas-liquid chromatography, high-performance liquid chromatography or more rapidly by colorimetry. The improved procedure described here for the removal of starch and hydrolysis of NSP applies to all three techniques, but only the method for measurement of sugars by gas-liquid chromatography is described here in full.

Chromatography, Gas↗

PubMed2000

The high-sensitivity determination of protein concentrations by the enhancement of Rayleigh light scattering of Arsenazo-DBN.

A new Rayleigh light scattering (RLS) assay of protein is presented in this paper. At the optimum pH 4.10, the weak RLS of Arsenazo-DBN can be greatly enhanced by the addition of proteins due to the interaction between protein and Arsenazo-DBN. Based on this, the reactions of Arsenazo-DBN and proteins, including bovine serum albumin, human serum album, gamma-globulin, egg albumin, lysozyme and trypsin, were studied. A new quantitative determination method for proteins has been developed. The linear range for human serum albumin, for example, is 0.085-34.62 micrograms mL-1 with a detection limit of 44.8 ng mL-1. Besides high sensitivity, the method is characterized by good reproducibility, rapidity of reaction, good stability, and few interfering substances. The determination of the proteins in human serum and urine samples by this method give results very close to those obtained using Coomassie Brilliant Blue G-250 colorimetry, with relative standard deviations of 0.7-2.5%.

Arsenazo III↗