Article

Selective Determination of Arbutin in Cosmetic Products Through Online Derivatization Followed by Disposable Electrochemical Sensor

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Abstract

An online derivatization followed by a disposable electrochemical sensor was used for the determination of arbutin (AR) in cosmetic products. The AR was chemically oxidized by MnO2 and subsequently reduced at inexpensive screen-printed carbon electrodes using a low detection potential which improved the selectivity of the method. The effects of various parameters, such as solution pH, detection potential, and flow rate of the mobile phase, were studied in detail. Under optimal conditions [pH 1.6 (0.1 M H3PO4), detection potential 0.0 V (versus Ag/AgCl), flow rate 0.6 mL/min], the linear range for AR was 0.1-1500 ppm (r2 = 0.999) with LOD of 30.06 ppb (S/N = 3). The practical application of the proposed method was demonstrated by the determination of arbutin concentration in commercial cosmetic products.

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... Arbutin may release hydroquinone following in vivo cleavage of the glycosidic bonds or via hydrolysis by human skin bacteria [13]. Several analytical methods have been reported for the quantitative determination of arbutin in cosmetics using high-performance liquid chromatography (HPLC) [6,[14][15][16][17][18], microdialysis sampling coupled to HPLC [19] and HPLC with chemiluminescence detection [20], gas chromatography/mass spectrometry [21], micellar electrokinetic capillary chromatography (MEKC) [22], MEKC with amperometric detection [23], and online derivatization followed by disposable electrochemical sensing [24]. Moreover, hydroquinone has been analysed in cosmetic creams and topical dermatologic drugs using HPLC [16,[25][26][27], capillary electrochromatography [28], MEKC [22,29], spectrophotometry [30], thin layer chromatography [31] and biomimetic sensor technology [32]. ...
Article
Arbutin is an effective agent for the treatment of melanin disorders. Arbutin may be converted to hydroquinone under conditions of high temperature, ultraviolet (UV) radiation, and dilute acid. The aim of the current study was to develop an analytical method to determine the levels of arbutin and hydroquinone in whitening cosmetic products using high-performance liquid chromatography with photodiode array detection (HPLC-DAD). In addition, we investigated the effects of high temperature and pH on the decomposition of arbutin. Samples extracted using two-step sonications were separated on a C18 column using a gradient mobile phase consisting of water and methanol. A 60-mm (40 μL) DAD cell was used to enhance the sensitivity of hydroquinone determination. Thermal decomposition of arbutin was evaluated at temperatures ranging from 60-120°C for 1-36 h. The method showed good linearity (R(2) ≥ 0.9997), precision (relative standard deviation, RSD < 5%), and acceptable extraction recovery (90-102.6%). The limits of quantitation (LOQ) for arbutin and hydroquinone were 0.0085 and 0.0119 μg mL(-1) , respectively. One sample out of 21 cosmetic products tested, contained arbutin at a concentration 1.61 g/100 g cream and 0.12 g/100 g cream of hydroquinone. Arbutin (327.18 ppm) decomposed after 4 h at 120°C, and produced 10.73 ppm of hydroquinone. The developed method is simple to detect both arbutin and hydroquinone simultaneously in cosmetic products, at an adequate level of sensitivity. Notably, temperature and pH did not influence the decomposition of arbutin to hydroquinone in a 2% arbutin cream. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.
... Arbutin may release hydroquinone following in vivo cleavage of the glycosidic bonds or via hydrolysis by human skin bacteria [13]. Several analytical methods have been reported for the quantitative determination of arbutin in cosmetics using high-performance liquid chromatography (HPLC) [6,[14][15][16][17][18], microdialysis sampling coupled to HPLC [19] and HPLC with chemiluminescence detection [20], gas chromatography/mass spectrometry [21], micellar electrokinetic capillary chromatography (MEKC) [22], MEKC with amperometric detection [23], and online derivatization followed by disposable electrochemical sensing [24]. Moreover, hydroquinone has been analysed in cosmetic creams and topical dermatologic drugs using HPLC [16,[25][26][27], capillary electrochromatography [28], MEKC [22,29], spectrophotometry [30], thin layer chromatography [31] and biomimetic sensor technology [32]. ...
Article
Synopsis OBJECTIVE: Arbutin is an effective agent for the treatment of melanin disorders. Arbutin may be converted to hydroquinone under conditions of high temperature, ultraviolet (UV) radiation and dilute acid. The aim of the current study was to develop an analytical method to determine the levels of arbutin and hydroquinone in whitening cosmetic products using high-performance liquid chromatography with photodiode array detection (HPLC-DAD). In addition, we investigated the effects of high temperature and pH on the decomposition of arbutin. METHODS: Samples extracted using two-step sonications were separated on a C 18 column using a gradient mobile phase consisting of water and methanol. A 60-mm (40 lL) DAD cell was used to enhance the sensitivity of hydroquinone determination. Thermal decomposition of arbutin was evaluated at temperatures ranging from 60 to 120°C for 1-36 h. RESULTS: The method showed good linearity (R 2 ≥ 0.9997), precision (relative standard deviation, RSD < 5%) and acceptable extraction recovery (90-102.6%). The limits of quantitation for arbutin and hydroquinone were 0.0085 and 0.0119 lg mL À1 , respectively. One sample of 21 cosmetic products tested contained arbutin at a concentration 1.61 g 100 g À1 cream and 0.12 g 100 g À1 cream of hydroquinone. Arbutin (327.18 ppm) decomposed after 6 h at 120°C and produced 10.73 ppm of hydroquinone. CONCLUSION: The developed method is simple to detect both arbutin and hydroquinone simultaneously in cosmetic products, at an adequate level of sensitivity. Notably, temperature and pH did not influence the decomposition of arbutin to hydroquinone in a 2% arbutin cream. R esum e OBJECTIFS: Arbutine est un agent efficace pour le traitement de troubles de la m elanine. Arbutine peutêtre converti en hydroqui-none dans des conditions de haute temp erature, des rayons ultraviolets (UV), et d'un acide dilu e. L'objectif de la pr esente etude etait de d evelopper une m ethode analytique pour d eterminer les niveaux de l'arbutine et hydroquinone dans les produits cosm etiques de blanchiment utilisant la chromatographie liquide a haute performance avec d etection de r eseau de photodiodes (HPLC-DAD). En outre, nous avons etudi e les effets de la temp erature et du pH sur la d ecomposition de l'arbutine. METHODES: Des echantillons extraits en utilisant la sonication en deux etapes ont et e s epar es sur une colonne C 18 en utilisant un gradient de phase mobile constitu ee d'eau et de m ethanol. Une cel-lule de 60 mm (40 µL) DAD a et e utilis ee pour am eliorer la sensib-ilit e de la d etermination de l'hydroquinone. La d ecomposition thermique de l'arbutine a et e evalu ee a des temp eratures allant de 60 a 120°C pendant 1 a 36 h. R ESULTATS: La m ethode a montr e une bonne lin earit e (R 2 ≥ 0,9997), une pr ecision (ecart type relatif, RSD < 5%), et une r ecup eration d'extraction acceptable (90 a 102,6% de). Les limites de quantification (LQ) pour arbutine et hydroquinone etaient 0,0085 et 0,0119 µg mL À1
... H. Lin, Wu, and Huang 2005;Wei et al. 2007;Masse et al. 2001;Thongchai, Liawruangrath, and Liawruangrath 2007;Desmedt et al. 2013), gas chromatography-mass spectrometry (Chisvert et al. 2010), capillary zone electrophoresis (Y. H. Lin, Yang, and Wu 2007), micellar electrokinetic capillary chromatography with amperometric detection (Jin et al. 2013), and online derivatization followed by disposable electrochemical sensing (Zen et al. 2011). Methods for the determination of niacinamide in cosmetics using HPLC (C. ...
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A preanodized clay-coated screen-printed electrode (CCSPE) is used for the determination of arbutin (hydroquinone-β-D-glucopyranoside) in cosmetic bleaching products by square-wave voltammetry. The preanodization process exhibits a marked enhancement in the current response of arbutin at the CCSPE. Compared to the performance at a preanodized SPE, the coating of clay was found to further improve the sensitivity and reproducibility. Under optimized conditions, the linear range for arbutin detection is up to 90μM (correlation coefficient=0.999) in pH 10.0 ammonium buffer with a detection limit of 0.18μM (S/N=3). The electrode can be either disposable or reused since renewal provides good reproducible surfaces. Quantitative analysis was performed by standard addition for the arbutin content in commercial available cosmetic bleaching products.
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Bearberry leaf extracts are used in herbal medicinal products for the treatment of lower urinary tract infections. Two metabolites of the major phenolic constituent in the extract, arbutin (hydroquinone-1-O-beta-D-glucoside), must be assumed to be precursors of the active disinfectant principle hydroquinone. In order to assay the renal elimination of these two metabolites. i.e., hydroquinone conjugates with glucuronic and sulfuric acid, two separate capillary electrophoresis methods have been developed. Both methods were validated according to the criteria for validation of pharmaceutical bioanalytical methods as drafted by the US Department of Health and Human Services. 1998. As there is little sample preparation necessary, both methods are very suitable for urine analysis with large sample numbers as frequently coming up in the course of pharmaceutical bioavailability, bioequivalence and pharmacokinetic studies.
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Bearberry leaves and preparations made from them are traditionally used for urinary tract infections. The urinary excretion of arbutin metabolites was examined in a randomized crossover design in 16 healthy volunteers after the application of a single oral dose of bearberry leaves dry extract (BLDE). There were two groups of application using either film-coated tablets (FCT) or aqueous solution (AS). The urine sample analysis was performed by a validated HPLC coolarray method (hydroquinone) and a validated capillary electrophoresis method (hydroquinone-glucuronide, hydroquinone-sulfate). The total amounts of hydroquinone equivalents excreted in the urine from BLDE were similar in both groups. With FCT, 64.8% of the arbutin dose administered was excreted; with AS, 66.7% was excreted (p = 0.61). The maximum mean urinary concentration of hydroquinone equivalents was a little higher and peaked earlier in the AS group versus the FCT group, although this did not reach statistical significance (Cur max = 1.6893 micromol/ml vs. 1.1250 micromol/ml, p = 0.13; tmax (t midpoint) = 3.60 h vs. 4.40 h, p = 0.38). The relative bioavailability of FCT compared to AS was 103.3% for total hydroquinone equivalents. There was substantial intersubject variability. No significant differences between the two groups were found in the metabolite patterns detected (hydroquinone, hydroquinone-glucuronide, and hydroquinone-sulfate).
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A high-performance liquid chromatographic method for quantifying four of the most common used hydrophilic whitening agent--glycolic acid (GA), ascorbic acid (AA), arbutin (ART) and Mg ascorbyl phosphate (MAP), has been developed. Isocratic separation was performed using a C18 column with ion-pair agent as mobile phase. The analytes were detected by ultraviolet light absorption at the wavelength of 220 and 240 nm, respectively. Calibration curves were found to be linear in the 8.0-36 mg/ml (GA), 10.0-300 microg/ml (AA and ART), and 5.6-451 microg/ml (MAP). The correlation coefficient of linear regression analysis were with the range 0.9974-0.9997. Recoveries of the four analytes were between 94.8 and 100.1% and the precision of this method was better than 6.9% relative standard deviation (R.S.D.) (n=3). It was found that AA degraded in an aqueous solution. To be sure that AA was stable during the HPLC analysis, all analytes were dissolved in distilled water and these solutions were purged with nitrogen gas to remove oxygen and stored at 25 degrees C. The testing results show that the procedure is rapid, simple, selective method and it is suitable for routine analysis of commercial cosmetics.
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A high performance liquid chromatographic (HPLC) and a ultraviolet derivative spectrophotometric (UVDS) methods were developed and validated for the quantitative determination of hydroquinone (HQ) in gels and creams containing this compound as a unique active principle. Validation parameters such as linearity, precision, accuracy, specificity, limit of detection (LOD) and limit of quantitation (LOQ) were determined. HPLC was carried out by reversed phase technique on a RP-18 column with a mobile phase composed of methanol and water (20:80, v/v). The linearity in the range of 6.0-30.0 microg/mL present a correlation coefficient (r) of 0.9999, calculated by least square method. The LOD and LOQ were 0.08 and 0.26 microg/mL, respectively. Based on the preliminary spectrophotometric profile of HQ, a signal at 302.0 nm of the first derivative spectrum (1D302.0) was found adequate for validation. The linearity between signal 1D302.0 and concentration of HQ in the range of 10.0-26.0 microg/mL in sulfuric acid (0.1N) present a correlation coefficient (r) of 0.9999. The LOD and LOQ were 0.14 and 0.46 microg/mL, respectively. Statistical analysis by t- and F-tests, showed no significant difference at 95% confidence level between the two proposed methods.
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An electrochemical cell coupled with disposable screen-printed electrodes (SPEs) that is specifically designed for use in flow injection analysis (FIA) is described in this study. The cell is made of foldable polyoxymethylene (acetal) thick platelets with the bottom portion consisting of a cavity track to drag the SPEs in position and the top portion having predrilled T-like holes to arrange the Ag/AgCl reference electrode and stainless steel inlet & outlet. An "O ring" is suitably fixed on the top of the working electrode to form a thin-layer space where the electrochemical reaction can take place. Hydrodynamic characterization was validated by using a benchmark hexacyanoferrate redox couple. The results of practical analysis of glucose in human plasma clearly demonstrate the characteristics and applicability of the proposed wall-jet electrochemical cell in FIA.
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A simple and accurate spectrophotometric method for the determination of arbutin (glycosylated hydroquinone) is described. It is based on the oxidation of arbutin by periodate in presence of iodate. Excess periodate causes liberation of iodine at pH 8.0. The unreacted periodate is determined by measurement of the liberated iodine spectrophotometrically in the wavelength range (300-500 nm). A calibration curve was constructed for more accurate results and the correlation coefficient of linear regression analysis was -0.9778. The precision of this method was better than 6.17% R.S.D. (n=3). Regression analysis of Bear-Lambert plot shows good correlation in the concentration range 25-125 ug/ml. The identification limit was determined to be 25 ug/ml a detailed study of the reaction conditions was carried out, including effect of changing pH, time, temperature and volume of periodate. Analyzing pure and authentic samples containing arbutin tested the validity of the proposed method which has an average percent recovery of 100.86%. An alternative method is also proposed which involves a complexation reaction between arbutin and ferric chloride solution. The produced complex which is yellowish-green in color was determined spectophotometrically.
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A statistical experimental design was used to optimize one micellar electrokinetic capillary electrophoresis (MEKC) for simultaneous analysis of arbutin (AR), kojic acid (KA) and hydroquinone (HQ). Untreated fused-silica capillaries were operated using a phosphate buffer (20mM, pH 6.5) under 20 kV and detection at 200 nm. Quantitative linear ranges were 20-200 microg/ml for AR, 20-100 microg/ml for KA and 8-80 microg/ml for HQ with correlation coefficients >or=0.9994. R.S.D. and R.E. were less than 3.0% for the intra-day and inter-day analysis, and all recoveries were greater than 99%. Our method was applied to assay commercial cosmetics. The results were within the labeled amount of 99.6-102.5%.
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A solvent extraction procedure of freeze-dried aliquots followed by the analysis of phenolic compounds by reversed-phase high-performance liquid chromatography (RP-HPLC) with photodiode array detection (DAD) has been developed for the analysis of polyphenolic compounds in fruit juices. This methodology is focussed on the characterization of fruit juices, mainly for quality control purposes. The effects of experimental variables, such as solvent composition and volume and time and temperature on extraction, have been studied. A unique gradient program for the separation of several phenolic classes (hydroquinones, hydroxybenzoic acids, flavan-3-oles, hydroxycinnamic acids, coumarins, flavanones, flavones, dihydrochalcones and flavonols) has been optimized, using standards of 55 commercially available phenolic compounds present in fruits, as well as representative real extracts from fruit juices. All phenolic compounds showed a high repeatability within-day (n=5) and between days (n=3) in peak area (RSD<8%) and excellent stability of their retention times. High precision was also observed in calibration slopes (RSD<8%). Detection limits ranged between 0.005 and 0.03 microg/mL for the different detected polyphenols. Complete recoveries (98-100%) were obtained for the majority of the phenolic structures of all representative phenolic families present in fruits. The method was successfully employed to measure diverse phenolic families in juices from 18 different fruits and consequently could be used for evaluate the quality of fruit juices.
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