Phenylglyoxylic Acid Concentrations Research Articles

Ultrastable Tb-Organic Framework as a Selective Sensor of Phenylglyoxylic Acid in Urine.

Industrial pollution and harmful chemicals seriously affect environment and human health. Styrene is a common air toxicant with widespread exposure sources, including smoking, automobile exhaust, and plastic pollutants. Phenylglyoxylic acid (PGA) is a typical biomarker for exposed styrene. Therefore, it is crucial to quickly identify and quantitatively detect PGA. Herein, an ultrastable terbium metal-organic framework (Tb-MOF 1) was developed, and the luminescence film (1/PLA) consisting of polylactic acid (PLA) and 1 was fabricated as a sensor for rapid detection of PGA. The sensor possesses the advantages of efficient detection [limit of detection (LOD) is 1.05 × 10-4 mg/mL] and rapid response speed (less than 10 s) for PGA in urine. Furthermore, this sensor exhibits high stability, outstanding anti-interference ability, and excellent recyclability. Based on this film technology, a paper-based probe was then developed for portable and convenient detection. The probe could easily distinguish different concentrations of PGA under the naked eye toward practical sensing applications. Meanwhile, photoinduced electron transfer was demonstrated to be responsible for the luminescence sensing. Hence, this study indicates that Tb-MOF is a promising material to detect PGA for evaluating the effect of styrene on the body.

Determination of mandelic acid and phenylglyoxylic acid in urine by reagent-free ion chromatography

To develop a method for determination of mandelic acid (MA) and phenylglyoxylic acid (PGA) in urine by reagent-free ion chromatography. Ion chromatography was performed on an AS19 column with a gradient elution solution containing 10-35 mmoL/L KOH at a flow rate of 1.00 ml/min, and MA and PGA were detected at ultraviolet wavelengths of 225 nm and 254 nm, respectively. The samples were diluted 10 times with purified water, then purified on a silver column to remove high concentrations of chloride ion, and injected after being filtered through a 0.2-µm m filter membrane. The recoveries of standard addition of MA and PGA were 96.5% and 99.3%, respectively, with both relative standard deviations less than 5.0%. Good linear relationships were noted in the range of 1.0-100.0 mg/L for both MA and PGA (r >0.9995). The detection limits of MA and PGA were 0.02 mg/L and 0.05 mg/L, respectively; the minimum detectable concentrations of MA and PGA were 0.2 mg/L and 0.5 mg/L (when the sampling amount was 5.0 ml and diluted to 50.0 ml with water, and the injection volume was 300 µL). This method is fast, convenient, and highly sensitive and selective. It can be used for the analysis of MA and PGA in the urine of styrene-exposed workers.

Influence of genetic polymorphisms of epoxide hydrolase 1 on metabolism of styrene in body

To investigate the role of genetic polymorphisms of epoxide hydrolase 1 (EPHX1) in the metabolism of styrene in vivo. Fifty-six styrene-exposed workers, who worked in the painting workshop of an enterprise for manufacturing glass fiber-reinforced plastic yachts in Shandong Province, China for over one year and were protected in approximately the same way, were selected as study subjects. The 8-hour time-weighted average concentration (8 h-TWA) of styrene and the concentrations of mandelic acid (MA) and phenyl glyoxylic acid (PGA) as urinary metabolites were measured. The genetic polymorphisms of EPHX1 were detected by polymerase chain reaction-restriction fragment length polymorphism analysis. The urinary concentrations of MA and PGA were 177.25±82.36 mg/g Cr and 145.91±69.73 mg/g Cr, respectively, and the 8 h-TWA of styrene was 133.28±95.81 mg/m3. Urinary concentrations of MA and PGA were positively correlated with 8 h-TWA of styrene (R=0.861, P < 0.05; R=0.868, P < 0.05). The subjects were divided into high-exposure group (8 h-TWA >50 mg/m(3)) and low-exposure group (8 h-TWA ≤ 50 mg/m(3), and in the two groups, the urinary concentrations of MA and PGA were significantly higher in the individuals carrying high-activity genotypes of EPHX1 than in those carrying low-activity genotypes of EPHX1 (P < 0.05). Genetic polymorphisms of EPHX1 play an important role in the metabolic process of styrene in vivo.

Determination of phenylglyoxylic acid in urine using a multi-pumping flow system

In this work a simple, fast and fully automated analytical methodology for the spectrophotometric determination of phenylglyoxylic acid is proposed. Phenylglyoxylic acid is a metabolite of styrene that is excreted in urine, being used as an indicator of styrene occupational exposure. The developed procedure was based on the phenylglyoxylic acid ability to inhibit the formation of the peroxovanadium cation produced by the reaction between vanadate and H2O2. The analytical process was implemented in a multi-pumping flow system that employs multiple solenoid actuated micro-pumps as the only active components. This enabled the reproducible insertion and efficient mixing of low volumes of sample and reagents as well as the transportation of the sample zone towards detection. Thus an easily controlled, low cost, compact and reliable analytical system was implemented. A linear working range for phenylglyoxylic acid concentrations up to 700 mg L−1 (r 2 = 0.995, n = 7), was obtained, with a detection limit of 37 mg L−1. The system handles about 43 determinations per hour yielding precise results (relative standard deviation < 5%, n = 10). The developed methodology was applied to the determination of phenylglyoxylic acid in urine samples and the obtained results were in agreement with those furnished by the comparison method with relative percentage deviations lower than 6.6%.

A Field Study to Determine the Effectiveness of Several Respiratory Protection Masks on the Styrene Exposure during Lamination Activities

The purpose of this study is to examine the effectiveness of several types of personal respiratory protection equipment at styrene exposed laminators under real work place conditions. 99 male styrene exposed workers were examined. During their lamination activities the average styrene concentrations in air ranged between 30 to 60 ppm (maximum: 205 ppm). The laminators were followed during an usual workweek from Monday to Thursday. The external styrene exposure was measured by means of passive active carbon badges. The excretion of mandelic acid (MA) and phenyl glyoxylic acid (PGA) in end-of-shift urine samples was used to quantify the internal styrene load. During the work shift some laminators did not use respiratory protection masks. The majority used either a half face mask with active carbon filter or an air purifying respirator. The respiratory masks were worn during an average between 31% and 72% of the work time. The styrene concentrations of the ambient air were -depending on the activity- in the range of 30 to 60 ppm. The end-of-shift concentrations of MA and PGA in urine samples varied considerably, their means range from 153 to 606 mg/g creatinine. The comparison shows that workers with air purifying respirators experience the lowest internal styrene body burden in spite of high external exposures. Their effectiveness during usual working condition was around 83% whereas the use of half face masks with active carbon filters reduce styrene exposure only of 26% as an average. The use of styrene-containing resins in boatbuilding can be associated with increased external styrene exposure of the laminators. During the use of different types of respiratory protection masks it is shown that only the application of air purifying respirators leads to a significant reduction of the internal styrene body burden of 83% when worn during 72% of the total work time. In this way it is possible to comply with or to stay clearly below the biological limit value of 600 mg MA + PGA/g creatinine (BAT-value).

Thyroid Function and Exposure to Styrene

Many natural substances and drugs have long been known to cause goiter or thyroid dysfunction. More recently, several environmental pollutants, such as pesticides and industrial compounds, have been investigated for their thyroid-disrupting activity and related adverse effects on human health. The aim of this study was to evaluate the effects of styrene on the thyroid axis in occupationally exposed workers. Thirty-eight exposed (E) and 123 nonexposed (NE) male workers (controls) were assessed. Serum concentrations of thyrotropin (TSH; basal and after thyrotropin-releasing hormone [TRH] administration.), free thyroxine (FT(4)), free triiodothyronine (FT(3)), anti-thyroglobulin, thyroid peroxidase antibody, and calcitonin were measured. Thyroid ultrasound examination was also performed. In E workers, urinary creatinine, mandelic acid (MA), and phenylglyoxylic acid (PGA) were also measured. No significant differences between E and NE workers were demonstrated, as far as thyroid volume, nodularity, serum thyroid antibodies, and calcitonin were analyzed. However, in the E group a positive correlation between duration of exposure and thyroid volume was detected. After exclusion of subjects with nodular or autoimmune thyroid diseases, serum concentrations of FT(4), FT(3), and TSH did not differ between the two groups. In E workers there was a positive correlation between the urinary concentrations of styrene metabolites (MA plus PGA) and FT(4) or FT(4)/FT(3) ratio (p < 0.05; r = 0.45 and p < 0.005; r = 0.61, respectively), while no correlation was observed between urinary concentrations of MA plus PGA and serum TSH (either basal and stimulated). Chronic exposure to styrene is not associated with an increase in nodular or autoimmune thyroid diseases. However, styrene could interfere with peripheral metabolism of thyroid hormones by inhibiting T(4) to T(3) conversion. Whether this is a direct effect on iodothyronine deiodinases or a consequence of a general distress, such as in nonthyroidal illnesses, remains to be established. Further studies in a larger population of exposed workers are needed to confirm these preliminary observations.

Kinetics of Asymmetric Reduction of Phenylglyoxylic Acid to R-(–)-Mandelic Acid by Saccharomyces Cerevisiae FD11b

Abstract The kinetics of asymmetric production of R-(–)-mandelic acid ( R-MA) from phenylglyoxylic acid (PGA) catalyzed by Saccharomyces cerevisiae sp. strain FD11b was studied by fed-batch cultures. The concentrations of glucose and PGA were controlled respectively with a dual feeding system. When the electron donor glucose was supplied at the rate of 0.0833mmol·gdw −1·h −1, the specific production rate ( q p) and the enantiomeric excess of R-MA reached the maximum 0.353mmol·gdw −1·h −1 and 97.1%, respectively. The apparent reduction activity of yeast FD11b was obviously affected by both substrate PGA and product MA. The q p value reached the maximum 0.36—0.38mmol-gdw −1·h −1 when the PGA concentration was controlled between 25 and 35mmol·L −1. The obvious substrate inhibition of bioconversion was observed at the PGA concentrations higher than 40mmol·L −1. The accumulation of product MA also caused a severe feed-back inhibition for its production when the product concentration was above 60mmol·L −1. The kinetic model with the inhibition effect of both substrate and product was simulated by a computer-based least-square arithmatic. The established kinetic model was in good agreement with the experimental data.

Bioreduction of phenylglyoxylic acid to R-(−)-mandelic acid by Saccharomyces cerevisiae FD11b

Screening from 40 microorganisms belonging to different taxonomical groups ( Saccharomyces cerevisiae, Lactoballius, Streptococcus faecalis and Candida albicans) was performed to select the strain with high production rate of R-(−)-mandelic acid (R-MA). A sp. strain S. cerevisiae FD11b with high yield and enantiomeric excess (e.e.) and little byproducts was obtained by means of UV-mutation breeding. In the optimal conditions of pH 6.5, 32 °C, anaerobic and glucose supply rate ( F glu) 0.0833 mmol gdw −1 h −1, the strain FD11b showed a high specific MA production rate ( q p = 0.35 mmol gdw −1 h −1) and enantioselectivity (e.e. = 97.1%). The phenylglyoxylic acid (PGA) concentration showed a remarkable effect on the apparent activity of MA dehydrogenase. The specific production rate ( q p) reached the maximum at 30–40 mM of PGA concentrations. At higher concentrations of PGA more than 40 mM, the q p decreased obviously in a linear way. However, the e.e. of R-MA kept about 95–96.5%, when the PGA concentration was below 60 mM, even at the concentration of PGA 80 mM, the e.e. was still higher than 90%. A modified Monod type equation based on a hypothesis of substrate inhibition could fit the experimental data well. The estimated maximum specific production rate ( q pm) and saturation constant ( K s) were 0.431 mmol gdw −1 h −1 and 5.88 mM, respectively.

Determination of urinary styrene metabolites in the general Italian population by liquid chromatography-tandem mass spectrometry.

To apply mass spectrometry-based techniques for the determination of background levels of metabolites of widespread organic solvents, such as styrene, in unexposed subjects from the general population. The study population consisted of 129 healthy Italian subjects, not occupationally exposed to styrene (67 men; 37% smokers). Urinary levels of mandelic acid (MA) and phenylglyoxylic acid (PGA) were determined by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Using LC-MS/MS, we were able to detect the peaks of MA and PGA in 100% of samples. The distribution of styrene metabolites was log-normal, the geometric means of MA and PGA concentrations being 0.443 mg/g creatinine [geometric standard deviation (GSD) 2.34] and 0.107 mg/g creatinine (GSD 3.49), respectively. The reference intervals estimated for MA and PGA were 0.084-2.339 and 0.009-1.238 mg/g creatinine, respectively. The application of highly sensitive and selective mass spectrometry-based analytical techniques could be useful in the definition of reference values for metabolites of organic pollutants and for better assessment of low-level occupational exposure to organic solvents.

Human urine certified reference material CZ 6009: creatinine, styrene metabolites (mandelic acid and phenylglyoxylic acid).

The reference material was prepared by freeze-drying pooled urine samples obtained from healthy persons occupationally exposed to styrene. The concentrations of mandelic acid (MA), phenylglyoxylic acid (PGA), and hippuric acid (HA) in urine were determined by three modes of high-performance liquid chromatography (HPLC). For isochronous stability testing the urinary mandelic acid and phenylglyoxylic acid concentrations were followed over a 24-month period for a preliminary batch by use of HPLC. No changes of the concentration values were found. The creatinine concentration was stable for more than five years. Standard Reference Material NIST 914a Creatinine was used for traceability purposes for creatinine. Pure chemicals MA and PGA were used for traceability purposes. Control material ClinChek-Urine Control (Recipe) was analyzed simultaneously. The mean values of MA and PGA compare well with the means and fall within the control range of control samples. Results from homogeneity, stability, and traceability testing were evaluated using the statistical program ANOVA. The certified values and their uncertainties were evaluated from the results of interlaboratory comparisons, and homogeneity and stability tests. The values are unweighed arithmetical averages of accepted results and their uncertainties are combined uncertainties (coverage factor=1).

Biological monitoring of styrene exposure and possible interference of acetone co-exposure.

The object of this study is the evaluation of some of the toxicokinetic effects of exposure to low concentrations of styrene, and the possible influence of simultaneous exposure to acetone. To this end we studied 19 workmen simultaneously exposed to both solvents. During a week of 4-h work shifts, the workmen underwent daily personal environmental monitoring and the collection of urine samples, at both the beginning and the end of the work period, for the determination of mandelic acid (MA) and phenylglyoxylic acid (PGA). The presence of the solvents in the atmosphere was evaluated using passive personal monitoring and gas chromatography. Average exposure to styrene and acetone were respectively 72.2 mg/m3 and 225.7 mg/m3. MA and PGA were quantified by high-performance liquid chromatography (HPLC). The daily urinary concentration averages, both at commencement and at the end of work shifts, of both the metabolites studied and of the sum of the two were in statistically significant linear correlation with the average daily styrene exposure. Concentrations of MA and PGA in urine samples collected at the start of the work shift averaged 61.5 mg/g creatinine and 45.2 mg/g creatinine respectively, representing 41% and 72% of those at the endo of the work shift which were 148.3 and 62.6 mg/g creatinine, respectively. With equal exposure to styrene, the average urinary concentrations of MA and PGA at both the beginning and end of the work shift increased significantly (P < 0.001) during the working week. Moreover, we found that with equal exposure to styrene, urinary excretion of MA, PGA and MA + PGA at the end of the shift was inversely correlated with the intensity of acetone exposure (r = 0.4659, 0.3410 and 0.542 respectively, P < 0.001). In conclusion, these results express slower urinary kinetics of styrene metabolites than is usually described in the literature, and favor a tendency to accumulate MA and PGA in the organism as a consequence of the retardation of urinary excretion kinetics. Acetone apparently represents one of the determining factors in this interference.