Determination of diacetyl in workplace air by high performance liquid chromatography using 4-nitro-o-phenylenediamine as precolumn derivatization / 环境与职业医学

Background Diacetyl (DC) is widely used in the food flavoring industry and excessive occupational exposure to DC can cause serious respiratory diseases. However, there is no corresponding national standard method for the determination of DC in the air of workplace. Objective To establish a method for the determination of DC in workplace air by high performance liquid chromatography using 4-nitro-o-phenylenediamine (NPDA) as precolumn derivatization. Methods DC in the air of workplace was collected by solution absorption method. This experiment used NPDA as the derivatization reagent. By adjusting acidity of solution and optimizing concentration ration of DC/NPDA, derivatization temperature, and time, a method for the determination of DC in workplace air was proposed, and its performance indexes such as linearity, detection limit, and lower limit of quantification were obtained. Sampling efficiency was evaluated by relative comparison method, and sample stability was evaluated by sample preservation test. Accuracy and precision of the method were evaluated by standard addition recovery test with blank samples, and an interference test was carried out by adding standard samples. The established method was applied to actual samples to evaluate its adaptability. Results A combination of 60 °C for 2 h was selected for derivatization because a higher derivatization reaction temperature and a longer reaction time associated with a higher derivatization efficiency. The solution was separated by SB-C18 column (250 mm×4.6 mm, 5 μm) at 30 ℃, using a mixture of methanol and water (v/v, 65%/35%) as mobile phase with an elution flow rate of 1.0 mL·min−1, and was detected with a variable wavelength detector (λmax=257 nm) by qualitative analysis based on retention time and quantitative analysis based on external standard method. In terms of the proposed method, the linear range of detection was from 5 μg·L−1 to 2000 μg·L−1, with a correlation coefficient of 0.9999, and a detection limit of 1.3 μg·L−1, the quantitative detection of the lower limit was 4.3 μg·L−1, with a sampling volume V0 of 3.0 L, the minimum detection concentration was 4.3 μg·m−3, and the minimum quantitative concentration was 14.3 μg·m−3. The recovery rate was 99.1%-100.8%, the intra-batch precision was 0.5%-3.0%, and the inter-batch precision was 1.2%-2.0%. The average sampling efficiency of this method was 94.5%, and the sample could be stored at 4 °C for at least 14 d. The coexisting components in the air of the workplace did not interfere with the determination of DC. The DC content in the air of a flavor workplace was 5.86-8.85 mg·m−3. Conclusion A determination method for DC in workplace air by high performance liquid chromatography using NPDA as precolumn derivatization after being collected by 1.0% phosphoric acid absorbent is proposed and has the advantages of simple operation, high sensitivity, and good accuracy. With no DC loss and degradation, the method may satisfy the request for DC determination in the air of workplace.

Reactive oxygen species and nitric oxide scavenging nanoparticles alleviating rheumatoid arthritis through adjusting the seeds and growing soils

Normalizing inflamed soils including reactive oxygen species (ROS), nitric oxide (NO), cell-free DNA, and regulating inflammation-related seeds such as macrophages, neutrophils, fibroblasts, represent a promising strategy to maintain synovial tissue homeostasis for rheumatoid arthritis (RA) treatment. Herein, ROS scavenging amphiphilic block copolymer PEGylated bilirubin and NO-scavenging PEGylated o-phenylenediamine were fabricated to self-assemble into a dually responsive nanoparticle loaded with JAK inhibitor notopterol (Not@BR/oPDA-PEG, NBOP NPs). The simultaneous ROS and NO depletion combined with JAK-STAT pathway inhibition could not only promote M2 polarization to reduce further ROS and NO generation, but also decrease cytokines and chemokines to prevent immune cell recruitment. Specifically, NBOP NPs responded to high level ROS and NO, and disintegrated to release notopterol in inflamed joints as the hydrophobic heads BR and oPDA were transformed into hydrophilic ones. The released notopterol could inhibit the JAK-STAT pathway of inflammatory cells to reduce the secretion of pro-inflammatory cytokines and chemokines. This strategy represented an effective way to regulate RA soils and seeds through breaking the positive feedback loop of inflammation aggravation, achieving an excellent anti-RA efficacy in a collagen-induced arthritis rat model. Taken together, our work offered a reference to adjust RA soils and seeds for enhanced RA treatment.

The Value of Adding 1,3-Diphenylguanidine, N-Cyclohexyl-N-Phenyl- 4-Phenylenediamine, N-Cyclohexylthiophthalimide and Ylangylang oil to the European Baseline Series to Improve the Detection of Rubber and Fragrance Allergy Among Patients Suspected with Contact Dermatitis in Hospital Selayang

@#Allergic contact dermatitis affects 15 to 20% of the population. The pattern of contact allergy varies across nations. Therefore, many countries utilize their unique individual baseline series for patch testing. In this study, we aimed to assess the outcome of rubber and fragrance allergy detection with the addition of 1,3-Diphenylguanidine. N-Cyclohexyl-N-Phenyl-4-Phenylenediamine, N-Cyclohexylthiophthalimide and Ylang ylang oil.

A case of hair dye-induced contact anaphylaxis

Anaphylaxis is a sudden-onset life-threatening systemic hypersensitivity reaction. Allergens, such as foods, stinging insect venoms, and drugs, are the globally important causative factors for anaphylaxis. Para-phenylenediamine (PPD), an aromatic amine, is a well-known hair dye component that can act as a skin irritant and/or a skin sensitizer. As an allergen, PPD can induce various reactions; the most common being contact dermatitis, a delayed-type hypersensitivity reaction. Anaphylaxis or other immediate hypersensitivity reactions by hair dye contact is extremely rare, with only a few cases reported worldwide. Here, we report a case of a 63-year-old female who presented to the Emergency Department with dyspnea, rash, vomiting, and diarrhea within minutes after using a hair dye product containing PPD. Her past medical history includes urticaria of unknown cause. Her total IgE antibody level was increased to 630 kU/L. Skin prick and patch tests with the hair dye she applied at the time of anaphylaxis demonstrated an immediate reaction. An additional patch test with 25 common contact allergens showed positive reaction to PPD. This is the first case report of hair dye-induced contact anaphylaxis presenting sensitization to PPD in Korea.

A Solid-State Electrochemical Sensor for Determination of Effective Acidity of Aqueous Solutions with High Acidity / 分析化学

A new all-solid state electrode modified with poly ( o-aminophenol-co-o-phenylenediamine ) film was prepared by cyclic voltammetry.The electrochemical response of the electrode to various solutions in the available acidity range of 1.00 × 10-12-10.0 mol/L was studied by cyclic voltammetry.The results showed that the reduction peak potentials and the available acidity of solution showed good linear relationship in 3 stages of 1.00×10-10-0.10 mol/L, 0.10-2.00 mol/L and 2.00-10.0 mol/L respectively, and the regression equations were Epc=0.0456lgC(H+)-0.295, Epc=0.0803c(H+)-0.309, and Epc=0.0278c(H+)-0.188, respectively.There were similar responses in the solutions of H2 SO4 , HNO3 and HClO4 in the concentration range of 1.00-8.00 mol/L.The preparation method of electrode was simple, and the determination range of available acidity was as wide as 1.0 ×10-10-10.0 mol/L, which laid the foundation for the development of solid-state electrochemical sensors for determination of acidity of high acidity solution.

Effects of p-Phenylene diamine on liver and kidney functions of occupational exposed workers / 中华劳动卫生职业病杂志

Objective@#To study the effect of p-phenylenediamine (PPD) on liver and kidney function in occupational exposed workers.@*Methods@#Workers in a hair dye production enterprise which used p-phenylenediamine as a raw material for production were selected as the main research population. Then we conducted a questionnaire survey on the basic conditions of workers and conducted occupational health checkups on general health status, liver and kidney function. Occupational health examination assessment results were tested in Taizhou Cancer Hospital. All data was built using EpiData 3.1 software, and statistical analysis was performed using software SPSS 20.0.@*Results@#The liver function indicators including direct bilirubin, prealbumin, total protein, and white protein, globulin, aspartate aminotransferase, glutamyl transpeptidase, and total bilirubin in the workers exposed to high concentration of PPD were at high normal values, and these indicators were significantly different from low PPD concentration group (P<0.05) . The serum creatinine and serum uric acid in the renal function index were significantly higher in workers exposed to PPD than in workers exposed to low concentrations and in the control group (P<0.05) .@*Conclusion@#Occupational exposed to PPD may have a hazard to the workers’ liver and kidney function. Long-term occupational exposure to PPD may lead to increased cumulative exposure of workers, which may cause potential chronic liver and kidney damage in occupationally exposed populations.

Effects of p-phenylenediamine on lung function and health-related quality of life of workers / 中华劳动卫生职业病杂志

Objective@#To study the effects p-phenylenediamine (PPD) on lung function and health-related quality of life of occupational exposed workers.@*Methods@#This study was based on data from a company that produce hair dye containing PPD in China. Workers who exposed to PPD were selected as the study group, and workers un-exposed to PPD were selected as the control group. Questionnaires on health-related quality of life of workers using the 36-item Short Form Health Survey (SF-36) . Occupational health examination assessment results were tested in Taizhou Cancer Hospital. The lung function test includes forced vital capacity (FVC) , forced expiratory volume in one second (FEV1.0) , and ratio of FEV1.0 to FVC (FEV1.0/FVC) .@*Results@#The difference in systolic blood pressure between the PPD exposed group and the control group was statistically significant (P<0.05) . FVC, FEV1.0, and FEV1.0/FVC of the lung function indexes in the exposed group were lower than those in the control group (P<0.05) . In the health-related quality of life, body pain (P=0.002) , general health (P=0.029) , vitality (P=0.038) , and mental health (P=0.003) were lower in the exposed group than in the control group.@*Conclusion@#Occupational exposed to PPD may induce hazard to the workers’lung function and may cause detrimental effect on workers’ health-related quality of life.

Patch tests with commercial hair dye products in patients with allergic contact dermatitis to para‑phenylenediamine.

Background: Hair dye is one of the most common causes of allergic contact dermatitis. The main allergen has been identified as para‑phenylenediamine. To prevent the recurrence of contact dermatitis to para‑phenylenediamine, patients should discontinue the use of para‑phenylenediamine‑containing hair dye products. However, many patients are unable to discontinue their use for cosmetic or social reasons. Sometimes, they continue to have symptoms even after switching to so‑called “less allergenic” hair dyes. Objectives: To evaluate the safety of 15 commercially available hair dye products in patients with allergic contact dermatitis due to para‑phenylenediamine. Methods: We performed patch tests using 15 hair dyes that were advertised as “hypoallergenic,” “no para‑phenylenediamine” and “non‑allergenic” products in the market. Results: Twenty three patients completed the study and 20 (87.0%) patients had a positive patch test reaction to at least one product. While four (26.7%) hair dye products contained para‑phenylenediamine, 10 (66.7%) out of 15 contained m‑aminophenol and 7 (46.7%) contained toluene‑2,5‑diamine sulfate. Only one product did not elicit a positive reaction in any patient. Limitations: Small sample size and possibility of false‑positive reactions. Conclusions: Dermatologists should educate patients with allergic contact dermatitis to para‑phenylenediamine about the importance of performing sensitivity testing prior to the actual use of any hair dye product, irrespective of how it is advertised or labelled.

Analysis of the Results from the Patch Test to Para-Phenylenediamine in the TRUE Test in Patients with a Hair Dye Contact Allergy

BACKGROUND: Para-phenylenediamine (PPD) is the primary patch test screening agent for hair dye contact allergy (HDCA). However, no recent studies have been published that describe the results of reactions to patch tests using PPD and hair dyes in Korea. OBJECTIVE: To analyze the results of the patch tests to PPD using the thin-layer rapid use epicutaneous (TRUE) Test system in patients with HDCA and to investigate patients' awareness that hair dyes contains allergens, which cause the development of HDCA. METHODS: Eighty-four patients with suspected HDCA (32 men and 52 women) underwent patch testing using the TRUE Test system and their own hair dyes. The patients' demographic data, behavior associated with hair dyeing, and clinical manifestations of HDCA were examined retrospectively. RESULTS: Positive patch-test reactions to hair dyes occurred in 53.6% of patients who used hair dyes, and they were diagnosed with HDCA. Although there was a significant correlation between HDCA and PPD sensitization (p=0.001), only 40% of the patients with HDCA showed positive reactions to PPD. Of the 45 patients diagnosed with HDCA, only 7 (15.6%) were aware that their hair dyes contained allergens that caused HDCA. CONCLUSION: This study's findings show that PPD is an effective HDCA marker. However, we propose that investigations on hair dye components other than PPD should be conducted to develop and validate additional predictive HDCA markers.

Determination of oxalate in human plasma and urine by RP-HPLC / 中草药

Objective: To establish a method of reversal phase-high performance liquid chromatography (RP-HPLC) for determining the mass concentration of oxalate in human plasma and urine and to monitor the variation of mass concentration of oxalate in the patients with primary hyperoxaluria (PH) before and after combined liver-kidney transplantation. Methods: Agilent XDBC18 (150 mm × 4.6 mm, 5 μm) column and Agilent Zorbax extend-C18 (12.5 mm × 4.6 mm, 5 μm) guard column were used. Methyl alcohol and aqueous solution containing 0.1 mol/L ammoniom acetate (15∶85) were used as mobile phase. The flow rate was at 1.2 mL/min, ultraviolent determination wavelength was 314 nm, column temperature was at 26.3 ℃, and injection volume was 50 μL. o-phenylenediamine was used as derivating agent, reacted with oxalate in human plasma and urine so as to obtain the compound with better ultraviolet absorption-2, 3-dyhydroxy quinoxaline. Results: The detection limit in human plasma was 0.3 mg/L, the linear range was 1.953-125 mg/L, the average recovery was 94.89%, and its RSD was 4.1%; The detection limit in urine was 0.5 mg/L, the linear range was 1.953-125 mg/L, the average recovery was 94.31%, and its RSD was 3.2%. Conclusion: The method is believable for determining the mass concentration of oxalate with its simplicity, sensibility, repeatability, and better recovery rate.

Contact dermatitis to hair dye: An update.

Exposure to hair dyes has long been known as a significant risk factor for development of allergic contact dermatitis among the exposed population as these lead to severe eczema of face and upper trunk in the consumer and hand eczema in hair-dressers. Currently, para-phenylenediamine (PPD) is the main ingredient used in permanent hair color products in the market and is the most important allergen. Prevalence of PPD sensitization is high in patients with contact dermatitis across all continents, with hair dye use being the commonest cause. In order to decrease the burden of disease, use of alternative natural dyeing agents among consumers and use of barrier neoprene gloves among hairdressers should be encouraged apart from stringent legislation to reduce the amount of PPD reaching the consumer.

Tatuajes de henna negra: revisión de la literatura a partir de un caso clínico / Black henna tattoos: case report and review of the literature

En la actualidad los tatuajes de henna negra se utilizan en forma muy frecuente, por lo que el número de reportes sobre reacciones adversas asociadas a su uso se ha incrementado. La Parafenilendiamina o PPD es el químico que más se adiciona a la henna para intensificar y prolongar la duración del color del tatuaje. Posee un gran poder sensibilizante y se le atribuyen la mayoría de las reacciones, desde dermatitis leve hasta reacciones generalizadas tipo eritema multiforme-like. Se presenta el caso de un paciente de 7 años con lesiones cutáneas frente a segunda exposición a tatuaje de henna. Con diagnóstico de dermatitis de contacto se maneja con corticoidestópicos con excelente respuesta clínica. Como prevención primaria planteamos la necesidad de programas que permitan educar a la comunidad en relación a los riesgos asociados a la exposición a PPD, recomendando el NO uso de tatuajes de henna negra.

Today, black henna tattoos are very commonly used, so the number of reports on adverse reactions associated with its use has increased. The paraphenylenediamine or PPD is the chemical that is most commonly added to henna to intensify and prolong the duration of the color tattoo. PPD act as sensitizer of most of the reactions, from mild dermatitis to generalized reactions erythema multiforme-like. We show a case of a 7 year old patient with skin lesions that appears during the second exposure to henna tattoos. We made the diagnosis of a contact dermatitis and we manage it with topical corticosteroids with excellent clinical response. As primary prevention we suggest the need of educational programs for the community regarding the risks associated with the exposure of PPD, and avoiding the use of black henna tattoos.

Contact Vitiligo Associated with Allergic Contact Dermatitis to Para-phenylenediamine / 대한피부과학회지

Contact vitiligo with allergic contact dermatitis is a rare condition. Early diagnosis of contact vitiligo is imperative, as it could halt the progression of depigmentation, unlike idiopathic vitiligo. We herein report a case of contact vitiligo with allergic contact dermatitis due to para-phenylenediamine.

Suicide by para-phenylenediamine poisoning.

Twenty three cases of acute para-phenylenediamine poisoning were examined clinically at emergency ward of Rama Medical College Hospital, Kanpur (Uttar Pradesh) irrespective of age, sex and socio-economic strata along with route and manner of administration of the poison. Albuminuria, anaemia, hypocalcemia, leucocytosis, thrombocytopenia, increased serum bilirubin, prolonged bleeding and clotting time alongwith increased levels of liver enzymes and serum creatinine were observed as significant bio-chemical parameters; on investigation in respect to complete haemogram, liver function test, renal function test, serum electrolytes, serum CPK levels and arterial blood gas analysis. The para-phenylenediamine is the ingredient of a traditional cosmetic hair dye available with the trade name Godrej expert powder hair dye, which is orally administered mainly with an intention to commit suicide, sometimes accidentally and very rarely as homicidal poison by hair dye users. The suicidal poisoning is more common in females as compared to males. The systemic toxicity of PPD has serious consequences which may eventually lead to death. The cases are reported with the advice “public education and strict control over the sale and distribution of para-phenylenediamine should be done to reduce poisoning by this agent”.

Severe inflammatory and keloidal, allergic reaction due to para-phenylenediamine in temporary tattoos.

Hair coloring with henna has been popular in Turkey for years. In recent years since the tattoos are applied by the street vendors in most of the beach places in Turkey, skin coloring with henna has also increased. Henna can be used alone or in combination with other coloring agents. Henna alone can be safe but due to additives such as para-phenylenediamine (PPD), p-toluenediamine and various essential oils, allergic contact reactions may occur. We report a 22-year-old man who developed severe inflammatory and keloidal, moderately bullous allergic reaction after henna paint-on tattoo. We did a patch test separately with these painting products (henna powder, PPD) and with the European standard series. PPD was strongly positive (+++) on day 2 and remained positive for following days. After treating with topical clobetasol-17 butyrate, resolution was obtained in two weeks. But some keloidal reaction remained.

Molecular Recognition Properties of p-Phenylenediamine-Imprinted Polymers / 分析化学

Two p-phenylenediamine (p-PD)-imprinted polymers, P (MAA) and P (AA), were synthesized using methacrylic acid (MAA) and acrylamide(AA) as functional monomer, respectively, in order to prepare molecular recognition material with high selectivity for p-PD and explore the feasibility of methods such as molecular spectrometry and computational approach of quantum chemistry for the selection of functional mono mer with high imprinting efficiency.The molecular recognition properties of the imprinted polymers were evaluated by high performance liquid chromatography.The results indicated that P(AA) exhibited no imprint ing effect for p-PD, while P(MAA) can bind p-PD selectively(k' =3.57), which showed remarkable imprint ing effect (IF=2.95), and p-PD and its analogues o-phenylenediamine and p-aminobenzoic acid can almost realize baseline separation on P (MAA) column in the mobile phase of methanol.Furthermore, we made a comparative study on the interaction of p-PD with MAA and AA by spectroscopic techniques such as UV and fluorometry as well as HF/6-31G~* computational approach.The results demonstrated that the complex of p-PD-MAA was more stable than that of p-PD-AA, which can give a good explanation for the molecular recog nition properties of P (MAA) and P (AA).The study indicated that both molecular spectrometry (UV and fluorometry)and computational approach of quantum chemistry can be employed as efficient means for the selection of efficient functional monomer.The results showed that fluorometry is sensitive and convenient for the choice of functional monomer if the template molecule is fluorescent.

Contact dermatitis with henna tattoo.

Allergic and irritant reactions to henna are rare. Para-phenylenediamine, which is sometimes added to obtain a dark, blackish henna, causes the majority of contact dermatitis reported related with tattoos. Allergic contact dermatitis due to temporary paint-on tattoo with black henna is described in two adolescents.

A Case of Allergic Contact Dermatitis due to Henna Tattooing / 대한피부과학회지

Tattooing and other forms of body art have recently become popular fashion accessories worldwide. Temporary henna tattooing has also become increasingly popular and is readily available. Henna, which is called Mehndi in Indian, is a plant that is commonly used as a temporary dyeing agent. Para-phenylenediamine (PPD) is added to the Henna tattooing process in most cases to hasten the drying process and enhance darkness. Since PPD is widely recognized as a sensitizer, the risk of allergic contact dermatitis from henna tattoo mixtures is increasing. We report a case of contact dermatitis from a henna tattoo mixture, which developed 2 weeks after henna tattooing.

Manufacture of glucose oxidase electrode immobilized in poly o-phenylenediamine film / 第三军医大学学报

0.05). Conclusion The sensors can eliminate the interference of Ac effectively and lay a basis for the development of practical blood sugar detector.

Determination of Phenylenediamine in Oxidative-type Hair Dyes by Capillary Column Gas Chromatography / 环境与健康杂志

Objective To establish a method for determination of p-phenylenediamine,m-phenylenediamine,o-phenylenediamine in oxidative-type hair dyes.Methods The samples of oxidatve-type hair dyes were solved by ethyl acetate,then followed by centrifuged,extracted.The extraction was qualitatively and quantitatively analyzed by gas chromatography,the working condition was optimized also.Results The linear range for p-phenylenediamine,m-phenylenediamine,o-phenylenediamine was 25-400 ?g/ml,r=0.999 1-0.999 9,the detection limits were 3.1,3.6,3.4 ?g/ml respectively,the standard recovery rates were 86.8%-104.3%,RSDs were 2.3%-4.5%(n=3).Conclusion This method was simple and rapid,it can be effectively applied in extraction and separation of phenylenediamine in oxidative-type hair dyes.