Background
Allergic contact dermatitis caused by p‐phenylenediamine (PPD) is a health concern for hair dye users. Because of its lower sensitization potency, the PPD derivative ...2‐methoxymethyl‐p‐phenylenediamine (ME‐PPD) has been developed as an alternative hair dye for primary prevention. However, cross‐elicitation responses can occur in PPD‐allergic subjects.
Objectives
To compare cross‐elicitation responses to ME‐PPD in open use and diagnostic patch testing of PPD‐allergic subjects with hair dye‐related allergic contact dermatitis.
Methods
Reactions to ME‐PPD were investigated in 25 PPD‐allergic subjects by performing (1) 45‐minute open use testing with a hair dye containing 2.0% of either ME‐PPD or PPD, and (2) patch testing with increasing ME‐PPD concentrations (0.1%–2.0% pet.).
Results
Of the 25 PPD‐allergic subjects, 21 (84%) reacted to open use testing with a hair dye containing 2.0% PPD, and testing with 2.0% ME‐PPD led to cross‐elicitation in 12 (48%). When patch tested with increasing ME‐PPD concentrations, 13 (52%) cross‐reacted at 0.1% (lowest dose) and 21 (84%) at 2.0% (highest dose), indicating decreased reactivity as compared with published PPD dose‐response data.
Conclusion
In line with the decreased cross‐reactivity of ME‐PPD in hair dye open use testing, PPD‐allergic subjects show an attenuated cross‐elicitation dose response to ME‐PPD in patch testing.
Recently, roadway releases of N,N′-substituted p-phenylenediamine (PPD) antioxidants and their transformation products (TPs) received significant attention due to the highly toxic 6PPD-quinone. ...However, the occurrence of PPDs and TPs in recycled tire rubber products remains uncharacterized. Here, we analyzed tire wear particles (TWPs), recycled rubber doormats, and turf-field crumb rubbers for seven PPD antioxidants, five PPD-quinones (PPDQs), and five other 6PPD TPs using liquid chromatography-tandem mass spectrometry. PPD antioxidants, PPDQs, and other TPs were present in all samples with chemical profiles dominated by 6PPD, DTPD, DPPD, and their corresponding PPDQs. Interestingly, the individual PPDQ/PPD and TP/PPD ratios significantly increased as total concentrations of the PPD-derived chemical decreased, indicating that TPs (including PPDQs) dominated the PPD-derived compounds with increased environmental weathering. Furthermore, we quantified 15 other industrial rubber additives (including bonding agents, vulcanization accelerators, benzotriazole and benzothiazole derivatives, and diphenylamine antioxidants), observing that PPD-derived chemical concentrations were 0.5–6 times higher than these often-studied additives. We also screened various other elastomeric consumer products, consistently detecting PPD-derived compounds in lab stoppers, sneaker soles, and rubber garden hose samples. These data emphasize that PPD antioxidants, PPDQs, and related TPs are important, previously overlooked contaminant classes in tire rubbers and elastomeric consumer products.
Poly(o‐phenylenediamine) (POPD)‐derived functional carbon materials with excellent capacitive performance (see figure) are successfully synthesized by means of an integrated one‐step process, in ...which FeCl3 not only oxidizes the polymerization of the organic monomers but also activates the carbonization. Furthermore, extensive research has proved that this strategy to discover novel carbons is useful not only for capacitors but also for other energy storage/conversion devices.
Summary
Henna, the dried and powdered leaf of Lawsonia inermis, is widely used as a dye for the skin, hair, and nails, and as an expression of body art, especially in Islamic and Hindu cultures. As ...it stains the skin reddish‐brown, it is also called red henna. Black henna is the combination of red henna with p‐phenylenediamine (PPD), and is used for temporary ‘black henna tattoos’. This article provides a full review of the side‐effects of topical application of red and black henna, both cutaneous (allergic and non‐allergic) and systemic. Red henna appears to be generally safe, with rare instances of contact allergy and type I hypersensitivity reactions. In children with glucose‐6‐phosphate dehydrogenase deficiency, topical application of henna may cause life‐threatening haemolysis. Black henna tattoos will induce contact allergy to its ingredient PPD at an estimated frequency of 2.5%. Once sensitized, the patients may experience allergic contact dermatitis from the use of hair dyes containing PPD. There are often cross‐reactions to other hair dyes, dyes used in textiles, local anaesthetics, and rubber chemicals. The sensitization of children to PPD may have important consequences for health and later career prospects. Systemic toxicity of black henna has been reported in certain African countries.
para-Phenylenediamine quinones (PPD-Qs) are a newly discovered class of transformation products derived from para-phenylenediamine (PPD) antioxidants. These compounds are prevalent in runoff, ...roadside soil, and particulate matter. One compound among these, N-1,3-dimethylbutyl-n′-phenyl-p-phenylenediamine quinone (6PPD-Q), was found to induce acute mortality of coho salmon, rainbow trout, and brook trout, with the median lethal concentrations even lower than its appearance in the surface and receiving water system. However, there was limited knowledge about the occurrence and fate of these emerging environmental contaminants in wastewater treatment plants (WWTPs), which is crucial for effective pollutant removal via municipal wastewater networks. In the current study, we performed a comprehensive investigation of a suite of PPD-Qs along with their parent compounds across the influent, effluent, and biosolids during each processing unit in four typical WWTPs in Hong Kong. The total concentrations of PPDs and PPD-Qs in the influent were determined to be 2.7–90 and 14–830 ng/L. In the effluent, their concentrations decreased to 0.59–40 and 2.8–140 ng/L, respectively. The median removal efficiency for PPD-Qs varied between 53.0 and 91.0% across the WWTPs, indicating that a considerable proportion of these contaminants may not be fully eliminated through the current processing technology. Mass flow analyses revealed that relatively higher levels of PPD-Qs were retained in the sewage sludge (20.0%) rather than in the wastewater (16.9%). In comparison to PPDs, PPD-Qs with higher half-lives exhibited higher release levels via effluent wastewater, which raises particular concerns about their environmental consequences to aquatic ecosystems.
Summary
Background
Penetration, autoxidation and N‐acetylation of p‐phenylenediamine (PPD) have been studied in vitro and ex vivo. However, a clear understanding of in vivo PPD penetration and the ...formation of PPD derivatives is lacking.
Objectives
To obtain insights into the in vivo penetration, clearance and formation of PPD derivatives in human skin.
Methods
Patch test chambers containing PPD 1% pet. were applied to the forearms of two human volunteers, with increasing application times. Non‐invasive Raman microspectroscopy was used for detection of PPD (derivatives) in skin at several follow‐up times.
Results
Application of a PPD 1% pet. patch for 30 min resulted in substantial amounts of PPD in the stratum corneum of 90 mg PPD/g keratin. PPD contents were highest after three applications for 1 h each (330 mg PPD/g keratin), followed by single applications for 2 h 40 min, 2 h, and 23 h. The PPD half‐time in the skin was 3 h. No spectral contributions of Bandrowski's base, monoacetyl‐PPD and diacetyl‐PPD were detected.
Conclusions
We have gained insights into the in vivo penetration of PPD in human skin by using non‐invasive Raman spectroscopy. Penetration into the skin was fast, and the PPD concentrations detected in the stratum corneum were high. PPD was detected in both the stratum corneum and the viable epidermis. Oxidized or acetylated PPD derivatives could not be detected.
p-Phenylenediamines (PPDs) are widely used as antioxidants in tire rubber, and their derived quinone transformation products (PPD-Qs) may pose a threat to marine ecosystems. A compelling example is ...N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine (6PPD)-derived quinone, called 6PPD-Q, as the causal toxicant for stormwater-linked acute mortality toward coho salmon. However, the knowledge of the co-occurrences of PPDs and PPD-Qs and their transport from freshwater to oceanic waterbodies on a large geographical scale remains unknown. Herein, we performed the first large-scale survey of these chemicals in sediments across urban rivers, estuaries, coasts, and deep-sea regions. Our results demonstrated that seven PPDs and four PPD-Qs are ubiquitously present in riverine, estuarine, and coastal sediments, and most of them also occur in deep-sea sediments. The most dominant chemicals of concern were identified as 6PPD and 6PPD-Q. Total sedimentary concentrations of PPDs and PPD-Qs presented a clear spatial trend with decreasing levels from urban rivers (medians: 39.7 and 15.2 ng/g) to estuaries (14.0 and 5.85 ng/g) and then toward coasts (9.47 and 2.97 ng/g) and deep-sea regions (5.24 and 3.96 ng/g). Interestingly, spatial variation in the ratios of 6PPD to 6PPD-Q (R 6PPD/6PPD‑Q) also presented a clear decreasing trend. Our field measurements implied that riverine outflows of PPDs and PPD-Qs may be an important route to transport these tire rubber-derived chemicals to coastal and open oceans.
In this study, we report on a bi-metal organic framework, MOF-919 (Fe-Cu), capable of bifunctional-enzyme mimicking activity with oxidase- and peroxidase-like activities. The catalytic activities ...were examined by using
-phenylenediamine (OPD) as a chromogenic substrate to study oxidase- and peroxidase-like mimetics. Based on our findings, we developed a simple epinephrine colorimetric biosensor with a broad linear range (1-100 μM) and a low detection limit (0.298 μM). This approach provides evidence for transition metal-based pristine bi-metallic MOFs capable of reproducing both oxidase-peroxidase properties, which could be applied as new nanosensors.
Tire wear compounds N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine (6PPD) and its derivative 6PPD-quinone have been considered as emerging pollutants and attracted much attention recently. As an ...antioxidant and antiozonant widely used, 6PPD would be released during the production or use of rubber-related products. Because of the mass production and wide use of rubber-related products, 6PPD and 6PPD-quinone have been identified to be ubiquitous in the environment. In this study, we firstly reviewed the current available literature on the analytical procedures, concentrations and distribution of 6PPD and 6PPD-quinone, and then investigated the potential toxic effects of these two compounds on aquatic organisms. Current studies have been mainly focused on the occurrence of 6PPD and 6PPD-quinone in dust and water, while available information on atmosphere, soil, sediments and organisms is limited. The fate and distribution of 6PPD and 6PPD-quinone would be influenced by environmental factors such as temperature, illumination, and storm events, etc. Although 6PPD and 6PPD-quinone have potential adverse effects on aquatic organisms, and 6PPD-quinone has species-specific toxicity, toxicological mechanisms of these compounds are still unclear. Based on the review and analysis of current studies, some suggestions for future research of 6PPD and 6PPD-quinone are given.
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•This is a first review for tire wear chemicals 6PPD and 6PPD-quinone in environment.•Analytical methods of 6PPD and 6PPD-quinone in different matrices were summarized.•Environmental occurrence and fate of 6PPD and 6PPD-quinone were discussed.•Potential toxicity of 6PPD and 6PPD-quinone to aquatic organisms was investigated.•Deficiencies and perspectives on research of 6PPD and 6PPD-quinone were identified.
N-(1,3-Dimethylbutyl)-N′-phenyl-p-phenylenediamine-quinone (6PPD-Q) is a recently identified contaminant that originates from the oxidation of the tire antidegradant 6PPD. 6PPD-Q is acutely toxic to ...select salmonids at environmentally relevant concentrations, while other fish species display tolerance to concentrations that surpass those measured in the environment. The reasons for these marked differences in sensitivity are presently unknown. The objective of this research was to explore potential toxicokinetic drivers of species sensitivity by characterizing biliary metabolites of 6PPD-Q in sensitive and tolerant fishes. For the first time, we identified an O-glucuronide metabolite of 6PPD-Q using high-resolution mass spectrometry. The semiquantified levels of this metabolite in tolerant species or life stages, including white sturgeon (Acipenser transmontanus), chinook salmon (Oncorhynchus tshawytscha), westslope cutthroat trout (Oncorhynchus clarkii lewisi), and nonfry life stages of Atlantic salmon (Salmo salar), were greater than those in sensitive species, including coho salmon (Oncorhynchus kisutch), brook trout (Salvelinus fontinalis), and rainbow trout (Oncorhynchus mykiss), suggesting that tolerant species might detoxify 6PPD-Q more effectively. Thus, we hypothesize that differences in species sensitivity are a result of differences in basal expression of biotransformation enzyme across various fish species. Moreover, the semiquantification of 6PPD-Q metabolites in bile extracted from wild-caught fish might be a useful biomarker of exposure to 6PPD-Q, thereby being valuable to environmental monitoring and risk assessment.
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