Squalene Monohydroperoxide Research Articles

A practical clinical device for evaluating changes to the skin's sebum from ozone.

It is known that tropospheric ozone (O3) generated from pollutants reacting with UV forms lipid peroxidation products and induces oxidative stress to the skin. With the ever-increasing consumer awareness of the effects pollution has on skin, more testing methods will be needed to evaluate cosmetic ingredients. Recently, others have shown how antioxidants are able to reduce the effects from ozone on skin through in vitro, ex vivo and clinical studies where human subjects place their arms into large stationary chambers. To develop a small, easy to use ozone exposure module (OEM) that can be used on various sites of the body and to validate this device for use in testing the ability of topical products to mitigate the effects of ozone exposure on the skin. We have produced an OEM which can generate levels of ozone in excess of 1000 ppb and can be set to achieve the equivalent exposure to what is found in polluted environmental conditions. After exposure we used D-squame discs to remove the sebum and analytically quantitate squalene depletion. Squalene, which is very sensitive to ROS, easily oxidizes into early metabolite squalene monohydroperoxide (SQOOH) with ozone exposure. We were able to show decreases in squalene levels after exposure and protective effects from a topical formulation. This generator will be a useful tool for researchers to easily create a small and safe exposure from ozone for clinical testing.

Unveiling an unexpected superoxide-mediated photooxidation mechanism of squalene monohydroperoxides to squalene hydroperoxy cyclic peroxides through ESR and LC–MS/MS analyses

Lipid cyclic peroxides are a rarely reported and documented class of compounds in the human organism. Recently, we reported the formation of squalene (SQ) hydroperoxy cyclic peroxides derived from SQ monohydroperoxide isomers (SQ-OOHs) for the first time. Notably, we successfully detected and quantified cis-2-OOH-3-(1,2-dioxane)-SQ in the human skin. Nevertheless, the underlying mechanism governing the formation of these compounds remained elusive. Therefore, in the current study, we set to determine the reaction’s mechanism. To this end, a comprehensive analysis of the precise conditions involved in the onset and propagation of this conversion was carried out by oxidizing total SQ-OOHs under different conditions, including singlet oxygen (1O2), thermal, and photoinduced oxidations monitored by quantifying the generated 2-OOH-3-(1,2-dioxane)-SQ using liquid chromatography-tandem mass spectrometry (LC–MS/MS). Radical intermediates were thoroughly investigated using Electron Spin Resonance (ESR) with the aid of spin traps and radical references. Moreover, calculations of SQ-OOHs’ electrostatic charges were performed on Spartan 18 software. We found that the reaction is ideally induced and favored under photooxidation in the presence of 3O2 in hexane, and that superoxide radical (O2•−) is the first key intermediate in this mechanism, whereas peroxyl radicals were the major species observed throughout the oxidation. Chemical calculations provided an explanation for the targeting of tertiary SQ-OOHs by this reaction and gave further evidence on the proposed heterolytic cleavage initiating the reaction. The novel oxidation mechanism suggested herein offers new insights into understanding lipid secondary oxidation and is a promising finding for further studying lipid cyclic peroxides in general.

Malassezia restricta-mediated Lipoperoxidation: A Novel Trigger in Dandruff

Dandruff is a common scalp disorder with multiple microbial and host-related factors contributing to its aetiology, including alterations in scalp sebum. Despite existing evidence that the yeast Malassezia restricta plays a key role in the onset of dandruff, the interplay of these factors is poorly understood. Recently, squalene monohydroperoxide and malondialdehyde were established as biomarkers of dandruff-afflicted scalp, highlighting the role of sebum lipoperoxidation in the triggering and maintenance of dandruff, although its mechanism of action is unknown. The current study provides evidence that M. restricta mediates sebum peroxidation, leading to production of squalene monohydroperoxide and malondialdehyde. Furthermore, in vitro data show that these lipoperoxidation products act on epidermal cells and alter the skin barrier. These results support the role of Malassezia restricta-induced lipoperoxides as triggers of dandruff, which suggests that blocking their production could be a novel anti-dandruff treatment approach.

Clinical Evaluation of Indian Sandalwood Oil and Its Protective Effect on the Skin against the Detrimental Effect of Exposome

The skin is constantly subject to external stressors (the exposome), including particulate matter and blue light. These can penetrate the deeper layers of the skin, inducing the release of free radicals and triggering an inflammatory cascade of events contributing to cutaneous aging and exacerbating inflammatory skin conditions. This study demonstrates the clinical efficacy of Indian sandalwood oil of varying concentrations against oxidative stress induced by urban dust and blue light. Twenty-two healthy human subjects entered and completed the study of 11 days. Test products containing 0.1%, 1% and 10% of sandalwood oil, as well as a placebo and a comparator control (α-tocopherol), were applied on the different investigational zones of the upper back of each subject. Exposure ensued on day 7, using a controlled pollution exposure system (CPES) and blue light at a wavelength of 412 nm. Sebum was sampled on each investigational zone following the last exposure. The level of squalene monohydroperoxide (SQOOH) was the primary endpoint. A dose-dependent decrease in SQOOH on the zones treated with 10%, 1% and 0.1% of the sandalwood oil formulation compared to the untreated zones was observed. The zone treated with the 10% sandalwood-containing formula demonstrated the highest protective efficacy with the lowest amount of SQOOH. Increasing the concentration of the sandalwood oil increased its protective antioxidant activity. The results collected from this intraindividual comparative is the first clinical trial to suggest that sandalwood oil at a concentration between 1% and 10% protects the skin against the oxidative stress induced by urban dust and blue light exposure.

A novel clinical method to measure skin staining reveals activation of skin damage pathways by cigarette smoke.

BackgroundLong‐term use of cigarettes can result in localised staining and aging of smokers’ skin. The use of tobacco heating products (THPs) and electronic cigarettes (ECs) has grown on a global scale; however, the long‐term effect of these products’ aerosols on consumers’ skin is unknown. This pilot clinical study aimed to determine whether THP or EC aerosol exposure results in skin staining or activation of biomarkers associated with oxidative stress.Materials and methodsEight areas were identified on the backs of 10 subjects. Two areas were used for air control, and two areas exposed to 32‐puffs of cigarette smoke (CS), THP or EC aerosols, which were delivered to the skin using a 3‐cm diameter exposure chamber and smoke engine. Skin colour was measured using a Chromameter. Squalene (SQ), SQ monohydroperoxide (SQOOH) and malondialdehyde (MDA) levels were measured in sebum samples by mass spectrometry and catalase colorimetry.ResultsCS exposure significantly increased skin staining, SQOOH and MDA levels and SQOOH/SQ ratio. THP and EC values were significantly lower than CS; EC values being comparable to air control. THP values were comparable to EC and air control at all endpoints, apart from skin staining. SQ and catalase levels did not change with exposure.ConclusionsCS stained skin and activated pathways known to be associated with skin damage. THPs and ECs produced significantly lower values, suggesting they could offer hygiene and cosmetic benefits for consumers who switch exclusively from smoking cigarettes. Further studies are required to assess longer‐term effects of ECs and THPs on skin function.

Protective effects of 3,4',5,7‐tetrahydroxyflavone against squalene monohydroperoxide‐induced skin wrinkles and its green extraction using deep eutectic solvents

AbstractThree flavone derivatives, 3,4′,5,7‐tetrahydroxyflavone (3,4′,5,7‐THF) and their glycosides 3,4′,5,7‐tetrahydroxyflavone‐3‐rhamnoglucoside, and 3,4′,5,7‐tetrahydroxyflavone‐3‐glucoside, were identified by partial enzymatic conversion of Camellia sinensis seed extract (CSSE). 2,2‐Diphenyl‐1‐picrylhydrazyl radical scavenging activity of these compounds and lipid peroxidation inhibition effects of 3.4′,5,7‐THF were tested to evaluate their antioxidant properties. To investigate the effects of 3,4′,5,7‐THF on squalene monohydroperoxide (SQLOOH)‐induced wrinkle formation, the dorsal skin of SKH1 hairless mice was used. Four weeks of treatment with 3,4′,5,7‐THF reduced wrinkle formation, in contrast to that observed in the group treated with SQLOOH only. A green and simple method has been suggested for the extraction of 3,4′,5,7‐THF from CSSE hydrolysate with nine deep eutectic solvents. A mixture of choline chloride and xylose yielded the best extraction result. These findings suggest that 3,4′,5,7‐THF is a natural compound with potential application in preventing SQLOOH associated skin aging.

Anti-pollution effects of two antioxidants and a chelator-Ex vivo electron spin resonance and in vivo cigarette smoke model assessments in human skin.

Skin damage arising from pollutants in gaseous and particulate matter forms is mainly mediated by oxidative stress. The pollutants directly or indirectly generate free radicals on and in the skin, leading, for example, to MMP up-regulation and damage of collagen fibers. Antioxidants and chelators are used in anti-pollution cosmetics to reduce the harmful effects of free radical generation. We investigated the efficacy of two antioxidants and one chelator in an anti-pollution cigarette smoke model. Free radical generation was measured directly after UV and cigarette smoke exposure ex vivo on pig skin (slaughterhouse waste), by use of Electron Spin Resonance (ESR). Effects of cigarette smoke were compared to those of Urban Dust (NIST-standard). ESR was also used to measure the copper chelation activity of the test products. Following cigarette smoke application in vivo, two markers of lipid peroxidation malondialdehyde (MDA), and squalene monohydroperoxide (SQOOH), were measured from swab solutions taken from the smoke-exposed skin sites. EDTA generated no effect and the non-chelator antioxidant Tocopherol only small antioxidant effects after exposed to cigarette smoke ex vivo as well as in vivo. Only the hydrophilic phenylethanoid H1 showed significant effects. A clear reduction of free radicals ex vivo and further a significant reduction of in vivo lipid peroxide formation was measured. The cigarette smoke model is an ideal method for in vivo assessment of anti-pollution efficacy of topical products with close relation to the real situation of subjects exposed to urban pollution. Further research is required to better understand the role of chelators in anti-pollution cosmetics.

Analysis of squalene and its transformation by-products in latent fingermarks by ultrahigh-performance liquid chromatography-high resolution accurate mass Orbitrap™ mass spectrometry

Transformation of squalene and its by-products in latent fingermarks over time under different storage conditions (light, dark, and underwater) was examined through ultrahigh-performance liquid chromatography-high resolution accurate mass Orbitrap™ mass spectrometry. Complications of assessing fingermark compositional variation over time using multiple samples with varying initial compositions were elucidated and a more rational approach was successfully demonstrated. Squalene was detected in all fresh natural fingermarks deposited on non-porous surfaces and the amount ranged between 0.20 and 11.32 μg/5 fingertips. A notable difference in the transformation of squalene was observed with different storage conditions, where a dark aquatic environment accelerated degradation of squalene compared to dark but dry conditions. Squalene monohydroperoxide was extremely short-lived in natural deposits while the amount of squalene epoxide was still increasing relative to the initial amount, after ageing under dark and aquatic conditions for up to 7 days. Some oxidation by-products of cholesterol were also tentatively identified, which exhibited a growth over time against their initial concentration under any of the storage condition tested. These by-products, therefore, show potential as biomarkers for targeted visualisation of aged deposits.

Significance of Squalene in Rice Bran Oil and Perspectives on Squalene Oxidation.

As an intermediate metabolite during the biosynthesis of sterols, squalene is found ubiquitously in plants and animals. In rice, squalene is contained in rice bran, and consequently, squalene in rice bran oil has gained attention. Studies have shown that the intake of squalene from food sources demonstrate various physiological benefits such as the prevention of cancer and cardiovascular disease. Squalene is also known as an effective antioxidant in edible oils. However, due to its chemical structure, squalene is susceptible to oxidation, which may cause a decline in the nutraceutical and antioxidative effects of squalene in edible oils. Oxidative degradation of squalene also results in the formation of scission products (i.e., aldehydes and ketones) which may lead to off-flavor. Since the rate of squalene oxidation depends on the factors that induce its oxidation (i.e., light or heat), emphasis on oxidation mechanisms is necessary. It has been demonstrated in previous studies that the oxidation products formed by the singlet oxygen oxidation and free radical oxidation of squalene are different, and more recently, we demonstrated that different squalene monohydroperoxide isomers are formed by each oxidation mechanism. We herein discuss the significance of squalene in rice bran oil as well as the oxidative degradation of squalene in edible oils with focus on oxidation mechanisms.

Evaluation of squalene oxidation mechanisms in human skin surface lipids and shark liver oil supplements.

Squalene is a terpenoid found in human skin surface lipids (SSLs) and foods that possesses beneficial properties. However, since oxidation of squalene causes various complications, it is necessary to identify the mechanisms by which squalene is oxidized. In this study, we aimed to determine the oxidation mechanisms of squalene in SSLs and shark liver oil (SLO) supplements by the analysis of squalene monohydroperoxide (SQOOH) isomers, on the basis of our previous finding that different oxidation mechanisms yield different SQOOH isomers. Liquid chromatography-tandem mass spectrometry analysis of SQOOH isomers revealed that squalene in human SSLs was oxidized by singlet oxygen oxidation, whereas squalene in SLO was oxidized mainly by free radicals. As a result, we have presented the first evidence suggesting that the analysis of SQOOH isomers enables estimation of oxidation mechanisms. Estimating oxidation mechanisms by analyzing SQOOH isomers may provide a foundation for the prevention of skin diseases and food deterioration via regulation of squalene oxidation.

A novel method for evaluating the effect of pollution on the human skin under controlled conditions.

Generally considered as a major risk factor for various respiratory diseases, air pollution can also have a significant impact on the skin. To date, there is a plethora of cosmetics products with "anti-pollution" claims. However, these claims have not been fully substantiated with robust scientific evidence and currently there is no standardized method in place for validating the anti-pollution efficacy of cosmetics products. This article discusses an innovative Controlled Pollution Exposure System (CPES) which allows quantified administration of pollutants on the skin and analysis of their direct impact. Using CPES, human subjects were exposed to ambient dust and ozone and sebum were sampled and analyzed for biomarkers. Following exposure of human subjects' skin to either ambient dust(100-450μg/cm3 ) or ozone(100-1000ppb), analysis of sebum revealed a significant decrease in squalene concentration, and significant increases in squalene monohydroperoxide and malondialdehyde concentration. The findings demonstrate cutaneous oxidative stress induced by ambient dust and ozone. The findings also demonstrate the efficacy of CPES to accurately measure the direct effect of controlled gaseous and particulate pollutants on human skin and indicate that squalene, squalene monohydroperoxide and malondialdehyde may serve as potent biomarkers for evaluating potential anti-pollution claims of cosmetics products.

Oxidation of squalene by singlet oxygen and free radicals results in different compositions of squalene monohydroperoxide isomers

Oxidation of squalene (SQ) causes a decline in the nutritional value of SQ in foods, as well as an accumulation of SQ oxidation products in skin lipids which lead to adverse skin conditions. However, mechanistic insights as to how SQ is oxidized by different oxidation mechanisms have been limited, and thus effective measures towards the prevention of SQ oxidation have not been identified. In this study, we oxidized SQ by either singlet oxygen oxidation or free radical oxidation, and monitored the formation of the six SQ monohydroperoxide (SQOOH) isomers, the primary oxidation products of SQ, at the isomeric level. While singlet oxygen oxidation of SQ resulted in the formation of similar amounts of the six SQOOH isomers, free radical oxidation of SQ mainly formed two types of isomers, 2-OOH-SQ and 3-OOH-SQ. The addition of β-carotene during singlet oxygen oxidation, and the addition of α-tocopherol during free radical oxidation lead to a dose-dependent decrease in the formation of SQOOH isomers. Such results suggest that the analysis of SQOOH at the isomeric level allows for the determination of the cause of SQ oxidation in various samples, and provides a foothold for future studies concerning the prevention of SQ oxidation.

Mass Spectrometric Discrimination of Squalene Monohydroperoxide Isomers.

Squalene (SQ), a main component of human sebum, is readily photooxidized by exposure to sunlight, producing six squalene monohydroperoxide (SQ-OOH) isomers. Despite its known connection to various skin conditions, few studies have sought to analyze SQ-OOH at the isomeric level. In this study, we aimed to develop a method to discriminate each SQ-OOH isomer with the use of tandem mass spectrometry (MS/MS). The six standard SQ-OOH isomers were prepared by photooxidizing SQ in the presence of rose bengal, a photosensitizer, and isolated by semipreparative high-performance liquid chromatography (HPLC). To purify each isomer, 2-methoxypropene, which reversibly reacts with the hydroperoxide group of SQ-OOH, was utilized. Product ion scanning was then performed on the standard SQ-OOH isomers in the absence and presence of the sodium ion. In the absence of the sodium ion, the fragmentation patterns produced by atmospheric pressure chemical ionization were similar between the isomers, whereas in the presence of the sodium ion by electrospray ionization, unique fragmentation patterns were achieved. Based on these fragment ions, HPLC-MS/MS multiple reaction monitoring analysis was conducted on a mixture of the standard SQ-OOH isomers. We achieved discrimination of SQ-OOH isomers with high selectivity and detected SQ-OOH isomers at nanogram levels. These results may improve our understanding of the effect of SQ-OOH on skin conditions as well as the mechanism behind SQ peroxidation.

Exploration of scalp surface lipids reveals squalene peroxide as a potential actor in dandruff condition.

Dandruff is a common but complex disorder with three major contributing factors: (1) individual predisposition, (2) scalp sebum and (3) Malassezia yeast colonization. To obtain further insights into the role of sebum in dandruff biogenesis, we analyzed scalp lipid species in a cohort of ten dandruff-free (control) and ten dandruff-afflicted volunteers by gas chromatography coupled to mass spectrometry. Lipid peroxidation levels and biochemical markers of oxidative stress were also assessed. Squalene, a major sebum component, was significantly more peroxidized in dandruff-affected scalps, resulting in significantly higher ratios of squalene monohydroperoxide (SQOOH)/squalene. This was observed when comparing dandruff-affected zones of dandruff subjects to both their non-affected zones and control subjects. In addition, other biomarkers such as malondialdehyde indicated that oxidative stress levels were raised on dandruff scalps. Surprisingly, differences regarding either free or bound fatty acids were fairly rare and minor. Certain novel findings, especially squalene peroxidation levels, were then confirmed in a validation cohort of 24 dandruff-affected subjects, by comparing dandruff-affected and non-dandruff zones from the same individuals. As SQOOH can induce both keratinocyte inflammatory responses and hyperproliferation in vitro, we hypothesized that increased SQOOH could be considered as a new etiological dandruff factor via its ability to impair scalp barrier function. Our results also indicated that Malassezia could be a major source of squalene peroxidation on the scalp.Electronic supplementary materialThe online version of this article (doi:10.1007/s00403-016-1623-1) contains supplementary material, which is available to authorized users.

Morphological and Histological Changes in Photoaged Hairless Mice Induced by Phellodendrin cortex Water Extract Application

This study was intended to evaluate the alleviating effects of Phellodendrin cortex water extract (PCWE) on skin aging in hairless mice via observing morphogical and histological changes. Skin aging was induced by UVB irradiation and squalene monohydroperoxide (Sq-OOH) application to the back skin of hairless mice for 6 weeks. And at the same time, saline (C), jojoba oil (VC), PCWE (E) and 0.01% retinoic acid diluted with polyethylene glycol (PC) were applied topically twice a day, 6 days a week for 6 weeks. Retinoic acid and PCWE application groups improved wrinkle formation in a pattern of shallow furrows and thin and narrow crests compared to the C group. As based on the morphologic analysis for skin wrinkles, E group showed lower levels in skin roughness, maximum roughness, average roughness, smoothness depth and arithmetic average roughness by 13.1, 17.2, 18.4, 15.4 and 16.1%, respectively than the C group, indicating that PCWE inhibited potential formation of wrinkles in the skin. The structure of lipid lamellae and collagen fibers were broken or deformed with an irregular arrangement in the C group. The retinoic acid and PCWE applications protect against the deformity of lipid lamellae and collagen fibers. Elastic fibers in dermis of the C group were also transformed severely but applications of retoinoic acid and PCWE significantly decreased the number of denatured elastic fibers. Therefore, PCWE could have a alleviating effects on the skin aging induced by UVB irradiation and Sq-OOH application.

Comprehensive analysis of the major lipid classes in sebum by rapid resolution high-performance liquid chromatography and electrospray mass spectrometry

Sebum is a complex lipid mixture that is synthesized in sebaceous glands and excreted on the skin surface. The purpose of this study was the comprehensive detection of the intact lipids that compose sebum. These lipids exist as a broad range of chemical structures and concentrations. Sebum was collected with SebuTape(TM) from the foreheads of healthy donors, and then separated by HPLC on a C8 stationary phase with sub 2 µm particle size. This HPLC method provided high resolution and excellent reproducibility of retention times (RT). Compound mining was performed with time of flight (TOF) and triple quadrupole (QqQ) mass spectrometers (MS), which allowed for the classification of lipids according to their elemental composition, degree of unsaturation, and MS/MS fragmentation. The combination of the two MS systems detected 95 and 29 families of triacylglycerols (TAG) and diacylglycerols (DAG), respectively. Assignment was carried out regardless of positional isomerism. Among the wax esters (WE), 28 species were found to contain the 16:1 fatty acyl moiety. This method was suitable for the simultaneous detection of squalene and its oxygenated derivative. A total of 9 cholesterol esters (CE) were identified and more than 48 free fatty acids (FFA) were detected in normal sebum. The relative abundance of each individual lipid within its own chemical class was determined for 12 healthy donors. In summary, this method provided the first characterization of the features and distribution of intact components of the sebum lipidome.

Modified Rancimat Method for Evaluation of Antioxidative Effect against Skin Lipids

Skin is a highly complicated tissue which possesses the largest surface area in the body and serves as the protective layer for internal organs. It is designed to give both physical and biochemical protection, and is equipped with a large number of defense mechanisms. 1 However, skin is very susceptible to oxidative reaction, because there are rich contents of lipids, proteins and DNA in the skin cell, all of which are very sensitive to the oxidation process. 2 Lipid peroxidation could be induced from excessive exposure to UV light, and has been considered as a major factor for skin aging processes. 3 In particular, squalene, main component of skin surface polyunsaturated lipids, is easily peroxidized. 4 The initial product of peroxidized squalene, squalene-monohydroperoxide (Sq-OOH), is produced at the human skin by natural exposure to sun light. Recently, the damages of hairless mice skin by the topical application of Sq-OOH 5 have been reported. Repeated application of Sq-OOH to the hairless mice induced clear skin wrinkles. Thus, in order to prevent or retard skin aging process, prevention of skin lipid peroxidation by natural or chemical antioxidants is desirable. To identify efficient antioxidants in cosmetic applications, a convenient assay method suitable for the estimation of skin lipid peroxidation is necessary. Rancimat 6 is a convenient method which can evaluate the lipid peroxidation by observing the change of electrical conductivity due to the formation of volatile dicarboxylic acids. It has been used in food industry to determine the peroxidation of unsaturated fatty acid components. However, the rancimat method is not suited for skin research, because the composition of oils used as a lipid source in this method is very different from that of skin lipid. 6c In this report, we demonstrate that modified rancimat method is a powerful tool for screening natural antioxidants for skin lipid peroxidation. We changed composition of lipid source to what is very close to skin lipid. At first, we tested antioxidative activities of several natural extracts by using general rancimat method. As shown in Table 1, extracts from Korean medicinal plants presented different induction time on retarding the peroxidation of corn oil. Their activities were compared with BHT as a positive control. Among the three natural extracts, Scutellaria baicalensis Georgi (SBG) extract was found to have the most powerful antioxidative activity. Portulaca oleracea L. (POL) extracts appeared to be the compound with the next activity and Rheum coreanum Nakai (RCN) extract was less active than other extracts. The order of activity is BHT > SBG > POL > RCN. However, ranges of Pf values of tested natural product are too small (from 1.2 to 1.6). Thus, sensitivity is not enough for primary screening of antioxidative activity. To establish the modified rancimat system suitable for skin lipid peroxidation studies, we prepared the artificial skin lipid and used it instead of corn oil. The prepared artificial skin lipid 7 was consisted of pork lard (33%), stearic acid (24%), lanolin (22%), squalene (12%) and cholesterol (4%). This composition is similar to that of human skin. According to the Table 2, the results of new rancimat method were different from previous general rancimat data. Surprisingly, SBG extract shows the strongest antioxidative activity among the tested samples. Induction period of SBG was 11.4 times longer than that of control with this new method. The sensitivity for evaluation of antioxidative activity was dramatically increased due to the wide ranges of Pf value (from 2.2 to 11.4). It is interesting to observe that the order of activity between RCN and ROL was reversed. In contrast to previous rancimat data, RCN is more active than POL. These interesting and meaningful differences between general rancimat and modified method may be due to changing of lipid composition which is suited to skin research. In search of new antioxidant applicable to prevent skin lipid peroxidation, we selected meso-dihydroguaiaretic acid (MDGA) 8 as a candidate. MDGA, a naturally occurring polyphenol,

Acne and smoking

BACKGROUND.: Post-adolescent acne is an inflammatory disorder, whose cause is unknown. Contrasting data are available on correlation between acne and smoking habit. OBJECTIVES.: To verify the frequency of clinically non-inflammatory (atypical) post-adolescent acne (APAA) among women, a possible correlation with cigarette smoking, possible differences in sebum composition in a group of female smokers with acne compared to healthy smokers and non-smokers. METHOD AND RESULTS.: 1046 randomly selected women (25-50-years-old) participated at the study. In 60 selected female subjects we analyzed sebum composition for alpha-tocopherol, squalene and squalene monohydroperoxide. We found a high prevalence of APAA among women (74.6%), a strong correlation with smoking habit (p < 0.0001), as well as an increase in the grade of sebum peroxidation (p < 0.05) with a reduction in vitamin E (p = 0.02), in the subjects with acne compared to the controls. CONCLUSIONS.: Clinical evidence and experimental data showed a straight correlation between smoking habit and post-pubertal acne in which the clinically non-inflammatory type-APAA-is the most frequent. In the more severe cases we could consider APAA as a new entity (smoker's acne).

Ion-trap tandem mass spectrometric analysis of squalene monohydroperoxide isomers in sunlight-exposed human skin

We previously discovered that squalene monohydroperoxide (SQ-OOH) was produced on human forehead skin and suggested that skin squalene (SQ) may be the principal target lipid for oxidative stress (e.g., sunlight exposure). Because of its six double bonds, SQ peroxidation can yield various positional hydroperoxide isomers. However, the structural characterization of skin SQ-OOH isomers has never been reported. Here, we prepared pure SQ-OOH isomers and developed an analytical method for SQ-OOH isomers using a quadrupole/linear ion-trap mass spectrometer (QTRAP) MS/MS system. Collision-induced dissociation produced specific fragment ions for each SQ-OOH isomer, which permitted discrimination between SQ-OOH isomers by multiple reaction monitoring (MRM). When lipid extract from human forehead skin was subjected to LC-MS/MS with MRM, individual SQ-OOH isomers could be separated and detected with a sensitivity of 0.05 ng/injection. The total concentration of SQ-OOH isomers in forehead skin was approximately 956 microg/g skin lipids, but it increased up to 2,760 microg/g skin lipids after 3 h of sunlight exposure. The LC-MS/MS method was useful for investigating the peroxidation mechanisms of SQ as well as SQ-OOH-mediated skin disorders.

Identification of Oxidation Products of Squalene in Solution and in Latent Fingerprints by ESI-MS and LC/APCI-MS

An investigation was carried out to identify oxidation products of squalene (SQ) in latent fingerprints. Oxidation products of SQ incubated in solution with Rose Bengal as a photooxidizer were isolated by semipreparative HPLC-UV and identified by direct infusion ESI-MS and flow injection APCI-MS. Squalene hydroperoxides ranging from squalene monohydroperoxide (SQ-[OOH]) to SQ-[OOH]5 were identified together with SQ epoxide. SQ-[OOH] was the main oxidation product. An LC/APCI-MS method was developed and used to monitor the fate of SQ in solution and in latent fingerprints and the formation of SQ-[OOH] and SQ epoxide. SQ-[OOH] and SQ epoxide were detected in freshly deposited prints but increased markedly after 1 day and continued to increase up to 5 days after print deposition. By day 7, these substances could no longer be detected in prints. SQ was rapidly depleted from prints such that by day 7 it was no longer detected. A similar pattern was seen for SQ stored in the light in dichloromethane but with a slower formation of SQ-[OOH] and SQ epoxide. The oxidation of SQ in solution in the presence and absence of photooxidizer was shown by TLC to proceed as follows: SQ-->SQ-[OOH]+SQ epoxide. SQ-[OOH]-->SQ-[OOH]2-->SQ-[OOH]3-->SQ-[OOH]4+SQ-[OOH]5, with oxidation being more rapid in the presence of photooxidizer. SQ-[OOH]4 and SQ-[OOH]5 could still be detected at 20 days in a solution of SQ aged in solution in the absence of photooxidizer. The oxidation products of SQ should make suitable targets for development of new reagents for visualizing latent fingerprints in forensic science.