Phenylbenzimidazole Research Articles

Sequential injection analysis for benzophenone-4 and phenylbenzimidazole sulphonic acid in sunscreen sprays by solid-phase extraction coupled with ultraviolet spectrometry

A sequential injection UV method was developed to determine benzophenone-4 (BZ4) and phenylbenzimidazole sulphonic acid (PBS) simultaneously, these being the most commonly used UV-filters in aqueous formulations used as sunscreen sprays. The selective elution of both was performed by on-line solid-phase extraction, by retention on a SAX microcolumn and separation by varying the pH of elution. The sensitivity obtained was 0.042±0.001 ml μg −1 for PBS and 0.0159±0.0003 ml μg −1 for BZ4. The limit of detection was 1.6 μg ml −1 for PBS and 0.6 μg ml −1 for BZ4. The R.S.D. of the results was 1–6% for PBS and 1–12% for BZ4. The method was validated using commercial sunscreen formulations with concentrations determined by a liquid chromatographic procedure. The two procedures gave comparable results. Automation of the method means the amount of reagents used and residues generated are decreased. The system allows the required analysis sequence to be programmed using suitable software.

Photoallergic contact dermatitis is uncommon.

Despite the enormous increase in sunscreen use, allergic contact (AC) and photoallergic (PA) reactions to ultraviolet (UV) filters are considered rare. To analyse the data from 2715 patients who underwent photopatch testing at St John's Institute of Dermatology during the period 1983-98. A retrospective analysis of all positive photopatch test episodes was undertaken with the results retrieved from the environmental dermatology database and further verified with the original archived patch test documentation for each individual patient. In 111 patients with positive reactions (4.1%), there were 155 AC or PA reactions to allergens in the photopatch test series. Eighty PA reactions were observed in 62 (2.3%) patients (32 men and 30 women, age range 28-75 years), with UV filters accounting for 52 positive reactions (65%), drugs 16 (20%), musk ambrette 11 (14%) and the antiseptic trichlorocarbanilide one (1%). The most common UV filter photoallergen was benzophenone-3 with 14 positive results, followed by benzophenone-10 (n = 9), isopropyl dibenzoylmethane (n = 6), p-aminobenzoic acid (PABA) (n = 5), octyl dimethyl PABA (n = 5), butyl methoxydibenzoylmethane (n = 4), isoamyl methoxycinnamate (n = 2), ethyl methoxycinnamate (n = 2), octyl methoxycinnamate (n = 2), amyl dimethyl PABA (n = 2) and phenylbenzimidazole sulphonic acid (n = 1). A similar number of AC reactions to UV filters was detected in this study. Thus 49 patients (1.8%) had a total of 75 reactions: 51 due to UV filters and 24 as a result of exposure to fragrances and therapeutic agents. Benzophenone-10 accounted for 13 AC reactions and benzophenone-3 for eight reactions. Twenty-two patients had a PA reaction alone, whereas 19 patients had chronic actinic dermatitis and 15 patients polymorphic light eruption (PLE) in addition. Thus, 34 of the 62 patients (55%) had a preceding underlying photodermatosis. These results show a low yield of positive photopatch tests. Thus, despite the large increase in the use of UV filters over the last decade, the development of PA reactions remains rare. Furthermore, most of the common UV filter photoallergens identified in this study, including PABA, amyl dimethyl PABA and benzophenone-10, are now rarely used in sunscreen manufacture, while isopropyl dibenzoylmethane was voluntarily removed from the market in 1993. Currently, benzophenone-3 is the commonest contact photoallergen still in widespread use. In contrast, the UVB filter octyl methoxycinnamate, used in a number of sunscreens, produced only two positive PA reactions in 12 years of testing. Nevertheless, although these reactions are extremely rare, patients with photodermatoses such as PLE and chronic actinic dermatitis do represent a group of patients at increased risk of developing photoallergy. Further photopatch test series should be regularly reviewed and updated, as the relevance of individual photoallergens changes over time. Currently, there is no evidence that PA reactions represent a common clinical problem.

7 years experience of photopatch testing with sunscreen allergens in Sweden.

Since 1990 7 sunscreen allergens have been included in the standard photopatch protocol at 2 Swedish dermatology clinics. 355 consecutive patients with suspected photosensitivity were tested, and in 28 of these (7.9%), a total of 42 allergic reactions were found. 80% of the reactions were of photocontact origin. The most common allergen was benzophenone-3 (Eusolex 4360), with 15 photocontact and 1 contact allergic reactions, followed by isopropyl dibenzoylmethane (Eusolex 8020) (8 photocontact, 4 contact) and butyl methoxydibenzoylmethane (Parsol 1789), with 6 photocontact reactions. There were 2 cases of photocontact allergy to phenylbenzimidazole sulfonic acid (Eusolex 232), which has not been reported previously. 1 case of contact urticaria from benzophenone-3 was accidentally found. In addition, 21 + reactions of doubtful relevance were noted in 14 patients: 16 on irradiated and 5 on non-irradiated test sites. Among these, irritant and phototoxic reactions may be included. These results indicate that the inclusion of UV filters in the standard photopatch protocol is important. Immediate-type testing for urticaria could also be of value.

Contact and photocontact sensitivity to sunscreens. Review of a 15-year experience and of the literature.

This review summarizes published and unpublished data of our 15-year experience with sunscreen allergy and photoallergy. From 1981-1996, 402 patients with suspected clinical photosensitivity were patch and photopatch tested with the commercial sunscreens and facial cosmetics that they had used and with chemical UV absorbers, fragrance materials, preservatives, and emollients. 80 patients (20%) (28 men, 52 women) demonstrated allergic and/or photoallergic contact dermatitis to 1 or more UV absorber(s). In 47 patients with photodermatoses or photo-aggravated dermatoses and in 33 subjects with normal photosensitivity, 91 allergic and 84 photoallergic reactions to UV filters were observed. Over the years sunscreens were added to the test series, which since 1989 comprised the following 10 UV absorbers and which induced allergic (a) and photoallergic (pa) reactions (number, type of reaction): 4 UVA absorbers--isopropyldibenzoylmethane (30a/32pa); butyl methoxydibenzoyl-methane (15a/13pa); benzophenone-3 (3a/9pa); benzophenone-4 (0a/0pa); and 6 UVB absorbers--PABA (2a/2pa); octyl dimethyl PABA (1a/2pa); methylbenzylidene camphor (32a/5pa); octyl methoxycinnamate (3a/4pa); isoamyl p-methoxycinnamate (4a/10pa); and phenylbenzimidazole sulfonic acid (1a/7pa). The frequent (photo)sensitization to isopropyldibenzoylmethane was the reason that its production was discontinued in 1993. 47 patients reacted to fragrance materials, 11 to preservatives and 2 to lanolin alcohol. These constituents were contained in the commercial sunscreens and cosmetics that they had used. Continuous revision of the UV absorber photopatch test series was necessary to be closer to the real frequency of exposure and of reported (photo)allergy to newer sunscreens. Clinicians should consider contact and photocontact allergy, especially in patients with photodermatoses and photo-aggravated dermatoses, and they should perform photopatch testing. Once the culprit has been identified, its INCI (International Nomenclature Cosmetic Ingredients) designation should be given to the patient, who must be warned to avoid products containing the (photo)allergen.

In vitro analysis of immunoprotective effects of topical sunscreens

The aim of this study was to evaluate procedures for the assessment of the immunoprotective capacities of topical sunscreens, using cell cultures. The exposure of humans to solar or ultraviolet radiation has been shown to induce numerous changes at the level of the immunoresponsiveness of the skin, which could be described as immune suppression. In this study, a sunscreen containing the commercially available UVB filters octyl triazone, phenylbenzimidazole sulfonic acid and methylbenzylidene camphor, was tested because of its capacity to protect from the immunosuppressive effects of UVB radiation. In contrast to control suncreens with a comparable sun protector factor (SPF), but that did not contain the UVB-filter octyl triazone, the immunoprotective sunscreen protected from two forms of immune suppression as assessed in vitro. Expression of the immune-relevant cellular communication structure intercellular adhesion molecule-1 is decreased on the cell surface of epidermal cells under the influence of UVB. This effect of immune suppression is totally abolished by the immunoprotective capacity of the tested sunscreen, as monitored cytofluorometrically. The mixed-lymphocyte reaction (MLR) was also used to assess the protective capacities of sunscreens against UVB-radiation-induced suppression of the immune response. Again, this UVB-induced suppression of the MLR was prevented by the sunscreen containing octyl triazone. In summary, the results of this study demonstrate the usefulness of the above-mentioned methods for the in vitro evaluation of the immunoprotective properties of topical sunscreens.

UV filters for hair protection

Synopsis Hair damage, caused by sunlight, and the possibility to protect hair against sunlight by means of cosmetic formulations was studied. For this, five UV-filters were tested: benzophenone-3 (UV-A/UV-B); benzophenone-4 (UV-A/UV-B); phenylbenzimidazole sulfonic acid (UV-B); butylmethoxydibenzoylmethane (UV-A); octyl dimethyl PABA (UV-B). The stability of the UV-filters was tested as pure substances as well as in two cosmetic formulations: a setting lotion and a shine spray. The degree of decolouration and stress strain behaviour were determined. The benzophenones had the best protection ability both on colour and on morphology. Stability data and UV-spectra are discussed.