Identification of nitrite treated tuna fish meat via the determination of nitrous oxide by head space-gas chromatography/mass spectrometry.

Tuna fish meat is an expensive and highly perishable sea food. Fresh meat has a bright red colour which soon turns into an unsightly brown during storage. To prolong the aspect of freshness, the red colour is stabilised or even enhanced e.g. with carbon monoxide or nitric oxide, the product of a nitrite / ascorbic acid treatment, which bind as a ligand to myoglobin. These procedures are illegal. Here we present a method for identifying tuna meat samples, which have undergone fraudulent wet salting with nitrite. The method uses headspace-gas chromatography/mass spectrometry (GC/MS) for the determination of nitrous oxide, which is formed as the final product of the two-step reduction nitrite (added agent) to nitric oxide (ligand) to nitrous oxide (target compound). Complex bound nitric oxide is set free with sulfuric acid, which also promotes the reduction to nitrous oxide. The method was validated using 15N labelled nitrite as well as treated and untreated reference fish samples. A survey of 13 samples taken from the Swiss market in 2019 showed that 45 % of all samples were illegally treated with nitrite.

Photooxidation of Octahydro Tetramethyl Naphthalenylethanone in Perfumes and Aftershaves.

For consumer safety reasons, cosmetics that are exposed to light are evaluated with respect to phototoxicity and/or photoallergy (photosensitization). For perfumes/aftershaves, however, these tests are not performed with the cosmetic product but only with single fragrance compounds, which may influence the outcome. In the presence of a sensitizer, photoinduced oxidation of unsaturated fragrances might result in the formation of unwanted products. Therefore, using real samples, we studied the photodegradation of the common fragrance octahydro tetramethyl naphthalenylethanone (OTNE) under in vitro irradiation, during indoor storage, and after application on skin. OTNE and its photoproducts were determined by liquid chromatography (LC) coupled to diode array detection (DAD). Whereas OTNE itself was photostable, irradiation in the presence of a sensitizer and of aftershave/perfume samples resulted in a strong degradation. Photooxygenation was identified as the major degradation reaction for all three trials. OTNE photooxidation products were characterized by LC-high resolution mass spectrometry (LC-HRMS) and by high-performance thin-layer chromatography (HPTLC) after derivatization with titanium ethoxide and nitrobenzyl pyridine. Both HPTLC and HRMS data indicate that OTNE hydroperoxides are formed during irradiation.

Identification of organic pigments in tattoo inks and permanent make-up using laser desorption ionisation mass spectrometry.

Nowadays, about 12% of the European and 20% of the US population are tattooed. Rising concerns regarding consumer safety, led to legal restrictions on tattoo and permanent make-up (PMU) inks. Restrictions also include bans on certain colourants. Both ink types use organic pigments for colour-giving, plus inorganic pigments for white and black and colour tones. Pigments are only sparingly soluble in common solvents and occur as suspended particles in the ink matrix. Their detection and identification therefore pose a major challenge for laboratories involved in monitoring the legal compliance of tattoo inks and PMU. We overcame this challenge by developing a direct laser desorption ionisation time-of-flight mass spectrometry method, which included an easy sample clean up. The method proved to be capable of detecting and identifying organic pigments in almost all of the tested ink samples. Method validation and routine deployment during market surveys showed the method to be fit for purpose. Pigment screening of 396 tattoo inks and 55 PMU taken from the Swiss market between 2009 and 2017 lead to the following conclusions: Pigment variety is much greater in tattoo inks (18) than in PMU (10); four prohibited pigments (Pigment Green 7, Pigment Red 122, Pigment Violet 19 and 23) were found in both ink types; for PMU, these four pigments made up 12% of the pigment findings, compared to 32% for tattoo inks. Therefore, legal compliance of PMU was at a higher level. A comparison of pigments found with those declared on tattoo ink labels clearly showed that banned pigments are rarely declared, but rather masked by listing non present legal pigments and label forging; therefore, highlighting the urgency of widespread market controls.

Chemical Analysis: An Indispensable Means for Uncovering Severe Cases of Fraud with Cosmetics and Tattoo Inks.

Three cases of fraud with commodities containing illegal stealth compounds are presented, which were uncovered by the State Laboratory Basel-City, Switzerland. All three commodities, grapefruit seed extracts, a phytocosmetical skin cream, and tattoo inks, were produced abroad, had forged declarations of ingredients and, in the case of the extracts and the cream, were marketed with far-reaching health claims. While inspections will identify suspicious products and would be able to eliminate health claims to some extent, only chemical analysis can uncover the illegal agents used and give law enforcement bodies the necessary evidence to immediately clamp down on those brands, where the stealth agent presents a serious health hazard to consumers.

Photostability and breakdown products of pigments currently used in tattoo inks.

Tattoos fade with time. Part of this fading can be attributed to the photodegradation of pigments. When people get tired of their tattoos, removal by laser irradiation is the method of choice. In vivo laser irradiation of tattoos on mice has shown that the degradation of pigments can result in toxic compounds. Various in vitro studies on photodegradation by sunlight or laser have shown similar degradation products for both irradiations. Even visible light was shown to be able to decompose some pigments to toxic degradation products in vitro. Whereas the investigated phthalocyanins (C.I. 74160, 74260), quinacridones (C.I. 73915) or dioxazines (C.I. 51319) were fairly photostable in vitro, all azo pigments exposed to sunlight or laser were degraded into a variety of products, some of which were toxic or even carcinogenic, such as 2-amino-4-nitrotoluene, 3,3'-dichlorobenzidine and o-toluidine. Up to now, the absence of specific toxicological data is the reason why legal restrictions for tattoo inks are derived from those for cosmetics, toys and textiles. Photodegradation has not been considered. In light of the present analytical findings, even with their possible shortcomings, the evidence weighs heavily enough to consider banning azo pigments containing carcinogenic aromatic amines or allergens in their structure from use in tattoo inks.

Methotrimeprazine for the management of end-of-life symptoms in infants and children.

OBJECTIVE: This retrospective chart review assessed the efficacy, dose, and safety of methotrimeprazine in palliating end-of-life symptoms in children and infants. METHODS: A retrospective chart review was conducted of 18 hospitalized pediatric patients who were treated with methotrimeprazine in their last two weeks of life. Data collected included age, diagnosis, symptoms, methotrimeprazine dose, route, efficacy, and any documented adverse effects. RESULTS: Patients' ages ranged from 16 days to 17 years. Underlying conditions included malignancies, trauma, and various neurodegenerative and congenital diseases. All patients (n = 18) were treated for symptoms of agitation, delirium, or restlessness. Most patients also experienced respiratory secretions/congestion (n = 15), pain (n = 13), and/ or dyspnea (n = 9). Less common symptoms included nausea/emesis (n = 5) and spasticity (n = 1). Methotrimeprazine dosages ranged from 0.02 mg/kg/dose to 0.5 mg/kg/dose. Routes of administration included intravenous (n = 13), oral/gastrostomy tube (n = 6), or subcutaneous (n = 4). Sedation (n = 6) was the only documented adverse effect, although when agitation was present, this was potentially an intended and perceived-to-be-beneficial effect. CONCLUSION: Methotrimeprazine, an old drug with diverse receptor activity and multiple routes of administration, appears to be an effective tool in treating complicated end-of-life symptoms in children and infants. This study provides a foundation for analysis with prospective and comparative trials, which may further quantify its benefit.

Rolling--a new application technique for luminescent bacteria on high-performance thin-layer chromatography plates.

High-performance thin-layer chromatography (HPTLC) coupled with bioluminescence detection using Vibrio fischeri bacteria can be used for screening for unknown substances. This is accomplished by dipping the HPTLC plate in an aqueous bacteria solution. Especially polar substances, however, can start to dissolve during this process, which leads to blurring and tailing of the zones on the plate. To overcome this disadvantage, we applied the bacteria solution by rolling. This method has been described for chemical derivatizations, but is very rarely used. The rolling device was made of commercially available household articles. Using octhilinone and methylparaben as test compounds, rolling was compared with dipping. Despite of performing the rolling process manually, the results were reproducible. Depending on the substance and its amount on the HPTLC plate, peaks were narrower, up to a factor of 4 higher and with a higher signal-to-noise ratio than after dipping.