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Objective 'Krokodil' is the street name for an impure homemade drug mixture used as a cheap substitute for heroin, containing desomorphine as the main opioid. Abscesses, gangrene, thrombophlebitis, limb ulceration and amputations, jaw osteonecrosis, skin discoloration, ulcers, skin infections, and bleeding are some of the typical reported signs in humans. This study aimed to understand the toxicity of krokodil using Wistar male rats as experimental model. Methods Animals were divided into seven groups and exposed subcutaneously to NaCl 0.9% (control), krokodil mixture free of psychotropic substances (blank krokodil), pharmaceutical grade desomorphine 1 mg/kg, and four different concentrations of krokodil (containing 0.125, 0.25, 0.5, and 1 mg/kg of desomorphine) synthesized accordingly to a 'domestic' protocol followed by people who inject krokodil (PWIK). Daily injections for five consecutive days were performed, and animals were sacrificed 24 hr after the last administration. Biochemical and histological analysis were carried out. Results It was shown that the continuous use of krokodil may cause injury at the injection area, with formation of necrotic zones. The biochemical results evidenced alterations on cardiac and renal biomarkers of toxicity, namely, creatine kinase, creatine kinase-MB, and uric acid. Significant alteration in levels of reduced and oxidized glutathione on kidney and heart suggested that oxidative stress may be involved in krokodil-mediated toxicity. Cardiac congestion was the most relevant finding of continuous krokodil administration. Conclusions These findings contribute notably to comprehension of the local and systemic toxicological impact of this complex drug mixture on major organs and will hopefully be useful for the development of appropriate treatment strategies towards the human toxicological effects of krokodil. [ABSTRACT FROM AUTHOR]

A simple, accurate, precise, rapid and sensitive capillary zone electrophoresis (CZE) method was developed, optimized and validated for the simultaneous determination of strontium ranelate (antiosteoporetic drug) and aspartame (sweetener excipient) in pharmaceutical formulation for the treatment of postmenopausal osteoporosis. The final optimized conditions obtained were: borate buffer 50 mmol L-1 at pH 9.4 (BGE), applied potential of 30 kV, temperature set to 35 °C and hydrodynamic injection time of 10 s at a pressure of 50 mbar. The separation was carried out into a fused-silica capillary column (55 cm total length × 75 μm ID) and took less than 8 min. A diode array detector was used for the detection of the anion ranelate and aspartame at 235 and 198 nm, respectively. For both analytes, the method showed linear range from 1 to 40 μg mL-1, with satisfactory detectability (limits of detection of 0.3 and 0.2 μμg mL-1 for aspartame and ranelate, respectively). In addition, acceptable accuracy, good repeatability and intermediate precision (RSD < 2.6%) were obtained. The feasibility of the method was verified with recovery tests of analytes in the pharmaceutical sample. Recoveries varied from 85 ± 5% to 111 ± 2%, indicating the usefulness and effectiveness of the proposed method. [ABSTRACT FROM AUTHOR]

Diabetic retinopathy (DR), the main cause of blindness among diabetic patients, affects both neuronal and vascular cells of the retina. Studies show that neuronal cell death begins after 4 weeks of diabetes and could be related with an increase in oxidative stress. System x c − is a glutamate/cystine exchanger, formed by a catalytic subunit called xCT and a regulatory subunit 4F2hc, whose activity is crucial to the synthesis of glutathione, which is a key antioxidant molecule for cells. Although some studies have shown that glutamate transport mediated by excitatory amino acid transporters (EAATs) in diabetic rats is downregulated, there are no studies investigating system x c − in this context. To evaluate whether system x c − is modified by early onset of diabetes, primary retinal cell culture exposed to high glucose and retinas of rats 3 weeks after streptozotocin injection were used. We observed that xCT subunit protein expression both in cultures and in vivo were diminished. Furthermore, system x c − activity and GSH levels were also decreased whereas oxidative stress was increased in retinas of diabetic animals. Therefore, this study raises the possibility that alterations in system x c − expression and activity could occur during early onset of diabetes. In that way, system x c − modifications could be related to increased ROS in diabetic retinopathy. [ABSTRACT FROM AUTHOR]

Formaldehyde has been illegally added to milk to reduce microbial activity and extend the shelf life of the product. In Brazil, the official method for formaldehyde detection in milk consists of a qualitative colorimetric analysis. This work aimed to develop a more sensitive method, based on Micellar Electrokinetic Chromatography with Diode Array Detection (MEKC-UV/DAD), to determine formaldehyde in bovine milk. Sample preparation consisted of formaldehyde derivatization with 2,4-dinitrophenylhydrazine followed by protein precipitation and extraction with acetonitrile. The method showed linearity in aqueous solutions and in milk in the range of 50.0–1000 μg/L (R2 > 0.99), LOQ of 50.0 μg/L, adequate precision (RSD <3.9%) and accuracy (average recovery: 94.2 ± 0.7%). Formaldehyde traces were found in two commercial milk samples. However, the concentration levels could not be considered adulteration because they were within the acceptable range of endogenous sources (0.1–0.3 mg/L). The usefulness and effectiveness of the developed method can contribute to increase food safety. • Formaldehyde is a dangerous adulterant added to milk due to its carcinogenic properties. • A new analytical method for milk quality assurance and control was developed. • First method reported to determine trace levels of formaldehyde in milk by MEKC-UV/DAD. • LOD was 160 times smaller than the official method recommended by Brazilian Surveillance Agency. [ABSTRACT FROM AUTHOR]

The interest in charcoal for agricultural use (biochar) has sharply increased in recent years. However, biochar can contain groups of compounds such as polycyclic aromatic hydrocarbons (PAHs) that are considered persistent pollutants, and are formed concomitantly with biochar during its production by pyrolysis. Soil samples were collected in three experimental areas at different intervals (1, 3, 5 or 6 years) after the application of 16 Mg ha −1 of biochar. The total concentrations of PAHs; benzo[ a ]pyrene; and the estimated total cancer risk in biochar treated plots were larger than found in the control ones, but they decreased over time, equaling the control values after three years in the high C content soil (11.2 g C kg −1 soil), or after six years in the low C content soil (6.8 g C kg −1 soil). Nevertheless, the sum of PAH concentrations found in the biochar amended plots, in the range of 15.80–39.40 ng g −1 , were around two orders of magnitude below the limits of prevention established by Brazilian legislation (8100 ng g −1 ) and some European regulations for soils (3000 ng g −1 ) and also lower than the observed in previous studies about biochar amended soils. Our results indicate that, under the conditions evaluated, the application of biochar to soil in the studied proportion (16 Mg ha −1 , every six years) is safe concerning soil contamination by PAHs. [ABSTRACT FROM AUTHOR]

Reliable analytical results are necessary to ensure effective consumer protection and the use of certified reference material (CRM) is an important tool for quality assurance. The Brazilian Metrology Institute (Inmetro) studied the feasibility of the production of a candidate CRM of chloramphenicol (CAP) in milk. CAP is an antibiotic banned for treatment of food-producing animals. A minimum required performance limit (MRPL) for analytical methods of 0.3 μg kg −1 was set by the European Community for the detection of CAP residues in food matrices. Liquid chromatography with isotope dilution mass spectrometry (LC–IDMS) was employed for CAP determination and water content was measured by Karl Fischer coulometric titration. The feasibility study showed milk powder processed with both spray dryer and lyophilization lead to the best results, showing good degree of inhomogeneity for CAP residues (5.0%) and for water content (3.0%), therefore demonstrating that the production of this candidate CRM was feasible. [ABSTRACT FROM AUTHOR]

A method of high performance liquid chromatography with fluorescence detection (HPLC-Fluo), based on previous studies of the natural fluorescence emission of melamine (250/365 nm), was developed and validated for melamine determination as an adulterant of bovine UHT whole milk. The clean up treatment of milk samples by deproteinization was thoroughly optimized. No matrix effect was observed and a linear range from 0.05 to 10.0 μg mL −1 was obtained, with a value of R 2 equal to 0.9998. The limits of detection and quantification of melamine were 0.0081 and 0.027 μg mL −1 respectively, or 0.023 and 0.076 μg g −1 of milk, respectively, considering the sample dilution during extraction. Extracts of milk samples fortified with melamine at three concentration levels, two of which corresponded to the levels established by WHO for melamine in foods, led to an overall mean recovery of 95.4 ± 1.2% ( n = 9). This recovery value satisfies the performance criteria established by the Codex Alimentarius for analytical methods suitable for determination of food residues, demonstrating the usefulness and effectiveness of the proposed method. [ABSTRACT FROM AUTHOR]

''Krokodil'' is the street name for the homemade injectable mixture that has been used as a cheap substitute for heroin. Its use begun in Russia and Ukraine and nowadays is being spread over several other countries. Desomorphine is the semi-synthetic opioid claimed to be the main component of krokodil and considered to be responsible for its psychoactive characteristics. The starting materials for desomorphine synthesis are codeine tablets, alkali solutions, organic solvent, acidified water, iodine and red phosphorus, all of which are easily available in retail outlets, such as supermarkets, drugstores, etc. The resulting product is a light brown liquid that is called krokodil. People who inject krokodil present a great variety of serious signs and symptoms, including thrombophlebitis, ulcerations, gangrene, and necrosis, quickly evolving to limb amputation and death. These effects are thought to result from the toxic components produced as byproducts during the homemade drug synthesis. In this work, we reviewed several aspects of krokodil use, including its epidemiology, pharmacology and the chemical properties of the main active ingredient (desomorphine). To enhance our understanding of the clinical and toxic effects and to support the implementation of harm reduction measures, we also describe the ''bathtub chemistry'' of krokodil and the content of the final solution. [ABSTRACT FROM AUTHOR]

The present work reports the variation of 31 carbonyl compounds (CC) in an apartment located at Niterói City, Rio de Janeiro State, Brazil. Eight sampling campaigns were conducted through a 1-year period, and three areas (living room, kitchen, and bedroom) were evaluated before, during, and after the renovation activities and reoccupation of the apartment. Samples were collected using SEP-PAK cartridges impregnated with 2,4-dinitrophenylhydrazine, and the hydrazones were analyzed using rapid resolution liquid chromatography with UV detection. The lowest total concentration of CC (19.0 ± 1.5 μg m(-3)) was found before the renovation when the apartment was empty, but door varnishing resulted in highest contamination of the apartment (1386 ± 384 μg m(-3)); however, an important dispersion of CC was observed in the subsequent sampling (148 ± 1.8 μg m(-3)). After apartment reoccupation, the indoor contamination seemed to depend on the routine activities taken there, such as household product use and cooking activities, but apparently, local temperature increase favored the vaporization of the volatile CC from the building materials in the apartment. As far as we are concerned, this is the first study comparing the concentrations of 31 CC in residential areas before, during, and after renovation activities taken in Brazil.

The data described in this work is related to be the subject of an article in the Forensic Science International, titled: "The harmful chemistry behind "krokodil": street-like synthesis and product analysis" (http://dx.doi.org/10.1016/j.forsciint.2015.07.042) [1]. The data presented here provides additional description of the chemical profile of "krokodil". Physicochemical and organoleptic characteristics, TLC profile, UV/Vis, (1)H NMR and FTIR spectrum are presented. These data validate the proposed synthetic procedure and pathway and give further information about the contaminants present in "krokodil".

This study describes the determination of 30 carbonyl compounds (CCs) in three areas (bus boarding platform, passenger circulation area, and a pastry shop) of the Presidente João Goulart Bus Terminal, located at Niterói City, RJ, Brazil, and in an open area 700 m distant from the terminal. Samples were collected using SEP-PAK cartridges impregnated with 2,4-dinitrophenylhydrazine, during May to July 2012. The hydrazones formed were analyzed using rapid resolution liquid chromatography with UV detection. The studied locations showed distinct profiles of distribution of CC. The circulation area, which is influenced by different pollution sources, presented an intermediate profile between that of the pastry shop and boarding platform. Formaldehyde and acetaldehyde were the most abundant CC, but acetaldehyde predominated in the pastry shop once it is a by-product of baking yeast fermentation. Samples taken in the pastry shop and circulation area showed significant concentrations of hexanaldehyde and nonanaldehyde emitted during cooking. The pastry shop showed the largest level of total CC among the studied areas followed by the circulation area, the boarding platform, and the open area.

A method based on CZE for the determination of glutamic acid, glycine, and alanine in a biopharmaceutical formulation containing recombinant human erythropoietin was developed. The separation was achieved within less than 5 min, using a fused-silica capillary column (55 cm × 50 μm id) and 30 mmol/L phosphate buffer at pH 11.5, containing 0.6 mmol/L CTAB and 10% v/v methanol, as BGE solution. Applied potential of -25 kV, temperature of 15°C and hydrodynamic injection time of 15 s, at 50 mbar, were employed. The detection of the analytes was carried out without any derivatization reaction, at 220 nm using an UV-DAD detector. Linear ranges from 50 to 2500 mg/L and quantification limits of 40, 39, and 37 mg/L were obtained for glutamic acid, glycine, and alanine, respectively. Sample preparation required only a dilution step. Considering peak area and migration time values, the method presented good repeatability (RSD <1.7%; n = 9) and intermediate precision (RSD <1.0%; n = 6). Recovery evaluation using a commercial sample led to values between 97.5 ± 5.2% and 101.5 ± 4.6%, demonstrating the feasibility of the method, which was successfully applied in the quantification of the amino acids of interest in biopharmaceutical samples., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)