Determination of the stability of sodium cyclamate during deep-frying using HPLC.

The oil used to fry food is often used multiple times to reduce costs. However, when foods containing sweeteners are processed in this way, the sweeteners may produce substances harmful to the body as a result of repeated frying at high temperatures. This article investigated the stability of sodium cyclamate during deep-frying by HPLC using a pre-column derivatization method. The results showed that cyclohexylamine was a decomposition product of a standard sample of sodium cyclamate when deep-fried at 200°C for 25 min. A pre-column derivatization/HPLC method was established to determine cyclohexylamine, a decomposition product of sodium cyclamate, under these conditions. Dansyl chloride was used as the derivatization reagent, the derivatization temperature was 60°C, the derivatization time was 20 min, the pH of sodium bicarbonate buffer solution was 11, and the concentration of dansyl chloride was 2.0 mg/mL. Detection was carried out by using an Agilent 1260 high-performance liquid chromatograph coupled with an ultraviolet detector. The ultraviolet detection wavelength was 254 nm, and the mobile phase was acetonitrile-1.0 g/L potassium dihydrogen phosphate solution at a flow rate of 1.0 mL/min. Gradient elution was adopted, the peak of the cyclohexylamine derivative appeared at a retention time of 17.75 min, and the peak area response value was the largest. The methodological validation analysis showed that the detection limit of cyclohexylamine was 0.5 mg/kg, the quantification limit was 2.0 mg/kg, and the spiked recoveries were in the range of 99.37-110.16%. The relative standard deviations (RSDs) were in the range of 0.17-1.26%. Four samples were tested and analyzed by the established method, and cyclohexylamine was not detected.

Fatal intoxication related to two new arylcyclohexylamine derivatives (2F-DCK and 3-MeO-PCE).

Continuous development and rapid turnover of drug market of new psychoactive substances (NPS) make it difficult to obtain up-to-date analytical methods for efficient detection of intoxication cases with new substances: no analytical data and no previously published concentration values in biological samples are indeed available. In this context, we aim to report the first fatal case involving two newly emerging arylcyclohexylamine derivatives (a group of dissociative ketamine-based substances): 2-fluoro-deschloroketamine (2F-DCK) and 3-methoxyeticyclidine (3-MeO-PCE). A 42-year-old man was found dead at his home with three plastic bags of "research chemicals" powders near him. Comprehensive screenings of drugs and toxic compounds as well as more selective assays (performed using NMR, HS-GC-FID, LC-MS/MS and LC-HRMS methods) allowed (1) to identify the three unknown powders, 2F-DCK, 3-MeO-PCE, and 5-methoxy-N,N-dimethyltryptamine (5-MeO-DMT, a hallucinogenic tryptamine-related NPS), with purity above 95%, and (2) to determine peripheral blood (1780, 90, and 52 µg/L), urine (6.1, 6.3, and 2.2 mg/L), bile (12, 3.5, and 1.7 mg/L), and vitreous humour (1500, 66 and 155 µg/L) concentrations of 2F-DCK, 3-MeO-PCE and 5-MeO-DMT, respectively. In addition, toxicological results also revealed recent use of cannabis, cocaine, and amphetamine by the victim, and hair analysis draw pathway of addiction (including experiments with various other NPS) for several months before death. This fatality was considered as the consequence of respiratory depression in a poly-drug user due to a "cocktail effect" of concurrent intakes of 2F-DCK (mainly), 3-MeO-PCE, 5-MeO-DMT, amphetamine, and cocaine. In addition, this case report provides analytical data that could support subsequent toxicological result interpretation in forensic cases involving such arylcyclohexylamine derivatives.

Identification and distribution of mycosporine-like amino acids in Brazilian cyanobacteria using ultrahigh-performance liquid chromatography with diode array detection coupled to quadrupole time-of-flight mass spectrometry.

RATIONALE: Mycosporine-like amino acids (MAAs) are UV-absorbing compounds produced by fungi, algae, lichens, and cyanobacteria when exposed to UV radiation. These compounds have photoprotective and antioxidant functions and have been widely studied for possible use in sunscreens and anti-aging products. This study aims to identify MAA-producing cyanobacteria with potential application in cosmetics. METHODS: A method for the identification of MAAs was developed using ultrahigh-performance liquid chromatography with diode array detection coupled to quadrupole time-of-flight mass spectrometry (UHPLC-DAD/QTOFMS). Chromatographic separation was carried out using a Synergi 4 µ Hydro-RP 80A column (150 × 2,0 mm) at 30°C with 0.1% formic acid aqueous solution + 2 mM ammonium formate and acetonitrile/water (8:2) + 0.1% formic acid as a mobile phase. RESULTS: Out of the 69 cyanobacteria studied, 26 strains (37%) synthesized MAAs. Nine different MAAs were identified using UHPLC-DAD/QTOFMS. Iminomycosporines were the major group detected (7 in 9 MAAs). In terms of abundance, the most representative genera for MAA production were heterocyte-forming groups. Oscilatoria sp. CMMA 1600, of homocyte type, produced the greatest diversity of MAAs. CONCLUSIONS: The UHPLC-DAD/QTOFMS method is a powerful tool for identification and screening of MAAs in cyanobacterial strains as well as in other organisms such as dinoflagellates, macroalgae, and microalgae. The different cyanobacterial genera isolated from diverse Brazilian biomes and environments are prolific sources of MAAs.

Determination of the Subcellular Localization and Mechanism of Action of Ferrostatins in Suppressing Ferroptosis.

Ferroptosis is a form of nonapoptotic cell death characterized by the unchecked accumulation of lipid peroxides. Ferrostatin-1 and its analogs (ferrostatins) specifically prevent ferroptosis in multiple contexts, but many aspects of their molecular mechanism of action remain poorly described. Here, we employed stimulated Raman scattering (SRS) microscopy coupled with small vibrational tags to image the distribution of ferrostatins in cells and found that they accumulate in lysosomes, mitochondria, and the endoplasmic reticulum. We then evaluated the functional relevance of lysosomes and mitochondria to ferroptosis suppression by ferrostatins and found that neither is required for effective ferroptosis suppression.

Determination of Dicyclohexylamine in Beeswax by Aqueous Normal Phase Liquid Chromatography Coupled With Tandem Mass Spectrometry.

Dicyclohexylamine (DCH) is an excipient present in commercial formulations of fumagillin (Fumagilin-B® and Fumidil-B®), an antibiotic which is employed in apiculture for the control of nosema disease. DCH has been demonstrated to be stable in harvested honey; however, its fate in the beehive has not been investigated. In this study, DCH residues were determined in beeswax samples collected from brood chambers and honey supers from various apiaries throughout Alberta. The determination of DCH was performed using a simple extraction procedure followed by low-temperature cleanup and finally analysis with aqueous normal phase liquid chromatography-electrospray ionization tandem mass spectrometry. The method was found to yield high accuracy and precision (94.9 ± 1.7% to 110.8 ± 6.6%) for replicate beeswax samples spiked with 4, 80, 360 and 2,000 µg kg-1 of DCH. With a limit of quantification of 1 µg kg-1, 100% of the 61 beeswax samples analyzed were found to contain residues of DCH ranging from 15 to 6,410 µg kg-1. The results indicate that DCH can accumulate in beeswax when Fumagilin-B® or Fumidil-B® is applied in apiculture and that these concentrations can vary significantly among beekeeping operations.

Resistance to Hydrogen Peroxide Highlights Gymnodinium catenatum (Dinophyceae) Sensitivity to Geomagnetic Activity.

The chain-forming dinoflagellate Gymnodinium catenatum was exposed to hydrogen peroxide. Microscopical examination revealed striking dose-response alterations in chain formation above 245 µm: singlets replaced the dominance of long chain formations. These observations were valid for cells acclimated to halogen light. Under fluorescent light, cells were more resistant to modifications in chain length after H2 O2 exposure. Growth along 9 h in the presence of extracellular H2 O2 followed an hormesis response in both light regimes. Under halogen light conditions, alterations in chain formation and net growth were related to culture time, inocula concentration and geomagnetic activity (GMA) in the proceeding hours. Below a 16 nT threshold in GMA average growth was 0%, while above 16 nT it was circa +9%, independently if the local static magnetic field was altered by a permanent magnet or not. Mycosporine-like amino acids that can have an antioxidant role and are easily oxidized decreased from 7.1 to 6.5 pg cell-1 (P < 0.05) under halogen light and exposure to 245 µm H2 O2 . GMA, as well as UV-A, increased stress responsiveness that can momentarily protect cells from extracellular H2 O2 addition. However, stress response is dependent on bio-availability of several micronutrients and macronutrients, many found at limiting concentrations in oceanic waters.

Hair Testing for Drugs of Abuse and New Psychoactive Substances in a High-Risk Population.

Hundreds of new psychoactive substances (NPS) have emerged in the drug market over the last decade. Few drug surveys in the USA, however, ask about use of NPS, so prevalence and correlates of use are largely unknown. A large portion of NPS use is unintentional or unknown as NPS are common adulterants in drugs like ecstasy/Molly, and most NPS are rapidly eliminated from the body, limiting efficacy of urine, blood and saliva testing. We utilized a novel method of examining prevalence of NPS use in a high-risk population utilizing hair-testing. Hair samples from high-risk nightclub and dance music attendees were tested for 82 drugs and metabolites (including NPS) using ultra-high performance liquid chromatography-tandem mass spectrometry. Eighty samples collected from different parts of the body were analyzed, 57 of which detected positive for at least one substance-either a traditional or new drug. Among these, 26 samples tested positive for at least one NPS-the most common being butylone (25 samples). Other new drugs detected include methylone, methoxetamine, 5/6-APB, α-PVP and 4-FA. Hair analysis proved a powerful tool to gain objective biological drug-prevalence information, free from possible biases of unintentional or unknown intake and untruthful reporting of use. Such testing can be used actively or retrospectively to validate survey responses and inform research on consumption patterns, including intentional and unknown use, polydrug-use, occasional NPS intake and frequent or heavy use.

Determination of cathinones and other stimulant, psychedelic, and dissociative designer drugs in real hair samples.

The detection of new psychoactive substances (NPS) in hair proved to provide insight into their current diffusion among the population and the social characteristics of these synthetic drugs' users. Therefore, a UHPLC-MS/MS method was developed in order to determine 31 stimulant and psychedelic substituted phenethylamines, and dissociative drugs in hair samples. The method proved to be simple, fast, specific, and sensitive. The absence of matrix interferents, together with excellent repeatability of both retention times and relative abundances of diagnostic transitions, allowed the correct identification of all analytes tested. The method showed optimal linearity in the interval 10-1000 pg/mg, with correlation coefficient values varying between 0.9981 and 0.9997. Quantitation limits ranged from 1.8 pg/mg for 4-methoxyphencyclidine (4-MeO-PCP) up to 35 pg/mg for 6-(2-aminopropyl)benzofuran (6-APB). The method was applied to (i) 23 real samples taken from proven MDMA and ketamine abusers and (ii) 54 real hair samples which had been previously tested negative during regular drug screening in driver's license recovery. Six samples tested positive for at least one target analyte. Methoxetamine (MXE) was found in three cases (range of concentration 7.7-27 pg/mg); mephedrone (4-MMC) was found in two cases (50-59 pg/mg) while one sample tested positive for methylone at 28 pg/mg. Other positive findings included 4-methylethcathinone (4-MEC), alpha-pyrrolidinovalerophenone (α-PVP), 4-fluoroamphetamine (4-FA), 3,4-methylenedioxypyrovalerone (MDPV), and diphenidine. The present study confirms the increasing diffusion of new designer drugs with enhanced stimulant activity among the target population of poly-abuse consumers.

Salting-out-assisted liquid-liquid extraction as a suitable approach for determination of methoxetamine in large sets of tissue samples.

A new designer drug, a dissociative anesthetic, and a putative N-methyl-D-aspartate receptor antagonist, methoxetamine (MXE) noted by the EU Early Warning System has been already identified as a cause of several fatalities worldwide. The primary objective of this work was to develop a suitable sample preparation method allowing for isolation of MXE and its main metabolites in high yields from rat brain, liver, and lungs. For the purpose of the project, MXE and five metabolites were synthesized in-house, specifically O-desmethyl-normethoxetamine, O-desmethylmethoxetamine, dihydro-O-desmethylmethoxetamine, normethoxetamine, and dihydromethoxetamine. A sample preparation procedure consisted in the homogenization of the tissue applying salting-out-assisted liquid-liquid extraction (SALLE). A subsequent liquid chromatography-mass spectrometry (LC-MS) analysis was based on reversed-phased chromatography hyphenated with a triple quad MS system in a positive electrospray mode. Multiple reaction monitoring (MRM) was used for qualification and quantification of the analytes. The quantification was based on the application of an isotopically labeled internal standard, normethoxetamine-d3. The matrix-matched calibrations were prepared for each type of matrix with regression coefficients 0.9943-1.0000. The calibration curves were linear in the concentration range of 2.5-250 ng g(-1). Limits of quantification (LOQs) were estimated as 2.5 and 5 ng g(-1), respectively. Recovery (80-117%) and matrix effect (94-110%) at 100 ng g(-1) and intra- and inter-day accuracy and precision at low (2.5 ng g(-1)), middle (25 ng g(-1)), and upper (250 ng g(-1)) concentration levels for all the analytes in all three types of tissues were also determined. The developed analytical method was applied to a set of real samples gathered in toxicological trials on rats and MXE, and its metabolites were determined successfully.

Sun-screening bioactive compounds mycosporine-like amino acids in naturally occurring cyanobacterial biofilms: role in photoprotection.

AIMS: To investigate the occurrence of UV sunscreening biomolecules and their role in photoprotection in cyanobacterial biofilms growing in brightly lit habitats with high UV fluxes. METHODS AND RESULTS: High performance liquid chromatography with photodiode-array and mass spectrometry revealed the presence of mycosporine-like amino acids (MAAs) shinorine (λ(max) 334 nm, m/z 333), porphyra-334 (λ(max) 334 nm, m/z 347), mycosporine-glycine (λ(max) 310 nm, m/z 246) and palythinol (λ(max) 332 nm, m/z 303). Two unknown MAAs with λ(max) at 320 (m/z 289) and 329 nm (m/z 318) were also found. Biosynthesis of MAAs was found to increase with increase in exposure time under UV radiation. The MAAs from biofilms showed efficient radical scavenging activity as well as photoprotective potential on the survival of UV-treated Escherichia coli cells. CONCLUSIONS: Biosynthesis of photoprotectants is an important mechanism to prevent photodamage in Cyanobacteria. UV-induction and photoprotective function of MAAs may facilitate them to perform important ecological functions under harsh environmental conditions. SIGNIFICANCE AND IMPACT OF THE STUDY: There are very few reports on qualitative and quantitative characterization of different MAAs in cyanobacterial biofilms. Due to strong UV absorption and photoprotective function, MAAs may be used as an active ingredient in cosmetic and other pharmaceutical industries.

Analytical findings of an acute intoxication after inhalation of methoxetamine.

Methoxetamine (MXE) is increasingly used and abused, as it is frequently presented as being safer than ketamine, and legal. Cases of only MXE consumption being associated with the occurrence of seizures are rarely reported. A single MXE intoxication case by inhalation is described concerning a 21-year-old man, not known to be epileptic, who was found collapsed in his bedroom, supposedly after an epileptic seizure. He was transferred to the Emergency Department of the Henri Mondor Hospital, Aurillac, France. He was conscious, but with a sinus bradycardia (48/min) and an ST-segment elevation on the electrocardiogram, and a slightly increased creatine kinase level (270 U/L) and hyponatremia (127 mmol/L). New seizure activity occurred during hospitalization, but the clinical course in the intensive care unit was favorable. Quantitation of MXE in serum and urine using gas chromatography coupled to mass spectrometry (GC-MS) was developed, as well as a liquid chromatography coupled to tandem mass spectrometry (LC-MS-MS) method for the determination of MXE in hair. Limits of detection and quantification were, respectively, 2 and 10 µg/L for the GC-MS method and both 0.5 pg/mg for the LC-MS-MS method. Concentrations of 30 and 408 µg/L were, respectively, measured in serum and urine. Concentrations of 135 and 145 pg/mg were detected in two 2.5 cm hair strands, consistent with one or several consumptions during the 2 ½ months prior to sampling. A sample of the powder consumed was available and also analyzed. This case illustrates the dangers of this drug, which justify its classification as a narcotic in France since August 2013.

From the street to the laboratory: analytical profiles of methoxetamine, 3-methoxyeticyclidine and 3-methoxyphencyclidine and their determination in three biological matrices.

Three psychoactive arylcyclohexylamines, advertised as "research chemicals," were obtained from an online retailer and characterized by gas chromatography ion trap electron and chemical ionization mass spectrometry, nuclear magnetic resonance spectroscopy and diode array detection. The three phencyclidines were identified as 2-(ethylamino)-2-(3-methoxyphenyl)cyclohexanone (methoxetamine), N-ethyl-1-(3-methoxyphenyl)cyclohexanamine and 1-[1-(3-methoxyphenyl)cyclohexyl]piperidine. A qualitative/quantitative method of analysis was developed and validated using liquid chromatography (HPLC) electrospray tandem mass spectrometry and ultraviolet (UV) detection for the determination of these compounds in blood, urine and vitreous humor. HPLC-UV proved to be a robust, accurate and precise method for the qualitative and quantitative analysis of these substances in biological fluids (0.16-5.0 mg/L), whereas the mass spectrometer was useful as a confirmatory tool.

An automated method for measurement of methoxetamine in human plasma by use of turbulent flow on-line extraction coupled with liquid chromatography and mass spectrometric detection.

Methoxetamine is a new ketamine derivative designer drug which has recently become available via the Internet marketed as "legal ketamine". It is a new dissociative recreational drug, acting as an NMDA receptor antagonist and dopamine reuptake inhibitor. The objective of this study was to develop on-line automated sample preparation using a TurboFlow device coupled with liquid chromatography with ion-trap mass spectrometric detection for measurement of methoxetamine in human plasma. Samples (100 µL) were vortex mixed with internal standard solution (ketamine-d4 in acetonitrile). After centrifugation, 20 µL of the supernatant was injected on to a 50 mm × 0.5-mm C18XL Turboflow column. The retained analytes were then back-flushed on to a 50 mm × 3-mm (3 µm) Hypersil Gold analytical column for chromatographic separation, then eluted with a formate buffer-acetonitrile gradient. Methoxetamine and the IS were ionized by electrospray in positive mode. Parent [M + H](+) ions were m/z 248.1 for methoxetamine and m/z 242.0 for the IS. The most intense product ions from methoxetamine (m/z 203.0) and the IS (m/z 224.0) were used for quantification. The assay was accurate (96.8-108.8% range) and precise (intra and inter-day coefficients of variation <8.8%) over the range of 2.0 (lower limit of quantification) to 1000.0 ng mL(-1) (upper limit of quantification). No matrix effect was observed. This method has been successfully applied to determination of plasma concentrations of methoxetamine in the first French hospitalization case report after acute intoxication; the plasma concentration was 136 ng mL(-1).

Distribution of mycosporine-like amino acids along a surface water meridional transect of the Atlantic.

The composition and abundance of mycosporine-like amino acids (MAAs) were investigated in the surface waters along a 13,000-km meridional transect (52° N to 45° S) in the Atlantic Ocean (Atlantic Meridional Transect programme: Cruise AMT 18: 4/10/2008-10/11/2008). MAAs were ubiquitous along the transect, although the composition of the MAAs was variable. Highest concentrations were in the far south (below 40° S; MAA >1 µg L(-1)) and in north subtropical equatorial region (NER: 0-25° N; MAA up to 0.8 µg L(-1)). Highest MAA relative to chlorophyll-a occurred in the NER (MAA/chl-a ratio between 2 and 5). MAA/chl-a significantly correlated with the preceding month's mean daily UV dose and with UV-B/UV-A. In the far south, high MAA concentrations coincided with high phytoplankton biomass, high nutrients and a deep mixed layer associated with the austral spring. Here, the phytoplankton community was dominated by micro- and nano-eukaryotes. At the NER, the high MAA/chl-a coincided with low nutrient concentrations, a shallow mixed layer depth (20-70 m) and to a lesser extent to a shallow nitracline (40-90 m). Here, the phytoplankton consisted primarily of picophytoplankton (0-0.2 µm), dominated by the pico-cyanobacteria Synechococcus sp. and Prochlorococcus sp. and by the nitrogen fixing filamentous cyanobacterium Trichodesmium. The low nitrate concentrations (<0.1 µmol L(-1)) at the NER suggest that nitrogen fixation was required for MAA production. Specific MAAs could not easily be assigned to particular groups of phytoplankton and we could not rule out the possibility that MAAs were associated with symbiotic cyanobacteria contained within heterotrophic dinoflagellates or diatoms.

Ultra-trace level analysis of morpholine, cyclohexylamine, and diethylaminoethanol in steam condensate by gas chromatography with multi-mode inlet, and flame ionization detection.

Steam condensate water treatment is a vital and integral part of the overall cooling water treatment process. Steam condensate often contains varying levels of carbon dioxide and oxygen which acts as an oxidizer. Carbon dioxide forms corrosive carbonic acid when dissolved in condensed steam. To neutralize the harmful effect of the carbonic acid, volatile amine compounds such as morpholine, cyclohexylamine, and diethylaminoethanol are often employed as part of a strategy to control corrosion in the water treatment process. Due to the high stability of these compounds in a water matrix, the indirect addition of such chemicals into the process via steam condensate often results in their presence throughout the process and even into the final product. It is therefore important to understand the impact of these chemicals and their fate within a chemical plant. The ability to analyze such compounds by gas chromatography has historically been difficult due to the lack of chromatographic system inertness at the trace level concentrations especially in an aqueous matrix. Here a highly sensitive, practical, and reliable gas chromatographic approach is described for the determination of morpholine, cyclohexylamine, and diethylaminoethanol in steam condensate at the part-per-billion (ppb) levels. The approach does not require any sample enrichment or derivatization. The technique employs a multi-mode inlet operating in pulsed splitless mode with programmed inlet temperature for sample introduction, an inert base-deactivated capillary column for solute separation and flame ionization detection. Chromatographic performance was further enhanced by the incorporation of 2-propanol as a co-solvent. Detection limits for morpholine, cyclohexylamine, diethylaminoethanol were established to be 100 ppb (v/v), with relative standard deviations (RSD) of less than 6% at the 95% confidence level (n=20) and a percent recovery of 96% or higher for the solutes of interest over a range of 0.1-100 ppm (v/v). A complete analysis can be conducted in less than 10 min.

Here today, gone tomorrow and back again? A review of herbal marijuana alternatives (K2, Spice), synthetic cathinones (bath salts), kratom, Salvia divinorum, methoxetamine, and piperazines.

Despite their widespread Internet availability and use, many of the new drugs of abuse remain unfamiliar to health care providers. The herbal marijuana alternatives, like K2 or Spice, are a group of herbal blends that contain a mixture of plant matter in addition to chemical grade synthetic cannabinoids. The synthetic cathinones, commonly called "bath salts," have resulted in nationwide emergency department visits for severe agitation, sympathomimetic toxicity, and death. Kratom, a plant product derived from Mitragyna speciosa Korth, has opioid-like effects, and has been used for the treatment of chronic pain and amelioration of opioid-withdrawal symptoms. Salvia divinorum is a hallucinogen with unique pharmacology that has therapeutic potential but has been banned in many states due to concerns regarding its psychiatric effects. Methoxetamine has recently become available via the Internet and is marked as "legal ketamine." Moreover, the piperazine derivatives, a class of amphetamine-like compounds that includes BZP and TMFPP, are making a resurgence as "legal Ecstasy." These psychoactives are available via the Internet, frequently legal, and often perceived as safe by the public. Unfortunately, these drugs often have adverse effects, which range from minimal to life-threatening. Health care providers must be familiar with these important new classes of drugs. This paper discusses the background, pharmacology, clinical effects, detection, and management of synthetic cannabinoid, synthetic cathinone, methoxetamine, and piperazine exposures.

Mycosporine-like amino acids (MAAs) profile of a rice-field cyanobacterium Anabaena doliolum as influenced by PAR and UVR.

The mycosporine-like amino acid (MAA) profile of a rice-field cyanobacterium, Anabaena doliolum, was studied under PAR and PAR + UVR conditions. The high-performance liquid chromatographic analysis of water-soluble compounds reveals the biosynthesis of three MAAs, mycosporine-glycine (lambda (max) = 310 nm), porphyra-334 (lambda (max) = 334 nm) and shinorine (lambda (max) = 334 nm), with retention times of 4.1, 3.5 and 2.3 min, respectively. This is the first report for the occurrence of mycosporine-glycine and porphyra-334 in addition to shinorine in Anabaena strains studied so far. The results indicate that mycosporine-glycine (monosubstituted) acts as a precursor for the biosynthesis of the bisubstituted MAAs shinorine and porphyra-334. Mycosporine-glycine was under constitutive control while porphyra-334 and shinorine were induced by UV-B radiation, indicating the involvement of UV-regulated enzymes in the biotransformation of MAAs. It seems that A. doliolum is able to protect its cell machinery from UVR by synthesizing a complex set of MAAs and thus is able to survive successfully during the summer in its natural brightly lit habitats.

New designer drug N-(1-phenylcyclohexyl)-3-ethoxypropanamine (PCEPA): studies on its metabolism and toxicological detection in rat urine using gas chromatographic/mass spectrometric techniques.

Studies are described on the metabolism and toxicological detection of the phencyclidine-derived designer drug N-(1-phenylcyclohexyl)-3-ethoxypropanamine (PCEPA) in rat urine using gas chromatographic/mass spectrometric techniques. The identified metabolites indicated that PCEPA was metabolized by N-dealkylation, O-deethylation partially followed by oxidation of the resulting alcohol to the corresponding carboxylic acid, hydroxylation of the cyclohexyl ring at different positions of PCEPA, N-dealkyl PCEPA, O-deethyl PCEPA, and of the corresponding carboxylic acids. Finally, aromatic hydroxylation of PCEPA, the corresponding carboxylic acids, and O-deethyl PCEPA, the latter partially followed by oxidation to the corresponding carboxylic acid and hydroxylation of the cyclohexyl ring could be observed. All metabolites were partially excreted in the conjugated form. The authors' systematic toxicological analysis (STA) procedure using full-scan GC/MS after acid hydrolysis, liquid-liquid extraction, and microwave-assisted acetylation allowed the detection in rat urine of an intake of a common drug users' dose of PCEPA. Assuming a similar metabolism in humans, the STA in human urine should be suitable as proof of intake of PCEPA.

Mycosporine-like amino acids in the zooxanthella-ciliate symbiosis Maristentor dinoferus.

Coral reef organisms living in mutualistic symbioses with phototrophic dinoflagellates are widespread in shallow UV-transparent waters. Maristentor dinoferus is a recently discovered species of marine benthic ciliate that hosts symbiotic dinoflagellates of the genus Symbiodinium. In this study, we tested this ciliate for the occurrence of mycosporine-like amino acids, a family of secondary metabolites that minimize damage from exposure to solar UV radiation by direct screening. Using high-performance liquid chromatography and liquid chromatography coupled to mass spectrometry, five mycosporine-like amino acids (shinorine, palythenic acid, palythine, mycosporine-2-glycine, and porphyra-334) were identified in aqueous methanolic extracts of the symbiosis. This is the first report of mycosporine-like amino acids in a marine ciliate.