SciCombinator

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Concept: Time-of-flight

170

Brine shrimp are primitive crustacean arthropodal model organisms, second to daphnia, which can survive in high-salinity environments. Their oviposited cysts, cuticle-covered diapausing eggs, are highly resistant to dryness. To elucidate specialties of brine shrimp, this study characterized glycosphingolipids, which are signal transduction-associated material. A group of novel and complex fucosyl glycosphingolipids were separated and identified from cysts of the brine shrimp Artemia franciscana by repeated lipid extraction, alkaline methanolysis, acid treatment, successive column chromatography, and post-source decay measurements by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Structures of the glycosphingolipids were elucidated by conventional structural characterization and mass spectrometry, and the compounds were identified as GlcNAcβ1-3GalNAcβ1-4(GlcNAcα1-2Fucα1-3)GlcNAcβ1-3Manβ1-4Glcβ1-Cer, GalNAcβ1-4(Fucα1-3)GlcNAcβ1-3GalNAcβ1-4(GlcNAcα1-2Fucα1-3)GlcNAcβ1-3Manβ1-4Glcβ1-Cer, and GalNAcβ1-4(GlcNAcα1-2Fucα1-3)GlcNAcβ1-3GalNAcβ1-4(GlcNAcα1-2Fucα1-3)GlcNAcβ1-3Manβ1-4Glcβ1-Cer. These compounds also contained a branching, non-arthro-series disaccharide with an α-GlcNAc terminus, similar to that found in a previously reported ceramide hexasaccharide (III(3)(GlcNAcα2Fucα)-At4Cer). The glycans within these complex GSLs are longer than reported glycans of the animal kingdom containing α-GlcNAc terminus. These complex GSLs as well as the longest GSL with ten sugar residues, ceramide decasaccharide (CDeS), contain the fucosylated LacdiNAc sequence reported to associate with parasitism/immunosuppression and the α-GlcNAc terminus reported to show a certain antibacterial effect in other reports. CDeS, the longest GSL of this species, was found in the highest amount, which indicates that CDeS may be functionally important.

Concepts: Mass spectrometry, Arthropod, Crustacean, Brine shrimp, Branchiopoda, Time-of-flight, Artemia salina, Fairy shrimp

75

Earthquakes are lethal natural disasters frequently burying people alive under collapsed buildings. Tracking entrapped humans from their unique volatile chemical signature with hand-held devices would accelerate urban search and rescue (USaR) efforts. Here, a pilot study is presented with compact and orthogonal sensor arrays to detect the breath- and skin-emitted metabolic tracers acetone, ammonia, isoprene, CO2and relative humidity (RH), all together serving as sign of life. It consists of three nanostructured metal-oxide sensors (Si-doped WO3, Si-doped MoO3and Ti-doped ZnO), each specifically tailored at the nanoscale for highly sensitive and selective tracer detection along with commercial CO2and humidity sensors. When tested on humans enclosed in plethysmography chambers to simulate entrapment, this sensor array rapidly detected sub-ppm acetone, ammonia and isoprene concentrations with high accuracies (19, 21 and 3 ppb, respectively) and precision, unprecedented by portable sensors but required for USaR. These results were in good agreement (Pearson’s correlation coefficients ≥ 0.9) with bench-top selective reagent ionization time-of-flight mass spectrometry (SRI-TOF-MS). As a result, an inexpensive sensor array is presented that can be integrated readily into hand-held or even drone-carried detectors for first responders to rapidly screen affected terrain.

Concepts: Mass spectrometry, Humidity, Relative humidity, Pearson product-moment correlation coefficient, Sensor, Sensors, Time-of-flight

28

Agarwood is the resinous material harvested from threatened Aquilaria species. We investigated how many protonated 2-(2-phenylethyl)chromone ions were sufficient to make an accurate identification of agarwood. Analysis of 125 reference samples was carried out by direct analysis in real time time-of-flight mass spectrometry (DART-TOFMS). The identification criteria developed were applied to commercial samples.

Concepts: Mass spectrometry, Calculus, Ion source, Time-of-flight, Agarwood, Aquilaria, Aquilaria malaccensis

28

The increasing role of hair analysis in forensic toxicological investigations principally owes to recent improvements of mass spectrometric instrumentation. Research achievements during the last 6 years in this distinctive application area of analytical toxicology are reviewed. The earlier state of the art of hair analysis was comprehensively covered by a dedicated book (Kintz, 2007a. Analytical and practical aspects of drug testing in hair. Boca Raton: CRC Press and Taylor & Francis, 382 p) that represents key reference of the present overview. Whereas the traditional organization of analytical methods in forensic toxicology divided target substances into quite homogeneous groups of drugs, with similar structures and chemical properties, the current approach often takes advantage of the rapid expansion of multiclass and multiresidue analytical procedures; the latter is made possible by the fast operation and extreme sensitivity of modern mass spectrometers. This change in the strategy of toxicological analysis is reflected in the presentation of the recent literature material, which is mostly based on a fit-for-purpose logic. Thus, general screening of unknown substances is applied in diverse forensic contexts than drugs of abuse testing, and different instrumentation (triple quadrupoles, time-of-flight analyzers, linear and orbital traps) is utilized to optimally cope with the scope. Other key issues of modern toxicology, such as cost reduction and high sample throughput, are discussed with reference to procedural and instrumental alternatives. © 2012 Wiley Periodicals, Inc. Mass Spec Rev.

Concepts: Mass spectrometry, Toxicology, Chemical structure, Time-of-flight, Forensic toxicology

27

We investigated whether wood metabolite profiles from direct analysis in real time (time-of-flight) mass spectrometry (DART-TOFMS) could be used to determine the geographic origin of Douglas-fir wood cores originating from two regions in western Oregon, USA.

Concepts: Mass spectrometry, United States, Calculus, Oregon, Time-of-flight, Washington, Origin

27

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) has emerged as a promising tool to rapidly characterize Staphylococcus aureus. Different protocols have been employed, but effects of experimental factors, such as culture condition and sample preparation, on spectrum quality and reproducibility have not been rigorously examined. We applied MALDI-TOF MS to characterize a model system consisting of five methicillin-sensitive (MSSA) and five methicillin-resistant S. aureus isolates (MRSA) under two culture conditions (agar and broth) and using two sample preparation methods [intact cell method (ICM) and protein extraction method (PEM)]. The effects of these treatments on spectrum quality and reproducibility were quantified. PEM facilitated increases in the number of peaks and mass range width. Broth cultures further improved spectrum quality in terms of increasing the number of peaks. In addition, PEM increased reproducibility in samples prepared using identical culture conditions. MALDI imaging data suggested that the improvement in reproducibility may result from a more homogeneous distribution of sample associated with the broth/PEM treatment. Broth/PEM treatment also yielded the highest rate (96%) of correct classification for MRSA. Taken together, these results suggest that broth/PEM maximizes the performance of MALDI-TOF MS to characterize S. aureus. This article is protected by copyright. All rights reserved.

Concepts: Mass spectrometry, Staphylococcus aureus, Matrix-assisted laser desorption/ionization, Time-of-flight, Copyright, Michael Karas, Franz Hillenkamp

27

Benzalkonium (BAK) chloride is the most commonly used preservative in eye drops. It is generally composed of benzyldimethyldodecylammonium C(12) and benzyldimethyltetradecylammonium C(14) and is supposed to increase penetration of active compounds. However, numerous studies have reported its toxic effect to ocular surface especially in long-term treatments like against glaucoma, a sight-threatening disease. Albino rabbits were treated with a hyperosmolar solution and a high concentration of BAK solution for 1 month. Enucleated eyes were cryo-sectioned and analysed by mass spectrometry. Mass spectrometry imaging using time-of-flight secondary ion mass spectrometry (TOF-SIMS) has been used to characterize the spatial distribution and to determine the relative quantity of BAK at the surface of rabbit eye sections. Liquid chromatography coupled with mass spectrometry (LC-MS) using a hybrid linear ion trap-Orbitrap® mass spectrometer was used to obtain relative quantification of BAK at the sample surface. TOF-SIMS images of BAK ions indicated a distribution at the ocular surface and in deeper structures. Didecyldimethylammonium (DDMAC), which is used in hospitals as a substitute for BAK, was also detected and showed an accumulation around the eyes. After extraction with acetonitrile and chromatographic separation using a Gemini C18 column and an original elution gradient, the relative quantities of BAK and DDMAC present in the whole eye section surface were determined. This LC-MS method was validated in terms of limits of quantification, linearity, repeatability and reproducibility and its feasibility was evaluated in surgically obtained human samples. Specimens of iris, lens capsule or trabecular meshwork were found with significant levels of BAK and DDMAC, thus confirming the penetration of BAK in deep ocular structures, with potential deleterious effects induced by this cytotoxic compound. The analytical method developed here could therefore be of primary interest in the field of pharmaco-toxicology in order to localise, identify and quantify drugs or xenobiotic compounds present at biological sample surfaces.

Concepts: Mass spectrometry, Eye, Chromatography, Analytical chemistry, Ion, Gas chromatography, Time-of-flight, Secondary ion mass spectrometry

27

Functional foods are one of the most interesting areas of research and innovation in the food industry. A functional food or functional ingredient is considered to be any food or food component that provides health benefits beyond basic nutrition. Recently, consumers have shown interest in natural bioactive compounds as functional ingredients in the diet owing to their various beneficial effects for health. Water-soluble fibers and nondigestible oligosaccharides and polysaccharides can be defined as functional food ingredients. Fructooligosaccharides (FOS) and inulin are resistant to direct metabolism by the host and reach the caecocolon, where they are used by selected groups of beneficial bacteria. Furthermore, they are able to improve physical and structural properties of food, such as hydration, oil-holding capacity, viscosity, texture, sensory characteristics, and shelf-life. This article reviews major innovative analytical developments to screen and identify FOS, inulins, and the most employed nonstarch carbohydrates added or naturally present in functional food formulations. High-performance anion-exchange chromatography with pulsed electrochemical detection (HPAEC-PED) is one of the most employed analytical techniques for the characterization of those molecules. Mass spectrometry is also of great help, in particularly matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS), which is able to provide extensive information regarding the molecular weight and length profiles of oligosaccharides and polysaccharides. Moreover, MALDI-TOF-MS in combination with HPAEC-PED has been shown to be of great value for the complementary information it can provide. Some other techniques, such as NMR spectroscopy, are also discussed, with relevant examples of recent applications. A number of articles have appeared in the literature in recent years regarding the analysis of inulin, FOS, and other carbohydrates of interest in the field and they are critically reviewed.

Concepts: Spectroscopy, Bacteria, Nutrition, Mass spectrometry, Food, Carbohydrate, Time-of-flight, Fructooligosaccharide

27

Airborne ultrasonic ranging is used in a variety of different engineering applications for which other positional metrology techniques cannot be used, for example in closed-cell locations, when optical line of sight is limited, and when multipath effects preclude electromagnetic-based wireless systems. Although subject to fundamental physical limitations, e.g., because of the temperature dependence of acoustic velocity in air, these acoustic techniques often provide a cost-effective solution for applications in mobile robotics, structural inspection, and biomedical imaging. In this article, the different techniques and limitations of a range of airborne ultrasonic ranging approaches are reviewed, with an emphasis on the accuracy and repeatability of the measurements. Simple timedomain approaches are compared with their frequency-domain equivalents, and the use of hybrid models and biologically inspired approaches are discussed.

Concepts: Measurement, Metrology, Psychometrics, Test method, Units of measurement, Time-of-flight, Debut albums, Wireless

27

Yersinia enterocolitica biotype 1A strains are frequently isolated from the environment, foods, and animals, and also from humans with yersiniosis. There are controversial reports on the pathogenicity of biotype 1A strains. In this study, 811 fecal samples from asymptomatic humans from Switzerland were studied for the presence of Y. enterocolitica. Nine (1.1 %) of the 811 samples were positive for Y. enterocolitica 1A. These strains were compared with 12 Y. enterocolitica 1A strains from Swiss patients with diarrhea isolated in the same year. Almost all (20/21) Y. enterocolitica 1A strains carried the ystB gene, seven strains carried the hreP gene, and none carried the ail, ystA, myfA, yadA, or virF genes. Most (17/21) Y. enterocolitica 1A strains belonged to two major clusters, A and B, by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). Strains of cluster B were only isolated from humans with diarrhea; however, ystB and hreP genes were detected in strains from both clinical and non-clinical samples and from strains of clusters A and B. Using ribotyping, six restriction patterns among biotype 1A strains were obtained with HindIII enzyme. The most common ribotype (RT I) was found in strains isolated from humans with and without diarrhea. All biotype 1A strains had a unique NotI profile by pulsed-field gel electrophoresis (PFGE), showing a very high genetic diversity. In this study, Y. enterocolitica 1A strains from clinical and non-clinical samples could not be clearly differentiated from each other. More research is needed in order to prove that biotype 1A strains are a primary cause for human yersiniosis and not only a secondary finding.

Concepts: Protein, Genetics, Molecular biology, Mass spectrometry, Matrix-assisted laser desorption/ionization, Time-of-flight, Yersinia enterocolitica, Yersinia