- Target quantification of azole antifungals and retrospective screening of other emerging pollutants in wastewater effluent using UHPLC -QTOF-MS. [Journal Article]
- EPEnviron Pollut 2019 Jul 16; 253:655-666
- The information acquired by high resolution quadrupole-time of flight mass spectrometry (QTOF-MS) allows target analysis as well as retrospective screening for the presence of suspect or unknown emer…
The information acquired by high resolution quadrupole-time of flight mass spectrometry (QTOF-MS) allows target analysis as well as retrospective screening for the presence of suspect or unknown emerging pollutants which were not included in the target analysis. Targeted quantification of eight azole antifungal drugs in wastewater effluent as well as new and relatively simple retrospective suspect and non-target screening strategy for emerging pollutants using UHPLC-QTOF-MS is described in this work. More than 300 (parent compounds and transformation products) and 150 accurate masses were included in the retrospective suspect and non-target screening, respectively. Tentative identification of suspects and unknowns was based on accurate masses, peak intensity, blank subtraction, isotopic pattern (mSigma value), compound annotation using data bases such as KEGG and CHEBI, and fragmentation pattern interpretation. In the targeted analysis, clotrimazole, fluconazole, itraconazole, ketoconazole and posaconazole were detected in the effluent wastewater sample, fluconazole being with highest average concentration (302.38 ng L-1). The retrospective screening resulted in the detection of 27 compounds that had not been included in the target analysis. The suspect compounds tentatively identified included atazanavir, citalopram, climbazole, bezafibrate estradiol, desmethylvenlafaxine, losartan carboxylic acid and cetirizine, of which citalopram, estradiol and cetirizine were confirmed using a standard. Carbamazepine, atrazine, efavirenz, lopinavir, fexofenadine and 5-methylbenzotriazole were among the compounds detected following the non-targeted screening approach, of which carbamazepine was confirmed using a standard. Given the detection of the target antifungals in the effluent, the findings are a call for a wide assessment of their occurrence in aquatic environments and their role in ecotoxicology as well as in selection of drug resistant fungi. The findings of this work further highlights the practical benefits obtained for the identification of a broader range of emerging pollutants in the environment when retrospective screening is applied to high resolution and high accuracy mass spectrometric data.
- Development of a high-resolution traffic emission model: Lessons and key insights from the case of Bogotá, Colombia. [Journal Article]
- EPEnviron Pollut 2019 Jul 13; 253:552-559
- This paper presents a traffic-related air emissions inventory of a developing megacity using a traffic assignment model that results in a detailed temporal and spatial emission representation, disagg…
This paper presents a traffic-related air emissions inventory of a developing megacity using a traffic assignment model that results in a detailed temporal and spatial emission representation, disaggregating emissions sources by vehicle type and hour of the day, for five criteria air pollutants.
- Analysis of impurities of cannabidiol from hemp. Isolation, characterization and synthesis of cannabidibutol, the novel cannabidiol butyl analog. [Journal Article]
- JPJ Pharm Biomed Anal 2019 Jul 12; 175:112752
- Cannabidiol (CBD), one of the two major active principles present in Cannabis sativa, is gaining great interest among the scientific community for its pharmaceutical, nutraceutical and cosmetic appli…
Cannabidiol (CBD), one of the two major active principles present in Cannabis sativa, is gaining great interest among the scientific community for its pharmaceutical, nutraceutical and cosmetic applications. CBD can be prepared either by chemical synthesis or extraction from Cannabis sativa (hemp). The latter is more convenient from several points of view, including environmental and economic, but mainly for the absence of harmful organic solvents generally employed in the chemical synthesis. Although CBD produced by hemp extraction is the most widely employed, it carries two major impurities. The first one is the already known cannabidivarin (CBDV), whereas the second one is supposed to be the butyl analog of CBD with a four-term alkyl side chain. In this work, we report the isolation by semi-preparative liquid chromatography and the unambiguous identification of this second impurity. A comprehensive spectroscopic characterization, including NMR, UV, IR, circular dichroism and high-resolution mass spectrometry (HRMS), was carried out on this natural cannabinoid. In order to confirm its absolute configuration and chemical structure, the stereoisomer (1R,6R) of the supposed cannabinoid was synthesized and the physicochemical and spectroscopic properties, along with the stereochemistry, matched those of the natural isolated molecule. According to the International Nonproprietary Name, we suggested the name of cannabidibutol (CBDB) for this cannabinoid. Lastly, an HPLC-UV method was developed and validated for the qualitative and quantitative determination of CBDV and CBDB in samples of CBD extracted from hemp and produced according to Good Manufacturing Practices regulations for pharmaceutical and cosmetic use.
- Nuclear loci developed from multiple transcriptomes yield high resolution in phylogeny of scaly tree ferns (Cyatheaceae) from China and Vietnam. [Journal Article]
- MPMol Phylogenet Evol 2019 Jul 19; :106567
- The scaly tree ferns, Cyatheaceae, form a large natural group of ca. 640 species. They comprise an ideal model for studying the biogeography of plants due to their broad distribution across the tropi…
The scaly tree ferns, Cyatheaceae, form a large natural group of ca. 640 species. They comprise an ideal model for studying the biogeography of plants due to their broad distribution across the tropical to south-temperate areas of the world. However, tracing the biogeographic history of this highly diversified group has been hampered by unresolved evolutionary relationships among the major clades. Here, we generated transcriptome sequences of five species in three genera of Cyatheaceae (Alsophila, Gymnosphaera, and Sphaeropteris) and used them to search for single-copy nuclear loci for phylogenetic reconstruction. We identified a total of 818 candidate single-copy loci across multiple Cyatheaceae species. To test their phylogenetic utility, we further obtained sequence data of 12 of these loci for 76 samples representing all 13 known species of scaly tree ferns in China and Vietnam. Phylogenetic analyses based on multispecies coalescent and, alternatively, concatenation models yielded congruent results with high resolution. Additionally, we used the 12 loci to identify genetic signals of hybridization. Overall, our results demonstrated that multiple, single-copy loci are informative and efficient tools for phylogenetic or evolutionary studies of scaly tree ferns.
- Speciation, gene flow, and seasonal migration in Catharus thrushes (Aves:Turdidae). [Journal Article]
- MPMol Phylogenet Evol 2019 Jul 19; :106564
- New World thrushes in the genus Catharus are small, insectivorous or omnivorous birds that have been used to explore several important questions in avian evolution, including the evolution of seasona…
New World thrushes in the genus Catharus are small, insectivorous or omnivorous birds that have been used to explore several important questions in avian evolution, including the evolution of seasonal migration and plumage variation. Within Catharus, members of a clade of obligate long-distance migrants (C. fuscescens, C. minimus, and C. bicknelli) have also been used in the development of heteropatric speciation theory, a divergence process in which migratory lineages (which might occur in allopatry or sympatry during portions of their annual cycle) diverge despite low levels of gene flow. However, research on Catharus relationships has thus far been restricted to the use of small genetic datasets, which provide limited resolution of both phylogenetic and demographic histories. We used a large, multi-locus dataset from loci containing ultraconserved elements (UCEs) to study the demographic histories of the migratory C. fuscescens-minimus-bicknelli clade and to resolve the phylogeny of the migratory species of Catharus. Our dataset included more than 2,000 loci and over 1,700 variable genotyped sites, and analyses supported our prediction of divergence with gene flow in the fully migratory clade, with significant gene flow among all three species. Our phylogeny of the genus differs from past work in its placement of C. ustulatus, and further analyses suggest historic gene flow throughout the genus, producing genetically reticulate (or network) phylogenies. This raises questions about trait origins and suggests that seasonal migration and the resulting migratory condition of heteropatry is likely to promote hybridization not only during pairwise divergence and speciation, but also among non-sisters.
- Real time quantification of intracellular nickel using genetically encoded FRET-based nanosensor. [Journal Article]
- IJInt J Biol Macromol 2019 Jul 19
- Nickel (Ni2+) is an essential mineral nutrient that is required in trace quantities, but exposure to excess amounts can be toxic or carcinogenic. Mechanisms underlying Ni2+ imbalance and toxicity are…
Nickel (Ni2+) is an essential mineral nutrient that is required in trace quantities, but exposure to excess amounts can be toxic or carcinogenic. Mechanisms underlying Ni2+ imbalance and toxicity are poorly understood because most analytical methods currently used to probe this metal are invasive or also have toxic effects. To address these problems, a genetically encoded FRET-based probe for nickel metal (FProNiM) was constructed for real-time detection of Ni2+ in live cells. FProNiM was constructed by sandwiching the bacterial periplasmic nickel-binding protein NikA between the fluorescent protein variants ECFP and Venus. Ni2+ binding to FProNiM induced a conformational change that could be detected by a change in fluorescence resonance energy transfer (FRET) ratio (acceptor/donor fluorescence). In vitro studies demonstrated that FProNiM is specific for Ni2+, insensitive to changes in pH from 5.0 to 8.0, and has an affinity (Kd) of 21.6 μM, which allows detection of Ni2+ concentrations from 0.1 to 5000 μM. The sensor variant FProNiM-5 was also expressed in Escherichia coli (E. coli), yeast, and mammalian cells. In each cell type, changes in Ni2+ concentrations were detected with subcellular resolution using confocal microscopy.
- Regional changes in the elastic properties of myopic Guinea pig sclera. [Journal Article]
- EEExp Eye Res 2019 Jul 19; :107739
- Biomechanical changes in the sclera likely underlie the excessive eye elongation of axial myopia. We studied the biomechanical characteristics of myopic sclera at the microscopic level using scanning…
Biomechanical changes in the sclera likely underlie the excessive eye elongation of axial myopia. We studied the biomechanical characteristics of myopic sclera at the microscopic level using scanning acoustic microscopy (SAM) with 7-μm in-plane resolution. Guinea pigs underwent form-deprivation (FD) in one eye from 4 to 12 days of age to induce myopia, and 12-μm-thick scleral cryosections were scanned using a custom-made SAM. Two-dimensional maps of the bulk modulus (K) and mass density (ρ) were derived from the SAM data using a frequency-domain approach. We assessed the effect on K and ρ exerted by: 1) level of induced myopia, 2) region (superior, inferior, nasal or temporal) and 3) eccentricity from the nerve using univariate and multivariate regression analyses. Induced myopia ranged between -3D and -9.3D (Mean intraocular difference of -6.2 ± 1.7D, N = 11). K decreased by 0.036 GPa for every 1.0 D increase in induced myopia across vertical sections (p < 0.001). Among induced myopia right eyes, K values in the inherently more myopic superior region were 0.088 GPa less than the inferior region (p = 0.002) and K in the proximal nasal region containing the central axis were 0.10 GPa less than temporal K (p = 0.036). K also increased 0.12 GPa for every 1 mm increase in superior vertical distance (p < 0.001), an effect that was blunted after 1 week of FD. Overall, trends for ρ were less apparent than for K. ρ values increased by 20.7 mg/cm3 for every 1.00 D increase in induced myopia across horizontal sections (p < 0.001), and were greatest in the region containing the central posterior pole. ρ values in the inherently more myopic superior region were 13.1 mg/cm3 greater than that found in inferior regions among control eyes (p = 0.002), and increased by 11.2 mg/cm3 for every 1 mm increase in vertical distance (p = 0.001). This peripheral increase in ρ was blunted after 1 week of FD. Scleral material properties vary depending on the location in the sclera and the level of induced myopia. Bulk modulus was most reduced in the most myopic regions (both induced myopia and inherent regional myopia), and suggests that FD causes microscopic local decreases in sclera stiffness, while scleral mass density was most increased in the most myopic regions.
- High-resolution remote sensing-based spatial modeling for the prediction of potential risk areas of schistosomiasis in the Dongting Lake area, China. [Journal Article]
- ATActa Trop 2019 Jul 19; :105102
- The geographical distribution of snail (i.e., the intermediate host of schistosomiasis) is consistent with that of endemic areas. The suitable snail habitus requires necessary environmental condition…
The geographical distribution of snail (i.e., the intermediate host of schistosomiasis) is consistent with that of endemic areas. The suitable snail habitus requires necessary environmental conditions for snail population. The high-resolution remote sensing provides an important tool for the spatio-temporal analysis of disease monitoring and prediction. This study conducted a typical schistosomiasis epidemic area in the marshland and lake regions along the Yangtze River, Yueyang City, Hunan Province of China. And three types of environmental factors, i.e., NDVI, soil moisture, and shortest distance to water body, associated with the geographical distribution of snail population, were extracted from the high-resolution remoting sensing data. The predicted distribution of snail habitus from the high-resolution environmental factors were compared with the data of annual program of snail survey. The results have shown that the application of high-resolution remote sensing can improve the accuracy of the modeled and predicted the potential risk areas of schistosomiasis, and may become an important tool for the ongoing national schistosomiasis control program.
- π-Extended Pyrene-Fused Double Carbohelicene as a Chiral Polycyclic Aromatic Hydrocarbon. [Journal Article]
- JAJ Am Chem Soc 2019 Jul 22
- A π-extended double carbohelicene 2 with fused pyrene units was synthesized, revealing considerable intra- and intermolecular π-π interactions as confirmed with X-ray crystallography. Compared wit…
A π-extended double carbohelicene 2 with fused pyrene units was synthesized, revealing considerable intra- and intermolecular π-π interactions as confirmed with X-ray crystallography. Compared with the previous double carbohelicene 1, the π-extended homologue 2 demonstrated considerably red-shifted absorption with an onset at 645 nm (1: 550 nm) corresponding to a smaller optical gap of 1.90 eV (1: 2.25 eV). A broad near-infrared emission from 600 to 900 nm with a large Stokes shift of ~100 nm was recorded for 2, implying formation of an intramolecular excimer upon excitation, which was corroborated with femtosecond transient absorption spectroscopy. Moreover, 2 revealed remarkable chiral stability with a fairly high isomerization barrier of 46 kcal mol-1, according to density functional theory calculations, which allowed optical resolution by chiral HPLC and suggests potential applications in chiroptical devices.
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- Characterization of aporphine alkaloids by electrospray ionization tandem mass spectrometry and DFT calculations. [Journal Article]
- RCRapid Commun Mass Spectrom 2019 Jul 22
- CONCLUSIONS: Taken together, the diagnostic product ions and the series of radical and neutral eliminations provided information about the location of methylenedioxy, aromatic methoxy, and methoxy-hydroxy groups in aporphine alkaloids, assisting their characterization via MS/MS.