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Oil biodegradation in second and also supratidal seashores.
Background The epigenetic effects of individual environmental toxicants in tobacco remain largely unexplored. Cadmium (Cd) has been associated with smoking-related health effects, and its concentration in tobacco smoke is higher in comparison with other metals. Objectives We studied the association of Cd and smoking exposures with human blood DNA methylation (DNAm) profiles. We also evaluated the implication of findings to relevant methylation pathways and the potential contribution of Cd exposure from smoking to explain the association between smoking and site-specific DNAm. NF-κB inhibitor Methods We conducted an epigenome-wide association study of urine Cd and self-reported smoking (current and former vs. never, and cumulative smoking dose) with blood DNAm in 790,026 CpGs (methylation sites) measured with the Illumina Infinium Human MethylationEPIC (Illumina Inc.) platform in 2,325 adults 45-74 years of age who participated in the Strong Heart Study in 1989-1991. In a mediation analysis, we estimated the amount of change d to smoking-related DNAm. Conclusions Beyond replicating well-known smoking epigenetic signatures, we found novel DMPs related to smoking. Moreover, increases in smoking-related Cd exposure were associated with differential DNAm. Our integrative analysis supports a biological link for Cd and smoking-associated health effects, including the possibility that Cd is partly responsible for smoking toxicity through epigenetic changes. https//doi.org/10.1289/EHP6345.Background Dopaminergic symptoms may be extremely pronounced in some migraine patients during the attack, representing a major source of disability. Objectives We aimed to carefully characterize the clinical picture of migraine patients with dopaminergic symptoms in a large patients' population as a putative migraine endophenotype, allowing more precise disease management, treatment and outcome prediction. Methods We screened 1148 consecutive tertiary care episodic and chronic migraine patients with face-to-face interviews collecting thorough data on lifestyle, socio-demographic factors, and clinical migraine features. Results We identified 374 patients with migraine with dopaminergic symptoms (32.6%). The most frequent dopaminergic symptom was yawning followed by somnolence, nausea, vomiting, fatigue, mood changes and diuresis. Migraine patients with dopaminergic symptoms had longer attack duration (OR 1.82; 95% CI 1.41-2.36, p less then 0.0001), more frequent osmophobia (OR 2.01; 95% CI 1.50-2.69, p less then 0.0001), allodynia (OR 1.43; 95% CI 1.10-1.85, p = 0.0071) and unilateral cranial autonomic symptoms (OR 1.31; 95% CI 1.01-1.68, p = 0.045), but used less preventative treatments (OR 0.74; 95% CI 0.57-0.98, p = 0.033) than patients without dopaminergic symptoms. Conclusions Migraine patients with dopaminergic symptoms are characterized by a full-blown, more disabling migraine. Dopaminergic system modulation should be carefully considered in individuals with migraine with dopaminergic symptoms for both acute and preventative treatments in future ad hoc designed studies.Pomegranate is a kind of fruit with low temperature sensitivity. Abnormal low temperature can easily lead to chilling injury, which negatively impacts the appearance of fruit, accelerates browning and deterioration, as well as seriously reduces the consumption quality and commodity value of pomegranate. This study was carried out to determine the effect of methyl jasmonate on chilling injury of pomegranate during low temperature storage. The result showed that methyl jasmonate treatment effectively maintained edible quality of pomegranate, suppressed the polyphenol oxidase activity and the development of chilling injury index, and inhibited the decline of total phenol content and the increase of malondialdehyde content and cell membrane permeability. In addition, methyl jasmonate could also enhance the disease resistance of fruit by increasing the content of soluble protein, and effectively maintain the integrity of epidermal cell structure and tissue structure. Overall, the conclusion of this paper is that methyl jasmonate can be used as an effective means to suppress chilling injury in postharvest storage of pomegranate.The reaction of 1,2-disubstituted 2-imidazolines with electron-deficient alkynes proceeds as a pseudo-three-component process and forms imidazolidines with an N-vinylpropargylamine fragment. Heating the resulting imidazolidines in xylene on air leads to an effective formation of polysubstituted pyrroles through a domino sequence of aza-Claisen rearrangement/transannular nucleophilic addition/oxidative ring opening reactions. The direct one-pot transformation of 2-imidazolines to pyrroles has been also realized.We herein report the development of a sterically hindered and electron-rich P-chiral monophosphorus biaryl ligand that has enabled a general and efficient enantioselective intramolecular α-arylation, providing access to a wide series of [4.4], [4.5], and [4.6]-spirocycles with chiral benzylic quaternary carbons in high yields with good to excellent enantioselectivities. A pronounced water effect on enantioselectivity is observed.Coherent charge transport along ballistic paths can be introduced into graphene by Andreev reflection, for which an electron reflects from a superconducting contact as a hole, while a Cooper pair is transmitted. We use liquid-helium cooled scanning gate microscopy (SGM) to image Andreev reflection in graphene in the magnetic focusing regime, where carriers move along cyclotron orbits between contacts. Images of flow are obtained by deflecting carrier paths and displaying the resulting change in conductance. When electrons enter the superconductor, Andreev-reflected holes leave for the collecting contact. To test the results, we destroy Andreev reflection with a large current and by heating above the critical temperature. In both cases, the reflected carriers change from holes to electrons.The halogen-bonding interaction between I2 and N-iodosuccinimide (NIS) stabilized by a Lewis base (LB) has been explored. 1H NMR, nuclear Overhauser effect (NOE), and diffusion-ordered NMR spectroscopy (DOSY) suggest the generation of a 111 assembly, LB-I2-NIS. In contrast, when N-iodotrifluoromethanesulfonimide (INTf2) is used instead of NIS, LB-I5+-LB is generated. On the basis of these results in combination with density functional theory (DFT) calculations, we propose a mechanism for the formation of I2-NIS and the subsequent generation of an active iodinating species LB-I+.Herein, we report the development of aryl halide-dependent chemoselective reactions, viz., the Buchwald-Hartwig type coupling reaction of an aryl iodide with an arylboronic acid and an aryl amine in the presence of a heterogeneous and reusable nickel catalyst and the Suzuki-Miyaura type coupling of an aryl chloride under similar conditions. Control experiments revealed that the presence of stoichiometric amounts of the phenylboronic acid/ester and aryl amine are essential for both reactions. NMR and XAFS studies suggested the formation of a boron-amine "ate" complex.Herein we report the hydrodefluorination reaction of trifluoromethylated alkenes to access terminal monofluoroalkenes. The use of LiAlH4 allowed the stereoselective synthesis of the terminal monofluoroalkenes in good to excellent yields with good to excellent diastereoselectivities. Mechanistic studies suggested a hydroalumination reaction followed by a stereoselective fluoride elimination.Cupriavidus taiwanensis LMG19424, a β-rhizobial symbiont of Mimosa pudica, harbors phc and tqs quorum sensing (QS), which are the homologous cell-cell communication systems previously identified from the plant pathogen Ralstonia solanacearum and the human pathogen Vibrio cholerae, respectively. However, there has been no experimental evidence reported that these QS systems function in C. taiwanensis LMG19424. We identified (R)-methyl 3-hydroxymyristate (3-OH MAME) and (S)-3-hydroxypentadecan-4-one (C15-AHK) as phc and tqs QS signals, respectively, and characterized these QS systems. The expression of the signal synthase gene phcB and tqsA in E. coli BL21(DE3) resulted in the high production of 3-OH MAME and C15-AHK, respectively. Their structures were elucidated by comparison of EI-MS data and GC/chiral LC retention times with synthetic standards. The deletion of phcB reduced cell motility and increased biofilm formation, and the double deletion of phcB/tqsA caused the accumulation of the metal chelator coproporphyrin III in its mutant culture. Although the deletion of phcB and tqsA slightly reduced its ability to nodulate on aseptically grown seedlings of M. pudica, there was no significant difference in nodule formation between LMG19424 and its QS mutants when commercial soils were used. Taken together, this is the first example of the simultaneous production of 3-OH MAME/C15-AHK as QS signals in a bacterial species, and the importance of the phc/tqs QS systems in the saprophytic stage of C. taiwanensis LMG19424 is suggested.For a comprehensive and detailed microscopic understanding of the hydration properties of primary aqueous phosphorus species of valence states V (viz. H3PO4, H2PO4-, HPO42-, and PO43-), a series of extensive ab initio molecular dynamics (AIMD) simulations are conducted at ambient temperatures. In each of these cases, the spatially resolved, three-dimensional (3D) hydration shells are computed, allowing for a direct microscopic visual understanding of the hydration shells around the species. Since these species are excellent agents for the formation of hydrogen bonds (H-bonds) in water, that determine a wide range of their structural, dynamic and spectroscopic features, a detailed analysis of the qualitative and quantitative aspects of the H-bonds, including their lifetime calculations, is performed. Vibration density of states (VDOS) are calculated for each of the species in solute phases, resolved for each H-bonding site, and compared against the gas phase normal modes of H3PO4 for the purpose of understanding the signatures of its peaks in VDOS plots, and in particular, the effects of solvation and H-bonding mechanisms. The results are well in line with available experimental data and other recent computer-aided studies in literature.Photoexcited fluorescent markers are extensively used in spectroscopy, imaging, and analysis of biological systems. The performance of fluorescent markers depends on high levels of emission, which are limited by competing nonradiative decay pathways. Small-molecule fluorescent dyes have been increasingly used as markers due to their high and stable emission. Despite their prevalence, the nonradiative decay pathways of these dyes have not been determined. Here, we investigate these pathways for a widely used indocarbocyanine dye, Cy3, using transient grating spectroscopy. We identify a nonradiative decay pathway via a previously unknown dark state formed within ∼1 ps of photoexcitation. Our experiments, in combination with electronic structure calculations, suggest that the generation of the dark state is mediated by picosecond vibrational mode coupling, likely via a conical intersection. We further identify the vibrational modes, and thus structural elements, responsible for the formation and dynamics of the dark state, providing insight into suppressing nonradiative decay pathways in fluorescent markers such as Cy3.
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