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We provide an overview of the isotopic signatures of presolar supernova grains, specifically focusing on 44 Ti-containing grains with robustly inferred supernova origins and their implications for nucleosynthesis and mixing mechanisms in supernovae. Recent technique advancements have enabled the differentiation between radiogenic (from 44 Ti decay) and nonradiogenic 44 Ca excesses in presolar grains, made possible by enhanced spatial resolution of Ca-Ti isotope analyses with the Cameca NanoSIMS (Nano-scale Secondary Ion Mass Spectrometer) instrument. Within the context of presolar supernova grain data, we discuss ( i ) the production of 44 Ti in supernovae and the impact of interstellar medium heterogeneities on the galactic chemical evolution of 44 Ca/ 40 Ca, ( ii ) the nucleosynthesis processes of neutron bursts and explosive H-burning in Type II supernovae, and ( iii ) challenges in identifying the progenitor supernovae for 54 Cr-rich presolar nanospinel grains. Drawing on constraints and insights derived from presolar supernova grain data, we also provide an overview of our current understanding of the roles played by various supernova types – including Type II, Type Ia, and electron capture supernovae – in accounting for the diverse array of nucleosynthetic isotopic variations identified in bulk meteorites and meteoritic components. We briefly overview the potential mechanisms that have been proposed to explain these nucleosynthetic variations by describing the transport and distribution of presolar dust carriers in the protoplanetary disk. We highlight existing controversies in the interpretation of presolar grain data and meteoritic nucleosynthetic isotopic variations, while also outlining potential directions for future research.

Production and use of most organochlorine pesticides (OCPs) was banned through the Stockholm Convention on persistent organic pollutants. However, appreciable amounts are still detected in the environment due to their persistence, illegal use, and releases from contaminated soils and obsolete stocks. The present study investigated the levels of OCP residues in Nairobi River. Sediment and water samples were collected from three sites along the river and screened for 17 OCPs using gas chromatography electron capture detector (GC-ECD). Mean pesticide residues ranged from 0.01 to 41.9 μg kg −1 in sediment and below detection limit to 39.7 ng L −1 in water. In sediment α-HCH, β-HCH, γ-HCH, heptachlor epoxide, and p,p′ -DDD were detected in all samples, while α-HCH, γ-HCH, δ-HCH, heptachlor epoxide, endosulfan I, and endrin were detected in all water samples. Levels of OCPs in water were below the WHO maximum allowable limits for surface water. However, values higher than the sediment quality guidelines for sediment samples in Racecourse Road Bridge and Outering Road Bridge were reported, thus confirming the toxicity to aquatic organisms. Consequently, as these compounds are known to bio-accumulate in fatty tissues, continued use of the river water poses a health risk to animals and humans.

Electrospray ionization mass spectrometry (ESI-MS) experiments, including ion mobility spectrometry mass spectrometry (ESI-IMS-MS) and electron capture dissociation (ECD) of proteins ionized from aqueous solutions, have been used for the study of solution-like structures of intact proteins. By mixing aqueous proteins with denaturants online before ESI, the amount of protein unfolding can be precisely controlled and rapidly analyzed, permitting the characterization of protein folding intermediates in protein folding pathways. Herein, we mixed various pH solutions online with aqueous cytochrome C for unfolding and characterizing its unfolding intermediates with ESI-MS charge state distribution measurements, IMS, and ECD. The presence of folding intermediates and unfolded cytochrome c structures were detected from changes in charge states, arrival time distributions (ATDs), and ECD. We also compared structures from nondenaturing and denaturing solution mixtures measured under “gentle” (i.e., low energy) ion transmission conditions with structures measured under “harsh” (i.e., higher energy) transmission. This work confirms that when using “gentle” instrument conditions, the gas-phase cytochrome c ions reflect attributes of the various solution-phase structures. However, “harsh” conditions that maximize ion transmission produce extended structures that no longer correlate with changes in solution structure. Graphical abstract

Structural characterization of intrinsically disordered proteins (IDPs) has been a major challenge in the field of protein science due to limited capabilities to obtain full-length high-resolution structures. Native ESI-MS with top-down MS was utilized to obtain structural features of protein-ligand binding for the Parkinson’s disease-related protein, α-synuclein (αSyn), which is natively unstructured. Binding of heavy metals has been implicated in the accelerated formation of αSyn aggregation. Using high-resolution Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry, native top-down MS with various fragmentation methods, including electron capture dissociation (ECD), collisional activated dissociation (CAD), and multistage tandem MS (MS 3 ), deduced the binding sites of cobalt and manganese to the C-terminal region of the protein. Ion mobility MS (IM-MS) revealed a collapse toward compacted states of αSyn upon metal binding. The combination of native top-down MS and IM-MS provides structural information of protein-ligand interactions for intrinsically disordered proteins. Graphical Abstract ᅟ

Native top-down mass spectrometry (MS) and ion mobility spectrometry (IMS) were applied to characterize the interaction of a molecular tweezer assembly modulator, CLR01, with tau, a protein believed to be involved in a number of neurodegenerative disorders, including Alzheimer’s disease. The tweezer CLR01 has been shown to inhibit aggregation of amyloidogenic polypeptides without toxic side effects. ESI-MS spectra for different forms of tau protein (full-length, fragments, phosphorylated, etc.) in the presence of CLR01 indicate a primary binding stoichiometry of 1:1. The relatively high charging of the protein measured from non-denaturing solutions is typical of intrinsically disordered proteins, such as tau. Top-down mass spectrometry using electron capture dissociation (ECD) is a tool used to determine not only the sites of post-translational modifications but also the binding site(s) of non-covalent interacting ligands to biomolecules. The intact protein and the protein-modulator complex were subjected to ECD-MS to obtain sequence information, map phosphorylation sites, and pinpoint the sites of inhibitor binding. The ESI-MS study of intact tau proteins indicates that top-down MS is amenable to the study of various tau isoforms and their post-translational modifications (PTMs). The ECD-MS data point to a CLR01 binding site in the microtubule-binding region of tau, spanning residues K294-K331, which includes a six-residue nucleating segment PHF6 (VQIVYK) implicated in aggregation. Furthermore, ion mobility experiments on the tau fragment in the presence of CLR01 and phosphorylated tau reveal a shift towards a more compact structure. The mass spectrometry study suggests a picture for the molecular mechanism of the modulation of protein-protein interactions in tau by CLR01. Graphical Abstract ᅟ

Based on the harmonic cascade model, the rate constants of radiative cooling of the molecular negative ions of phenazine were calculated. It was determined that radiative cooling of molecular negative ions does not significantly affect the rates of electron autodetachment and makes no distortion to the results of measuring the negative ions lifetime by resonance electron capture mass spectrometry.

Trihalomethanes (THMs) are one of the most common classes of disinfection by-products. In this study, the temporospatial trends and health risks due to exposure to THMs in the Tabriz water distribution network were investigated. THM series were analyzed using gas chromatography equipped with electron capture detector. The non-carcinogenic and carcinogenic risks due to exposure to THMs were calculated using Monte Carlo simulations. Mean concentrations of THMs in winter and spring were 10.2 ± 9.3 μg/l and 252 ± 185.9 μg/l, respectively. More than 80% of THMs identified were bromodichloromethane. The mean values of lifetime cancer risk (LTCR) of THMs were calculated as 4.23E−06 and 2.38E−04 for winter and spring, respectively. This study showed that there were noticeable levels of THMs in Tabriz water distribution network, especially in the center of the city. Although the non-cancer risk through THMs was below permissible recommended levels, the cancer risk likely remains due to high levels of THMs in some locations.

Computer experiments are performed on total cross sections for capture of both electrons from helium targets at 100-10000 keV. Employed are four quantum-mechanical perturbative four-body distorted wave methods (one of the first and three of the second order). The goal is to determine the cross section sensitivity to the perturbation strengths in distorted waves from the second-order methods. The perturbation strength is parametrized by the Sommerfeld factor (the quotient of the nuclear charge and the relative velocity of the colliding particles). At each fixed impact energy, the sought sensitivity is monitored by gradually modifying the nuclear charges in the Sommerfeld factors. These factors reside in the Coulomb distortions of the unperturbed channels states. The focus is on the electronic distortions through the eikonal Coulomb logarithmic phases and the full Coulomb waves. The logarithmic phases are the constituents of the compound phases for the net charges of the two heavy scattering aggregates in relative motions. A striking perturbation strength sensitivity of the obtained total cross sections is recorded.

A network of three tall tower measurement stations was set up in 2012 across the United Kingdom to expand measurements made at the long-term background northern hemispheric site, Mace Head, Ireland. Reliable and precise in situ greenhouse gas (GHG) analysis systems were developed and deployed at three sites in the UK with automated instrumentation measuring a suite of GHGs. The UK Deriving Emissions linked to Climate Change (UK DECC) network uses tall (165–230 m) open-lattice telecommunications towers, which provide a convenient platform for boundary layer trace gas sampling. In this paper we describe the automated measurement system and first results from the UK DECC network for CO2, CH4, N2O, SF6, CO and H2. CO2 and CH4 are measured at all of the UK DECC sites by cavity ring-down spectroscopy (CRDS) with multiple inlet heights at two of the three tall tower sites to assess for boundary layer stratification. The short-term precisions (1σ on 1 min means) of CRDS measurements at background mole fractions for January 2012 to September 2015 is < 0.05 µmol mol−1 for CO2 and < 0.3 nmol mol−1 for CH4. Repeatability of standard injections (1σ) is < 0.03 µmol mol−1 for CO2 and < 0.3 nmol mol−1 for CH4 for the same time period. N2O and SF6 are measured at three of the sites, and CO and H2 measurements are made at two of the sites, from a single inlet height using gas chromatography (GC) with an electron capture detector (ECD), flame ionisation detector (FID) or reduction gas analyser (RGA). Repeatability of individual injections (1σ) on GC and RGA instruments between January 2012 and September 2015 for CH4, N2O, SF6, CO and H2 measurements were < 2.8 nmol mol−1, < 0.4 nmol mol−1, < 0.07 pmol mol−1, < 2 nmol mol−1 and < 3 nmol mol−1, respectively. Instrumentation in the network is fully automated and includes sensors for measuring a variety of instrumental parameters such as flow, pressures, and sampling temperatures. Automated alerts are generated and emailed to site operators when instrumental parameters are not within defined set ranges. Automated instrument shutdowns occur for critical errors such as carrier gas flow rate deviations. Results from the network give good spatial and temporal coverage of atmospheric mixing ratios within the UK since early 2012. Results also show that all measured GHGs are increasing in mole fraction over the selected reporting period and, except for SF6, exhibit a seasonal trend. CO2 and CH4 also show strong diurnal cycles, with night-time maxima and daytime minima in mole fractions.

Indoor Residual Spraying (IRS), insecticide-treated nets (ITNs) and long-lasting insecticidal nets (LLINs) are key components in malaria prevention and control strategy. However, the development of resistance by mosquitoes to insecticides recommended for IRS and/or ITNs/LLINs would affect insecticide-based malaria vector control. We assessed the susceptibility levels of Anopheles arabiensis to insecticides used in malaria control, characterized basic mechanisms underlying resistance, and evaluated the role of public health use of insecticides in resistance selection. Susceptibility status of An. arabiensis was assessed using WHO bioassay tests to DDT, permethrin, deltamethrin, malathion and propoxur in Ethiopia from August to September 2009. Mosquito specimens were screened for knockdown resistance (kdr) and insensitive acetylcholinesterase (ace-1(R)) mutations using AS-PCR and PCR-RFLP, respectively. DDT residues level in soil from human dwellings and the surrounding environment were determined by Gas Chromatography with Electron Capture Detector. An. arabiensis was resistant to DDT, permethrin, deltamethrin and malathion, but susceptible to propoxur. The West African kdr allele was found in 280 specimens out of 284 with a frequency ranged from 95% to 100%. Ace-1(R) mutation was not detected in all specimens scored for the allele. Moreover, DDT residues were found in soil samples from human dwellings but not in the surrounding environment. The observed multiple-resistance coupled with the occurrence of high kdr frequency in populations of An. arabiensis could profoundly affect the malaria vector control programme in Ethiopia. This needs an urgent call for implementing rational resistance management strategies and integrated vector control intervention.