Interaction of H2_2S with H atoms on grain surfaces under molecular cloud conditions

Hydrogen sulfide (H$_2$S) is thought to be efficiently formed on grain surfaces through the successive hydrogenation of S atoms. Its non-detection so far in astronomical observations of icy dust mantles thus indicates that effective destruction pathways must play a significant role in its interstellar abundance. While chemical desorption has been shown to remove H$_2$S very efficiently from the ice, in line with H$_2$S gas-phase detections, possible solid-state chemistry triggered by the related HS radical have been largely disregarded so far -- despite it being an essential intermediate in the H$_2$S + H reaction scheme. We aim to thoroughly investigate the fate of H$_2$S upon H-atom impact under molecular cloud conditions, providing a comprehensive analysis combined with detailed quantification of both the chemical desorption and ice chemistry that ensues. Experiments are performed in an ultrahigh vacuum chamber at temperatures between 10--16 K. The changes in the solid phase during H-atom bombardment are monitored in situ by means of reflection absorption infrared spectroscopy (RAIRS), and desorbed species are measured with a quadrupole mass spectrometer (QMS). We confirm the formation of H$_2$S$_2$ via reactions involving H$_2$S + H, and quantify its formation cross section under the employed experimental conditions. Additionally, we directly assess the chemical desorption of H$_2$S by measuring the gas-phase desorption signals with the QMS, providing unambiguous desorption cross sections. Chemical desorption of H$_2$S$_2$ was not observed. The relative decrease of H$_2$S ices by chemical desorption changes from ~85% to ~74% between temperatures of 10 and 16 K, while the decrease as the result of H$_2$S$_2$ formation is enhanced from ~5% to ~26%, suggesting an increasingly relevant sulfur chemistry induced by HS radicals at warmer environments. The astronomical implications are further discussed.Comment: 11 pages, 9 Figures, 3 Tables. Accepted for publication in Astronomy and Astrophysic

The hunt for formamide in interstellar ices: A toolkit of laboratory infrared spectra in astronomically relevant ice mixtures and comparisons to ISO, Spitzer, and JWST observations

This work aims at characterizing the mid-IR spectra of formamide in its pure form as well as in mixtures of the most abundant interstellar ices via laboratory simulation of such ices, as well as demonstrating how these laboratory spectra can be used to search for formamide in ice observations. Mid-IR spectra (4000 - 500 cm$^{-1}$, 2.5 - 20 $\mu$m) of formamide, both in its pure form as well as in binary and tertiary mixtures with H$_2$O, CO$_2$, CO, NH$_3$, CH$_3$OH, H$_2$O:CO$_2$, H$_2$O:NH$_3$, CO:NH$_3$, and CO:CH$_3$OH, are collected at temperatures ranging from 15 - 212 K. Apparent band strengths and positions of eight IR bands of pure amorphous and crystalline formamide at various temperatures are provided. Three bands are identified as potential formamide tracers in observational ice spectra: the overlapping C=O stretch and NH$_2$ scissor bands at 1700.3 and 1630.4 cm$^{-1}$ (5.881 and 6.133 $\mu$m), the CH bend at 1388.1 cm$^{-1}$ (7.204 $\mu$m), and the CN stretch at 1328.1 cm$^{-1}$ (7.529 $\mu$m). The relative apparent band strengths, positions, and FWHM of these features in mixtures at various temperatures are also determined. Finally, the laboratory spectra are compared to observational spectra of low- and high-mass young stellar objects as well as pre-stellar cores observed with the Infrared Space Observatory, the Spitzer Space Telescope, and the JWST. A comparison between the formamide CH bend in laboratory data and the 7.24 $\mu$m band in the observations tentatively indicates that, if formamide ice is contributing significantly to the observed absorption, it is more likely in a polar matrix. Upper limits ranging from 0.35-5.1\% with respect to H$_{2}$O are calculated. These upper limits are in agreement with gas-phase formamide abundances and take into account the effect of a H$_{2}$O matrix on formamide's band strengths.Comment: Accepted for publication in A&A. 25 pages, 11 figures, 9 table

Searches for Interstellar HCCSH and H₂CCS

A longstanding problem in astrochemistry is the inability of many current models to account for missing sulfur content. Many relatively simple species that may be good candidates to sequester sulfur have not been measured experimentally at the high spectral resolution necessary to enable radioastronomical identification. On the basis of new laboratory data, we report searches for the rotational lines in the microwave, millimeter, and submillimeter regions of the sulfur-containing hydrocarbon HCCSH. This simple species would appear to be a promising candidate for detection in space owing to the large dipole moment along its b-inertial axis, and because the bimolecular reaction between two highly abundant astronomical fragments (CCH and SH radicals) may be rapid. An inspection of multiple line surveys from the centimeter to the far-infrared toward a range of sources from dark clouds to high-mass star-forming regions, however, resulted in nondetections. An analogous search for the lowest-energy isomer, H₂CCS, is presented for comparison, and also resulted in nondetections. Typical upper limits on the abundance of both species relative to hydrogen are 10^(−9)–10^(−10). We thus conclude that neither isomer is a major reservoir of interstellar sulfur in the range of environments studied. Both species may still be viable candidates for detection in other environments or at higher frequencies, providing laboratory frequencies are available

Searches for Interstellar HCCSH and H₂CCS

A longstanding problem in astrochemistry is the inability of many current models to account for missing sulfur content. Many relatively simple species that may be good candidates to sequester sulfur have not been measured experimentally at the high spectral resolution necessary to enable radioastronomical identification. On the basis of new laboratory data, we report searches for the rotational lines in the microwave, millimeter, and submillimeter regions of the sulfur-containing hydrocarbon HCCSH. This simple species would appear to be a promising candidate for detection in space owing to the large dipole moment along its b-inertial axis, and because the bimolecular reaction between two highly abundant astronomical fragments (CCH and SH radicals) may be rapid. An inspection of multiple line surveys from the centimeter to the far-infrared toward a range of sources from dark clouds to high-mass star-forming regions, however, resulted in nondetections. An analogous search for the lowest-energy isomer, H₂CCS, is presented for comparison, and also resulted in nondetections. Typical upper limits on the abundance of both species relative to hydrogen are 10^(−9)–10^(−10). We thus conclude that neither isomer is a major reservoir of interstellar sulfur in the range of environments studied. Both species may still be viable candidates for detection in other environments or at higher frequencies, providing laboratory frequencies are available

Serine Protease PRSS23 Is Upregulated by Estrogen Receptor α and Associated with Proliferation of Breast Cancer Cells

Serine protease PRSS23 is a newly discovered protein that has been associated with tumor progression in various types of cancers. Interestingly, PRSS23 is coexpressed with estrogen receptor α (ERα), which is a prominent biomarker and therapeutic target for human breast cancer. Estrogen signaling through ERα is also known to affect cell proliferation, apoptosis, and survival, which promotes tumorigenesis by regulating the production of numerous downstream effector proteins

Implicating genes, pleiotropy, and sexual dimorphism at blood lipid loci through multi-ancestry meta-analysis

Funding GMP, PN, and CW are supported by NHLBI R01HL127564. GMP and PN are supported by R01HL142711. AG acknowledge support from the Wellcome Trust (201543/B/16/Z), European Union Seventh Framework Programme FP7/2007–2013 under grant agreement no. HEALTH-F2-2013–601456 (CVGenes@Target) & the TriPartite Immunometabolism Consortium [TrIC]-Novo Nordisk Foundation’s Grant number NNF15CC0018486. JMM is supported by American Diabetes Association Innovative and Clinical Translational Award 1–19-ICTS-068. SR was supported by the Academy of Finland Center of Excellence in Complex Disease Genetics (Grant No 312062), the Finnish Foundation for Cardiovascular Research, the Sigrid Juselius Foundation, and University of Helsinki HiLIFE Fellow and Grand Challenge grants. EW was supported by the Finnish innovation fund Sitra (EW) and Finska Läkaresällskapet. CNS was supported by American Heart Association Postdoctoral Fellowships 15POST24470131 and 17POST33650016. Charles N Rotimi is supported by Z01HG200362. Zhe Wang, Michael H Preuss, and Ruth JF Loos are supported by R01HL142302. NJT is a Wellcome Trust Investigator (202802/Z/16/Z), is the PI of the Avon Longitudinal Study of Parents and Children (MRC & WT 217065/Z/19/Z), is supported by the University of Bristol NIHR Biomedical Research Centre (BRC-1215–2001) and the MRC Integrative Epidemiology Unit (MC_UU_00011), and works within the CRUK Integrative Cancer Epidemiology Programme (C18281/A19169). Ruth E Mitchell is a member of the MRC Integrative Epidemiology Unit at the University of Bristol funded by the MRC (MC_UU_00011/1). Simon Haworth is supported by the UK National Institute for Health Research Academic Clinical Fellowship. Paul S. de Vries was supported by American Heart Association grant number 18CDA34110116. Julia Ramierz acknowledges support by the People Programme of the European Union’s Seventh Framework Programme grant n° 608765 and Marie Sklodowska-Curie grant n° 786833. Maria Sabater-Lleal is supported by a Miguel Servet contract from the ISCIII Spanish Health Institute (CP17/00142) and co-financed by the European Social Fund. Jian Yang is funded by the Westlake Education Foundation. Olga Giannakopoulou has received funding from the British Heart Foundation (BHF) (FS/14/66/3129). CHARGE Consortium cohorts were supported by R01HL105756. Study-specific acknowledgements are available in the Additional file 32: Supplementary Note. The views expressed in this manuscript are those of the authors and do not necessarily represent the views of the National Heart, Lung, and Blood Institute; the National Institutes of Health; or the U.S. Department of Health and Human Services.Peer reviewedPublisher PD

Implicating genes, pleiotropy, and sexual dimorphism at blood lipid loci through multi-ancestry meta-analysis

Publisher Copyright: © 2022, The Author(s).Background: Genetic variants within nearly 1000 loci are known to contribute to modulation of blood lipid levels. However, the biological pathways underlying these associations are frequently unknown, limiting understanding of these findings and hindering downstream translational efforts such as drug target discovery. Results: To expand our understanding of the underlying biological pathways and mechanisms controlling blood lipid levels, we leverage a large multi-ancestry meta-analysis (N = 1,654,960) of blood lipids to prioritize putative causal genes for 2286 lipid associations using six gene prediction approaches. Using phenome-wide association (PheWAS) scans, we identify relationships of genetically predicted lipid levels to other diseases and conditions. We confirm known pleiotropic associations with cardiovascular phenotypes and determine novel associations, notably with cholelithiasis risk. We perform sex-stratified GWAS meta-analysis of lipid levels and show that 3–5% of autosomal lipid-associated loci demonstrate sex-biased effects. Finally, we report 21 novel lipid loci identified on the X chromosome. Many of the sex-biased autosomal and X chromosome lipid loci show pleiotropic associations with sex hormones, emphasizing the role of hormone regulation in lipid metabolism. Conclusions: Taken together, our findings provide insights into the biological mechanisms through which associated variants lead to altered lipid levels and potentially cardiovascular disease risk.Peer reviewe

Implicating genes, pleiotropy, and sexual dimorphism at blood lipid loci through multi-ancestry meta-analysis

Abstract Background Genetic variants within nearly 1000 loci are known to contribute to modulation of blood lipid levels. However, the biological pathways underlying these associations are frequently unknown, limiting understanding of these findings and hindering downstream translational efforts such as drug target discovery. Results To expand our understanding of the underlying biological pathways and mechanisms controlling blood lipid levels, we leverage a large multi-ancestry meta-analysis (N = 1,654,960) of blood lipids to prioritize putative causal genes for 2286 lipid associations using six gene prediction approaches. Using phenome-wide association (PheWAS) scans, we identify relationships of genetically predicted lipid levels to other diseases and conditions. We confirm known pleiotropic associations with cardiovascular phenotypes and determine novel associations, notably with cholelithiasis risk. We perform sex-stratified GWAS meta-analysis of lipid levels and show that 3–5% of autosomal lipid-associated loci demonstrate sex-biased effects. Finally, we report 21 novel lipid loci identified on the X chromosome. Many of the sex-biased autosomal and X chromosome lipid loci show pleiotropic associations with sex hormones, emphasizing the role of hormone regulation in lipid metabolism. Conclusions Taken together, our findings provide insights into the biological mechanisms through which associated variants lead to altered lipid levels and potentially cardiovascular disease risk

Juxtaposing BTE and ATE – on the role of the European insurance industry in funding civil litigation

One of the ways in which legal services are financed, and indeed shaped, is through private insurance arrangement. Two contrasting types of legal expenses insurance contracts (LEI) seem to dominate in Europe: before the event (BTE) and after the event (ATE) legal expenses insurance. Notwithstanding institutional differences between different legal systems, BTE and ATE insurance arrangements may be instrumental if government policy is geared towards strengthening a market-oriented system of financing access to justice for individuals and business. At the same time, emphasizing the role of a private industry as a keeper of the gates to justice raises issues of accountability and transparency, not readily reconcilable with demands of competition. Moreover, multiple actors (clients, lawyers, courts, insurers) are involved, causing behavioural dynamics which are not easily predicted or influenced. Against this background, this paper looks into BTE and ATE arrangements by analysing the particularities of BTE and ATE arrangements currently available in some European jurisdictions and by painting a picture of their respective markets and legal contexts. This allows for some reflection on the performance of BTE and ATE providers as both financiers and keepers. Two issues emerge from the analysis that are worthy of some further reflection. Firstly, there is the problematic long-term sustainability of some ATE products. Secondly, the challenges faced by policymakers that would like to nudge consumers into voluntarily taking out BTE LEI

Penilaian Kinerja Keuangan Koperasi di Kabupaten Pelalawan

This paper describe development and financial performance of cooperative in District Pelalawan among 2007 - 2008. Studies on primary and secondary cooperative in 12 sub-districts. Method in this stady use performance measuring of productivity, efficiency, growth, liquidity, and solvability of cooperative. Productivity of cooperative in Pelalawan was highly but efficiency still low. Profit and income were highly, even liquidity of cooperative very high, and solvability was good