Diffusion activation energy and desorption activation energy for astrochemically relevant species on water ice show no clear relation

The activation energy for desorption (Edes) and that for surface diffusion (Esd) of adsorbed molecules on dust grains are two of the most important parameters for the chemistry in the interstellar medium. Although Edes is often measured by laboratory experiments, the measurement of Esd is sparse. Due to the lack of data, astrochemical models usually assume a simple scaling relation, Esd = fEdes, where f is a constant, irrespective of adsorbed species. Here, we experimentally measure Esd for CH4, H2S, OCS, CH3OH, and CH3CN on water-ice surfaces using an ultra-high-vacuum transmission electron microscope (UHV-TEM). Compiling the measured Esd values and Edes values from the literature, we find that the value of f ranges from ~0.2 to ~0.7, depending on the species. Unless f (or Esd) for the majority of species is available, a natural alternative approach for astrochemical models is running multiple simulations, varying f for each species randomly. In this approach, ranges of molecular abundances predicted by multiple simulations, rather than abundances predicted by each simulation, are important. We here run 10,000 simulations of astrochemical models of molecular clouds and protostellar envelopes, randomly assigning a value of f for each species. In the former case, we identify several key species whose Esd most strongly affects the uncertainties of the model predictions; Esd for those species should be investigated in future laboratory and quantum chemical studies. In the latter case, uncertainties in the Esd of many species contribute to the uncertainties in the model predictions.Comment: Accepted for publication in ApJ

EXPERIMENTAL STUDY OF CO 2 FORMATION BY SURFACE REACTIONS OF NON-ENERGETIC OH RADICALS WITH CO MOLECULES

Surface reactions between carbon monoxide and non-energetic hydroxyl radicals were carried out at 10 K and 20 K in order to investigate possible reaction pathways to yield carbon dioxide in dense molecular clouds. Hydroxyl radicals, produced by dissociating water molecules in microwave-induced plasma, were cooled down to 100 K prior to the introduction of CO. The abundances of species were monitored in situ using a Fourier transform infrared spectrometer. Formation of CO2 was clearly observed, even at 10 K, suggesting that reactions of CO with OH proceed with little or no activation barrier. The present results indicate that CO2 formation, due to reactions between CO and OH, occurs in tandem with H2O formation, and this may lead to the formation of CO2 ice in polar environments, as typically observed in molecular clouds

FORMATION OF CARBONIC ACID (H2CO3) BY SURFACE REACTIONS OF NON-ENERGETIC OH RADICALS WITH CO MOLECULES AT LOW TEMPERATURES

We present the experimental results of carbonic acid (H2CO3) formation through surface reactions of CO molecules with non-energetic hydroxyl (OH) radicals at 10-40 K. The formation of H2CO3 was clearly identified both in the IR spectra and in the thermally programmed desorption mass spectra. The H2CO3 yield was rather high, amounting to approximately 40%-70% relative to that of CO2 formed by the reaction of CO with OH. The structure of H2CO3 formed by reactions of CO with OH may differ from that formed by energetic processes such as UV irradiation, ion irradiation, and electron irradiation of H2O/CO2 binary ices. In this paper, we envisage some of the possible roles H2CO3 may have in the interstellar medium, such as enriching grain mantles of new molecules via acid-base reactions with basic species and contributing to the formation of the unidentified band at 6.8 μm; we suggest possible reasons for its non-detection yet and discuss the restoration of carbonic acid molecules in the gas phase

Radioligand Assay-Based Detection of Antibodies against SARS-CoV-2 in Hospital Workers Treating Patients with Severe COVID-19 in Japan.

This study aimed to clarify whether infection by severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) is prevalent among the staff of a hospital providing treatment to patients with severe coronavirus disease 2019 (COVID-19) using radioligand assay (RLA). One thousand samples from the staff of a general hospital providing treatment to patients with severe COVID-19 were assayed for SARS-CoV-2 nucleocapsid protein (N) IgG using RLA. Nine patients with COVID-19 who had been treated in inpatient settings and had already recovered were used as control subjects, and 186 blood donor samples obtained more than 10 years ago were used as negative controls. Four of the 1000 samples showed apparently positive results, and approximately 10 or more samples showed slightly high counts. Interestingly, a few among the blood donor samples also showed slightly high values. To validate the results, antibody examinations using ELISA and neutralizing antibody tests were performed on 21 samples, and chemiluminescence immunoassay (CLIA) was performed on 201 samples, both resulting in a very high correlation. One blood donor sample showed slightly positive results in both RLA and CLIA, suggesting a cross-reaction. This study showed that five months after the pandemic began in Japan, the staff of a general hospital with a tertiary emergency medical facility had an extremely low seroprevalence of the antibodies against SARS-CoV-2. Further investigation will be needed to determine whether the slightly high results were due to cross-reactions or a low titer of anti-SARS-CoV-2 antibodies. The quantitative RLA was considered sensitive enough to detect low titers of antibodies

Omentin Prevents Myocardial Ischemic Injury Through AMP-Activated Protein Kinase- and Akt-Dependent Mechanisms

ObjectivesThis study examined the impact of omentin on myocardial injury in a mouse model of ischemia/reperfusion (I/R) and explored its underlying mechanisms.BackgroundObesity is a major risk factor for ischemic heart disease. Omentin is a circulating adipokine that is down-regulated by obesity.MethodsIn patients who underwent successful reperfusion treatment after acute myocardial infarction, cardiac function and perfusion defect were assessed by using scintigraphic images. Mice were subjected to myocardial ischemia followed by reperfusion.ResultsThis study found that high levels of plasma omentin were associated with improvement of heart damage and function after reperfusion therapy in patients with acute myocardial infarction. Systemic administration of human omentin to mice led to a reduction in myocardial infarct size and apoptosis after I/R, which was accompanied by enhanced phosphorylation of AMP-activated protein kinase (AMPK) and Akt in the ischemic heart. Fat-specific overexpression of human omentin also resulted in reduction of infarct size after I/R. Blockade of AMPK or Akt activity reversed omentin-induced inhibition of myocardial ischemic damage and apoptosis in mice. In cultured cardiomyocytes, omentin suppressed hypoxia/reoxygenation-induced apoptosis, which was blocked by inactivation of AMPK or Akt.ConclusionsOur data indicate that omentin functions as an adipokine that ameliorates acute ischemic injury in the heart by suppressing myocyte apoptosis through both AMPK- and Akt-dependent mechanisms

Chiral Ice Crystals in Space

We observed the formation of CO, CH3OH, and H2O ices using a cryogenic transmission electron microscope, to determine if chiral ice crystals could form under the conditions of interstellar molecular clouds and young stellar objects (protoplanetary disks) and to clarify the crystalline structure of these ices. Our results suggest that the following ice crystals are chiral: crystalline CO (α-CO) formed on amorphous H2O (a-H2O) grains in a 10-K molecular cloud, crystalline CH3OH formed by the heating of amorphous CH3OH on a-H2O grains at 40–60 K in young stellar objects, and several polymorphs of hydrogen-ordered cubic ice crystals formed by the heating of a-H2O at 80–100 K and direct condensation at 120–140 K in protoplanetary disks. We also investigated candidates for other chiral ices using published data. We found that NH3 I and NH3·H2O I are chiral at low temperature and pressure conditions. If one-handed circularly polarized light is irradiated during the nucleation of these chiral ice crystals, homochiral crystals can be formed. These results have important implications for the origin of interstellar organic molecule homochirality

Gene Transfer Using Micellar Nanovectors Inhibits Choroidal Neovascularization In Vivo

PURPOSE: Age-related macular degeneration caused by choroidal neovascularization (CNV) remains difficult to be treated despite the recent advent of several treatment options. In this study, we investigated the in vivo angiogenic control by intravenous injection of polyion complex (PIC) micelle encapsulating plasmid DNA (pDNA) using a mice CNV model. METHODS: The transfection efficiency of the PIC micelle was investigated using the laser-induced CNV in eight-week-old male C57 BJ/6 mice. Firstly, each mouse received intravenous injection of micelle encapsulating pDNA of Yellow Fluorescent Protein (pYFP) on days 1,3 and 5. The expression of YFP was analyzed using fluorescein microscopy and western blotting analysis. In the next experiments, each mouse received intravenous injection of micelle encapsulating pDNA of soluble Fms-like tyrosine kinase-1 (psFlt-1) 1,3 and 5 days after the induction of CNV and the CNV lesion was analyzed by choroidal flatmounts on day 7. RESULTS: Fluorescein microscopy and western blotting analysis revealed that the expression of YFP was confirmed in the CNV area after injection of the PIC micelle, but the expression was not detected neither in mice that received naked pDNA nor those without CNV. Furthermore, the CNV area in the mice that received intravenous injection of the psFlt-1-encapsulated PIC micelle was significantly reduced by 65% compared to that in control mice (p<0.01). CONCLUSIONS: Transfection of sFlt-1 with the PIC micelle by intravenous injection to mice CNV models showed significant inhibition of CNV. The current results revealed the significant potential of nonviral gene therapy for regulation of CNV using the PIC micelle encapsulating pDNA

Negative catalytic effect of water on the reactivity of hydrogen abstraction from the C-H bond of dimethyl ether by deuterium atoms through tunneling at low temperatures

We report an experimental study on the catalytic effect of solid water on the reactivity of hydrogen abstraction (H-abstraction) from dimethyl ether (DME) in the low-temperature solid DME-H2O complex. When DME reacted with deuterium atoms on a surface at 15-25 K, it was efficiently deuterated via successive tunneling H-abstraction and deuterium (D)-addition reactions. The 'effective rate constant for DME-H2O + D was found to be about 20 times smaller than that of pure DME + D. This provides the first evidence that the presence of solid water has a negative catalytic effect on tunneling H-abstraction reactions. (C) 2016 Elsevier B.V. All rights reserved

DEUTERIUM FRACTIONATION DURING AMINO ACID FORMATION BY PHOTOLYSIS OF INTERSTELLAR ICE ANALOGS CONTAINING DEUTERATED METHANOL

Deuterium (D) atoms in interstellar deuterated methanol might be distributed into complex organic molecules through molecular evolution by photochemical reactions in interstellar grains. In this study, we use a state-of-the-art high-resolution mass spectrometer coupled with a high-performance liquid chromatography system to quantitatively analyze amino acids and their deuterated isotopologues formed by the photolysis of interstellar ice analogs containing singly deuterated methanol CH2DOH at 10 K. Five amino acids (glycine, alpha-alanine, beta-alanine, sarcosine, and serine) and their deuterated isotopologues whose D atoms are bound to carbon atoms are detected in organic residues formed by photolysis followed by warming up to room temperature. The abundances of singly deuterated amino acids are in the range of 0.3-1.1 relative to each nondeuterated counterpart, and the relative abundances of doubly and triply deuterated species decrease with an increasing number of D atoms in a molecule. The abundances of amino acids increase by a factor of more than five upon the hydrolysis of the organic residues, leading to decreases in the relative abundances of deuterated species for alpha-alanine and beta-alanine. On the other hand, the relative abundances of the deuterated isotopologues of the other three amino acids did not decrease upon hydrolysis, indicating different formation mechanisms of these two groups upon hydrolysis. The present study facilitates both qualitative and quantitative evaluations of D fractionation during molecular evolution in the interstellar medium