Formic acid (HCOOH) is one of the most abundant acids in the atmosphere, with an important influence on precipitation chemistry and acidity. Here we employ a chemical transport model (GEOS-Chem CTM) ...to interpret recent airborne and ground-based measurements over the US Southeast in terms of the constraints they provide on HCOOH sources and sinks. Summertime boundary layer concentrations average several parts-per-billion, 2-3 larger than can be explained based on known production and loss pathways. This indicates one or more large missing HCOOH sources, and suggests either a key gap in current understanding of hydrocarbon oxidation or a large, unidentified, direct flux of HCOOH. Model-measurement comparisons implicate biogenic sources (e.g., isoprene oxidation) as the predominant HCOOH source. Resolving the unexplained boundary layer concentrations based (i) solely on isoprene oxidation would require a 3 increase in the model HCOOH yield, or (ii) solely on direct HCOOH emissions would require approximately a 25 increase in its biogenic flux. However, neither of these can explain the high HCOOH amounts seen in anthropogenic air masses and in the free troposphere. The overall indication is of a large biogenic source combined with ubiquitous chemical production of HCOOH across a range of precursors. Laboratory work is needed to better quantify the rates and mechanisms of carboxylic acid production from isoprene and other prevalent organics. Stabilized Criegee intermediates (SCIs) provide a large model source of HCOOH, while acetaldehyde tautomerization accounts for ~ 15% of the simulated global burden. Because carboxylic acids also react with SCIs and catalyze the reverse tautomerization reaction, HCOOH buffers against its own production by both of these pathways. Based on recent laboratory results, reaction between CH3O2 and OH could provide a major source of atmospheric HCOOH; however, including this chemistry degrades the model simulation of CH3OOH and NOx : CH3OOH. Developing better constraints on SCI and RO2 + OH chemistry is a high priority for future work. The model neither captures the large diurnal amplitude in HCOOH seen in surface air, nor its inverted vertical gradient at night. This implies a substantial bias in our current representation of deposition as modulated by boundary layer dynamics, and may indicate an HCOOH sink underestimate and thus an even larger missing source. A more robust treatment of surface deposition is a key need for improving simulations of HCOOH and related trace gases, and our understanding of their budgets.
Optically luminous quasars at
z
> 5 are important probes of super-massive black hole (SMBH) formation. With new and future radio facilities, the discovery of the brightest low-frequency radio ...sources in this epoch would be an important new probe of cosmic reionization through 21-cm absorption experiments. In this work, we systematically study the low-frequency radio properties of a sample of 115 known spectroscopically confirmed
z
> 5 quasars using the second data release of the Low Frequency Array (LOFAR) Two Metre Sky survey (LoTSS-DR2), reaching noise levels of ∼80 μJy beam
−1
(at 144 MHz) over an area of ∼5720 deg
2
. We find that 41 sources (36%) are detected in LoTSS-DR2 at > 2
σ
significance and we explore the evolution of their radio properties (power, spectral index, and radio loudness) as a function of redshift and rest-frame ultra-violet properties. We obtain a median spectral index of −0.29
−0.09
+0.10
by stacking 93 quasars using LoTSS-DR2 and Faint Images of the Radio Sky at Twenty Centimetres (FIRST) data at 1.4 GHz, in line with observations of quasars at
z
< 3. We compare the radio loudness of the high-
z
quasar sample to a lower-
z
quasar sample at
z
∼ 2 and find that the two radio loudness distributions are consistent with no evolution, although the low number of high-
z
quasars means that we cannot rule out weak evolution. Furthermore, we make a first order empirical estimate of the
z
= 6 quasar radio luminosity function, which is used to derive the expected number of high-
z
sources that will be detected in the completed LoTSS survey. This work highlights the fact that new deep radio observations can be a valuable tool in selecting high-
z
quasar candidates for follow-up spectroscopic observations by decreasing contamination of stellar dwarfs and reducing possible selection biases introduced by strict colour cuts.
Some individuals are endowed with a biology that renders them more reactive to novelty and potential threat. When extreme, this anxious temperament (AT) confers elevated risk for the development of ...anxiety, depression and substance abuse. These disorders are highly prevalent, debilitating and can be challenging to treat. The high-risk AT phenotype is expressed similarly in children and young monkeys and mechanistic work demonstrates that the central (Ce) nucleus of the amygdala is an important substrate. Although it is widely believed that the flow of information across the structural network connecting the Ce nucleus to other brain regions underlies primates' capacity for flexibly regulating anxiety, the functional architecture of this network has remained poorly understood. Here we used functional magnetic resonance imaging (fMRI) in anesthetized young monkeys and quietly resting children with anxiety disorders to identify an evolutionarily conserved pattern of functional connectivity relevant to early-life anxiety. Across primate species and levels of awareness, reduced functional connectivity between the dorsolateral prefrontal cortex, a region thought to play a central role in the control of cognition and emotion, and the Ce nucleus was associated with increased anxiety assessed outside the scanner. Importantly, high-resolution 18-fluorodeoxyglucose positron emission tomography imaging provided evidence that elevated Ce nucleus metabolism statistically mediates the association between prefrontal-amygdalar connectivity and elevated anxiety. These results provide new clues about the brain network underlying extreme early-life anxiety and set the stage for mechanistic work aimed at developing improved interventions for pediatric anxiety.
The Give and Take of Alcohol Activation Watson, Andrew J. A.; Williams, Jonathan M. J.
Science (American Association for the Advancement of Science),
08/2010, Letnik:
329, Številka:
5992
Journal Article
Recenzirano
Catalysts make alcohols more reactive by taking away hydrogen to create carbonyl compounds and then returning the hydrogen to the final products.
Alcohols are relatively common starting materials for ...chemical reactions, even though they are quite unreactive. For example, reactions that would substitute another functional group (a nucleophile) for OH often fail because the hydroxide group (HO
−
) is difficult to displace—it is a poor leaving group. Alcohols are usually activated by turning the hydroxide into a better leaving group, either by protonating the alcohol or by converting it into a sulfonate or halide. However, both of these activation methods have some disadvantages (
1
). The acidic environment required for protonating the alcohol also protonates and deactivates the incoming nucleophile, especially amines. Conversion of the alcohol into a sulfonate or halide can lead to toxicity problems; many alkyl halides and alkyl sulfonates are mutagenic.
Electronic circular dichroism and circularly polarized luminescence acid/base switching activity has been demonstrated in helicene‐bipyridine proligand 1 a and in its “rollover” cycloplatinated ...derivative 2 a. Whereas proligand 1 a displays a strong bathochromic shift (>160 nm) of the nonpolarized and circularly polarized luminescence upon protonation, complex 2 a displays slightly stronger emission. This strikingly different behavior between singlet emission in the organic helicene and triplet emission in the organometallic derivative has been rationalized by using quantum‐chemical calculations. The very large bathochromic shift of the emission observed upon protonation of azahelicene‐bipyridine 1 a has been attributed to the decrease in aromaticity (promoting a charge‐transfer‐type transition rather than a π–π* transition) as well as an increase in the HOMO–LUMO character of the transition and stabilization of the LUMO level upon protonation.
Rollover platination: A 6helicene‐bipyridine derivative has been used as a proligand for “rollover” cycloplatination and for the conception of acid/base chiroptical switches. Protonation triggers a change in the nature of the HOMO–LUMO transition, from a π–π* to a charge‐transfer transition, and significantly modifies the circularly polarized luminescence and electronic circular dichroism spectra of the organic and organometallic helicenes (see figure).
Abstract
Over the past decade, observations of relativistic outflows from outbursting X-ray binaries in the Galactic field have grown significantly. In this work, we present the first detection of ...moving and decelerating radio-emitting outflows from an X-ray binary in a globular cluster. MAXI J1848−015 is a recently discovered transient X-ray binary in the direction of the globular cluster GLIMPSE-C01. Using observations from the Karl G. Jansky Very Large Array, and a monitoring campaign with the MeerKAT observatory for 500 days, we model the motion of the outflows. This represents some of the most intensive, long-term coverage of relativistically moving X-ray binary outflows to date. We use the proper motions of the outflows from MAXI J1848−015 to constrain the component of the intrinsic jet speed along the line of sight,
β
int
cos
θ
ejection
, to be =0.19 ± 0.02. Assuming it is located in GLIMPSE-C01, at 3.4 kpc, we determine the intrinsic jet speed,
β
int
= 0.79 ± 0.07, and the inclination angle to the line of sight,
θ
ejection
= 76° ± 2°. This makes the outflows from MAXI J1848−015 somewhat slower than those seen from many other known X-ray binaries. We also constrain the maximum distance to MAXI J1848−015 to be 4.3 kpc. Finally, we discuss the implications of our findings for the nature of the compact object in this system, finding that a black hole primary is a viable (but as-of-yet unconfirmed) explanation for the observed properties of MAXI J1848−015. If future data and/or analysis provide more conclusive evidence that MAXI J1848−015 indeed hosts a black hole, it would be the first black hole X-ray binary in outburst identified in a Galactic globular cluster.
Aims/hypothesis
The aim of this study was to investigate whether small doses of intense exercise before each main meal (‘exercise snacks’) would result in better blood glucose control than a single ...bout of prolonged, continuous, moderate-intensity exercise in individuals with insulin resistance.
Methods
Nine individuals completed three exercise interventions in randomised order. Measures were recorded across 3 days with exercise performed on the middle day, as either: (1) traditional continuous exercise (CONT), comprising 30 min moderate-intensity (60% of maximal heart rate HR
max
) incline walking before dinner; (2) exercise snacking (ES), consisting of 6 × 1 min intense (90% HR
max
) incline walking intervals 30 min before each meal; or (3) composite exercise snacking (CES), encompassing 6 × 1 min intervals alternating between walking and resistance-based exercise, 30 min before meals. Meal timing and composition were controlled within participants for exercise interventions.
Results
ES attenuated mean 3 h postprandial glucose concentration following breakfast (by 1.4 ± 1.5 mmol/l,
p
= 0.02) but not lunch (0.4 ± 1.0 mmol/l,
p
= 0.22), and was more effective than CONT following dinner (0.7 ± 1.5 mmol/l below CONT;
p
= 0.04). ES also reduced 24 h mean glucose concentration by 0.7 ± 0.6 mmol/l (
p
= 0.01) and this reduction persisted for the subsequent 24 h (lower by 0.6 ± 0.4 mmol/l vs CONT, relative to their baselines;
p
= 0.01). CES was just as effective as ES (
p
> 0.05 for all glycaemic variables) at improving glycaemic control.
Conclusions/interpretation
Dosing exercise as brief, intense ‘exercise snacks’ before main meals is a time-efficient and effective approach to improve glycaemic control in individuals with insulin resistance.
Abstract
Radio emission is a key indicator of star formation activity in galaxies, but the radio luminosity–star formation relation has to date been studied almost exclusively at frequencies of ...1.4 GHz or above. At lower radio frequencies, the effects of thermal radio emission are greatly reduced, and so we would expect the radio emission observed to be completely dominated by synchrotron radiation from supernova-generated cosmic rays. As part of the LOFAR Surveys Key Science project, the Herschel-ATLAS NGP field has been surveyed with LOFAR at an effective frequency of 150 MHz. We select a sample from the MPA-JHU catalogue of Sloan Digital Sky Survey galaxies in this area: the combination of Herschel, optical and mid-infrared data enable us to derive star formation rates (SFRs) for our sources using spectral energy distribution fitting, allowing a detailed study of the low-frequency radio luminosity–star formation relation in the nearby Universe. For those objects selected as star-forming galaxies (SFGs) using optical emission line diagnostics, we find a tight relationship between the 150 MHz radio luminosity (L150) and SFR. Interestingly, we find that a single power-law relationship between L150 and SFR is not a good description of all SFGs: a broken power-law model provides a better fit. This may indicate an additional mechanism for the generation of radio-emitting cosmic rays. Also, at given SFR, the radio luminosity depends on the stellar mass of the galaxy. Objects that were not classified as SFGs have higher 150-MHz radio luminosity than would be expected given their SFR, implying an important role for low-level active galactic nucleus activity.
PDF
