The relative importance of competing pathways for the formation of high-molecular-weight peroxides in the ozonolysis of organic aerosol particles

High-molecular-weight (HMW) organic compounds are an important component of atmospheric particles, although their origins, possibly including in situ formation pathways, remain incompletely understood. This study investigates the formation of HMW organic peroxides through reactions involving stabilized Criegee intermediates (SCI's). The model system is methyl oleate (MO) mixed with dioctyl adipate (DOA) and myristic acid (MA) in submicron aerosol particles, and Criegee intermediates are formed by the ozonolysis of the double bond in methyl oleate. An aerosol flow tube coupled to a quadrupole aerosol mass spectrometer (AMS) is employed to determine the relative importance of different HMW organic peroxides following the ozonolysis of different mixing mole fractions of MO in DOA and MA. Possible peroxide products include secondary ozonides (SOZ's), α-acyloxyalkyl hydroperoxides and α-acyloxyalkyl alkyl peroxides (αAAHP-type compounds), diperoxides, and monoperoxide oligomers. Of these, the AMS data identify two SOZ's as major HMW products in the ozonolysis of pure methyl oleate as well as in an inert matrix of DOA to as low as 0.04 mole fraction MO. In comparison, in mixed particles of MO and MA, αAAHP-type compounds form in high yields for MO mole fractions of 0.5 or less, suggesting that SCI's efficiently attack the carboxylic acid group of myristic acid. The reactions of SCI's with carboxylic acid groups to form αAAHP-type compounds therefore compete with those of SCI's with aldehydes to form SOZ's, provided that both types of functionalities are present at significant concentrations. The results therefore suggest that SCI's in atmospheric particles contribute to the transformation of carboxylic acids and other protic groups into HMW organic peroxides

Nature of a Strongly-Lensed Submillimeter Galaxy SMM J14011+0252

We have carried out near-infrared JHK spectroscopy of a gravitationally lensed submillimeter galaxy SMM J14011+0252 at z=2.565, using OHS and CISCO on the Subaru telescope. This object consists of two optical components, J1 and J2, which are lensed by the cluster Abell 1835. J1 suffers additional strong lensing by a foreground galaxy at z=0.25 in the cluster. The rest-optical H-alpha, H-beta, and [O II]3727 lines are detected in both J1 and J2, and [N II]6548,6583 lines are also detected in J1. A diagnosis of emission-line ratios shows that the excitation source of J1 is stellar origin, consistent with previous X-ray observations. The continua of J1 and J2 show breaks at rest 4000A, indicating relatively young age. Combined with optical photometry, we have carried out model spectrum fitting of J2 and find that it is a very young (~50 Myr) galaxy of rather small mass (~10e8 M_sol) which suffers some amount of dust extinction. A new gravitational lensing model is constructed to assess both magnification factor and contamination from the lensing galaxy of the component J1, using HST-F702W image. We have found that J1 suffers strong lensing with magnification of ~30, and its stellar mass is estimated to be < 10e9 M_sol. These results suggest that SMM J14011+0252 is a major merger system at high redshift that undergoes intense star formation, but not a formation site of a giant elliptical. Still having plenty of gas, it will transform most of the gas into stars and will evolve into a galaxy of < 10e10 M_sol. Therefore, this system is possibly an ancestor of a less massive galaxy such as a mid-sized elliptical or a spiral at the present.Comment: 21 pages, 11 figures. Accepted for publication in Astronomical Journa

The Wigner caustic on shell and singularities of odd functions

We study the Wigner caustic on shell of a Lagrangian submanifold L of affine symplectic space. We present the physical motivation for studying singularities of the Wigner caustic on shell and present its mathematical definition in terms of a generating family. Because such a generating family is an odd deformation of an odd function, we study simple singularities in the category of odd functions and their odd versal deformations, applying these results to classify the singularities of the Wigner caustic on shell, interpreting these singularities in terms of the local geometry of L.Comment: 24 page

Circadian factors BMAL1 and RORα control HIF-1α transcriptional activity in nucleus pulposus cells: implications in maintenance of intervertebral disc health.

BMAL1 and RORα are major regulators of the circadian molecular oscillator. Since previous work in other cell types has shown cross talk between circadian rhythm genes and hypoxic signaling, we investigated the role of BMAL1 and RORα in controlling HIF-1-dependent transcriptional responses in NP cells that exist in the physiologically hypoxic intervertebral disc. HIF-1-dependent HRE reporter activity was further promoted by co-transfection with either BMAL1 or RORα. In addition, stable silencing of BMAL1 or inhibition of RORα activity resulted in decreased HRE activation. Inhibition of RORα also modulated HIF1α-TAD activity. Interestingly, immunoprecipitation studies showed no evidence of BMAL1, CLOCK or RORα binding to HIF-1α in NP cells. Noteworthy, stable silencing of BMAL1 as well as inhibition of RORα decreased expression of select HIF-1 target genes including VEGF, PFKFB3 and Eno1. To delineate if BMAL1 plays a role in maintenance of disc health, we studied the spinal phenotype of BMAL1-null mice. The lumbar discs of null mice evidenced decreased height, and several parameters associated with vertebral trabecular bone quality were also affected in nulls. In addition, null animals showed a higher ratio of cells to matrix in NP tissue and hyperplasia of the annulus fibrosus. Taken together, our results indicate that BMAL1 and RORα form a regulatory loop in the NP and control HIF-1 activity without direct interaction. Importantly, activities of these circadian rhythm molecules may play a role in the adaptation of NP cells to their unique niche

Diurnal variation and size dependence of the hygroscopicity of organic aerosol at a forest site in Wakayama, Japan: their relationship to CCN concentrations

Formation of biogenic secondary organic aerosol (BSOA) and its subsequent evolution can modify the hygroscopicity of the organic aerosol component (OA) in the forest atmosphere, and affect the concentrations of cloud condensation nuclei (CCN) there. In this study, size-resolved aerosol hygroscopic growth at 85&thinsp;% relative humidity and size-resolved aerosol composition were measured using a hygroscopic tandem differential mobility analyzer and an aerosol mass spectrometer, respectively, at a forest site in Wakayama, Japan, in August and September 2015. The hygroscopicity parameter of OA (κorg) presented daily minima in the afternoon hours, and it also showed an increase with the increase in particle dry diameter. The magnitudes of the diurnal variations in κorg for particles with dry diameters of 100 and 300&thinsp;nm were on average 0.091 and 0.096, respectively, and the difference in κorg between particles with dry diameters of 100 and 300&thinsp;nm was on average 0.056. The relative contributions of the estimated fresh BSOA and regional OA to total OA could explain 40&thinsp;% of the observed diurnal variations and size dependence of κorg. The hygroscopicity parameter of fresh BSOA was estimated to range from 0.089 to 0.12 for particles with dry diameters from 100 to 300&thinsp;nm. Compared with the use of time- and size-resolved κorg, the use of time- and size-averaged κorg leads to under- and over-estimation of the fractional contribution of OA to CCN number concentrations in the range from −5.0&thinsp;% to 26&thinsp;%. This indicates that the diurnal variations and size dependence of κorg strongly affect the overall contribution of OA to CCN concentrations. The fractional contribution of fresh BSOA to CCN number concentrations could reach 0.28 during the period of intensive BSOA formation. The aging of the fresh BSOA, if it occurs, increases the estimated contribution of BSOA to CCN number concentrations by 52&thinsp;%–84&thinsp;%.</p

Role of glycosaminoglycans of biglycan in BMP-2 signaling

Recently we have reported that biglycan (BGN) promotes osteoblast differentiation and that this function is due in part to its ability to positively modulate bone morphogenetic protein (BMP) functions. In this study we investigated the role of glycosaminoglycans (GAGs) of BGN in this function using in vitro and in vivo models. C2C12 myogenic cells were treated or untreated with BMP-2 alone or in combination with glycanated, partially glycanated or de-glycanated BGN, and the effects on BMP signaling and function were assessed by Smad1/5/8 phosphorylation and alkaline phosphatase (ALP) activity. Furthermore, the effect of de-glycanation of BGN on BMP-2 induced osteogenesis was investigated employing a rat mandible defect model. The defects were filled with collagen scaffolds loaded with glycanated, partially glycanated or de-glycanated BGN alone or in combination with a sub-optimal dose of BMP-2 (subBMP). In in vitro experiments, BMP signaling and function were the greatest when BMP-2 was combined with de-glycanated BGN among the groups tested. In the rat mandible experiments, μCT analyses revealed that the newly formed bone was significantly increased only when subBMP was combined with de-glycanated BGN. The data indicate that the GAG component of BGN functions as a suppressor for the BGN-assisted BMP function