Isoprene photooxidation : new insights into the production of acids and organic nitrates

We describe a nearly explicit chemical mechanism for isoprene photooxidation guided by chamber studies that include time-resolved observation of an extensive suite of volatile compounds. We provide new constraints on the chemistry of the poorly-understood isoprene δ-hydroxy channels, which account for more than one third of the total isoprene carbon flux and a larger fraction of the nitrate yields. We show that the cis branch dominates the chemistry of the δ-hydroxy channel with less than 5% of the carbon following the trans branch. The modelled yield of isoprene nitrates is 12±3% with a large difference between the δ and β branches. The oxidation of these nitrates releases about 50% of the NOx. Methacrolein nitrates (modelled yield ≃15±3% from methacrolein) and methylvinylketone nitrates (modelled yield ≃11±3% yield from methylvinylketone) are also observed. Propanone nitrate, produced with a yield of 1% from isoprene, appears to be the longest-lived nitrate formed in the total oxidation of isoprene. We find a large molar yield of formic acid and suggest a novel mechanism leading to its formation from the organic nitrates. Finally, the most important features of this mechanism are summarized in a condensed scheme appropriate for use in global chemical transport models

Superconducting, Insulating, and Anomalous Metallic Regimes in a Gated Two-Dimensional Semiconductor-Superconductor Array

The superconductor-insulator transition in two dimensions has been widely investigated as a paradigmatic quantum phase transition. The topic remains controversial, however, because many experiments exhibit a metallic regime with saturating low-temperature resistance, at odds with conventional theory. Here, we explore this transition in a novel, highly controllable system, a semiconductor heterostructure with epitaxial Al, patterned to form a regular array of superconducting islands connected by a gateable quantum well. Spanning nine orders of magnitude in resistance, the system exhibits regimes of superconducting, metallic, and insulating behavior, along with signatures of flux commensurability and vortex penetration. An in-plane magnetic field eliminates the metallic regime, restoring the direct superconductor-insulator transition, and improves scaling, while strongly altering the scaling exponent

About the dynamics and thermodynamics of trapped ions

This tutorial introduces the dynamics of charged particles in a radiofrequency trap in a very general manner to point out the differences between the dynamics in a quadrupole and in a multipole trap. When dense samples are trapped, the dynamics is modified by the Coulomb repulsion between ions. To take into account this repulsion, we propose to use a method, originally developed for particles in Penning trap, that model the ion cloud as a cold fluid. This method can not reproduce the organisation of cold clouds as crystals but it allows one to scale the size of large samples with the trapping parameters and the number of ions trapped, for different linear geometries of trap.Comment: accepted for publication in the "Modern Applications of Trapped Ions" special issu

Unimolecular Reactions Following Indoor and Outdoor Limonene Ozonolysis

Limonene is one of the monoterpenes with the largest biogenic emissions and is also widely used as an additive in cleaning products, leading to significant indoor emissions. Studies have found that the formation of secondary organic aerosols (SOAs) from limonene oxidation has important implications for indoor air quality. Although ozonolysis is considered the major limonene oxidation pathway under most indoor conditions, little is known about the mechanisms for SOA formation from limonene ozonolysis. Here, we calculate the rate coefficients of the possible unimolecular reactions of the first-generation peroxy radicals formed by limonene ozonolysis using a high-level multiconformer transition state theory approach. We find that all of the peroxy radicals formed initially in the ozonolysis of limonene react unimolecularly with rates that are competitive both indoors and outdoors, except under highly polluted conditions. Differences in reactivity between the peroxy radicals from ozonolysis and those formed by OH, NO₃, and Cl oxidation are discussed. Finally, we sketch possible oxidation mechanisms for the different peroxy radicals under both indoor and pristine atmospheric conditions and in more polluted environments. In environments with low concentrations of HO₂ and NO, efficient autoxidation will lead to the formation of highly oxygenated organic compounds and thus likely aid in the growth of SOA

Thermalized Epoxide Formation in the Atmosphere

Epoxide formation was established a decade ago as a possible reaction pathway for beta-hydroperoxy alkyl radicals in the atmosphere. This epoxide-forming pathway required excess energy to compete with O-2 addition, as the thermal reaction rate coefficient is many orders of magnitude too slow. However, recently, a thermal epoxide forming reaction was discovered in the ISOPOOH + OH oxidation pathway. Here, we computationally investigate the effect of substituents on the epoxide formation rate coefficient of a series of substituted beta-hydroperoxy alkyl radicals. We find that the thermal reaction is likely to be competitive with O-2 addition when the alkyl radical carbon has a OH group, which is able to form a hydrogen bond to a substituent on the other carbon atom in the epoxide ring being formed. Reactants fulfilling these requirements can be formed in the OH-initiated oxidation of many biogenic hydrocarbons. Further, we find that beta-OOR alkyl radicals react similarly to beta-OOH alkyl radicals, making epoxide formation a possible decomposition pathway in the oxidation of ROOR peroxides. GEOS-Chem modeling shows that the total annual production of isoprene dihydroxy hydroperoxy epoxide is 23 Tg, making it by far the most abundant C-5-tetrafunctional species from isoprene oxidation.Peer reviewe

The prevalence of MRI-defined spinal pathoanatomies and their association with Modic changes in individuals seeking care for low back pain

Modic changes are of increasing interest, however their age and gender prevalence are not well described. To date, the associations between Modic changes and other common vertebral pathologies have only been described in small samples (n < 100). Our aim was, in a large dataset of people with low back pain, to (1) describe the prevalence of a range of spinal pathoanatomies, and (2) examine the association between Modic changes and stages of intervertebral disc (IVD) pathology. Common pathologies were coded from the lumbar spine MRIs from 4,233 consecutive people imaged while attending a publicly-funded secondary care outpatient facility in Denmark. Prevalence data were calculated by pathology and by vertebral level. Prevalence was also calculated by age and gender categories for Modic changes. The association between stages of IVD pathology (degeneration, bulge, herniation) and Modic changes at L4/5 and L5/S1 was expressed using prevalence ratios (PR) and 95% confidence intervals. The prevalence of Modic changes and IVD pathology were greater in L4/5 and L5/S1, compared with the upper lumbar spine. There was no significant gender difference in prevalence of Modic changes (p = 0.11). The prevalence of IVD disc pathology occurring concurrently with Modic changes ranged from 11.5 to 17.5% (Type 1), 8.5 to 12.7% (Type 2) and 17.1 to 25.6% (Type 1 and/or 2) while the prevalence occurring in the absence of Modic changes ranged from 0.5 to 6.3% (Type 1), 0.3 to 4.9 (Type 2), 0.8 to 9.7% (Type 1 and/or 2). The associated PR for IVD pathology occurring concurrently with Modic changes ranged from 1.8 to 29.2 (p < 0.05). The highest PR (29.2) was between degeneration and Modic changes, indicating that it is rare for Modic changes to occur without disc degeneration.Spinal pathoanatomy was common in this population, particularly IVD pathologies, and a consistent trend of a relatively greater prevalence in the lower lumbar spine was identified. Modic changes were more likely to be present among individuals with IVD pathology than without, which may implicate mechanical factors as being one aetiological pathway for Modic changes, although other hypotheses may equally explain this association

Quantized conductance doubling and hard gap in a two-dimensional semiconductor-superconductor heterostructure

The prospect of coupling a two-dimensional (2D) semiconductor heterostructure to a superconductor opens new research and technology opportunities, including fundamental problems in mesoscopic superconductivity, scalable superconducting electronics, and new topological states of matter. For instance, one route toward realizing topological matter is by coupling a 2D electron gas (2DEG) with strong spin-orbit interaction to an s-wave superconductor. Previous efforts along these lines have been hindered by interface disorder and unstable gating. Here, we report measurements on a gateable InGaAs/InAs 2DEG with patterned epitaxial Al, yielding multilayer devices with atomically pristine interfaces between semiconductor and superconductor. Using surface gates to form a quantum point contact (QPC), we find a hard superconducting gap in the tunneling regime, overcoming the soft-gap problem in 2D superconductor-semiconductor hybrid systems. With the QPC in the open regime, we observe a first conductance plateau at 4e^2/h, as expected theoretically for a normal-QPC-superconductor structure. The realization of a hard-gap semiconductor-superconductor system that is amenable to top-down processing provides a means of fabricating scalable multicomponent hybrid systems for applications in low-dissipation electronics and topological quantum information.Comment: includes main text, supplementary information and code for simulations. Published versio

Peroxy radical chemistry and OH radical production during the NO_3-initiated oxidation of isoprene

Peroxy radical reactions (RO_2 + RO_2) from the NO3-initiated oxidation of isoprene are studied with both gas chromatography and a chemical ionization mass spectrometry technique that allows for more specific speciation of products than in previous studies of this system. We find high nitrate yields (~ 80%), consistent with other studies. We further see evidence of significant hydroxyl radical (OH) formation in this system, which we propose comes from RO_2 + HO_2 reactions with a yield of ~38–58%. An additional OH source is the second generation oxidation of the nitrooxyhydroperoxide, which produces OH and a dinitrooxyepoxide with a yield of ~35%. The branching ratio of the radical propagating, carbonyl- and alcohol-forming, and organic peroxide-forming channels of the RO_2 + RO_2 reaction are found to be ~18–38%, ~59–77%, and ~3–4%, respectively. HO_2 formation in this system is lower than has been previously assumed. Addition of RO_2 to isoprene is suggested as a possible route to the formation of several isoprene C_(10)-organic peroxide compounds (ROOR). The nitrooxy, allylic, and C_5 peroxy radicals present in this system exhibit different behavior than the limited suite of peroxy radicals that have been studied to date