A Unified Mechanism on the Formation of Acenes, Helicenes, and Phenacenes in the Gas Phase.

A unified low-temperature reaction mechanism on the formation of acenes, phenacenes, and helicenes-polycyclic aromatic hydrocarbons (PAHs) that are distinct via the linear, zigzag, and ortho-condensed arrangements of fused benzene rings-is revealed. This mechanism is mediated through a barrierless, vinylacetylene mediated gas-phase chemistry utilizing tetracene, [4]phenacene, and [4]helicene as benchmarks contesting established ideas that molecular mass growth processes to PAHs transpire at elevated temperatures. This mechanism opens up an isomer-selective route to aromatic structures involving submerged reaction barriers, resonantly stabilized free-radical intermediates, and systematic ring annulation potentially yielding molecular wires along with racemic mixtures of helicenes in deep space. Connecting helicene templates to the Origins of Life ultimately changes our hypothesis on interstellar carbon chemistry

Synthesis of Polycyclic Aromatic Hydrocarbons by Phenyl Addition-Dehydrocyclization: The Third Way.

Polycyclic aromatic hydrocarbons (PAHs) represent the link between resonance-stabilized free radicals and carbonaceous nanoparticles generated in incomplete combustion processes and in circumstellar envelopes of carbon rich asymptotic giant branch (AGB) stars. Although these PAHs resemble building blocks of complex carbonaceous nanostructures, their fundamental formation mechanisms have remained elusive. By exploring these reaction mechanisms of the phenyl radical with biphenyl/naphthalene theoretically and experimentally, we provide compelling evidence on a novel phenyl-addition/dehydrocyclization (PAC) pathway leading to prototype PAHs: triphenylene and fluoranthene. PAC operates efficiently at high temperatures leading through rapid molecular mass growth processes to complex aromatic structures, which are difficult to synthesize by traditional pathways such as hydrogen-abstraction/acetylene-addition. The elucidation of the fundamental reactions leading to PAHs is necessary to facilitate an understanding of the origin and evolution of the molecular universe and of carbon in our galaxy

Reactivity of the Indenyl Radical (C9 H7 ) with Acetylene (C2 H2 ) and Vinylacetylene (C4 H4 ).

The reactions of the indenyl radicals with acetylene (C2 H2 ) and vinylacetylene (C4 H4 ) is studied in a hot chemical reactor coupled to synchrotron based vacuum ultraviolet ionization mass spectrometry. These experimental results are combined with theory to reveal that the resonantly stabilized and thermodynamically most stable 1-indenyl radical (C9 H7 . ) is always formed in the pyrolysis of 1-, 2-, 6-, and 7-bromoindenes at 1500 K. The 1-indenyl radical reacts with acetylene yielding 1-ethynylindene plus atomic hydrogen, rather than adding a second acetylene molecule and leading to ring closure and formation of fluorene as observed in other reaction mechanisms such as the hydrogen abstraction acetylene addition or hydrogen abstraction vinylacetylene addition pathways. While this reaction mechanism is analogous to the bimolecular reaction between the phenyl radical (C6 H5 . ) and acetylene forming phenylacetylene (C6 H5 CCH), the 1-indenyl+acetylene→1-ethynylindene+hydrogen reaction is highly endoergic (114 kJ mol-1 ) and slow, contrary to the exoergic (-38 kJ mol-1 ) and faster phenyl+acetylene→phenylacetylene+hydrogen reaction. In a similar manner, no ring closure leading to fluorene formation was observed in the reaction of 1-indenyl radical with vinylacetylene. These experimental results are explained through rate constant calculations based on theoretically derived potential energy surfaces

Gas-Phase Synthesis of Triphenylene (C18 H12 ).

For the last decades, the hydrogen-abstraction-acetylene-addition (HACA) mechanism has been widely invoked to rationalize the high-temperature synthesis of PAHs as detected in carbonaceous meteorites (CM) and proposed to exist in the interstellar medium (ISM). By unravelling the chemistry of the 9-phenanthrenyl radical ([C14 H9 ]. ) with vinylacetylene (C4 H4 ), we present the first compelling evidence of a barrier-less pathway leading to a prototype tetracyclic PAH - triphenylene (C18 H12 ) - via an unconventional hydrogen abstraction-vinylacetylene addition (HAVA) mechanism operational at temperatures as low as 10 K. The barrier-less, exoergic nature of the reaction reveals HAVA as a versatile reaction mechanism that may drive molecular mass growth processes to PAHs and even two-dimensional, graphene-type nanostructures in cold environments in deep space thus leading to a better understanding of the carbon chemistry in our universe through the untangling of elementary reactions on the most fundamental level

Molecular mass growth through ring expansion in polycyclic aromatic hydrocarbons via radical–radical reactions

Polycyclic aromatic hydrocarbons (PAHs) represent key molecular building blocks leading to carbonaceous nanoparticles identified in combustion systems and extraterrestrial environments. However, the understanding of their formation and growth in these high temperature environments has remained elusive. We present a mechanism through laboratory experiments and computations revealing how the prototype PAH—naphthalene—can be efficiently formed via a rapid 1-indenyl radical—methyl radical reaction. This versatile route converts five- to six-membered rings and provides a detailed view of high temperature mass growth processes that can eventually lead to graphene-type PAHs and two-dimensional nanostructures providing a radical new view about the transformations of carbon in our universe

XMM-NEWTON Detection of X-ray Emission from the Compact Steep Spectrum Radio Galaxy 3C303.1

Using XMM we detect faint unresolved X-ray emission from the Compact Steep Spectrum radio galaxy 3C303.1. We detect a thermal component at kT = 0.8 keV which seems likely to be produced in the ISM of the host galaxy. There is evidence for a second component in the spectrum whose nature is currently ambiguous. Plausible hypotheses for the second component include (1) hot gas shocked by the expansion of the radio source, and (2) Synchrotron self-Compton emission from the southern radio lobe if the magnetic field is below the equipartition value by a factor of about 3.5

A Study of Brain Networks Associated with Swallowing Using Graph-Theoretical Approaches

Functional connectivity between brain regions during swallowing tasks is still not well understood. Understanding these complex interactions is of great interest from both a scientific and a clinical perspective. In this study, functional magnetic resonance imaging (fMRI) was utilized to study brain functional networks during voluntary saliva swallowing in twenty-two adult healthy subjects (all females, 23.1±1.52 years of age). To construct these functional connections, we computed mean partial correlation matrices over ninety brain regions for each participant. Two regions were determined to be functionally connected if their correlation was above a certain threshold. These correlation matrices were then analyzed using graph-theoretical approaches. In particular, we considered several network measures for the whole brain and for swallowing-related brain regions. The results have shown that significant pairwise functional connections were, mostly, either local and intra-hemispheric or symmetrically inter-hemispheric. Furthermore, we showed that all human brain functional network, although varying in some degree, had typical small-world properties as compared to regular networks and random networks. These properties allow information transfer within the network at a relatively high efficiency. Swallowing-related brain regions also had higher values for some of the network measures in comparison to when these measures were calculated for the whole brain. The current results warrant further investigation of graph-theoretical approaches as a potential tool for understanding the neural basis of dysphagia. © 2013 Luan et al

The clustering of galaxies in the SDSS-III Baryon Oscillation Spectroscopic Survey: measuring structure growth using passive galaxies

We explore the benefits of using a passively evolving population of galaxies to measure the evolution of the rate of structure growth between z=0.25 and z=0.65 by combining data from the SDSS-I/II and SDSS-III surveys. The large-scale linear bias of a population of dynamically passive galaxies, which we select from both surveys, is easily modeled. Knowing the bias evolution breaks degeneracies inherent to other methodologies, and decreases the uncertainty in measurements of the rate of structure growth and the normalization of the galaxy power-spectrum by up to a factor of two. If we translate our measurements into a constraint on sigma_8(z=0) assuming a concordance cosmological model and General Relativity (GR), we find that using a bias model improves our uncertainty by a factor of nearly 1.5. Our results are consistent with a flat Lambda Cold Dark Matter model and with GR.Comment: Accepted for publication in MNRAS (clarifications added, results and conclusions unchanged

The impact of maternal BMI status on pregnancy outcomes with immediate short-term obstetric resource implications : a meta-analysis.

Obesity is rising in the obstetric population, yet there is an absence of services and guidance for the management of maternal obesity. This systematic review aimed to investigate relationships between obesity and impact on obstetric care. Literature was systematically searched for cohort studies of pregnant women with anthropometric measurements recorded within 16-weeks gestation, followed up for the term of the pregnancy, with at least one obese and one comparison group. Two researchers independently data-extracted and quality-assessed each included study. Outcome measures were those that directly or indirectly impacted on maternity resources. Primary outcomes included instrumental delivery, caesarean delivery, duration of hospital stay, neonatal intensive care, neonatal trauma, haemorrhage, infection and 3rd/4th degree tears. Meta-analysis shows a significant relationship between obesity and increased odds of caesarean and instrumental deliveries, haemorrhage, infection, longer duration of hospital stay and increased neonatal intensive care requirement. Maternal obesity significantly contributes to a poorer prognosis for mother and baby during delivery and in the immediate post-partum period. National clinical guidelines for management of obese pregnant women, and public health interventions to help safeguard the health of mothers and their babies are urgently required