Functionalization of Pyrene To Prepare Luminescent Materials—Typical Examples of Synthetic Methodology

Pyrene-based π-conjugated materials are considered to be an ideal organic electro-luminescence material for application in semiconductor devices, such as organic light-emitting diodes (OLEDs), organic field-effect transistors (OFETs) and organic photovoltaics (OPVs), and so forth. However, the great drawback of employing pyrene as an organic luminescence material is the formation of excimer emission, which quenches the efficiency at high concentration or in the solid-state. Thus, in order to obtain highly efficient optical devices, scientists have devoted much effort to tuning the structure of pyrene derivatives in order to realize exploitable properties by employing two strategies, 1) introducing a variety of moieties at the pyrene core, and 2) exploring effective and convenient synthetic strategies to functionalize the pyrene core. Over the past decades, our group has mainly focused on synthetic methodologies for functionalization of the pyrene core; we have found that formylation/acetylation or bromination of pyrene can selectly lead to functionalization at K-region by Lewis acid catalysis. Herein, this Minireview highlights the direct synthetic approaches (such as formylation, bromination, oxidation, and de-tert-butylation reactions, etc.) to functionalize the pyrene in order to advance research on luminescent materials for organic electronic applications. Further, this article demonstrates that the future direction of pyrene chemistry is asymmetric functionalization of pyrene for organic semiconductor applications and highlights some of the classical asymmetric pyrenes, as well as the latest breakthroughs. In addition, the photophysical properties of pyrene-based molecules are briefly reviewed. To give a current overview of the development of pyrene chemistry, the review selectively covers some of the latest reports and concepts from the period covering late 2011 to the present day

Petersen cores and the oddness of cubic graphs

Let $G$ be a bridgeless cubic graph. Consider a list of $k$ 1-factors of $G$. Let $E_i$ be the set of edges contained in precisely $i$ members of the $k$ 1-factors. Let $\mu_k(G)$ be the smallest $|E_0|$ over all lists of $k$ 1-factors of $G$. If $G$ is not 3-edge-colorable, then $\mu_3(G) \geq 3$. In [E. Steffen, 1-factor and cycle covers of cubic graphs, J. Graph Theory 78(3) (2015) 195-206] it is shown that if $\mu_3(G) \not = 0$, then $2 \mu_3(G)$ is an upper bound for the girth of $G$. We show that $\mu_3(G)$ bounds the oddness $\omega(G)$ of $G$ as well. We prove that $\omega(G)\leq \frac{2}{3}\mu_3(G)$. If $\mu_3(G) = \frac{2}{3} \mu_3(G)$, then every $\mu_3(G)$-core has a very specific structure. We call these cores Petersen cores. We show that for any given oddness there is a cyclically 4-edge-connected cubic graph $G$ with $\omega(G) = \frac{2}{3}\mu_3(G)$. On the other hand, the difference between $\omega(G)$ and $\frac{2}{3}\mu_3(G)$ can be arbitrarily big. This is true even if we additionally fix the oddness. Furthermore, for every integer $k\geq 3$, there exists a bridgeless cubic graph $G$ such that $\mu_3(G)=k$.Comment: 13 pages, 9 figure

The sub-mm J=6-5 line of 13CO in Orion

We present a fully sampled map covering the Orion Hot Core and dense molecular ridge, in the sub-millimeter J=6-5 rotational transition of 13CO, at 0.45 mm with a resolution of 13 arcsec and 0.5 km s^-1. The map covers 3 arc min by 2arc min . The profile centered on the Hot Core peaks at 8.5 km s^-1 and has a peak intensity of 40 K, corrected antenna temperature. It shows line wings from 30 km s^-1 to -20 km s^-1. The map of intensity, integrated from 0 to +18 km s^-1, shows a prominent maximum <5 arcsec from the center of the Orion Hot Core. The FWHP is 3 arcsec, larger than the regions containing complex molecules. Single dish measurements of lines from the J=2-1 or J=1-0 transitions of CO isotopes show no such distinct maximum. Correcting for optical depth 1.5 in the J=6-5 line of 13CO, and assuming that the level populations are thermalized at 150 K, the beam averaged column density between 0 to +18 km s^-1 is N(13CO )=6.8 10^17 cm^-2 and N(CO)=5.2 10^19 cm-2. When combined with published dust emission data, the CO/ H2 number ratio is 2 {\cdot} 10^-5, a factor of ~5 lower than the canonical value, 10^-4. For the Orion South and Orion Ridge region, the column density of CO is <25% of that found for the Hot Core but CO/H2 ratios are similar. Models of Photodissociation Regions, PDRs, predict that CO lines from PDRs are only marginally optically thick. Thus our map traces warm and dense molecular gas rather than PDRs.Comment: 23 pages total, including 5 figure

On the chemical ladder of esters. Detection and formation of ethyl formate in the W51 e2 hot molecular core

The detection of organic molecules with increasing complexity and potential biological relevance is opening the possibility to understand the formation of the building blocks of life in the interstellar medium. One of the families of molecules with astrobiological interest are the esters, whose simplest member, methyl formate, is rather abundant in star-forming regions. The next step in the chemical complexity of esters is ethyl formate, C$_2$H$_5$OCHO. Only two detections of this species have been reported so far, which strongly limits our understanding of how complex molecules are formed in the interstellar medium. We have searched for ethyl formate towards the W51 e2 hot molecular core, one of the most chemically rich sources in the Galaxy and one of the most promising regions to study prebiotic chemistry, especially after the recent discovery of the P$-$O bond, key in the formation of DNA. We have analyzed a spectral line survey towards the W51 e2 hot molecular core, which covers 44 GHz in the 1, 2 and 3 mm bands, carried out with the IRAM 30m telescope. We report the detection of the trans and gauche conformers of ethyl formate. A Local Thermodynamic Equilibrium analysis indicates that the excitation temperature is 78$\pm$10 K and that the two conformers have similar source-averaged column densities of (2.0$\pm$0.3)$\times$10$^{16}$ cm$^{-2}$ and an abundance of $\sim$10$^{-8}$. We compare the observed molecular abundances of ethyl formate with different competing chemical models based on grain surface and gas-phase chemistry. We propose that grain-surface chemistry may have a dominant role in the formation of ethyl formate (and other complex organic molecules) in hot molecular cores, rather than reactions in the gas phase.Comment: Accepted in A&A; 11 pages, 6 figures, 7 Table

Develop, demonstrate, and verify large area composite structural bonding with polyimide adhesives

The technology required to produce graphite-polyimide structural components with operational capability at 598 K (600 F) is considered. A series of polyimide adhesives was screened for mechanical and physical properties and processibility in fabricating large midplane bonded panels and honeycomb sandwich panels in an effort to fabricate a structural test component of the space shuttle aft body flap. From 41 formulations, LaRC-13, FM34B-18, and a modified LaRC-13 adhesive were selected for further evaluation. The LaRC-13 adhesive was rated as the best of the three adhesives in terms of availability, cost, processibility, properties, and ability to produce void fee large area (12" x 12") midplane bonds. Surface treatments and primers for the adhesives were evaluated and processes were developed for the fabrication of honeycomb sandwich panels of very good quality which was evidenced by rupture in the honeycomb core rather than in the facesheet bands on flatwise tensile strength testing. The fabrication of the adhesively bonded honeycomb sandwich cover panels, ribs, and leading edge covers of Celion graphite/LARC-160 polyimide laminates is described

Gap Labeling

This joint review covers: Moulay-Tahar Benameur and Hervé Oyono-Oyono, Gap-labelling for quasi-crystals (proving a conjecture by J. Bellissard). (English summary) Operator algebras and mathematical physics, (Constanţa, 2001), 11-22, Theta, Bucharest, 2003. Jerome Kaminker and Ian Putnam, A proof of the gap labeling conjecture, Michigan Mathematical Journal 51(3) (2003), 537-546. Jean Bellisard, Riccardo Benedetti and Jean-Marc Gambaudo, Spaces of tilings, finite telescopic approximations, and gap-labeling, Communications in Mathematical Physics 261(1) (2006), 1-41. The gap labeling theorem was originally conjectured by Bellissard [in From number theory to physics (Les Houches, 1989), 538-630, Springer, Berlin, 1992; MR1221111 (94e:46120)]. The problem arises in a mathematical version of solid state physics in the context of aperiodic tilings. Its three proofs, discovered independently by the authors above, all lie in K-theory. Here is the core result of these papers: Let Σ be a Cantor set and let Σ × ℤd → Σ be a free and minimal action of ℤd on Σ with invariant probability measure μ. Let μ:C(Σ) → ℂ and τμ:C(Σ) ⋊ ℤd → ℂ be the traces induced by μ and denote likewise their induced maps in K-theory. Then μ(K0(C(Σ))) = τμ(K0(C(Σ) × ℤd)) as subsets of ℝ. We shall try to explain why this core result has anything to do with something called gap labeling

A necklace of dense cores in the high-mass star forming region G35.20-0.74N: ALMA observations

The present study aims at characterizing the massive star forming region G35.20N, which is found associated with at least one massive outflow and contains multiple dense cores, one of them recently found associated with a Keplerian rotating disk. We used ALMA to observe the G35.20N region in the continuum and line emission at 350 GHz. The observed frequency range covers tracers of dense gas (e.g. H13CO+, C17O), molecular outflows (e.g. SiO), and hot cores (e.g. CH3CN, CH3OH). The ALMA 870 um continuum emission map reveals an elongated dust structure (0.15 pc long and 0.013 pc wide) perpendicular to the large-scale molecular outflow detected in the region, and fragmented into a number of cores with masses 1-10 Msun and sizes 1600 AU. The cores appear regularly spaced with a separation of 0.023 pc. The emission of dense gas tracers such as H13CO+ or C17O is extended and coincident with the dust elongated structure. The three strongest dust cores show emission of complex organic molecules characteristic of hot cores, with temperatures around 200 K, and relative abundances 0.2-2x10^(-8) for CH3CN and 0.6-5x10^(-6) for CH3OH. The two cores with highest mass (cores A and B) show coherent velocity fields, with gradients almost aligned with the dust elongated structure. Those velocity gradients are consistent with Keplerian disks rotating about central masses of 4-18 Msun. Perpendicular to the velocity gradients we have identified a large-scale precessing jet/outflow associated with core B, and hints of an east-west jet/outflow associated with core A. The elongated dust structure in G35.20N is fragmented into a number of dense cores that may form massive stars. Based on the velocity field of the dense gas, the orientation of the magnetic field, and the regularly spaced fragmentation, we interpret this elongated structure as the densest part of a 1D filament fragmenting and forming massive stars.Comment: 24 pages, 26 figures, accepted for publication in Astronomy and Astrophysics (abstract modified to fit arXiv restrictions

The formation of IRIS diagnostics II. The formation of the Mg II h&k lines in the solar atmosphere

NASA's Interface Region Imaging Spectrograph (IRIS) small explorer mission will study how the solar atmosphere is energized. IRIS contains an imaging spectrograph that covers the Mg II h&k lines as well as a slit-jaw imager centered at Mg II k. Understanding the observations requires forward modeling of Mg II h&k line formation from 3D radiation-MHD models. We compute the vertically emergent h&k intensity from a snapshot of a dynamic 3D radiation-MHD model of the solar atmosphere, and investigate which diagnostic information about the atmosphere is contained in the synthetic line profiles. We find that the Doppler shift of the central line depression correlates strongly with the vertical velocity at optical depth unity, which is typically located less than 200 km below the transition region (TR). By combining the Doppler shifts of the h and the k line we can retrieve the sign of the velocity gradient just below the TR. The intensity in the central line depression is anticorrelated with the formation height, especially in subfields of a few square Mm. This intensity could thus be used to measure the spatial variation of the height of the transition region. The intensity in the line-core emission peaks correlates with the temperature at its formation height, especially for strong emission peaks. The peaks can thus be exploited as a temperature diagnostic. The wavelength difference between the blue and red peaks provides a diagnostic of the velocity gradients in the upper chromosphere. The intensity ratio of the blue and red peaks correlates strongly with the average velocity in the upper chromosphere. We conclude that the Mg II h&k lines are excellent probes of the very upper chromosphere just below the transition region, a height regime that is impossible to probe with other spectral lines.Comment: 15 pages, 12 figures, accepted for ApJ, astro-ph abstract shortened to confirm to submission requirement