Diethyl 4-(4,5-dihydro­furan-2-yl)-3,5-di­methyl-1-phenyl-1,4-dihydro­pyrazine-2,6-dicarboxyl­ate

In the title compound, C22H26N2O5, the central 1,4-dihydro­pyrazine ring adopts a boat conformation, while the benzene ring and the two disordered components of the furan ring are inclined at angles of 77.9 (5) and 61.9 (7)°. Three of the C atoms of the furan ring are disordered over two positions with occupancies of 0.655 (18) and 0.345 (18). In the crystal structure, weak inter­molecular C—H⋯O hydrogen bonds link the mol­ecules into chains propagating in [010]

Center or Limit Cycle: Renormalization Group as a Probe

Based on our studies done on two-dimensional autonomous systems, forced non-autonomous systems and time-delayed systems, we propose a unified methodology - that uses renormalization group theory - for finding out existence of periodic solutions in a plethora of nonlinear dynamical systems appearing across disciplines. The technique will be shown to have a non-trivial ability of classifying the solutions into limit cycles and periodic orbits surrounding a center. Moreover, the methodology has a definite advantage over linear stability analysis in analyzing centers

Turning ABO3_3 antiferroelectrics into ferroelectrics: Design rules for practical rotation-driven ferroelectricity in double perovskites and A3_3B2_2O7_7 Ruddlesden-Popper compounds

Ferroic transition metal oxides, which exhibit spontaneous elastic, electrical, magnetic or toroidal order, exhibit functional properties that find use in ultrastable solid-state memories to sensors and medical imaging technologies. To realize multifunctional behavior, where one order parameter can be coupled to the conjugate field of another order parameter, however, requires a common microscopic origin for the long-range order. Here, we formulate a complete theory for a novel form of ferroelectricity, whereby a spontaneous and switchable polarization emerges from the destruction of an antiferroelectric state due to octahedral rotations and ordered cation sublattices. We then construct a materials design framework based on crystal-chemistry descriptors rooted in group theory, which enables the facile design of artificial oxides with large electric polarizations, P, simultaneous with small energetic switching barriers between +P and -P. We validate the theory with first principles density functional calculations on more than 16 perovskite-structured oxides, illustrating it could be operative in any materials classes exhibiting two- or three-dimensional corner-connected octahedral frameworks. We show the principles governing materials selection of the "layered" systems originate in the lattice dynamics of the A cation displacements stabilized by the pervasive BO$_6$ rotations of single phase ABO$_3$ materials, whereby the latter distortions govern the optical band gaps, magnetic order and critical transition temperatures. Our approach provides the elusive route to the ultimate multifunctionality property control by an external electric field.Comment: 13 pages, 11 figure

Fourth generation effects in rare exclusive B -> K^* l^+ l^- decay

Influence of the fourth generation, if ever exists, on the experimentally measurable quantities such as invariant dilepton mass distribution, lepton forward-backward asymmetry, and the ratio (Gamma_L/Gamma_T) of the decay widths when K* meson is longitudinally and transversally polarized, is studied. Using the experimental results on the branching ratios for the (B -> X_s) gamma and semileptonic (B -> X_c l nu) decays, the two possible solutions of the 4x4 Cabibbo-Kobayashi-Maskawa factor (V_{t's} V_{t^'b}) are obtained as a function of the t'-quark mass. It is observed that the results for the above-mentioned physical quantities are essentially different from the standard model predictions only for one solution of the CKM factor. In this case the above-mentioned physical quantities can serve as efficient tools in search of the fourth generation. The other solution yields almost identical results with the SM.Comment: 19 pages, 10 postscripted figures, LaTeX formatte

Syngeneic animal models of tobacco-associated oral cancer reveal the activity of in situ anti-CTLA-4.

Head and neck squamous cell carcinoma (HNSCC) is the sixth most common cancer worldwide. Tobacco use is the main risk factor for HNSCC, and tobacco-associated HNSCCs have poor prognosis and response to available treatments. Recently approved anti-PD-1 immune checkpoint inhibitors showed limited activity (≤20%) in HNSCC, highlighting the need to identify new therapeutic options. For this, mouse models that accurately mimic the complexity of the HNSCC mutational landscape and tumor immune environment are urgently needed. Here, we report a mouse HNSCC model system that recapitulates the human tobacco-related HNSCC mutanome, in which tumors grow when implanted in the tongue of immunocompetent mice. These HNSCC lesions have similar immune infiltration and response rates to anti-PD-1 (≤20%) immunotherapy as human HNSCCs. Remarkably, we find that >70% of HNSCC lesions respond to intratumoral anti-CTLA-4. This syngeneic HNSCC mouse model provides a platform to accelerate the development of immunotherapeutic options for HNSCC

Synthesis of [7]phenacene incorporating tetradecyl chains in the axis positions and its application in field-effect transistors

Field-effect transistors (FETs) were fabricated using a new type of phenacene molecule, 3,12-ditetradecyl[7]phenacene ((C14H29)2-[7]phenacene), and solid gate dielectrics or an electric double layer (EDL) capacitor with an ionic liquid (1-butyl-3-methylimidazolium hexafluorophosphate (bmim[PF6])). The new molecule, (C14H29)2-[7]phenacene, was efficiently synthesized via the Mallory photoreaction. Its crystal structure and electronic properties were determined, using X-ray diffraction, scanning tunneling microscopy/spectroscopy (STM and STS), absorption spectroscopy, and photoelectron yield spectroscopy, which showed a monoclinic crystal lattice (space group P21 (no. 4)) and an energy gap of ∼3.0 eV. The STM image clearly showed the molecular structure of (C14H29)2-[7]phenacene, as well as the closed molecular stacking, indicative of a strong fastener effect between alkyl chains. The X-ray diffraction pattern of thin films of (C14H29)2-[7]phenacene formed on a SiO2/Si substrate suggested that the molecule stood on the surface with an inclined angle of 30° with respect to the normal axis of the surface. The FET properties were recorded in two-terminal measurement mode, showing p-channel normally-off characteristics. The averaged values of field-effect mobility, μ, were 1.6(3) cm2 V−1 s−1 for a (C14H29)2-[7]phenacene thin-film FET with a SiO2 gate dielectric and 6(4) × 10−1 cm2 V−1 s−1 for a (C14H29)2-[7]phenacene thin-film EDL FET with bmim[PF6]. Thus, higher FET performance was obtained with an FET using a thin film of (C14H29)2-[7]phenacene compared to parent [7]phenacene. This study could pioneer an avenue for the realization of high-performance FETs through the addition of alkyl chains to phenacene molecules

Search for radiative pumping lines of OH masers: I. The 34.6um absorption line towards 1612 MHz OH maser sources

The 1612 MHz hydroxyl maser in circumstellar envelopes has long been thought to be pumped by 34.6um photons. Only recently, the Infrared Space Observatory has made possible spectroscopic observations which enable the direct confirmation of this pumping mechanism in a few cases. To look for the presence of this pumping line, we have searched the Infrared Space Observatory Data Archive and found 178 spectra with data around 34.6um for 87 galactic 1612MHz masers. The analysis performed showed that the noise level and the spectral resolution of the spectra are the most important factors affecting the detection of the 34.6um absorption line. Only 5 objects from the sample (3 red supergiants and 2 galactic center sources) are found to show clear 34.6um absorption (all of them already known) while two additional objects only tentatively show this line. The 3 supergiants show similar pump rates and their masers might be purely radiatively pumped. The pump rates of OH masers in late type stars are found to be about 0.05, only 1/5 of the theoretical value of 0.25 derived by Elitzur (1992). We have also found 16 maser sources which, according to the analysis assuming Elitzur's pump rate, should show the 34.6 $\mu$m absorption line but do not. These non-detections can be tentatively explained by far-infrared photon pumping, clumpy nature of the OH masing region or a limb-filling emission effect in the OH shell.Comment: 11 pages, 8 figures, 3 table

Intrinsic Correlation between Hardness and Elasticity in Polycrystalline Materials and Bulk Metallic Glasses

Though extensively studied, hardness, defined as the resistance of a material to deformation, still remains a challenging issue for a formal theoretical description due to its inherent mechanical complexity. The widely applied Teter's empirical correlation between hardness and shear modulus has been considered to be not always valid for a large variety of materials. Here, inspired by the classical work on Pugh's modulus ratio, we develop a theoretical model which establishes a robust correlation between hardness and elasticity for a wide class of materials, including bulk metallic glasses, with results in very good agreement with experiment. The simplified form of our model also provides an unambiguous theoretical evidence for Teter's empirical correlation.Comment: 10 pages, 4 figures and 3 table