Atom Economical, One-Pot, Three-Reaction Cascade to Novel Tricyclic 2,4-Dihydro-1H-benzo[f]isochromenes

A three-step domino reaction between 1-aryl-3-hexyne-2,6-diol derivatives and aldehydes is used to construct tricyclic 1,4-dihydro-2H-benzo[f]isochromenes. The cascade is initiated by BF3·OEt2 and involves alkynyl-Prins cyclization, Friedel–Crafts alkenylation, and dehydration/aromatization to create a new, central aromatic ring and eliminate 2 equiv. of water. Electron-donating substituents on the aryl ring of the 1-aryl-3-hexyne-2,6-diols significantly increase overall yields as do electron-rich aldehyde reaction partners. For 2,4-disubstituted 2H-benzo[f]isochromene products, diastereoselectivities in the alkynyl-Prins reaction are ∼1.4 : 1 in favor of the cis-diastereomer. The stereochemistry of one cis-product was verified by X-ray crystallographic analysis and a second structure was also verified by X-ray analysis

Bi(OTf)3-, TfOH-, and TMSOTf-Mediated, One-Pot Epoxide Rearrangement, Addition, and Intramolecular Silyl-Modified Sakurai (ISMS) Cascade toward Dihydropyrans: Comparison of Catalysts and Role of Bi(OTf)3

Catalytic quantities of bismuth(III) triflate efficiently initiate the rearrangement of epoxides to aldehydes, which subsequently react with (Z)-δ-hydroxyalkenylsilanes to afford 2,6-disubstituted 3,6-dihydro-2H-pyrans. Isolated yields of desired products using Bi(OTf)3 were compared with yields obtained when the reactions were run with TfOH and TMSOTf in the presence and absence of several additives. These studies, as well as NMR spectroscopic analyses, indicate an initial Lewis acid/base interaction between Bi(OTf)3 and substrates providing TfOH in situ

In-situ characterization of Ga2O passivation of In0.53Ga0.47As prior to high-k dielectric atomic layer deposition

Ga2O interfacial passivation layers (IPLs) on In0.53Ga0.47As are investigated using in-situ monochromatic x-ray photoelectron spectroscopy. The oxide is entirely composed of Ga2O when deposited with an effusion cell temperature of 1500 degrees C and substrate temperature of 425 degrees C. The growth on In0.53Ga0.47As reveals slight chemical modification of the surface. The Ga2O behavior and ability to protect the III-V surface are observed following Al2O3 deposition by atomic layer deposition following each precursor pulse. Al2O3 growth by trimethyl-Al (TMA) and water reveals that the IPL undergoes the "clean-up" effect following TMA exposures causing As-As bonding formation resulting in a high interface state density. (C) 2011 American Institute of Physics. (doi:10.1063/1.3615666

SN 2006bp: Probing the Shock Breakout of a Type II-P Supernova

HET optical spectroscopy and unfiltered ROTSE-III photometry spanning the first 11 months since explosion of the Type II-P SN 2006bp are presented. Flux limits from the days before discovery combined with the initial rapid brightening suggest the supernova was first detected just hours after shock breakout. Optical spectra obtained about 2 days after breakout exhibit narrow emission lines corresponding to HeII 4200, HeII 4686, and CIV 5805 in the rest frame, and these features persist in a second observation obtained 5 hours later; however, these emission lines are not detected the following night nor in subsequent observations. We suggest that these lines emanate from material close to the explosion site, possibly in the outer layers of the progenitor that have been ionized by the high energy photons released at shock breakout. A P-Cygni profile is observed around 4450 A in the +2 and +3 day spectra. Previous studies have attributed this feature to high velocity H-beta, but we discuss the possibility that this profile is instead due to HeII 4687. Further HET observations (14 nights in total) covering the spectral evolution across the photometric plateau up to 73 days after breakout and during the nebular phase around day +340 are presented, and expansion velocities are derived for key features. The measured decay slope for the unfiltered light curve is 0.0073 +/- 0.0004 mag/day between days +121 and +335, which is significantly slower than the decay of rate 56Co. We combine our HET measurements with published X-ray, UV, and optical data to obtain a quasi-bolometric light curve through day +60. We see a slow cooling over the first 25 days, but no sign of an early sharp peak; any such feature from the shock breakout must have lasted less than ~1 day.[ABRIDGED]Comment: ApJ accepted, 43 page

Synthesis of 2,6-disubstituted dihydropyrans via an efficient BiBr3-initiated three component, one-pot cascade

The rapid synthesis of cis-2,6-disubstituted dihydropyrans is achieved in a three-component, one-pot cascade reaction. BiBr3-mediated addition of ketene silyl acetals or silyl enol ethers to beta,gamma-unsaturated cis-4-trimethylsilyl-3-butenal provides a Mukaiyama aldol adduct containing a vinylsilane moiety tethered to a silyl ether. Addition of a second aldehyde initiates a domino sequence involving intermolecular addition followed by an intramolecular silyl-modified Sakurai (ISMS) reaction. Isolated yields of this one-pot reaction vary from 44 to 80% and all compounds were isolated as the cis-diastereomers (10 examples). (C) 2009 Elsevier Ltd. All rights reserved

Probing interface defects in top-gated MoS2 transistors with impedance spectroscopy

The electronic properties of the HfO2/MoS2 interface were investigated using multifrequency capacitance–voltage (C–V) and current–voltage characterization of top-gated MoS2 metal–oxide–semiconductor field effect transistors (MOSFETs). The analysis was performed on few layer (5–10) MoS2 MOSFETs fabricated using photolithographic patterning with 13 and 8 nm HfO2 gate oxide layers formed by atomic layer deposition after in-situ UV-O3 surface functionalization. The impedance response of the HfO2/MoS2 gate stack indicates the existence of specific defects at the interface, which exhibited either a frequency-dependent distortion similar to conventional Si MOSFETs with unpassivated silicon dangling bonds or a frequency dispersion over the entire voltage range corresponding to depletion of the HfO2/MoS2 surface, consistent with interface traps distributed over a range of energy levels. The interface defects density (Dit) was extracted from the C–V responses by the high–low frequency and the multiple-frequency extraction methods, where a Dit peak value of 1.2 × 1013 cm–2 eV–1 was extracted for a device (7-layer MoS2 and 13 nm HfO2) exhibiting a behavior approximating to a single trap response. The MoS2 MOSFET with 4-layer MoS2 and 8 nm HfO2 gave Dit values ranging from 2 × 1011 to 2 × 1013 cm–2 eV–1 across the energy range corresponding to depletion near the HfO2/MoS2 interface. The gate current was below 10–7 A/cm2 across the full bias sweep for both samples indicating continuous HfO2 films resulting from the combined UV ozone and HfO2 deposition process. The results demonstrated that impedance spectroscopy applied to relatively simple top-gated transistor test structures provides an approach to investigate electrically active defects at the HfO2/MoS2 interface and should be applicable to alternative TMD materials, surface treatments, and gate oxides as an interface defect metrology tool in the development of TMD-based MOSFETs

Corticortophin releasing factor 2 receptor agonist treatment significantly slows disease progression in mdx mice

<p>Abstract</p> <p>Background</p> <p>Duchenne muscular dystrophy results from mutation of the dystrophin gene, causing skeletal and cardiac muscle loss of function. The mdx mouse model of Duchenne muscular dystrophy is widely utilized to evaluate the potential of therapeutic regimens to modulate the loss of skeletal muscle function associated with dystrophin mutation. Importantly, progressive loss of diaphragm function is the most consistent striated muscle effect observed in the mdx mouse model, which is the same as in patients suffering from Duchenne muscular dystrophy.</p> <p>Methods</p> <p>Using the mdx mouse model, we have evaluated the effect that corticotrophin releasing factor 2 receptor (CRF2R) agonist treatment has on diaphragm function, morphology and gene expression.</p> <p>Results</p> <p>We have observed that treatment with the potent CRF2R-selective agonist PG-873637 prevents the progressive loss of diaphragm specific force observed during aging of mdx mice. In addition, the combination of PG-873637 with glucocorticoids not only prevents the loss of diaphragm specific force over time, but also results in recovery of specific force. Pathological analysis of CRF2R agonist-treated diaphragm muscle demonstrates that treatment reduces fibrosis, immune cell infiltration, and muscle architectural disruption. Gene expression analysis of CRF2R-treated diaphragm muscle showed multiple gene expression changes including globally decreased immune cell-related gene expression, decreased extracellular matrix gene expression, increased metabolism-related gene expression, and, surprisingly, modulation of circadian rhythm gene expression.</p> <p>Conclusion</p> <p>Together, these data demonstrate that CRF2R activation can prevent the progressive degeneration of diaphragm muscle associated with dystrophin gene mutation.</p

On the calculation of effective electric field in In0.53Ga0.47As surface channel metal-oxide-semiconductor field-effect-transistors

The effective electron mobility of In0.53Ga0.47As metal-oxide-semiconductor field-effect-transistors with HfO2 gate oxide was measured over a wide range of channel doping concentration. The back bias dependence of effective electron mobility was used to correctly calculate the vertical effective electric field. The effective electron mobility at moderate to high vertical effective electric field shows universal behavior independent of substrate impurity concentration. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3588255