Regioselective Synthesis of 1,2‐ and 1,4‐Dihydroquinolines by Palladium‐Catalyzed Intramolecular N‐Arylation

A series of 1,2‐ and 1,4‐dihydroquinolines has been successfully prepared. The Pd‐catalyzed intramolecular N‐arylation of Z‐enamines, formally prepared by the Horner–Wadsworth–Emmons olefination, proceeded efficiently to furnish the cyclized products. Depending on the cyclization conditions, substituted 1,4‐dihydroquinolines and further isomerized 1,2‐dihydroquinolines were independently obtained in high yields with an excellent control of isomerization of the double bond.

     

Palladium‐Catalyzed Direct Arylations of 1,2‐Azolo[1,5‐a]pyridines using Copper(I) Chloride as a Lewis Acid Activator and the Synthesis of 2,6‐Disubstituted Pyridines

A direct method for the arylation of 1,2‐azolo[1,5‐a]pyridines has been developed. In the process, the fused pyridines react with aryl halides in the presence of the palladium complex Pd(OAc)₂(Phen) as a catalyst and copper(I) chloride (CuCl) as a Lewis acid to form arylated derivatives. While pyrazolo[1,5‐a]pyridines and [1,2,4]triazolo[1,5‐a]pyridines are arylated at ortho‐positions of their pyridine rings using this method, in situ ring‐opening of the formed C‐7 arylated [1,5‐a]pyridine takes place to generate the 2,6‐disubstituted pyridine. Also, upon treatment with lithium diisopropylamide (LDA), C‐7 arylated pyrazolo[1,5‐a]pyridine‐3‐carboxylates react to produce diversely substituted 2,6‐disubstituted pyridines. Finally, a sequential C‐3 arylation was accomplished through a two‐step sequence involving hydrolysis of pyrazolo[1,5‐a]pyridine‐3‐carboxylates followed by the bimetallic Pd/Cu‐catalyzed decarboxylative coupling reaction with aryl bromide.

     

Computational Analysis of Oxide Ion Conduction in Orthorhombic Perovskite Structured La0.9A0.1InO2.95 (A = Ca,Sr and Ba)

Oxide ion conduction in orthorhombic perovskite structured oxides, La_0.9A_0.1InO_2.95 (A = Ca, Sr and Ba) is analyzed using molecular dynamics simulation. Factors influencing oxide ion conductivity of the compositions considered are analyzed using radial distribution function, bond energies between dopant and oxide ions, and the diffusion path. It is known that perovskite oxides with smaller ion size mismatch between host and dopant ions have higher electrical conductivities. However, exceptions exist, such as a La_0.9A_0.1InO_2.95 (A = Ca, Sr and Ba) system, where high electrical conductivities occur with large ion size mismatches. Based on this study, a dopant with smaller ion than host ion results in the formation of strong ionic bonds with oxide ions, suggesting that the A‐site dopant should be larger than the host ion for forming weaker O–A bonds. Consequently, the trade‐off between ion size mismatch and O–A bond needs to be considered for enhancing oxide ion conductivity of perovskite oxides.     

Preparation of dual‐layer acetylated methyl cellulose hollow fiber membranes via co‐extrusion using thermally induced phase separation and non‐solvent induced phase separation methods

Dual‐layer acetylated methyl cellulose (AMC) hollow fiber membranes were prepared by coupling the thermally induced phase separation (TIPS) and non‐solvent induced phase separation (NIPS) methods through a co‐extrusion process. The TIPS layer was optimized by investigating the effects of coagulant composition on morphology and tensile strength. The solvent in the aqueous coagulation bath caused both delayed liquid–liquid demixing and decreased polymer concentration at the membrane surface, leading to porous structure. The addition of an additive (triethylene glycol, (TEG)) to the NIPS solution resolved the adhesion instability problem of the TIPS and NIPS layers, which occurred due to the different phase separation rates. The dual‐layer AMC membrane showed good mechanical strength and performance. Comparison of the fouling resistance of the AMC membranes with dual‐layer polyvinylidene fluoride (PVDF) hollow fiber membranes fabricated with the same method revealed less fouling of the AMC than the PVDF hollow fiber membrane. This study demonstrated that a dual‐layer AMC membrane with good mechanical strength, performance, and fouling resistance can be successfully fabricated by a one‐step process of TIPS and NIPS. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42715.     

A Surface Tailoring Method of Ultrathin Polymer Gate Dielectrics for Organic Transistors: Improved Device Performance and the Thermal Stability Thereof

Tailoring the surface of the dielectric layer is of critical importance to form a good interface with the following channel layer for organic thin film transistors (OTFTs). Here, a simple surface treatment method is applied onto an ultrathin (<15 nm) organosilicon‐based dielectric layer via the initiated chemical vapor deposition (iCVD) to make it compatible with organic semiconductors without degrading its insulating property. A molecular‐thin oxide capping layer is formed on a 15 nm thick poly(1,3,5‐trimetyl‐1,3,5‐trivinyl cyclotrisiloxane) (pV3D3) by a brief oxygen plasma treatment. The capping layer greatly enhances the thermal stability of the dielectrics, without degrading the original mechanical flexibility and insulating performance of the dielectrics. Moreover, the surface silanol functionalities formed by the plasma treatment can also be utilized for the surface modification with silane compounds. The surface‐modified dielectrics are applied to fabricate low‐voltage operating (<5 V) pentacene‐based OTFTs. The highest field‐effect mobility of the device with the surface‐treated 15 nm thick pV3D3 is 0.59 cm² V^?1 s^?1, which is improved up to two times compared to the TFT with the pristine pV3D3. It is believed that the simple surface treatment method can widely extend the applicability of the highly robust, ultrathin, and flexible pV3D3 gate dielectrics to design the surface of the dielectrics to match well various kinds of organic semiconductors.     

Inference on a Structural Break in Trend with Fractionally Integrated Errors

Perron and Zhu (2005) established the consistency, convergence rate and limiting distributions of parameter estimates in time trends with a change in slope with or without a concurrent level change for the cases with I(1) or I(0) errors. We extend their analysis to the general case of fractionally integrated errors with memory parameter d^?. Our results uncover interesting features; e.g., with a level shift allowed, the convergence rate for the break date estimate is the same for all d^?∈(?0.5,0.5). In other cases, it is decreasing as d^? increases. We also provide results about the so‐called spurious break issue.