First-principles determination of electromechanical responses of solids under finite electric fields

We describe a first-principles, easy-to-implement, and efficient approach for determining the structural geometry of insulating solids under finite electric fields. This method consists of simultaneously minimizing the field-induced total ionic forces and the electric free energy. Moreover, we present a theory to analyze its predictions that provides a microscopic understanding of electro-mechanical responses in materials. We illustrate this approach by computing piezoelectric and dielectric responses of two rather different compounds, namely, ferroelectric PbTiO3 and semiconductor GaN.     

Electronic stability of magnetic Fe/Co superlattices with monatomic layer alternation

We report a surprising observation that the growth of the [Fe(1 ML)/Co(1 ML)](n) superlattice of L1(0) structure on Cu(100) is stable only up to six atomic layers (n=3), which cannot be rationalized by stress arguments. Instead, first-principles calculations reveal a transition from the L1(0) to the B2 structure due to the effect of dimensionality on the stability of the electronic structure of the superlattice. Whereas the majority-spin electrons are energetically insensitive to the layer thickness, the minority-spin electrons induce the transition at n=3.     

Ordered mesoporous organic-inorganic hybrid materials containing microporous functional calix[8]arene amides

Ordered mesoporous organic-inorganic hybrid materials containing microporous functional calix[8]arene amides have been synthesized and characterized for the first time, and are shown to be effective in removal of trace humic acid contaminant from water.     

Catalytic enantioselective allylation with chiral Lewis bases

The advent of chiral Lewis base-promoted allylation of aldehydes has opened a new direction in the catalytic enantioselective construction of homoallylic alcohols. This short review outlines the conceptual framework for the creation of this new process and the interplay of mechanistic investigations and synthetic studies that have conspired to produce a useful new reaction. The current state-of-the-art in catalyst design and application of the reaction in synthesis are briefly illustrated.     

A novel family of ordered,mesoporous inorganic/organic hybrid polymers containing covalently and multiply bound microporous organic hosts

We have prepared a new family of periodic hybrid polymers containing microporous cavities provided by covalently bound organic hosts. Cyclodextrin (CD) or calixarene (CX) hosts are attached to four or more trialkoxysilyl groups, which are polymerized to form a polysilsesquioxane matrix. Structural integrity is provided by copolymerization with tetraethoxysilane, which produces a polysilicate co-matrix. Periodic order is created by carrying out the polymerization in the presence of a surfactant, cetyltrimethylammonium bromide. The resulting as-synthesized polymers from these three starting materials were characterized by solid-state nuclear magnetic resonance spectroscopy. The (13)C and (29)Si spectra provided evidence for intact polysilsesquioxane, polysilicate, organic host, and surfactant. Removal of the surfactant by washing produced a polymer containing cavities of mesoporous dimensions, in addition to the microporous host cavities. The purpose of introducing mesoporosity is to allow enhanced access of guests to the microporous hosts. Transmission electron microscopy demonstrated that both as-synthesized and solvent-extracted polymers have a periodic structure. All polymers are completely insoluble in water. The as-synthesized CD-containing polymers extracted up to >99% of 4-nitrophenol from aqueous solution, and the solvent-extracted CX-containing polymers extracted up to 67% of Fe(3+) and lesser amounts of other metal cations from aqueous solution, with interesting selectivity patterns. Simple filtration then removes the polymer containing the extracted organic molecule or metal cation. These extraction abilities are superior to previous materials.     

An azide-bridged homospin single-chain magnet: [Co(2,2'-bithiazoline)(N3)2]n

A novel end-on azide-bridged homospin 1D chain, Co(bt)(N3)2 (1) (bt = 2,2'-bithiazoline), is constructed by sharing edges of Co(II) distorted octahedrons to form a helix, which shows magnetic hysteresis with steps and slow relaxation below 5-6 K, typical of single-chain magnet behavior.     

Parallel kinetic resolution of 4-alkynals catalyzed by Rh(I)/Tol-BINAP: synthesis of enantioenriched cyclobutanones and cyclopentenones

A Rh(I)/(R)-Tol-BINAP catalyst reacts with a racemic mixture of 4-alkynals to selectively furnish a cyclobutanone from the (R)-substrate and a cyclopentenone from the (S)-substrate. This method is noteworthy from several standpoints, including the scarcity of parallel kinetic resolutions (especially those that are catalyzed or that involve carbon-carbon bond formation) and the dearth of catalytic processes that generate enantioenriched cyclobutanones.     

Interpenetration in [Cd(isonicotinate)2(1,2-bis(4-pyridyl)-ethane)0.5(H2O)]n,a novel octahedral polymer containing an unusual two-dimensional bilayer motif generated by self-assembly of rectangle building blocks

A hydrothermally synthesized mixed-ligand molecular solid composed of pillared bilayers has been formulated; it presents a new remarkable three-dimensional architecture sustained by the catenation of two-fold decked layers, and exhibits intense photoluminescence upon photoexcitation at 314 nm.     

Evolution of three-dimensional coherent structures in compressible axisymmetric jet

A high order difference scheme is used to simulate the spatially developing compressible axisymmetric jet. The results show that the Kelvin-Helmholtz instability appears first when the jet loses its stability, and then with development of jet the increase in nonlinear effects leads to the secondary instability and the formation of the streamwise vortices. The evolution of the three-dimensional coherent structure is presented. The computed results verify that in axisymmetric jet the secondary instability and formation of the streamwise vortices are the important physical mechanism of enhancing the flow mixing and transition occurring.