Excitation-density-dependent generation of broadband terahertz radiation in an asymmetrically excited photoconductive antenna

The generation of terahertz (THz) transients in photoconductive emitters has been studied by varying the spatial extent and density of the optically excited photocarriers in asymmetrically excited, biased low-temperature-grown GaAs antenna structures. We find a pronounced dependence of the THz pulse intensity and broadband (>6.0 THz) spectral distribution on the pump excitation density and simulate this with a three-dimensional carrier dynamics model. We attribute the observed variation in THz emission to changes in the strength of the screening field.     

Metal- and Catalyst-Free Synthesis of 2-Substituted-Phthalimides Using 2-(Arenesulfonyl)Phthalimide as Key Reagents

Phthalimide derivatives are important in medicinal chemistry, several phthalimidation methodologies have been developed. Here, we report a facile, metal-free, and catalyst-free method for the preparation of N-phthalimides in good to excellent yield by reacting 2-(arenesulfonyl)phthalimides with various amine substrates.     

E- and Z-stereoselectivity in the preparation of enamides from glycidyl sulfonamides and carbamates

Treatment of glycidyl sulfonamides with LDA delivers the corresponding enesulfonamide with good selectivity for the E-isomer, whereas the corresponding carbamates exhibit selectivity for the Z-enecarbamate. An E1cB elimination mechanism proceeding from a substrate-base chelate complex is advanced as rationalisation of the latter set of Z-selective outcomes.     

Solvent-enhanced magnetic ordering temperature for mixed-valent chromium hexacyanovanadate(II), Cr(II)0.5Cr(III)[V(II)(CN)6].zMeCN, magnetic materials

The reaction of V(III)(THF)3Cl3 with NEt(4)CN in acetonitrile (MeCN) forms (NEt4)3[V(III)(CN)6].4MeCN (1), which after characterization was used as a molecular building block toward the synthesis of Prussian blue structured magnets. The reaction of 1 with [Cr(II)(NCMe)4](BF4)2 forms Cr(II)(0.5)Cr(III)[V(II)(CN)6].zMeCN via internal electron transfer, whose structure and magnetic properties are dependent on the degree of solvation, z. When solvated, Cr(II)(0.5)Cr(III)[V(II)(CN)6].1.2MeCN (2) is a mixture of crystalline and amorphous fractions that yield a material with two magnetic phases: bulk ferrimagnetic phase/crystalline [faced-centered-cubic lattice with a = 10.55(2) A] and cluster-glass phase/amorphous. The bulk ferrimagnetic phase exhibits a critical temperature, Tc, of 110 K, while the amorphous cluster-glass phase exhibits a freezing temperature, Tf, of approximately 25 K. Amorphous Cr(II)(0.5)Cr(III)[V(II)(CN)6].0.1MeCN (3) was determined to be the pure cluster-glass phase. This is an overall enhancement of 85 K (350%) in the magnetic ordering temperature via solvation, z. The coercivity was also increased 4-fold from 890 (2) and 3900 Oe (3) via desolvation.     

Anharmonic transitions in nearly dry L-cysteine I

Two special dynamical transitions of universal character have recently been observed in macromolecules (lysozyme, myoglobin, bacteriorhodopsin, DNA and RNA) at T* ~100-150 K and T(D) ~180-220 K. The underlying mechanisms governing these transitions have been the subject of debate. In the present work, a survey is reported on the temperature dependence of structural, vibrational and thermodynamical properties of a nearly anhydrous amino acid (orthorhombic polymorph of the amino acid l-cysteine at a hydration level of 3.5%). The temperature dependence of x-ray powder diffraction patterns, Raman spectra and specific heat revealed these two transitions at T* = 70 K and T(D) = 230 K for this sample. The data were analyzed considering amino acid-amino acid, amino acid-water, water-water phonon-phonon interactions and molecular rotor activation. Our results indicated that the two referred temperatures define the triggering of very simple and particular events that govern all the interactions of the biomolecular: activation of CH(2) rigid rotors (T < T* ), phonon-phonon interactions between specific amino acid and water dimer vibrational modes (T* < T < T(D)), and water rotational barriers surpassing (T > T(D)).     

The copolymerisation of methyl and ethyl methacrylate in supercritical carbon dioxide

This paper reports the free radical dispersion copolymerisation of methyl and ethyl methacrylate in supercritical carbon dioxide. The polymerisation uses a poly(dimethyl siloxane) monomethacrylate macromonomer as the stabiliser. A range of different reaction times was investigated in order to probe the amount of each monomer incorporated in the copolymer. Analysis by ¹H NMR spectroscopy reveals that the monomers behave as in conventional solvents to form a random copolymer. The effect of varying the initiator concentration (initiator 2,2′‐azobisisobutyronitrile, AIBN) on the composition and molecular weights of the resultant copolymers has also been studied.     

Solubilisation of triolein by microemulsions containing C12E4/hexadecane/water: equilibrium and dynamics

Increasing triolein content of oil-in-water microemulsions in the pure C(12)E(4)/water/n-hexadecane/triolein system while maintaining a fixed surfactant concentration and volume fraction of drops raises the temperature of the solubilisation boundary, where excess oil separates, but has only a slight effect on the (higher) cloud point temperature, where excess water appears. Thus, the temperature range of the single-phase microemulsion shrinks and ultimately disappears. When such microemulsions are in equilibrium with excess oil, the hexadecane/triolein ratio is greater in the microemulsion, probably because the larger triolein molecules are unable to penetrate the hydrocarbon chain region of the surfactant films of the microemulsion droplets. Indeed, monolayer studies and calculations based on microemulsion and excess oil compositions indicate that the films have minimal triolein and similar ratios of hexadecane to surfactant. Triolein drops brought into contact with hexadecane-in-water microemulsions first swell as they incorporate hexadecane, then shrink owing to solubilisation. Interfacial tension decreases during this process until it becomes almost constant near 0.01 mN m(-1), suggesting that the drops in the final stages of solubilisation have high hexadecane contents. A microemulsion containing 10 wt% C(12)E(4) and 15 wt% hexadecane was able to remove over 50% of triolein from polyester fabric at 25 degrees C, more than twice that removed by an oil-free solution with the same surfactant concentration in similar experiments.     

A posteriori error estimates for linear equations

Summary This paper describes upper and lowerp-norm error bounds for approximate solutions of the linear system of equationsAx=b. These bounds imply that the error is proportional to the quantity wherer is the residual andq is the conjugate index top. The constant of proportionality is larger than 1 and lies in a specified range. Similar results are obtained for approximations toA ^–1 and solutions of nonsingular linear equations on general spaces.Research was partially supported by NSF Grant DMS8901477     

Related necessary conditions for completing partial latin squares

Three classes of necessary conditions for completing partial latin squares are studied. These condition classes are derived via network flow theory, bipartite graph matching theory and by relating the completion problem to triply stochastic matrices. The latter formulation suggest an integer programming model of the completion problem which is convenient for analyzing the relative strength of the three condition classes. It is shown that these classes are nested and examples are given to demonstrate that this nesting is proper.