Dynamical structure of peptide molecules: Fourier transform microwave spectroscopy and ab initio calculations of N-methylformamide

Rotational spectra of both trans and cis forms of the N-methylformamide normal as well as deuterated (HCONDCH₃, referred to as N-D) species were observed by Fourier transform microwave spectroscopy in the frequency region from 5 to 118 GHz. Samples were prepared in the form of a beam by a pulsed jet valve maintained at 50 °C and were introduced in a high-vacuum cavity cell, with either Ne or Ar as a carrier gas at a backing pressure of 100 kPa. The observed spectra were analyzed to yield molecular parameters including rotational constants and barrier, V₃, to CH₃ internal-rotation: 53.9 (6) and 301 (4) cm⁻¹ for the trans and cis forms of the normal species, respectively, and 41.9 (6) and 309 (4) cm⁻¹ for the trans and cis forms of the N-D species, respectively. Spectra of four trans isotopologues with ¹³C, ¹⁵N, or ¹⁸O singly-substituted in the internal-rotation A state were observed and analyzed to derive the r_s structure of the trans form. For comparison with the experimental data, ab initio calculations were carried out at MP2/6-31G∗∗ level to derive molecular structure, potential barrier to CH₃ internal rotation, and the energy difference between the cis and trans forms. An extensive coupling was found between the CH₃ internal rotation and N-H out-of-plane bending, suggesting that the potential function for the CH₃ internal-rotation deviates considerably from a simple cos(3α) form. The effects of the V₆ term is briefly discussed.     

Metallic conductivity and ferromagnetic interaction of iron(III) d spins in the needle crystals of (ethylenedithiotetrathiafulvalenoquinone-1,3-dithiolemethide)(2).FeBr(4) salt

The 2:1 charge-transfer (CT) salts (1(2).FeBr(4) and 1(2).GaBr(4)) of ethylenedithiotetrathiafulvalenoquinone-1,3-dithiolemethide (1) with FeBr(4)(-) and GaBr(4)(-) counteranions were obtained as needle crystals, whose structures are almost the same as each other. The 1 molecules form a one dimensionally stacked column with alternation of their molecular axis direction, while the counteranions are aligned in parallel with the 1-stacked columns with the direction of their distorted-tetrahedral geometry maintained. The room-temperature electrical conductivities measured on the single crystals of 1(2).FeBr(4) and 1(2).GaBr(4) were 4.6 and 2.1 S cm(-1), respectively. From the temperature dependences of their electrical conductivities in both cases the electrical conducting properties were metallic between ca. 170 and 300 K, but below ca. 170 K converted to be semiconducting and continued till 5 K, although the activation energies are very small (4-10 meV). For 1(2).FeBr(4) very weak and antiferromagnetic interaction occurred between the d spins of FeBr(4)(-) ions in the temperature range of ca. 1-300 K. However, below ca. 15 K the ferromagnetic interaction was reversely preferential possibly by participation of the pi spin of 1.     

Luminescence of Ca-doped (Y1-x, Gdx)2O2S

Broad-band yellow luminescence peaking around 575–595 nm has been found in Ca-doped (Y_1-x, Gd_x)₂O₂S. The doping of Ca into Y₂O₂S with the concentration up to 1 mol% is possible. At the optimum concentration (about 0.2 mol%), the cathodoluminescence brightness of Ca-doped Y₂O₂S is 10% of that of yellow-emitting (Zn, Cd)S: Ag.The emission peak is 575 nm in Y₂O₂S: Ca and 595 nm in Gd₂O₂S: Ca. The phosphor exhibits strong thermoluminescence after UV excitation at 77 K. In (Y_1-x, Gd_x)₂O₂S, neither emission spectra nor the temperatures of thermal glow peak depend on x, indicating localized characters of the traps concerned. The photoluminescence is slow in buildup and persistent in decay. These results are explained by a model: the substitution of Y(Gd) by Ca creates acceptor levels in which holes are captured, giving rise to subsequent radiative recombination with excited electrons. Trapped electrons recombine with mobile holes nonradiatively, but exhibit thermoluminescence with high efficiency when they are thermally released.     

Convergence of the arithmetic-geometric mean procedure for the complex variables and the calculation of the complete elliptic integrals with complex modulus

The convergence of the arithmetic-geometric mean procedure is checked for complex variables. The procedure is shown to be useful for the evaluation of the complete elliptic integrals of the first and second kinds with complex modulus. It is suggested that the procedure will be useful also for the numerical calculation of the elliptic integrals and the Jacobian elliptic functions with complex modulus in general.     

Heats of pyridine intercalation with α- and γ-zirconium phosphates

Calorimetric measurements at 25°C were made to determine the thermodynamic quantities for the intercalation of pyridine with α- and γ-zirconium phosphates. These phosphates showed exothermic reactions with ΔH⁰ = ?59.3 and ?21.9 kJ mole^?1, respectively. The large difference between the depyridination temperatures for both intercalates is rediscussed with the aid of the ΔG⁰ data obtained.     

Structure ofN=1 conformal and Poincaré supergravity in 1+1 and 2+1 dimensions

We discuss a component formalism ofN=1 supergravity theories in 2 and 3 spacetime dimensions. Starting from gauge theories of the superconformal group, we derive the tensor calculus for conformal and Poincaré supergravity theories. A supersymmetric extension of the non-trivial analog of Einstein's equation for 2 dimensions is given in terms of the scalar curvature multiplet.     

Multicanonical Monte Carlo simulations on intramolecular micelle formation in copolymers

The formation of intramolecular micelles in copolymers with periodic sequence, where hydrophobic units (stickers) are periodically placed along the chain, is studied by using multicanonical Monte Carlo computer simulations for an off-lattice bead-rod model in three dimensions. With decreasing the temperature, a transition from random-coil conformations to micelles occurs and flower-type micelles are formed via the transition. The number of stickers forming a micelle core is limited by the excluded-volume effect of loop chains around micelle cores. By this effect, two intramolecular micelles are formed for long polymer chains with 60 bonds via the coil-to-micelle transition. By further decreasing the temperature, we find that another transition, i.e., a micelle-to-micelle transition, takes place. At this transition point, the two intramolecular micelles merge into one micelle. Furthermore, we extend the multicanonical MC method to study elastic properties of single polymer chains with strong attractive interactions under external force fields, and study how the intramolecular micellization affects the elastic property of single polymer chains.