Redox regulation of helical structures in short peptides with an intramolecular ferrocenyl cross-linking agent

We redox-regulated alpha-helicity of short peptides intramolecularly cross-linked with a ferrocenyl linker between amino acid side chains. The helical content of the cross-linked peptide was estimated to be 56% in the neutral state of the ferrocene core at 25 degrees C. The addition of an oxidant to the solution of the cross-linked peptide enhanced the helicity up to 75%. The increased helical content returned to the same level as that in the previous ferrocene state by further addition of a reductant.     

Density functional theory investigation of novel Eu(III) complexes with asymmetric bis(phosphine) oxides

Recently, we have developed novel Eu(III) complexes with three beta-diketonates and one asymmetric bis(phosphine) oxide whose light emission intensity is drastically increased. In this paper, one of these complexes is investigated by the density functional theory calculation. Sixteen isomers of this complex have been considered. The ratio of the existence for the most stable isomer (B1_1a) is found to be about 51%, and the sum of the ratio of the existence for the six most stable isomers (B1_1a, B1_3a, B1_8a, B1_2a, B1_1b, and B1_5a) is about 100%, assuming the Boltzmann distribution (T = 300 K). The coordination structures of the six most stable isomers in the ground states are similar, and we can expect asymmetric ligand fields for them, favorable for the efficient light emission. Vertical excitation energies and oscillator strengths for each isomer have been obtained by the time-dependent density functional theory. With the red-shift of the wavelength and the interpolation by Gaussian convolution, both the calculated absorption spectra for the most stable isomer B1_1a and the calculated absorption spectra for the ensemble average of the isomers are found to be similar to the experimental fluorescence excitation spectra. The efficiency of energy transfer from the triplet excited state to the Eu(III) ion is considered by calculating DeltaEET (difference between the adiabatic excitation energy of the complex for the lowest triplet state and the emission energy of the Eu(III) ion for 5D0 to 7F2). The characters for the lowest triplet states for the isomers are investigated by the spin density distributions of the triplet states.     

Uptake kinetics of deuteriated water vapor by plants: Experiments of D2O release in a greenhouse as a substitute for tritiated water

Potted plants were exposed to D₂O vapor in a greenhouse and uptake of D₂O by leaf and deposition of D₂O to pot soil were examined. Atmospheric D₂O concentration in the greenhouse increased rapidly after starting the release and reached constant level in a few hours. Although the variation of D₂O concentration in leaf followed that in air with showing a time delay, D₂O concentration in leaf did not become the same level as that in air and vein showed lower concentration that lamina. D₂O concentration in the pot soil increased slowly with diffusing in deeper layer.     

On a higher‐order bounded discretization scheme

This paper presents a new higher‐order bounded scheme, weighted‐average coefficient ensuring boundedness (WACEB), for approximating the convective fluxes in solving transport equations with the finite volume difference method (FVDM). The weighted‐average formulation is used for interpolating the variables at cell faces and the weighted‐average coefficient is determined from normalized variable formulation and total variation diminishing (TVD) constraints to ensure the boundedness of solution. The new scheme is tested by solving three problems: (1) a pure convection of a box‐shaped step profile in an oblique velocity field, (2) a sudden expansion of an oblique velocity field in a cavity, and (3) a laminar flow over a fence. The results obtained by the present WACEB are compared with the UPWIND and the QUICK schemes and it is shown that this scheme has at least second‐order accuracy, while ensuring boundedness of solutions. Moreover, it is demonstrated that this scheme produces results that better agree with the experimental data in comparison with other schemes. Copyright © 2000 John Wiley & Sons, Ltd.     

The role of the Mg2+ cation in ATPsynthase studied by electron paramagnetic resonance using VO2+ and Mn2+ paramagnetic probes

The electron paramagnetic resonance (EPR), electron spin echo envelope modulation (ESEEM) and hyperfine sublevel correlation (HYSCORE) spectra of Mg2+-depleted chloroplast F1-ATPase substituted with stoichiometric VO2+ are reported. The ESEEM and HYSCORE spectra of the complex are dominated by the hyperfine and quadrupole interactions between the VO2+ paramagnet and two different nitrogen ligands with isotropic hyperfine couplings /A1/ = 4.11 MHz and /A2/ = 6.46 MHz and nuclear quadrupole couplings e2qQ1 approximately 3.89-4.49 MHz and e2qQ2 approximately 1.91-2.20 MHz, respectively. Aminoacid functional groups compatible with these magnetic couplings include a histidine imidazole, the epsilon-NH2 of a lysine residue, and the guanidinium group of an arginine. Consistent with this interpretation, very characteristic correlations are detected in the HYSCORE spectra between the 14N deltaM1 = 2 transitions in the negative quadrant, and also between some of the deltaM1 = 1 transitions in the positive quadrant. The interaction of the substrate and product ADP and ATP nucleotides with the enzyme has been studied in protein complexes where Mg2+ is substituted for Mn2+. Stoichiometric complexes of Mn x ADP and Mn x ATP with the whole enzyme show distinct and specific hyperfine couplings with the 31P atoms of the bonding phosphates in the HYSCORE (ADP, A(31Pbeta) = 5.20 MHz: ATP, A(31Pbeta) = 4.60 MHz and A(31Pgamma) = 5.90 MHz) demonstrating the role of the enzyme active site in positioning the di- or triphosphate chain of the nucleotide for efficient catalysis. When the complexes are formed with the isolated alpha or beta subunits of the enzyme, the HYSCORE spectra are substantially modified, suggesting that in these cases the nucleotide binding site is only partially structured.     

On the irrationality measure for certain series

Let K be either the rational number field \Bbb Q{\Bbb Q} or an imaginary quadratic field. We give irrationality results for the number q = ?_n=1^￥rⁿ/(qⁿ-r^l)\theta=\sum_{n=1}^{\infty}{r^n}/(q^n-r^l), where q (∣q∣ > 1) is an integer in K, r∈ K ^× (∣r∣ < ∣q∣), and 1 ￡ l ? \Bbb Z1\le l\in{\Bbb Z} with q ⁿ ≠ r ^l (n ≥ 1).     

Vibrational predissociation of H5 +

The full nine-dimensional vibrational Hamiltonian for H5 + described in the literature [Kraemer et al., J. Mol. Spectrosc. 164, 500 (1994)] is adopted here for an approximate evaluation of the spectral linewidths of the observed H-H stretching modes of the H5 + ion and the corresponding modes of its D5 + isotopomer. In this approximation the high dimensionality of the original Hamiltonian is reduced to a three-dimensional model Hamiltonian which takes only the H-H stretching modes and the molecular dissociation mode into consideration assuming that they are adiabatically separable from the remaining modes. To make the calculations numerically feasible, the molecular degenerate ("skeletal") vibrations are assumed to take place in harmonic potentials, and the effect of the internal propeller rotation is completely disregarded. The linewidths calculated in this approximation are too small to explain the broad shapes of the observed spectral transitions. It can thus be argued that the failure to resolve rotational structure in the observed bands is mainly due to spectral congestion and only partly due to predissociation of the H5 + cluster.     

MOVPE growth of nonpolar a-plane GaN with low oxygen contamination and specular surface on a freestanding GaN substrate

We investigated unintentionally doped nonpolar a- and m-plane GaN layers grown by metalorganic vapor phase epitaxy under several sets of conditions on freestanding a- and m-plane GaN substrates. Oxygen contamination in a-plane GaN is greatly reduced by increasing the V/III ratio during growth. As a result, a high-resistivity GaN buffer layer for an AlGaN/GaN heterostructure field-effect transistor was realized.     

Photoluminescence of InGaN/GaN multiple quantum wells grown by mass transport

We report on studies of an In_0.12Ga_0.88N/GaN structure with three 35 Å thick quantum wells (QWs) grown by metalorganic vapor phase epitaxy with employment of mass transport. The mass-transport regions demonstrate a threading dislocation density less than 10⁷ cm⁻². The photoluminescence (PL) spectrum is dominated by a 40 meV—narrow line centered at 2.97 eV at 2 K. This emission has a typical PL decay time of about 5 ns at 2 K within the PL contour. An additional line with longer decay time (about 200 ns) is observed at an energy about 2.85 eV. The position of this line shifts towards higher energies with increasing excitation power. The data are consistent with a model, where the PL originates from at least two nonequivalent QWs, which could be realized due to a potential gradient across the layers.     

CONCEPTUAL DESIGN OF BESSEL BEAM CAVITY FOR FREE-ELECTRON LASER

The conventional cavity for a free-electron laser (FEL) oscillator usually forms an optical beam of Gaussian mode, which undergoes transverse spread along the interaction region. The transverse divergence of an optical beam will induce reduction of the FEL gain from three aspects: degenerating filling factor, causing diffraction loss and limiting the effective interaction distance. Bessel optical beam has been experimentally demonstrated diffraction-free characteristics in its propagation, which provides a possibility of improvement of FEL gain. In this paper, we present a conceptual design of a Bessel beam cavity for the free-electron laser oscillator. This cavity generates nondiffracting optical beam in the wiggler, resulting in improving the filling factor, decreasing the diffraction loss and elongating the effective interaction distance.