Dual-Site Lidar Observations and Satellite Data Analysis for Regional Cloud Characterization

Lidar data observed by two continuously operated portable automated lidar (PAL) systems and images from the visible and thermal infrared channels of the advanced very high resolution radiometer (AVHRR) sensor on board the noaa16 satellite are employed for the characterization of cloud heights and cloud types. The PAL systems are located in Chiba and Ichihara city areas, separated by approximately 10 km. Measurements from October 2003 to March 2005 reveal that monthly averages of cloud base height and cloud cover ratio show good agreement between the two sites. The characteristics of the vertical (Chiba) and slant (Ichihara) measurements are also discussed. The PAL data are used to adjust threshold values of a cloud-type classification method in split-window data of noaa16-AVHRR. Comparisons between the lidar signals and the cloud classification results from the concurrent AVHRR images show that the classification method can reasonably be applied to this mid-latitude case, although the split-window technique was originally developed for tropical clouds.     

Synthesis of pyroglutamic acid derivatives via double michael reactions of alkynones

In the presence of substoichiometric quantities of potassium tert-butoxide and an additional metal salt, amide-tethered diacids undergo double Michael reactions with alkynones to provide highly functionalized pyroglutamic acid derivatives. The metal salt was found to play an important role in improving the diastereoselectivities of the reactions.     

Chemical shifts for the unusual DNA structure in Pf1 bacteriophage from dynamic-nuclear-polarization-enhanced solid-state NMR spectroscopy

Solid-state NMR spectra, including dynamic nuclear polarization enhanced 400 MHz spectra acquired at 100 K, as well as non-DNP spectra at a variety of field strengths and at temperatures in the range 213-243 K, have allowed the assignment of the (13)C and (15)N resonances of the unusual DNA structure in the Pf1 virion. The (13)C chemical shifts of C3' and C5', considered to be key reporters of deoxyribose conformation, fall near or beyond the edges of their respective ranges in available databases. The (13)C and (15)N chemical shifts of the DNA bases have above-average values for AC4, AC5, CC5, TC2, and TC5, and below average values for AC8, GC8, and GN2, pointing to an absence of Watson-Crick hydrogen bonding, yet the presence of some type of aromatic ring interaction. Crosspeaks between Tyr40 of the coat protein and several DNA atoms suggest that Tyr40 is involved in this ring interaction. In addition, these crosspeak resonances and several deoxyribose resonances are multiply split, presumably through the effects of ordered but differing interactions between capsid protein subunits and each type of nucleotide in each of the two DNA strands. Overall, these observations characterize and support the DNA model proposed by Liu and Day and refined by Tsuboi et al., which calls for the most highly stretched and twisted naturally occurring DNA yet encountered.     

Jahn-Teller-distorted dimeric anions in (cat)[Mn2F8(H2O)2]·2H2O (cat = pipzH2, dabcoH2) and (dabcoH2)2[Mn2F8(H2PO4)2]

Using biprotonated dabco (1,4-diazabicyclo[2.2.2]octane) or pipz (piperazine) as counter cations, mixed-ligand fluoromanganates(III) with dimeric anions could be prepared from hydrofluoric acid solutions. The crystal structures were determined by X-ray diffraction on single crystals: dabcoH₂[Mn₂F₈(H₂O)₂]·2H₂O (1), space group P2₁, Z = 2, a = 6.944(1), b = 14.689(3), c = 7.307(1) Å, β = 93.75(3)°, R₁ = 0.0240; pipzH₂[Mn₂F₈(H₂O)₂]·2H₂O (2), space group , Z = 2, a = 6.977(1), b = 8.760(2), c = 12.584(3) Å, α = 83.79(3), β = 74.25(3), γ = 71.20(3)°, R₁ = 0.0451; (dabcoH₂)₂[Mn₂F₈(H₂PO₄)₂] (3), space group P2₁/n, Z = 4, a = 9.3447(4), b = 12.5208(4), c = 9.7591(6) Å, β = 94.392(8)°, R₁ = 0.0280. All three compounds show dimeric anions formed by [MnF₅O] octahedra (O from oxo ligands) sharing a common edge, with strongly asymmetric double fluorine bridges. In contrast to analogous dimeric anions of Al or Fe(III), the oxo ligands (H₂O (1,2) or phosphate (3)) are in equatorial trans-positions within the bridging plane. The strong pseudo-Jahn-Teller effect of octahedral Mn(III) complexes is documented in a huge elongation of an octahedral axis, namely that including the long bridging Mn-F bond and the Mn-O bond. In spite of different charge of the anion in the fluoride phosphate, the octahedral geometry is almost the same as in the aqua-fluoro compounds. The strong distortion is reflected also in the ligand field spectra.     

First observation of edge localized modes mitigation with resonant and nonresonant magnetic perturbations in ASDEX Upgrade

First experiments with nonaxisymmetric magnetic perturbations, toroidal mode number n=2, produced by newly installed in-vessel saddle coils in the ASDEX Upgrade tokamak show significant reduction of plasma energy loss and peak divertor power load associated with type-I edge localized modes (ELMs) in high-confinement mode plasmas. ELM mitigation is observed above an edge density threshold and is obtained both with magnetic perturbations that are resonant and not resonant with the edge safety factor profile. Compared with unperturbed type-I ELMy reference plasmas, plasmas with mitigated ELMs show similar confinement, similar plasma density, and lower tungsten impurity concentration.     

High‐temperature tensile cell for in situ real‐time investigation of carbon fibre carbonization and graphitization processes

A new high‐temperature fibre tensile cell is described, developed for use at the Advanced Photon Source at Argonne National Laboratory to enable the investigation of the carbonization and graphitization processes during carbon fibre production. This cell is used to heat precursor fibre bundles to temperatures up to ～2300°C in a controlled inert atmosphere, while applying tensile stress to facilitate formation of highly oriented graphitic microstructure; evolution of the microstructure as a function of temperature and time during the carbonization and higher‐temperature graphitization processes can then be monitored by collecting real‐time wide‐angle X‐ray diffraction (WAXD) patterns. As an example, the carbonization and graphitization behaviour of an oxidized polyacrylonitrile fibre was studied up to a temperature of ～1750°C. Real‐time WAXD revealed the gradual increase in microstructure alignment with the fibre axis with increasing temperature over the temperature range 600–1100°C. Above 1100°C, no further changes in orientation were observed. The overall magnitude of change increased with increasing applied tensile stress during carbonization. As a second example, the high‐temperature graphitizability of PAN‐ and pitch‐derived commercial carbon fibres was studied. Here, the magnitude of graphitic microstructure evolution of the pitch‐derived fibre far exceeded that of the PAN‐derived fibres at temperatures up to ～2300°C, indicating its facile graphitizability.     

Diffusion within ultrathin, dense nanoporous silica films

In this work the origin of permselectivity in dense silica films which possess a pore structure with pore sizes commensurate with the molecular size of the diffusing gas species is investigated. Much of the recently reported work in this field has involved the development of composite membrane films, and while it is generally assumed that the transport process of the gas species within the selective layer of these films is activated in nature, there are anomalies with this simplified picture. In this paper a new model is developed which, for the first time, explains the permselective behavior of the thin selective coatings ubiquitous to membrane separation processes. The model involves the existence of two primary transport domains within the solid film, one of which rapidly conducts the permeating gas (under non-Fickian conditions), while the second domain involves a slow diffusion mode characterized by normal Fickian transport. To validate the model, molecular dynamics simulations are conducted for diffusion of a number of simple gases (He, N(2), and CO(2)) within silica glasses over a range of solid densities. The silica media employed in these studies are based on a novel approach developed in this work for the construction of three-dimensionally periodic atomistic structures of silica of arbitrary density in which network bond connectivity is ensured. The results obtained from this work are in qualitative agreement with experimental observations and confirm the existence of dual mode transport which is central to the interpretation of the permselectivity in composite membranes systems.     

XeCu covalent bonding in XeCuF and XeCuCl, characterized by fourier transform microwave spectroscopy supported by quantum chemical calculations

XeCu covalent bonding has been found in the complexes XeCuF and XeCuCl. The molecules were characterized by Fourier transform microwave spectroscopy, supported by MP2 ab initio calculations. The complexes were prepared by laser ablation of Cu in the presence of Xe and SF(6) or Cl(2) and stabilized in supersonic jets of Ar. The rotational constants and centrifugal distortion constants show the XeCu bonds to be short and rigid. The (131)Xe, Cu, and Cl nuclear quadrupole coupling constants indicate major redistributions of the electron densities of Xe and CuF or CuCl on complex formation which cannot be accounted for by simple electrostatic effects. The MP2 calculations corroborate the XeCu bond lengths and predict XeCu dissociation energies approximately 50-60 kJ mol(-)(1). The latter cannot be accounted for in terms of induction energies. The MP2 calculations also predict valence molecular orbitals with significant shared electron density between Xe and Cu and negative local energy densities at the XeCu bond critical points. All evidence is consistent with XeCu covalent bonding.     

PAMAM Dendrimers as Potential Agents against Fibrillation of α‐Synuclein,a Parkinson's Disease‐Related Protein

The effect of PAMAM dendrimers (generations G3, G4 and G5) on the fibrillation of α‐synuclein was examined by fluorescence and CD spectroscopy, TEM and SANS. PAMAM dendrimers inhibited fibrillation of α‐synuclein and this effect increased both with generation number and PAMAM concentration. SANS showed structural changes in the formed aggregates of α‐synuclein – from cylindrical to dense three‐dimensional ones – as the PAMAM concentration increased, on account of the inhibitory effect. PAMAM also effectively promoted the breaking down of pre‐existing fibrils of α‐synuclein. In both processes – that is, inhibition and disassociation of fibrils – PAMAM redirected α‐synuclein to an amorphous aggregation pathway.