Dendrimers with a Pentaphenylene Core: A Photophysical Study

Novel dendrimers G2PC and G4PC consisting of a p‐pentaphenylene core ( PC ) appended in the para position with two second‐generation ( G2 ) or two fourth‐generation ( G4 ) sulfonimide branches and two n‐octyl chains, as well as a model compound of the pentaphenylene core ( G0PC ), are prepared. The photophysical properties (absorption, emission, and excitation spectra; fluorescence decay lifetime; and fluorescence anisotropy spectra) of the three compounds are investigated under different experimental conditions (dichloromethane solution and solid state at 293 K, dichloromethane/methanol rigid matrix at 77 K). In the absorption spectra contributions from both the branches and the core can be clearly identified. The fluorescence spectra show only the characteristic fluorescence of the pentaphenylene unit with λ_max around 410 nm in fluid solution and 420 nm in the solid state. In solution the fluorescence quantum yields are 0.78, 0.76, and 0.72 for G0PC , G2PC , and G4PC , respectively, and the fluorescence lifetime is about 0.7 ns in all cases. Energy transfer from the chromophoric groups of the dendrimer branches to the core does not occur. The three compounds show the same, high steady‐state anisotropy value (0.35) in dilute rigid‐matrix solution at 77 K. In dichloromethane at 293 K, the increasing anisotropy values along the series G0PC (0.17), G2PC (0.27), and G4PC (0.32), with increasing molecular volume of the three compounds, show that depolarization takes place by molecular rotation. In the solid state the anisotropy is very low (0.015, 0.017, and 0.035 for G0PC , G2PC , and G4PC , respectively), probably because of fast depolarization via energy migration.     

High pressure effect on the crystal and magnetic structure of Pr0.1Sr0.9MnO3 manganite

The crystal and magnetic structure of Pr_0.1Sr_0.9MnO₃ manganite has been studied by the neutron diffraction at high pressures up to 5 GPa in the temperature range 10?C295 K. At normal pressure and decreasing temperature the appearance of the C-type (T _N = 220 K) and G-type (T _N = 180 K) antiferromagnetic states occurs, which is accompanied by a structural phase transition from the cubic structure (Pm $ \bar 3 $ m space group) to the tetragonal structure (I4/mcm space group). It is shown that the temperature of the transition to the C-type antiferromagnetic phase increases with pressure with the pressure coefficient dT _N/dP = 4.0(5) K/GPa and the temperature of the transition to the G-type antiferromagnetic phase weakly depends on pressure.     

From quantum disorder to magnetic order in an s=1/2 kagome lattice: a structural and magnetic study of herbertsmithite at high pressure

The structural and magnetic properties of deuterated herbertsmithite have been studied by means of neutron powder diffraction and magnetic susceptibility measurements in a wide range of temperatures and pressures. The experimental data demonstrate that a phase transition from the quantum-disordered spin-liquid phase to the long-range ordered antiferromagnetic phase with the Néel temperature T(N)=6 K is induced at P=2.5 GPa. The observed decrease of T(N) upon compression correlates with the anomalies in pressure behavior of Cu-O bond length and Cu-O-Cu bond angles. The reasons for the observed spin-freezing transition are discussed within the framework of the available theoretical models and the recent observation of the field-induced spin freezing.     

Rheological properties and the mechanism of a viscous flow of aqueous pectin solutions

The rheological properties and mechanisms of a viscous flow of diluted apple pectin solutions are investigated. It is found that the rise in solution viscosity upon an increase in concentration and a drop in temperature is, along with the corresponding degree to which the interaction between pectin molecules and solvent is reduced, associated with the processes of structuring. The entropy of a viscous flow of pectin solutions is found to be positive: it grows with a rise in concentration is virtually temperature independent. It is established that the entropy factor makes the main contribution to the free energy value of a viscous flow.     

Fluctuations of light waves in a medium with large-scale discrete inhomogeneities

In the approximation of a model of a continuous, randomly inhomogeneous medium a solution is found to the problem of the statistical characteristics of the fluctuations of the field of a Gaussian wave beam that passes through a thin layer of atmosphere with a large number of optically soft large-scale discrete inhomogeneities. Calculations are made of the mean field, the mean intensity, the mutual coherence function, the variance, and the spatial correlation function of the intensity fluctuations.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 8, pp. 51–55, August, 1980.     

NMR and X-ray crystallography, complementary tools in structural proteomics of small proteins

NMR spectroscopy and X-ray crystallography, the two primary experimental methods for protein structure determination at high resolution, have different advantages and disadvantages in terms of sample preparation and data collection and analysis. It is therefore of interest to assess their complementarity when applied to small proteins. Structural genomics/proteomics projects provide an ideal opportunity to make such comparisons as they generate data in a systematic manner for large enough numbers of proteins to allow firm conclusions to be drawn. Here we report a comparison for 263 unique proteins screened by both NMR spectroscopy and X-ray crystallography in our structural proteomics pipeline. Only 21 targets (8%) were deemed amenable to both methods based on an initial 2D 15N-HSQC NMR spectrum and optimized crystallization trials. However, the use of both methods in the pipeline increased the total number of targets amenable to structure determination to 107, with 43 amenable to NMR only and 43 amenable to X-ray crystallographic methods only. We did not observe a correlation between 15N-HSQC spectral quality and the success of the same protein in crystallization screens. Similar results were found for an independent set of 159 proteins as reported in the accompanying paper by Snyder et al. Thus, we conclude that both methods are highly complementary, and in order to increase the number of proteins suited for structure determination, we suggest that both methods be used in parallel in screening of all small proteins for structure determination.     

Determination of Silicon Impurities in High-Purity Arsenic Using Atomic Emission Spectrometry with Matrix Distillation from a Tipped Electrode

A procedure for analyzing high-purity arsenic by atomic emission spectrometry (AES) was proposed that provides the preconcentration of silicon and other nonvolatile impurities in a crater of a graphite electrode using matrix distillation from 2-g sample portions as As₂O₃. The procedure is characterized by a low correction for the blank experiment. The detection limit for silicon was 4 × 10^–7 wt %.     

Coherent control of stationary light pulses

We present a detailed analysis of the recently demonstrated technique to generate quasi-stationary pulses of light [M. Bajcsy, A.S. Zibrov, M.D. Lukin, Nature (London) 426 (2003) 638] based on electromagnetically induced transparency. We show that the use of counter-propagating control fields to retrieve a light pulse, previously stored in a collective atomic Raman excitation, leads to quasi-stationary light field that undergoes a slow diffusive spread. The underlying physics of this process is identified as pulse matching of probe and control fields. We then show that spatially modulated control-field amplitudes allow us to coherently manipulate and compress the spatial shape of the stationary light pulse. These techniques can provide valuable tools for quantum nonlinear optics and quantum information processing.     

Resonant dislocation motion in NaCl crystals in the EPR scheme in the Earth’s magnetic field with pulsed pumping

Resonant dislocation motions in NaCl(Ca) crystals under the simultaneous action of the Earth’s magnetic field B _Earth (～66 μT) and a pulsed pump field $\tilde B$ of sufficient amplitude $\tilde B_m $ and certain duration τ have been detected and studied. The measured dislocation path peaks l(τ) have a maximum at τ = τ _r ≈ 0.53 μs. The resonance criterion has been found to be the ordinary EPR condition in which the g-factor is close to 2 and the optimum inverse pulse duration τ _r ^?1 is used instead of the harmonic pump field frequency ν _r . The largest peak l(τ) height is reached at mutually orthogonal dislocation (L) and magnetic field (B _Earth and $\tilde B$ ) orientations. Pulsed field rotation to the position $\tilde B$ ‖ B _Earth significantly decreases but does not “kill” the effect. For dislocations parallel to the Earth’s field (L ‖ B _Earth), the resonance almost disappears even at $\tilde B$ ⊥ B _Earth. In the optimum geometry of experiments, as the pump field amplitude $\tilde B_m $ decreases from 17.6 to 10 μT, the path peak height l _r = l(τ _r ) decreases only by 7.5%, remaining at the level of l _r ～ 10² μm, and at a $\tilde B_m $ further fall-off to 4 μT, it rapidly decreases to background values. In this case, the relative density of mobile dislocations similarly decreases from ～90 to 40%. Possible physical mechanisms of the observed effect have been discussed.