Intramolecular charge transfer assisted by conformational changes in the excited state of fluorene-dibenzothiophene-S,S-dioxide co-oligomers

The strong solvatochromism observed for two fluorene-dibenzothiophene-S,S-dioxide oligomers in polar solvents has been investigated using steady-state and time-resolved fluorescence techniques. A low-energy absorption band, attributed to a charge-transfer (CT) state, is identified by its red shift with increasing solvent polarity. In nonpolar solvents, the emission of these conjugated luminescent oligomers shows narrow and well-resolved features, suggesting that the emission comes from a local excited state (LE), by analogy to their conjugated fluorene-based polymer counterparts. However, in polar solvents, only a featureless broad emission is observed at longer wavelengths (CT emission). A linear correlation between the energy maximum of the fluorescence emission and the solvent orientation polarizability factor Deltaf (Lippert-Mataga equation) is observed through a large range of solvents. In ethanol, below 230 K, the emission spectra of both oligomers show dual fluorescence (LE-like and CT) with the observation of a red-edge excitation effect. The stabilization of the CT emissive state by solvent polarity is accompanied/followed by structural changes to adapt the molecular structure to the new electronic density distribution. In ethanol, above 220 K, the solvent reorganization occurs on a faster time scale (less than 10 ps at 290 K), and the structural relaxation of the molecule (CT(unrelaxed) --> CT(Relaxed)) can be followed independently. The magnitude of the forward rate constant, k(1)(20 degrees C) approximately 20 x 10(9) s(-1), and the reaction energy barrier, E(a) approximately 3.9 kcal mol(-1), close to the energy barrier for viscous flow in ethanol (3.54 kcal mol(-1)), show that large-amplitude molecular motions are present in the stabilization of the CT state.     

Cross-validation and evaluation of the performance of methods for the elemental analysis of forensic glass by μ-XRF, ICP-MS, and LA-ICP-MS

Elemental analysis of glass was conducted by 16 forensic science laboratories, providing a direct comparison between three analytical methods [micro-x-ray fluorescence spectroscopy (μ-XRF), solution analysis using inductively coupled plasma mass spectrometry (ICP-MS), and laser ablation inductively coupled plasma mass spectrometry]. Interlaboratory studies using glass standard reference materials and other glass samples were designed to (a) evaluate the analytical performance between different laboratories using the same method, (b) evaluate the analytical performance of the different methods, (c) evaluate the capabilities of the methods to correctly associate glass that originated from the same source and to correctly discriminate glass samples that do not share the same source, and (d) standardize the methods of analysis and interpretation of results. Reference materials NIST 612, NIST 1831, FGS 1, and FGS 2 were employed to cross-validate these sensitive techniques and to optimize and standardize the analytical protocols. The resulting figures of merit for the ICP-MS methods include repeatability better than 5 % RSD, reproducibility between laboratories better than 10 % RSD, bias better than 10 %, and limits of detection between 0.03 and 9 μg g^?1 for the majority of the elements monitored. The figures of merit for the μ-XRF methods include repeatability better than 11 % RSD, reproducibility between laboratories after normalization of the data better than 16 % RSD, and limits of detection between 5.8 and 7,400 μg g^?1. The results from this study also compare the analytical performance of different forensic science laboratories conducting elemental analysis of glass evidence fragments using the three analytical methods.

Valence-to-core X-ray emission spectroscopy: a sensitive probe of the nature of a bound ligand

The sensitivity of iron Kβ X-ray emission spectroscopy (XES) to the nature of the bound ligands (σ-donating, π-donating, and π-accepting) has been explored. A combination of experiment and theory has been employed, with a DFT approach being utilized to elucidate ligand effects on the spectra and to assign the spectral intensity mechanisms. Knowledge of the various contributions to the spectra allows for a deeper understanding of spectral features and demonstrates the sensitivity of this method to the identity of the interacting ligands. The potential of XES for identifying intermediate species in nonheme iron enzymes is highlighted.     

Demonstration of a narrow energy spread, ∼0.5 GeV electron beam from a two-stage laser wakefield accelerator

Laser wakefield acceleration of electrons holds great promise for producing ultracompact stages of GeV scale, high-quality electron beams for applications such as x-ray free electron lasers and high-energy colliders. Ultrahigh intensity laser pulses can be self-guided by relativistic plasma waves (the wake) over tens of vacuum diffraction lengths, to give >1 GeV energy in centimeter-scale low density plasmas using ionization-induced injection to inject charge into the wake even at low densities. By restricting electron injection to a distinct short region, the injector stage, energetic electron beams (of the order of 100 MeV) with a relatively large energy spread are generated. Some of these electrons are then further accelerated by a second, longer accelerator stage, which increases their energy to ～0.5 GeV while reducing the relative energy spread to <5% FWHM.     

On Gravitational Effects in the Schrödinger Equation

The Schrödinger  equation for a particle of rest mass $m$ and electrical charge $ne$ interacting with a four-vector potential $A_i$ can be derived as the non-relativistic limit of the Klein–Gordon  equation $\left( \Box '+m^2\right) \varPsi =0$ for the wave function $\varPsi $ , where $\Box '=\eta ^{jk}\partial '_j\partial '_k$ and $\partial '_j=\partial _j -\mathrm {i}n e A_j$ , or equivalently from the one-dimensional  action $S_1=-\int m ds +\int neA_i dx^i$ for the corresponding point particle in the semi-classical approximation $\varPsi \sim \exp {(\mathrm {i}S_1)}$ , both methods yielding the equation $\mathrm {i}\partial _0\varPsi \approx \left( \frac{1}{2m}\eta ^{\alpha \beta }\partial '_{\alpha }\partial '_{\beta } + m + n e\phi \right) \varPsi $ in Minkowski  space–time  , where $\alpha ,\beta =1,2,3$ and $\phi =-A_0$ . We show that these two methods generally yield equations  that differ in a curved background  space–time   $g_{ij}$ , although they coincide when $g_{0\alpha }=0$ if $m$ is replaced by the effective mass $\mathcal{M}\equiv \sqrt{m^2-\xi R}$ in both the Klein–Gordon  action $S$ and $S_1$ , allowing for non-minimal coupling to the gravitational  field, where $R$ is the Ricci scalar and $\xi $ is a constant. In this case $\mathrm {i}\partial _0\varPsi \approx \left( \frac{1}{2\mathcal{M}'} g^{\alpha \beta }\partial '_{\alpha }\partial '_{\beta } + \mathcal{M}\phi ^{(\mathrm g)} + n e\phi \right) \varPsi $ , where $\phi ^{(\mathrm g)} =\sqrt{g_{00}}$ and $\mathcal{M}'=\mathcal{M}/\phi ^{(\mathrm g)} $ , the correctness of the gravitational  contribution to the potential having been verified to linear order $m\phi ^{(\mathrm g)} $ in the thermal-neutron beam interferometry experiment due to Colella et al. Setting $n=2$ and regarding $\varPsi $ as the quasi-particle wave function, or order parameter, we obtain the generalization of the fundamental macroscopic Ginzburg-Landau equation of superconductivity to curved space–time. Conservation of probability and electrical current requires both electromagnetic gauge and space–time  coordinate conditions to be imposed, which exemplifies the gravito-electromagnetic analogy, particularly in the stationary case, when div ${{\varvec{A}}}=\hbox {div}{{\varvec{A}}}^{(\mathrm g)}=0$ , where ${{\varvec{A}}}^{\alpha }=-A^{\alpha }$ and ${{\varvec{A}}}^{(\mathrm g)\alpha }=-\phi ^{(\mathrm g)}g^{0\alpha }$ . The quantum-cosmological Schrödinger  (Wheeler–DeWitt) equation is also discussed in the $\mathcal{D}$ -dimensional  mini-superspace idealization, with particular regard to the vacuum potential $\mathcal V$ and the characteristics of the ground state, assuming a gravitational  Lagrangian   $L_\mathcal{D}$ which contains higher-derivative  terms up to order $\mathcal{R}^4$ . For the heterotic superstring theory  , $L_\mathcal{D}$ consists of an infinite series in $\alpha '\mathcal{R}$ , where $\alpha '$ is the Regge slope parameter, and in the perturbative approximation $\alpha '|\mathcal{R}| \ll 1$ , $\mathcal V$ is positive semi-definite for $\mathcal{D} \ge 4$ . The maximally symmetric ground state satisfying the field equations is Minkowski  space for $3\le {\mathcal {D}}\le 7$ and anti-de Sitter  space for $8 \le \mathcal {D} \le 10$ .     

Sub-Grain Scale Digital Image Correlation by Electron Microscopy for Polycrystalline Materials during Elastic and Plastic Deformation

Damage during loading of polycrystalline metallic alloys is localized at or below the scale of individual grains. Quantitative assessment of the heterogeneous strain fields at the grain scale is necessary to understand the relationship between microstructure and elastic and plastic deformation. In the present study, digital image correlation (DIC) is used to measure the strains at the sub-grain level in a polycrystalline nickel-base superalloy where plasticity is localized into physical slip bands. Parameters to minimize noise given a set speckle pattern (introduced by chemical etching) when performing DIC in a scanning electron microscope (SEM) were adapted for measurements in both plastic and elastic regimes. A methodology for the optimization of the SEM and DIC parameters necessary for the minimization of the variability in strain measurements at high spatial resolutions is presented. The implications for detecting the early stages of damage development are discussed.     

Contribution of the Adenosine 2A Receptor to Behavioral Effects of Tetrahydrocannabinol,Cannabidiol and PECS-101

The cannabis-derived molecules, ∆⁹ tetrahydrocannabinol (THC) and cannabidiol (CBD), are both of considerable therapeutic interest for a variety of purposes, including to reduce pain and anxiety and increase sleep. In addition to their other pharmacological targets, both THC and CBD are competitive inhibitors of the equilibrative nucleoside transporter-1 (ENT-1), a primary inactivation mechanism for adenosine, and thereby increase adenosine signaling. The goal of this study was to examine the role of adenosine A2A receptor activation in the effects of intraperitoneally administered THC alone and in combination with CBD or PECS-101, a 4′-fluorinated derivative of CBD, in the cannabinoid tetrad, elevated plus maze (EPM) and marble bury assays. Comparisons between wild-type (WT) and A2AR knock out (A2AR-KO) mice were made. The cataleptic effects of THC were diminished in A2AR-KO; no other THC behaviors were affected by A2AR deletion. CBD (5 mg/kg) potentiated the cataleptic response to THC (5 mg/kg) in WT but not A2AR-KO. Neither CBD nor THC alone affected EPM behavior; their combination produced a significant increase in open/closed arm time in WT but not A2AR-KO. Both THC and CBD reduced the number of marbles buried in A2AR-KO but not WT mice. Like CBD, PECS-101 potentiated the cataleptic response to THC in WT but not A2AR-KO mice. PECS-101 also reduced exploratory behavior in the EPM in both genotypes. These results support the hypothesis that CBD and PECS-101 can potentiate the cataleptic effects of THC in a manner consistent with increased endogenous adenosine signaling.     

Study of the reactions K−p → K+K−Λ and K−p → ppΛ, at 10 and 16 GeV/c

The reactions (1) K^?p → K⁺K^?Λ and (2) $\text{K}{}^{\mathrm{?}}\text{p}\text{→}\text{p}\text{p}\text{Λ}$ have been studied on samples of 109 and 64 events, respectively, at 10 GeV/c and 125 and 69 events at 16 GeV/c, reasonably free from contaminations. The investigation of the first reaction uses also 84 events of the $\text{K}{}^0\text{K}{}^0\text{Λ}$ final state at 10 GeV/c. Analysis of the Van Hove plots indicates that the K⁺K^?Λ and $\text{p}\text{p}\text{Λ}$ final states are produced by two main mechanisms: (i) a ΔQ = 0 process, with a strong diffractive component near threshold, involving the dissociations p → K⁺Λ in reaction (1) and $\text{K}{}^{\mathrm{?}}\text{→}\text{p}\text{Λ}$ in reaction (2) and (ii) a ΔQ = 1 process involving hypercharge exchange, and producing K⁺K^? and $\text{p}\text{p}$ systems in reactions (1) and (2), respectively, recoiling off the Λ. With increasing energy, this hypercharge exchange process decreases slowly when K⁺K^? is produced, but fast where the production of $\text{p}\text{p}$, violating the Zweig rule, occurs.     

Search for finite-mass neutrinos in the decay π+→μ+vμ

If neutrinos possess non-zero mass, pion decay might have small decay branches to neutrino states with large masses. We have searched for such branches in the decay of pions produced at the Indiana University Cyclotron. The energy spectrum of decay muons shows no evidence for such neutrino branches and if these decays do exist, their branching ratios must be less than 10^?2 to 10^?3 for neutrino masses in the ranFge 7–33 MeV.