Q-band EPR and ENDOR of low temperature X-irradiated beta-D-fructose single crystals

Beta-D-fructose single crystals were in situ X-irradiated at 80 K and measured using electron paramagnetic resonance (EPR), electron nuclear double resonance (ENDOR) and ENDOR-induced EPR (EIE) techniques at Q-band (34 GHz) microwave frequencies. The measurements revealed the presence of at least four carbon-centered radicals stable at 80 K. By means of ENDOR angular variations in the three principal crystallographic planes, six proton hyperfine coupling tensors could be determined and were assigned to four different radicals by the aid of EIE. Two of the radicals exhibit only beta-proton hyperfine couplings and reveal almost identical EIE spectra. For the other two radicals, the major hyperfine splitting originates from a single alpha-proton hyperfine coupling and their EIE spectra were also quite similar. The similarity of the EIE spectra and hyperfine tensors led to the assumption that there are only two essentially different radical structures. The radical exhibiting only beta-proton hyperfine couplings was assigned to a C3 centered radical arising from H3 abstraction and the other radical suggested to be an open-ring species with a disrupted C2-C3 bond and a double C2-O2 bond. A possible formation mechanism for the latter open-ring radical is presented. By means of cluster density functional theory (DFT) calculations, the structures of the two radicals were determined and a fairly good agreement between the calculated and experimental hyperfine tensors was found.     

Surface structure and composition of Pd8Ni92(1 1 1): A dynamic LEED study

The Pd₈Ni₉₂(1 1 1) surface was studied using low-energy electron diffraction (LEED). IV spectra collected close to normal incidence were analysed by dynamical tensor LEED. Composition and interlayer spacings were determined for first four atomic layers. The surface slab is found to be enriched in Pd (30% in total against 8% in bulk) but this extra palladium is irregularly distributed over the four topmost layers. Contrary to previous reports, the palladium amount, as compared to the bulk, is not significantly changed in the surface layer and it is enriched to 20% only in the third layer. The detected contractions of interlayer spacings are all but one (d₃₄) within the error limits of no contraction at all. We also discuss some aspects of correlations between the fit parameters.     

Optimizing the marriage market: An application of the linear assignment model

Research shows that the success of marriages and other intimate partnerships depends on objective attributes such as differences in age, cultural background, and educational level. This article proposes a mathematical approach to optimizing marriage by allocating spouses in such a way as to reduce the likelihood of divorce or separation. To produce our optimization model, we use the assumption of a central “agency” that would coordinate the matching of couples. Based on a representative and longitudinal sample of 1074 cohabiting and married couples living in Switzerland, we estimate various objective functions corresponding to age, education, ethnicity, and prior divorce concerning every possible combination of men and women. Our results show that the current state of marriages or partnerships is well below the social optimum. We reallocate approximately 68% of individuals (7 out of 10) to a new couple that we posit has a higher likelihood of survival. From this selection of new partners, we obtain our final “optimal” solutions, with a 21% reduction in the objective function.     

Direct observation of optical precursors in a region of anomalous dispersion

We create optical precursors by propagating a step-modulated optical pulse through a linear resonant dielectric absorber. The field emerging from the dielectric consists of a several-nanosecond-long spike with near 100% transmission, which decays to a constant value expected from Beer's law. This high-transmission spike might be useful for imaging applications requiring penetrating optical radiation. We compare our observations to two different theories, revealing that the spike consists of both the Sommerfeld and Brillouin precursors.     

Synthesis and properties of a functionalized heterobimetallic Re(I)–Gd(III) complex as a potential dual-contrast agent for molecular imaging

In the design of dual-imaging probes, the first functionalized and neutral heterobimetallic Re(I)–Gd(III) complex, highly soluble in aqueous solutions, has been prepared. This system exhibits interesting photophysical properties (λ_em = 578 nm, ? = 1.4%) for optical imaging and substantial higher relaxivity (r₁ = 6.6 mM⁻¹ s⁻¹ at 0.47 T and 37 °C) than the clinically used MRI contrast agents. Moreover, this system incorporates an aromatic ester functionality suitable for bioconjugation.     

Morphology of Polystyrene Core–dPoly(ethylene oxide) Shell Arborescent Copolymer Micelles from Small-Angle Neutron Scattering Analysis

Arborescent (dendrigraft) copolymers with a branched polystyrene (PS) core grafted at the chain termini with deuterated poly(ethylene oxide) segments (PS-dPEO) were characterized in benzene and acetone by small-angle neutron scattering measurements using the contrast matching technique. While copolymers incorporating a G1 (twice-grafted) PS core aggregated to some extent, the portion of the scattering curve corresponding to non-aggregated copolymer molecules could still be analyzed to determine the shape and segment radial density profile for core and shell. These were derived from the pair distance distribution function P(r) and the scattering length density contrast profile Δρ(r) = ρ(r) ? ρ(solvent), obtained by the indirect Fourier transformation and deconvolution methods. The profiles obtained for the G1 copolymer are consistent with a well-defined PS core–dPEO shell morphology, only observed previously for upper generation (G4) polymers with deuterated PS (dPS) chains grafted randomly on arborescent PS substrates. Detailed morphological analysis could not be carried out for an analogous G3 arborescent PS copolymer terminally grafted with dPEO segments due to extensive aggregation in both solvents.     

One-level reformulation of the bilevel Knapsack problem using dynamic programming

In this paper, we consider the Bilevel Knapsack Problem (BKP), which is a hierarchical optimization problem in which the feasible set is determined by the set of optimal solutions for a parametric Knapsack Problem. We introduce a new reformulation of the BKP into a one-level integer programming problem using dynamic programming. We propose an algorithm that allows the BKP to be solved exactly in two steps. In the first step, a dynamic programming algorithm is used to compute the set of follower reactions to leader decisions. In the second step, an integer problem that is equivalent to the BKP is solved using a branch-and-bound algorithm. Numerical results are presented to show the performance of our method.     

Blocked-micropores,surface functionalized,bio-compatible and silica-coated iron oxide nanocomposites as advanced MRI contrast agent

Quasi-critical fluctuations occur close to critical points or close to continuous phase transitions. In three-dimensional systems, precision tuning is required to access the fluctuation regime. Lowering the dimensionality enhances the parameter space for quasi-critical fluctuations considerably. This enables one to make use of novel properties emerging in fluctuating systems, such as giant susceptibilities, Casimir forces or novel quasi-particle interactions. Examples are discussed ranging from simple metal–adsorbate systems to unconventional superconductivity in iron-based superconductors.     

Conformational Analysis of (S)-4,5,6,7-Tetrahydro-5-Methylimidazo [4,5,1-jk][1,4]-Benzodiazepin-2(1H)-one (R78362)

The solution and solid state conformation of (S)-4,5,6,7-tetrahydro-5-methylimidazo [4,5,1-jk][1,4]-benzodiazepin-2(1H)-one (R78362) have been investigated by low temperature NMR and x-ray diffraction studies. The ¹H NMR spectrum of R78362 shows no evidence of the presence of multiple conformers in the temperature range 340K - 177K. Molecular mechanisms and semiempirical molecular orbital calculations suggest that the nitrogen and ring inversion barriers of R78362 are small and thus a time-averaged ¹H NMR spectrum is probably occurring at 298K. The x-ray diffraction data indicated that there were two independent molecules in the asymmetric unit of the crystal. The two molecules had similar conformations with the benzoimidazole ring being planar and the diazepine ring in a “half-chair” conformation.     

Practical Considerations for Continuum Models Applied to Surface Electrochemistry

Modelling the electrolyte at the electrochemical interface remains a major challenge in ab initio simulations of charge transfer processes at surfaces. Recently, the development of hybrid polarizable continuum models/ab initio models have allowed for the treatment of solvation and electrolyte charge in a computationally efficient way. However, challenges remain in its application. Recent literature has reported that large cell heights are required to reach convergence, which presents a serious computational cost. Furthermore, calculations of reaction energetics require costly iterations to tune the surface charge to the desired potential. In this work, we present a simple capacitor model of the interface that illuminates how to circumvent both of these challenges. We derive a correction to the energy for finite cell heights to obtain the large cell energies at no additional computational expense. We furthermore demonstrate that the reaction energetics determined at constant charge are easily mapped to those at constant potential, which eliminates the need to apply iterative schemes to tune the system to a constant potential. These developments together represent more than an order of magnitude reduction of the computational overhead required for the application of polarizable continuum models to surface electrochemistry.