Dual Emission from Precious Metal-Free Luminophores Consisting of C,H, O,Si, and S/P at Room Temperature

Fluorescence–phosphorescence dual-emissive compounds are valuable tools for ratiometric luminescence sensing. Herein, it is reported that 2,5-bis(phenylsulfonyl)- and 2,5-bis[bis(4-methoxyphenyl)phosphinyl]-1,4-disiloxybenzenes exhibit dual emission with emission peaks that were easily identified without performing time-gated measurement. The disiloxybenzenes in powder simultaneously fluoresced and phosphoresced at 358–374 and 457–470 nm, respectively, under vacuum. The intensity ratios of the phosphorescence/fluorescence maxima of the disiloxybenzenes in powder and in a thin film of poly(methyl methacrylate) were sensitive to temperature and molecular oxygen, respectively. The plots of the relative intensity versus temperature or partial pressure of molecular oxygen were well fitted with calibration curves defined by an exponential approximation with excellent correlation coefficients R² (0.9708–0.9921), demonstrating the high potential of the disiloxybenzenes as precious metal-free probes applicable to ratiometric luminescence sensing.     

Structural-Deformation-Energy-Modulation Strategy in a Soft Porous Coordination Polymer with an Interpenetrated Framework

To achieve unique molecular-recognition patterns, a rational control of the flexibility of porous coordination polymers (PCPs) is highly sought, but it remains elusive. From a thermodynamic perspective, the competitive relationship between the structural deformation energy (E_def) of soft PCPs and the guest interaction is key for selective a guest-triggered structural-transformation behavior. Therefore, it is vital to investigate and control E_def to regulate this competition for flexibility control. Driven by these theoretical insights, we demonstrate an E_def-modulation strategy via encoding inter-framework hydrogen bonds into a soft PCP with an interpenetrated structure. As a proof of this concept, the enhanced E_def of PCP enables a selective gate-opening behavior toward CHCl₃ over CH₂Cl₂ by changing the adsorption-energy landscape of the compounds. This study provides a new direction for the design of functional soft porous materials.     

ESR of Ni doped amorphous chalcogenide semiconductors

ESR signals with g = 2.08 and 2.13 due to Ni were observed for evaporated (Ge_0.32Se_0.32Te_0.32As_0.4) 100_-xNi_x and $\text{(Ge}{}_{\mathrm{<mtext>1</mtext><mtext>3</mtext>}}\text{Se}{}_{\mathrm{<mtext>2</mtext><mtext>3</mtext>}}\text{100}{}_{\mathrm{-x}}\text{Ni}{}_{\mathrm{x}}$ films respectively. The large increase of the electrical conductivity by the addition of Ni is discussed in connection with the ESR signal. Bulk glasses prepared by melt-quenching are also investigated for comparison.     

The inverse scattering problem and the equivalent local potential

We examine the role of the non-locality of the potential in the two-body scattering by taking the nucleon-Σ system as an example. We employ a non-local potential for the nucleon-Σ channel which has the characteristic features of the quark model and reproduces the phase shifts of widely used local potentials. We use inverse scattering methods to obtain the equivalent local potential from the non-local potential, and show that the obtained local potential has a strong short range repulsion.     

On well-posedness of incompressible two-phase flows with phase transitions: the case of non-equal densities

The basic model for incompressible two-phase flows with phase transitions consistent with thermodynamics is studied. The latter means that the total energy is conserved and the total entropy is nondecreasing. We consider the case of constant but non-equal densities of the phases, complementing our previous paper (Prüss et?al. in Evol Equ Control Theory 1:171–194, 2012) where the case of equal densities is analyzed. The local well-posedness of such problems is proved by means of the technique of maximal L _p -regularity, in a configuration where the interface is nearly flat and initial data are small.     

Higher Harmonic Operations of Submillimeter Wave Gyrotrons (Gyrotron FU Series)

Higher harmonic operation of gyrotrons is necessary to obtain high frequencies. Some gyrotrons included in the Gyrotron FU series developed at Fukui University have achieved operation at the third and even fourth harmonics of the electron cyclotron frequency. The output lies in the millimeter to submillimeter wavelength range and the output powers are several watts to several tens of watts. In this paper, the gyrotrons and the conditions under which they operate are described in detail.     

Capillary electrophoresis of small solutes in linear polymer solutions: relation between ionic mobility, diffusion coefficient and viscosity

Electrophoretic mobilities, mu, and diffusion coefficients, D, of a small ion (molecular weight 579) were determined in dependence on the viscosity, eta, of aqueous buffer solutions containing ethylene glycol, or polyethylene glycol (PEG) with average molecular weights of 400, 20000, 100000 or 2000000, respectively, as additives. The values for mu and D are inversely proportional to the viscosity for the solutions with small-sized additives (ethylene glycol and PEG400), in accordance to Walden's rule. In contrast, for the longest polymers the mobilities and the diffusion coefficients approximate the values observed for pure water, and are nearly independent of the viscosity. This result agrees with the model of fractional free volume and the obstruction theory. For solutions with equal viscosity, three ranges can be differentiated for mu and D in relation to the size of the additive: for small additives, on the one hand, and the long-chained polymers, on the other hand, the values for mu and D are nearly independent of the size of the additive. In contrast, a pronounced increase of mu and D is found with increasing polymer size in the molecular weight range between 20000 and 100000. The ratio mu/D, occurring in a number of expressions for the plate height contributions, exhibits a remarkably small change over the entire polymer size and viscosity range (between 1 and 7 cP) under consideration. Consequently, the separation efficiency, expressed by the plate number, is found to be nearly constant, and is independent of viscosity.     

Two-Dimensional Supramolecular Polymerization of a Bis-Urea Macrocycle into a Brick-Like Hydrogen-Bonded Network

We report on a dendronized bis-urea macrocycle 1 self-assembling via a cooperative mechanism into two-dimensional (2D) nanosheets formed solely by alternated urea-urea hydrogen bonding interactions. The pure macrocycle self-assembles in bulk into one-dimensional liquid-crystalline columnar phases. In contrast, its self-assembly mode drastically changes in CHCl₃ or tetrachloroethane, leading to 2D hydrogen-bonded networks. Theoretical calculations, complemented by previously reported crystalline structures, indicate that the 2D assembly is formed by a brick-like hydrogen bonding pattern between bis-urea macrocycles. This assembly is promoted by the swelling of the trisdodecyloxyphenyl groups upon solvation, which frustrates, due to steric effects, the formation of the thermodynamically more stable columnar macrocycle stacks. This work proposes a new design strategy to access 2D supramolecular polymers by means of a single non-covalent interaction motif, which is of great interest for materials development.     

Tandem conjugate addition-aldol cyclization of 2-formylbenzylidenemalonate with ether radicals by the mediation of dimethylzinc

The chemoselective radical conjugate addition reaction of THF or 4,4,5,5-tetramethyl-1,3-dioxolane with 2-formylbenzylidenemalonate gave tandem conjugate addition-aldol cyclization product in one pot. The radical tandem reaction was extended to the asymmetric reaction using bis(8-phenylmenthyl) 2-formylbenzylidenemalonate as a chiral Michael acceptor to provide an enantioenriched indane derivative.