From Nitro‐ to Sulfonyl‐Based Chromophores: Improvement of the Comprehensive Performance of Nonlinear Optical Dendrimers

Through the combination of the divergent and convergent approaches, coupled with the utilization of the powerful Sharpless “click‐chemistry” reaction, two series of sulfonyl‐based high‐generation NLO dendrimers were conveniently prepared with high purity and in satisfactory yields. Thanks to the perfect three‐dimensional (3D) spatial isolation from the highly branched structure and the isolation effect of the exterior benzene moieties and the interior triazole rings, these dendrimers exhibited large second harmonic generation coefficient (d₃₃) values up to 181 pm V^?1, which, to the best of our knowledge, is the highest value so far for polymers containing sulfonyl‐based chromophore moieties. Meanwhile, compared with the nitro‐chromophore‐based analogues, their optical transparency and NLO stability were improved in a large degree, due to the lower dipole moment (μ) and the special main‐chain structure of sulfonyl‐based chromophore in these dendrimers.     

Preparation and characterization of ZrCO/C composite aerogels

Zr-containing organic aerogels were synthesized by ligand substitution reaction of polyzirconoxone and 2, 4-dihydroxybenzoic acid, followed by polymerization with formaldehyde, and then supercritical drying using CO₂. After carbonization and carbothermal reduction under an argon atmosphere, ZrCO/C composite aerogels with controllable zirconium content (47.8–78.6 wt%) were obtained. The carbothermal reduction was substantially completed at 1,500 °C, and the obtained ZrCO/C composite aerogels exhibit low oxygen contents (9.4–6.7 wt%) and high surface areas (589–147 m²/g). Pore morphologies of the ZrCO/C composite aerogels were investigated in detail by nitrogen sorption measurements, scanning electron microscopy and its associated energy-dispersive X-ray microanalysis measurements. The results show that the aerogels are composed of carbon framework and Zr-conglomerations, and the surface area of aerogel is severely affected by its zirconium content. The presence of reductive ZrC crystals can greatly enhance the oxidation resistance ability of amorphous carbon framework and prevent collapse.     

EXAFS and DFT studies of microscopic structure with different density upon Zn(II) adsorption on anatase TiO2

Microscopic structures of Zn(II) adsorbed on anatase TiO₂ surface with different densities were studied using extended X-ray absorption fine structure (EXAFS) spectroscopy and density functional theory (DFT) calculation. Quantitative analysis of the EXAFS spectra showed that microscopic structures of Zn(II) were fourfold coordinated complexes, and different microscopic structures were present of the solid surface. Three modes of corner–corner/sharing-corner/sharing-edge adsorptions on anatase (101) face cluster were calculated by the DFT method. The results from DFT method were consistent with the EXAFS fittings. The optimized Zn–O average distance of the Zn–O tetrahedron was determined as about 2.00 Å. The Zn–Ti distance was 3.69 Å for the corner–corner adsorption, 3.35 Å for the sharing-corner adsorption, and 3.02 Å for the sharing-edge adsorption. According to the adsorption energies calculated by the DFT method, the microscopic structure of corner–corner adsorption was less stable than those of the other adsorption modes. With the increasing adsorption density, the corner–corner adsorption mode would be enhanced more intensively than the other adsorption modes.     

Deformations of Charged Axially Symmetric Initial Data and the Mass–Angular Momentum–Charge Inequality

We show how to reduce the general formulation of the mass–angular momentum–charge inequality, for axisymmetric initial data of the Einstein–Maxwell equations, to the known maximal case whenever a geometrically motivated system of equations admits a solution. It is also shown that the same reduction argument applies to the basic inequality yielding a lower bound for the area of black holes in terms of mass, angular momentum, and charge. This extends previous work by the authors (Cha and Khuri, Ann Henri Poincaré, doi: 10.1007/s00023-014-0332-6, arXiv:1401.3384, 2014), in which the role of charge was omitted. Lastly, we improve upon the hypotheses required for the mass–angular momentum–charge inequality in the maximal case.     

Synthesis and application of moisture-stable methallylsilanated phosphorylcholine as a surface modifier

New methallylsilanated phosphorylcholine (MASPCs) were synthesized via a copper-catalyzed ‘click’ reaction and demonstrated excellent moisture stability. Hydroxylated silicon compounds, silanol, and silica were grafted or modified by MASPCs in the presence of triflic acid (TfOH) and they possessed a good grafting efficiency and high loading rate.     

Transformations of iodine species inside elliptical channels of AlPO4‐11 crystals at low temperature: a Raman study

Raman spectra of iodine species confined in one‐dimensional elliptical channels of AlPO₄‐11 (AEL) crystals have been studied from room temperature down to −196 °C. As temperature decreases, thermal fluctuations of individual iodine molecules confined in AEL channels are slowed down and they prefer to rotate to channel axis direction, which increases the population of iodine molecules along channel axis (i.e., lying molecules and chains). Such temperature‐driven orientation transformation of iodine molecules is found to be reversible upon heating up to room temperature. The experimental observations are in good agreement with our theoretical simulations by molecular dynamics on low density iodine‐filled AEL crystals. We thus provide a new way to modulate the orientation of iodine molecules in nanochannels, which may have implications in low‐temperature‐sensitive nanoscale devices. Copyright © 2015 John Wiley & Sons, Ltd.     

Magnetic interactions in the geometrically frustrated triangular lattice antiferromagnet CuFeO2

The spin-wave excitations of the geometrically frustrated triangular lattice antiferromagnet CuFeO2 have been measured using high resolution inelastic neutron scattering. Antiferromagnetic interactions up to third nearest neighbors in the ab plane (J1, J2, J3, with J{2}/J{1} approximately 0.44 and J{3}/J{1} approximately 0.57), as well as out-of-plane coupling (J{z}, with J{z}/J{1} approximately 0.29) are required to describe the spin-wave dispersion relations, indicating a three-dimensional character of the magnetic interactions. Two energy dips in the spin-wave dispersion occur at the incommensurate wave vectors associated with multiferroic phase and can be interpreted as dynamic precursors to the magnetoelectric behavior in this system.     

Generation of a four-qubit cluster state for atoms in a thermal cavity

We propose two schemes for generating a four-atom cluster state in a thermal cavity. With the assistant of a strong classical field the photon-number-dependent parts in the effective Hamiltonian are canceled. Thus the schemes are insensitive to the thermal field. The schemes can also be used to generate the cluster state for the trapped ions in thermal motion.     

High-resolution in vivo imaging of blood vessels without labeling

We demonstrate that both oxyhemoglobin and deoxyhemoglobin have sequential two-color, two-photon absorption properties that can serve as endogenous contrasts in microvasculature imaging. Using a sensitive modulation transfer technique, we are able to image hemoglobin in red blood cells with micrometer resolution, both in vitro and in vivo. We show that excellent contrast from hemoglobin without any labeling can be obtained in tissue.