Fused-ring and linking group effects of proton donors and acceptors on simple H-bonded liquid crystals

Two fused-ring structures, 6-decyloxy-2-naphthoic acid C₁₀ONA (3) and 6-dodecyloxyisoquinoline IS (8), were synthesized and utilized as proton donor and acceptor moieties to construct a series of simple mesogenic supramolecules. The other complementary hydrogen-bonded (H-bonded) moieties are benzoic acids, thiophenecarboxylic acid and pyridines containing different alkyl chain lengths connected by ether and ester linkages, i.e. 4-alkoxybenzoic acid C _n OBA (1), terephthalic acid monoalkyl ester C _n COOBA (2), 2,5-thiophenedicarboxylic acid monodecyl ester C₁₀COOTHA (4), 4-alkoxypyridine C _n OP (6) and isonicotinic acid alkyl ester C _n COOP (7). Several series of simple mesogenic supramolecular dimers were constructed from 1:1 molar ratios of proton donors (C _n OBA, C _n COOBA, C₁₀ONA and C₁₀COOTHA) and proton acceptors (IS, C _n OP and C _n COOP), though the proton acceptor C _n COOP induced phase separation in all complexes. In order to investigate their fused-ring and linking group effects on the mesogenic properties of the H-bonded complexes, analogous simple supramolecular structures are compared. Supramolecular architecture and the distinct mesomorphism of these simple H-bonded liquid crystalline materials were confirmed by polarizing optical microscopy, DSC and powder X-ray diffraction experiments.     

Preparation of Unconventional Dendrimers that Contain Rigid NH?Triazine Linkages and Peripheral tert‐Butyl Moieties for CO2‐Selective Adsorption

Three unconventional dendrimers that contained rigid NH? triazine linkages and peripheral tert‐butyl moieties were prepared by using a convergent approach and characterized by ¹H and ¹³C NMR spectroscopy, mass spectrometry, and elemental analysis. Based on a thermogravimetric analysis study, these dendrimers were observed to display thermal stability at about 300 °C. The NH? triazine moiety, which possessed protonated and proton‐free nitrogen sites (like the imidazole unit), displayed the capture of polarizable CO₂ molecules through hydrogen‐bond and/or dipole–quadrupole interactions. In addition, the adsorption of various amounts of CO₂ and N₂ at different pressures suggests that the dendritic pores, which arise from the stacking of the middle co‐planar and rim protuberant dendrimers, G _n ‐N～N‐G _n (n=1–3), either swell or shrink at high pressure, thus indicating that these dendrimers may have a breathing ability.     

Phase‐preserved macroscopic visible‐light carpet cloaking beyond two dimensions

Transformation optics, a recent geometrical design strategy of light manipulation with both ray trajectories and optical phase controlled simultaneously, promises an invisibility cloaking device that can render a macroscopic object invisible even to a scientific instrument measuring optical phase. Recent “carpet” cloaks have extended their cloaking capability to broadband frequency ranges and macroscopic scales, but they only demonstrated the recovery of ray trajectories after passing through the cloaks, while whether the optical phase would reveal their existence still remains unverified. In this paper, a phase‐preserved macroscopic visible‐light carpet cloak is demonstrated in a geometrical construction beyond two dimensions. As an extension of previous two‐dimensional (2D) macroscopic carpet cloaks, this almost‐three‐dimensional carpet cloak exhibits three‐dimensional (3D) invisibility for illumination near its center (i.e. with a limited field of view), and its ideal wide‐angle invisibility performance is preserved in multiple 2D planes intersecting in the 3D space. Optical path length is measured with a broadband pulsed‐laser interferometer, which provides unique experimental evidence on the geometrical nature of transformation optics.

     

Secondary Metabolites of Clinacanthus nutans

Chemistry of Natural Compounds -     

Effect of selected dopants on conductivity and moisture stability of Li3PS4 sulfide solid electrolyte: a first-principles study

The first principle computational screening was performed to investigate the effect of selected dopants for Li₃PS₄ sulfide solid electrolyte on its ionic conductivity and stability toward moisture. The results suggest that substitution P⁵⁺ using isovalent cations whose electronegativity (EN) value is closer to the value of S has more significant effects on the ionic conductivity, whereby W⁵⁺ and Sb⁵⁺ can improve most. Similarly, aliovalent cation substitutions with compensating changes in the lithium-ion concentration, particularly those with a lower oxidation state and higher EN, such as Cu²⁺, effectively enhance the lithium-ion conductivity in this structure. For cation dopants, it is found that ionic conductivity improvement of Li₃PS₄ is the synergetic effect of EN and oxidation number of the dopant as well as the material's lattice parameter change. Oxides of the considered cation dopants can also improve the ionic conductivity of the material but have much lower lithium-ion conductivity than the cases of cation dopants. However, the metal oxide dopants, particularly those derived from soft Lewis' acid cations, show a marginal improvement in moisture stability of the Li₃PS₄ electrolyte. The effect of halides and metal halide dopants on the lithium-ion conductivity and moisture stability of Li₃PS₄ electrolyte are also studied. It is found that metal halides are more effective than any other dopants in improving the ionic conductivity of Li₃PS₄.     

Large Stabilization Effects by Intramolecular Beryllium Bonds in Ortho-Benzene Derivatives

Intramolecular interactions are shown to be key for favoring a given structure in systems with a variety of conformers. In ortho-substituted benzene derivatives including a beryllium moiety, beryllium bonds provide very large stabilizations with respect to non-bound conformers and enthalpy differences above one hundred kJ·mol⁻¹ are found in the most favorable cases, especially if the newly formed rings are five or six-membered heterocycles. These values are in general significantly larger than hydrogen bonds in 1,2-dihidroxybenzene. Conformers stabilized by a beryllium bond exhibit the typical features of this non-covalent interaction, such as the presence of a bond critical point according to the topology of the electron density, positive Laplacian values, significant geometrical distortions and strong interaction energies between the donor and acceptor quantified by using the Natural Bond Orbital approach. An isodesmic reaction scheme is used as a tool to measure the strength of the beryllium bond in these systems in terms of isodesmic energies (analogous to binding energies), interaction energies and deformation energies. This approach shows that a huge amount of energy is spent on deforming the donor–acceptor pairs to form the new rings.     

CP violations in predictive neutrino mass structures

We study the CP-violation effects from two types of neutrino mass matrices with (i) \((M_\nu )_{ee}=0\), and (ii) \((M_\nu )_{ee}=(M_\nu )_{e\mu }=0\), which can be realized by the high-dimensional lepton number violating operators \(\bar{\ell }_R^c\gamma ^\mu L_L (D_\mu \Phi )\Phi ^2\) and \(\bar{\ell }_R^c l_R (D_\mu {\Phi })^2\Phi ^2\), respectively. In (i), the neutrino mass spectrum is in the normal ordering with the lightest neutrino mass within the range \(0.002\,\mathrm{eV}\lesssim m_0\lesssim 0.007\,\mathrm{eV}\). Furthermore, for a given value of \(m_0\), there are two solutions for the two Majorana phases \(\alpha _{21}\) and \(\alpha _{31}\), whereas the Dirac phase \(\delta \) is arbitrary. For (ii), the parameters of \(m_0\), \(\delta \), \(\alpha _{21}\), and \(\alpha _{31}\) can be completely determined. We calculate the CP-violating asymmetries in neutrino–antineutrino oscillations for both mass textures of (i) and (ii), which are closely related to the CP-violating Majorana phases.