Novel Imidazole Liquid Crystals; Experimental and Computational Approaches.

The liquid crystalline materials named (E)-4-(2-(4-oxo-5,5-diphenyl-4,5-dihydro-1H-imidazol-2-yl)hydrazineylidene)methyl)phenyl and 4-(alkoxy)benzoate, In, were synthesized and their mesomorphic behaviors were examined. The chemical structures of the produced compounds were confirmed by Fourier-transform infrared spectroscopy (FT-IR), NMR, and elemental analysis. Differential scanning calorimetry (DSC) and polarized optical microscopy were used to investigate the mesomorphic properties of designed heterocyclic derivatives. All the compounds tested had suitable thermal stability and enantiotropic behavior of smectogenic temperature ranges. Furthermore, the enantiotropic smectic C phases were observed to cover all the homologues. Moreover, computational investigations corroborated the experimental findings of the mesomorphic behavior. The reactivity parameters were computed for the derivatives and linked with the experimental data. Theoretical calculations revealed that the polarizability of the studied series increases with the chain length, whereas the HOMO-LUMO energy gap or other reactivity descriptors were less sensitive to the size of the system. On the other hand, the predicted thermodynamic parameters revealed the size dependence of thermal stability of the compounds.

Wide Nematogenic Azomethine/Ester Liquid Crystals Based on New Biphenyl Derivatives: Mesomorphic and Computational Studies.

The thermal stability and mesomorphic behavior of a new biphenyl azomethine liquid crystal homologues series, (E)-4-(([1,1'-biphenyl]-4-ylmethylene)amino)phenyl 4-(alkoxy)benzoate, In, were investigated. The chemical structures of the synthesized compounds were characterized using FT-IR, NMR, and elemental analyses. Differential scanning calorimetry (DSC) and polarized optical microscopy were employed to evaluate the mesomorphic characteristics of the designed homologues. The examined homologues possessed high thermal stability and broad nematogenic temperature ranges. Furthermore, the homologues were covered by enantiotropic nematic phases. The experimental measurements of the mesomorphic behavior were substantiated by computational studies using the density functional theory (DFT) approach. The reactivity parameters, dipole moments, and polarizability of the studied molecules are discussed. The theoretical calculations demonstrated that as the chain length increased, the polarizability of the studied series increased; while it did not significantly affect the HOMO-LUMO energy gap and other reactivity descriptors, the biphenyl moiety had an essential impact on the stability of the possible geometries and their thermal as well as physical parameters.

Is conformation relevant for QSAR purposes? 2D Chemical representation in a 3D-QSAR perspective.

Conformation has a key role in the mechanism of interaction between small molecules and biological receptors. However, encoding this type of information in molecular descriptors for the construction of robust quantitative structure-activity relationships (QSAR) models is not an easy task and, so far, the dependence of these models on such feature has not been thoroughly investigated. In the present study, the authors explore the effects of conformational information on a 3D-QSAR technique by comparing models built with descriptors that encode fully described tridimensional aspects (structures docked inside a biological target), with descriptors in which this information is suppressed (flat structures) or not fully described (structures with quantum-chemically optimized geometries). As a result, the validation parameters indicate that the robustness of the models seems to be more related to the alignment aspect of the structures than to how well their tridimensional features are described.

Synthetic, Mesomorphic, and DFT Investigations of New Nematogenic Polar Naphthyl Benzoate Ester Derivatives.

Four new non-symmetrical derivatives based on central naphthalene moiety, 4-((4-(alkoxy)phenyl) diazenyl)naphthalen-1-yl 4-substitutedbenzoate (In/x), were prepared, and their properties were investigated experimentally and theoretically. The synthesized materials bear two wing groups: an alkoxy chain of differing proportionate length (n = 6 and 16 carbons) and one terminal attached to a polar group, X. Their molecular structures were elucidated via elemental analyses and FT-IR and NMR spectroscopy. Differential scanning calorimetry (DSC) and polarized optical microscopy (POM) were carried out to evaluate their mesomorphic properties. The results of the experimental investigations revealed that all the synthesized analogues possess only an enantiotropic nematic (N) mesophase with a high thermal stability and broad range. Density functional theory (DFT) calculations were in accordance with the experimental investigations and revealed that all prepared materials are to be linear and planar. Moreover, the rigidity of the molecule increased when an extra fused ring was inserted into the center of the structural shape, so its thermal and geometrical parameters were affected. Energy gap predictions confirmed that the I16/c derivative is more reactive than other compounds.

Irregular Load Adapted Scaffold Optimization: A Computational Framework Based on Mechanobiological Criteria.

By combining load adaptive algorithms with mechanobiological algorithms, a computational framework was developed to design and optimize the microarchitecture of irregular load adapted scaffolds for bone tissue engineering. Skeletonized cancellous bone-inspired lattice structures were built including linear fibers oriented along the internal flux of forces induced by the hypothesized boundary conditions. These structures were then converted into solid finite element models, which were optimized with mechanobiology-based optimization algorithms. The design variable was the diameter of the beams included in the scaffold, while the design objective was the maximization of the fraction of the scaffold volume predicted to be occupied by neo-formed bony tissue. The performance of the designed irregular scaffolds, intended as the capability to favor the formation of bone, was compared with that of the regular ones based on different unit cell geometries. Three different boundary and loading conditions were hypothesized, and for all of them, it was found that the irregular load adapted scaffolds perform better than the regular ones. Interestingly, the numerical predictions of the proposed framework are consistent with the results of experimental studies reported in the literature. The proposed framework appears to be a powerful tool that can be utilized to design high-performance irregular load adapted scaffolds capable of bearing complex load distributions.

New structures of hydronium cation clusters.

Four new hydronium ion structures are investigated by means of quantum mechanical calculations at the DFT/B3LYP6-311+G(2d,2p) level of theory. There exist experimental crystallographic hydronium cations (H11O5 +) of two different geometrical structures, one BEXFEQ (acyclic) and one IYEPEH (cyclic). Molecular calculations reveal their relative stability. Another hydronium cation NEBDII (H15O7 +) when optimized reveals a totally new and unexpected structure. All three optimized structures are shown to be quite stable as judged by their binding energies, and therefore may possibly be found in solution. A main result of this article is the discovery of three new optimized structures of hydronium ions, all of which are preferentially ring structures. The optimized structure of H15O7 + is a cube lacking a vertex. Putting a water molecule at the "empty" vertex leads by energy optimization to a structure of H17O8 + which has the approximate symmetry of a cube. This cubic structure, as judged by its fragments, is one of the most interesting of the hydronium ions studied in this paper. The addition of H3O+ to a group of seven neutral molecules in the hypothetical reaction H3O+ + 7 H2O → H17O8 + induces two water molecules to each capture a proton at the expense of two other water molecules (converting them into hydroxyl anions) leading to a cluster with the formula [ H 3 O + 0.7 ] 3 [ H 2 O ] 3 + 0.1 [ OH - 0.6 ] 2 , where the superscripts are the integrated QTAIM atomic charges (in atomic units) on the respective species (inside the bracket) or on groups of a given species (outside the bracket). The cubic arrangement of 3H3O+.3H2O.2OH- is accompanied with a significant redistribution of charge: Each hydronium cation carries ca. +0.7 au, the hydroxyl anions only around -0.6 au each, while the water molecules remain quasi-neutral with a slight positive charge.