First mesomorphic and DFT characterizations for 3- (or 4-) n-alkanoyloxy benzoic acids and their optical applications.

New liquid crystalline hydrogen bonded 3- (or 4)-n-alkanoyloxy benzoic acids were synthesized and probed theoretically and experimentally. The molecular structures of these compounds were elucidated by proton NMR, carbon-13 NMR and elemental analyses. Differential scanning calorimetry (DSC) was used to investigate the thermal and mesomorphic properties of all the symmetrical dimers that bearing identical alkanoyloxy chains. Moreover, polarized optical microscopy (POM) was used to determine their mesophases. The findings show that all the designed symmetrical dimers exhibit the smectic mesophase with relative thermal stability that depends on the length of their terminal side chain. Additionally, the experimental findings of the mesomorphic behavior are further supported by DFT calculations. The alkanoyloxy benzoic acid para-derivatives (In) were shown to be more stable than their meta-substituted (IIn) analogues due to stronger hydrogen bonding interactions. The computed reactivity parameters showed that the position of ester moiety has a significant impact on the acids reactivity. The absorbance spectra of both the 3- (or 4)-n-alkanoyloxy benzoic acids revealed a blue shift with the increment of the of alkyl chain size; however, the energy band gaps of 3-n-alkanoyloxy benzoic derivatives were found to be slightly higher than those of the 4-n-alkanoyloxy benzoic acids. Moreover, the photoluminescence spectrum of the prepared materials is rather broad, and exhibited a red shift as the alkyl chain length increases. The fluorescence lifetime shown to rise as alkyl chain length grows longer, and 3-n-alkanoyloxy benzoic acids have slightly longer lifetime compared to their 4-n-alkanoyloxy benzoic analogues.

Study of Ag Nanoparticles in a Polyacrylamide Hydrogel Dosimeters by Optical Technique.

The dosimetric characteristics of hydrogel dosimeters based on polyacrylamide (PAC) as a capping agent incorporating silver nitrate as a radiation-sensitive material are investigated using UV-Vis spectrophotometry within the dose range 0-100 Gy. Glycerol was used in the hydrogel matrix to promote the dosimetric response and increase the radiation sensitivity. Upon exposing the PAC hydrogel to γ-ray, it exhibits a Surface Plasmon Resonance (SPR) band at 453 nm, and its intensity increases linearly with absorbed doses up to 100 Gy. The results are compared with the silver nitrate gel dosimeter. Glycerol of 15% in the hydrogel matrix enhances the radiation sensitivity by about 30%. PAC hydrogel dosimeter can be considered a near water equivalent material in the 400 keV-20 MeV photon energy range. At doses less than 15 Gy, the PAC hydrogel dosimeter retains higher radiation sensitivity than the gel dosimeter. The total uncertainty (2σ) of the dose estimated using this hydrogel is about 4%. These results may support the validity of using this hydrogel as a dosimeter to verify radiotherapy techniques and dose monitoring during blood irradiation.

Polymorphic Phases of Supramolecular Liquid Crystal Complexes Laterally Substituted with Chlorine.

New supramolecular complexes, based on H-bonding interactions between 4-(pyridin-4-yl) azo-(2-chlorophenyl) 4-alkoxybenzoates (Bn) and 4-[(4-(n-hexyloxy)phenylimino)methyl]benzoic acid (A6), were prepared and their thermal and mesomorphic properties investigated via differential scanning calorimetry (DSC) and Fourier-transform infrared spectroscopy (FT-IR) in order to confirm their H-bonding interactions. The mesophase behavior of each mixture was examined by DSC and polarized optical microscopy (POM). According to the findings of the study, in all of the designed mixtures, the introduction of laterally polar chlorine atom to the supramolecular complexes produces polymorphic compounds possessing smectic A, smectic C and nematic mesophases, in addition, all products have low melting transitions. Thermal stabilities of the associated phases depend on the position and orientation of the lateral polar Cl- atom as well as the length of terminal flexible alkoxy chain. Comparisons were made between the present lateral Cl- complexes and previously investigated laterally-neat complexes in order to investigate the impact of the addition, nature and orientation of polar substituent on the mesomorphic behavior. The investigations revealed that, the polarity and mesomeric nature of inserted lateral substituent into the base component play an essential role in affecting their mesomorphic properties. Furthermore, for current complexes, induced polymorphic phases have been found by introducing the chlorine atom.

New Nitro-Laterally Substituted Azomethine Derivatives; Synthesis, Mesomorphic and Computational Characterizations.

Two new homologues series, based on two rings of the azomethine central group bearing the terminal alkoxy group of various chain lengths, were prepared. The alkoxy chain length varied between 6 and 16 carbons. The other terminal wing in the first series was the F atom, and the compound is named N-4-florobenzylidene-4-(alkoxy)benzenamine (In). The second group of compounds included a lateral NO2 substituent in addition to the terminal F atom, named N-(4-fluoro-3-nitrobenzylidene)-4-(alkyloxy)aniline (IIn). Mesomorphic and optical properties were carried out via differential scanning calorimetry (DSC) and polarized optical microscopy (POM). Elemental analyses, FT-IR, and NMR spectroscopy were carried out to elucidate the molecular structures of the synthesized groups. Mesomorphic investigations indicated that all the synthesized homologues (In) were monomorphic, possessing the smectic A (SmA) phase monotropically, while the second group (IIn) members were non-mesomorphic. The experimental data indicated that the formation of the mesophase is affected by the protrusion of the lateral nitro group. The disruption of the mesophase in the second group was attributed to the increase of its molecular width, which affects its lateral intermolecular interactions. The computational simulations were in agreement with the experimental data. On the other hand, the location of NO2 group within the molecular geometry increased the melting temperature of the molecule, and thus, affected their thermal and physical properties. By discussing the estimated parameters, it was found that the molecular architecture, the dipole moment, and the polarizability of the investigated compounds are highly affected by the electronic nature and position of the terminal and lateral substituents as well as their volumes.

Experimental and Computational Approaches of Newly Polymorphic Supramolecular H-Bonded Liquid Crystal Complexes.

New 1:2 liquid crystalline supramolecular H-bonded complexes (SMHBCs) were synthesized through double H-bond interactions between 4-(nicotinoyloxy) phenyl nicotinate as the base component and two molecules of 4-n-alkoxybenzoic acid (An). The base component was expected to be in two conformers according to the orientation of the N atom and the carboxylate group, syn conformer (I) and anti-conformer (II). DFT calculations revealed that only one of the two possible conformers of I exists, and the addition of the two molecules of the alkoxy acids (A n) did not affect its conformation. The mesomorphic properties of all of the prepared complexes (I/A n), bearing different terminal flexible alkoxy chains were investigated, and the formation of the H-bonds were confirmed by differential scanning calorimetry (DSC), and the phases were identified by polarized optical microscopy (POM), and FT-IR spectroscopy. Highly thermally stable mesophases possessing broad temperature ranges were observed for all investigated complexes compared to their individual components. Depending on the length of the terminal flexible alkoxy chain, the prepared SMHBCs were shown to exhibit di- or tri-morphic enantiotropic mesophases. The effect of replacing one of the -COO- connecting units by an azo group (-N=N-) in the basic molecule (I), on the mesomorphic properties has been investigated experimentally (via DSC) and theoretically (via DFT). The DFT calculations revealed that the polarizability, the dipole moment, and the aspect ratio of the investigated SMHBCs are lower than those of their corresponding ester/azo analogs. All these factors rationalize the enhanced smectic mesophase ranges of the complexes compared with those of the ester/azo analogs. The high aspect ratios and dipole moments of the SMHBCs of the azo derivative enforces the lateral intermolecular attraction that permits the formation of the more ordered smectic C mesophase with respect to the enhanced polymorphic mesophases of the diester derivative.