Mihaela Avadanei

FTIR investigations of phase transitions in an asymmetric azomethine liquid crystal

The liquid crystalline (LC) behavior of a literature-reported asymmetric azomethine compound (4-[4-(n-butyloxy)-benzylideneimino]-chlorobenzene, Cl.O4) was investigated by using optical polarized light microscopy, differential scanning calorimetry and medium-wide angle X-ray diffraction. FTIR in attenuated total internal reflection configuration was employed to study the microstructural changes occurring during phase transitions of the azomethine. Spectral modifications, associated with molecular conformation rearrangements, allowing the change of the molecular shape from a LC organization to another, have been found. The spectral analysis gave significant evidences for the different phase transitions, thus proving the efficiency of such method for investigating LC materials.

Silicon-containing bis-azomethines: synthesis, structural characterization, evaluation of the photophysical properties and biological activity.

A new diamine, (dimethylsilanediyl)bis(methylene)bis(4-aminobenzoate) (1), containing dimethylsilane spacer, was prepared by the condensation of p-aminobenzoic acid with bis(chloromethyl)dimethylsilane. This was subsequently reacted with salicylaldehyde, 3-hydroxy-salicylaldehyde, and 3-methoxy-salicyladehyde, when corresponding Schiff bases (E)-(dimethylsilanediyl)bis(methylene)bis(4-((E)-(2-hydroxybenzilidene)amino)benzoate (2), (E)-(dimethylsilanediyl)bis(methylene)bis(4-((E)-(2-hydroxybenzilidene)amino)benzoate (3), and (E)-(dimethylsilanediyl)bis(methylene) bis(4-((E)-(2-hydroxy-3-methoxybenzilidene)amino)benzoate (4), respectively were formed. All the obtained compounds were structurally characterized by spectral (FT-IR, (1)HNMR, (13)CNMR) analyses and single crystal X-ray diffraction. Photophysical studies revealed that the new prepared Schiff bases are good UV light absorbing and fluorescent materials. Thus, they exhibit strong UV/Vis-absorption at 250-400nm and violet or orange emission, in sensitive dependence on the polarity of the solvents and the nature of the substituent (H, OH and OCH3) at the aromatic ring. The antimicrobial activity of these compounds was first studied in vitro by the disk diffusion assay against two species of bacteria and three fungi. The minimum inhibitory concentration was then determined with the reference of standard compounds. The results displayed that Schiff bases 3 and 4 having hydroxy- and methoxy-substituents on the aromatic ring were better inhibitors of both types of species (bacteria and fungi) than standard compounds, Caspofungin and Kanamycin.

Phase transitions of a monotropic azomethine liquid crystal investigated by ATR–FTIR spectroscopy

The liquid crystalline behavior of an azomethine, namely 4-chlorobenzylidene-4-n-butoxyaniline (M), was investigated by using optical polarized light microscopy, differential scanning calorimetry, thermo-optical analysis and powder X-ray diffraction at temperature. Fourier transform infrared spectroscopy (FTIR), in attenuated total internal reflection configuration, was employed in order to analyze the microstructural changes occurring during the azomethine phase transitions. Specific sensitive absorption bands were used to observe the smectic A (SmA) mesophase. The hexatic smectic B (SmB) mesophase was evidenced by recording the CH2 scissoring domain, belonging to the butoxy tail. It was assumed that the hexagonal ordering of the SmB mesophase was proven by the band evolution at 1468 cm−1. The azomethine linkage – monitored by the CH=N moiety stretching vibration – showed insignificant response to temperature due to its rigidity.

Structure and Photochemistry of N-Salicylidene-p-carboxyaniline Isolated in Solid Argon.

Infrared matrix isolation spectroscopy and DFT/B3LYP/6-311++G(d,p) calculations have been used to characterize the conformational space of the enol-imine and keto-amine tautomers of N-salicylidene-p-carboxyaniline (SCA) in both their E and Z isomeric forms. Monomers of SCA were isolated in an argon matrix (15 K), which was shown to contain only the most stable conformer of the E-enol isomer of the compound. The matrix-isolated E-enol was then subjected to in situ UV irradiation (λ = 335; 345 nm, provided by a laser/MOPO system, or λ > 235 nm, provided by a Hg(Xe) broad-band source), and the photoinduced processes probed by infrared spectroscopy. Two photoreaction channels were observed, with a branching ratio of ∼1:1, corresponding to E-enol → Z-enol isomerization and E-enol → E-keto tautomerization. Both processes were found to be rather effective, with practically complete consumption of the reactant after broad-band irradiation by 1 min only. Identification among the photoproduced species of the Z-enol conformer that differs from the reactant only by E-to-Z isomerization suggests the initial photoproduction of this conformer, which subsequently decays into the lowest energy Z-enol conformer (also identified experimentally). The E-enol → E-keto tautomerization requires an excited state intramolecular proton transfer and twisting about the exocyclic CC bond of the molecule. These processes most probably take place sequentially. However, in the present study the Z-keto isomer, which should act as intermediate in this sequence of processes, could not be detected, most probably due to its short lifetime under the used experimental conditions. On the contrary, the detailed structural and vibrational characterization of the photoproduced E-keto form was successfully achieved.

Crystal smectic E revisited for(E)-N-(biphenyl-4-ylmethylene)-4-butylaniline – mesomorphism, crystal structure and FTIR study

ABSTRACT This paper recalls the attention to an interesting compound having aromatic azomethine structure, namely: (E)-N-(biphenyl-4-ylmethylene)-4-butylaniline (PB4A). The molecular structure of PB4A was determined by X-ray single-crystal diffraction analysis. Besides the enantiotropic smectic B and nematic phases, this compound exhibits a monotropic crystal E phase. By polarising optical microscopy and differential scanning calorimetry, we confirmed the existence of these phases. FTIR measurements in attenuated total reflection configuration have been performed to investigate the evolution of significant absorption bands during phase transitions. Graphical Abstract

Morphological changes induced in erythrocyte membrane by the antiepileptic treatment: An atomic force microscopy study

Atomic force microscopy (AFM), a powerful characterization tool widely applied in problems in a large range of disciplines of the natural sciences, including cellular biology, was used to obtain information about the morphological changes induced in the erythrocyte membrane at the patients with epilepsy that undergo a long time treatment that operates upon one or several neuronal ionic channels, comparative with a healthy donor. This technique allowed non‐invasive imaging of erythrocyte membrane, revealing details and specific characteristics down to the nanometer level with characterization of surface texture parameters, such as average height, average roughness and coefficient of kurtosis at micrometer/nanometer resolution. For the healthy donor the AFM morphology appears to have all the characteristics of a normal red blood cell membrane. Instead, the closer examination of the erythrocytes membrane surface morphology for the samples collected from the patients diagnosed with epilepsy and treated with specific drugs did not reveal similar structures with those obtained for the healthy donor. The nanostructure of the membrane was drastically damaged, depending on the administrated treatment, and probably in time will affect their functionality. Therefore, the anticomital drugs have influence not only at the neuronal level, but also at the red blood cell level.