Synthesis and thermal behaviour of salicylaldimine-based liquid crystalline symmetrical dimers

A series of symmetrical dimers consisting of salicylaldimine moieties connected by flexible alkylene central spacer via ether linkages has been synthesized. In order to validate the empirical rule suggested by Date et al. to account for the smectic behaviour of such dimers, the chain length of the terminal alkoxy chain has been kept constant (C₈) while the number of methylene units in the central spacer was varied from C₃ to C₁₁. Another aim of the present investigation was to understand structure-property relationship in these dimers in which the salicylaldimine mesogenic segment has been used for the first time in dimers. The mesomorphic behaviour of these dimers was evaluated using optical microscopy and differential scanning calorimetry and the structure of some of the mesophases has been further investigated with the help of X-ray diffraction. Our studies reveal that the dimers consisting of 3 to 8 methylene units in the flexible spacer show only smectic (smectic C and smectic A) phases. For the dimers containing 4, 6 and 8 methylene units in the central spacer, a unique filament growth pattern has been observed in the smectic A phase while cooling from the isotropic phase. The dimers containing of C₉ to C₁₁ methylene groups exhibit the nematic phase in addition to smectic modifications. This observation indicates that when the terminal chains are shorter than the spacer, the tendency to form smectic phases is not fully extinguished but is perhaps reduced.     

Dynamics of the two-dimensional melting transition of a liquid crystal confined in Anopore membranes

Dielectric measurements on a liquid crystal exhibiting the smectic A-crystal B transition and confined to Anopore membranes having 20 and 200 nm pore sizes are reported. The studies reveal that compared with the bulk, the confined material shows a decrease in transition temperature. More importantly, the confinement leads to a slowing of the relaxation mechanism by about three orders of magnitude.     

Collision induced and resonantly enhanced extra resonances in four-wave mixing in inhomogeneously broadened four level systems

Role of collisions in inducing and enhancing extra resonances in non-linear generation by four-wave mixing in inhomogeneously broadened four level systems is studied. It is shown that collision induced three and two-photon resonances can be enhanced further by tuning to exact one photon (non-absorbing) transitions between unpopulated upper levels. In addition we also find existence of collision induced interference dip at the three-photon resonance that arises due to complete cancellation of signal at the line center.     

On the variation of magnetic susceptibility of a molecular crystal with temperature: the 2,4,6-triphenylverdazyl system

Magnetic susceptibilities of spin-1/2 systems of orthorhombic and higher crystal symmetries have been numerically investigated while taking possible anisotropy in the coupling constants along different crystal axes into account. The work relies on the magnon-based theory of ferromagnetic (FM) and antiferromagnetic (AFM) crystal systems of types FFF, AFF, AAF, and AAA [J. Chem. Phys. 111, 9009 (1999)]. The AAF crystal, in particular, shows interesting changes in the temperature dependence of magnetic susceptibility when the ferromagnetic exchange coupling constant is varied. We especially show that the susceptibility anomalies of molecular crystals fit naturally within the framework of the extended magnon-theoretical formalism, and do not necessarily imply a FM --> AFM or a reverse phase transition. A real system, molecular crystal of 2,4,6-triphenylverdazyl (2,4,6-TPV), has been investigated here. It was previously interpreted as an AAF system from observed susceptibility data [Tomiyoshi et al., Phys. Rev. B 49, 16031 (1994)]. The trend of the temperature dependence of magnetic susceptibility studied in the present work also indicates that the crystal belongs to the AAF category with a less prominent FM exchange coupling constant. To reinforce our conclusions, we have adopted a two-pronged strategy. First, the geometry of the 2,4,6-TPV monomer has been optimized here by ab initio unrestricted Hartree-Fock (UHF) calculations using the STO-3G basis set. The optimized geometry is almost planar. A subsequent calculation has been carried out with the phenyl rings twisted out of the plane of the nitrogen atoms. The STO-3G optimized geometry, and the same geometry except for the twisted phenyl rings, have been used to perform ab initio coupled-cluster (UCCSD-T) calculations with the same basis, and UHF as well as density-functional (UB3LYP) calculations using the 6-31G basis set. The calculated data can easily rationalize the twists while the species remains in crystal. The magnetic category of the crystal has been unambiguously confirmed as AFA from ab initio UHF and UB3LYP calculations of the total energy in different spin states of dimers and trimers along the crystal axes. The computed energy values, however, fail to yield accurate estimates of the exchange coupling constants Ja, Jb, and Jc, because the latter are on the order of 1kBK corresponding to energy differences on the order of 10(-6) hartree between different spin states. In the second approach, the observed features of the susceptibility minimum and maximum have been used to determine the best values of the exchange coupling constants from the theoretical formulas for an anisotropic AFA crystal. The AFM (Ja and Jc) and FM (Jb) exchange coupling constants and the Neel temperature (TN) found from this analysis correspond to Ja + Jc = -1.05 kBK, Jb = 1.35 kBK, and TN = 1.75 K. The calculated J values significantly differ from those estimated from a linear Heisenberg chain model, but generate a susceptibility versus temperature graph that mimics the experimental plot.     

EPR of Mn2+ in cobalt fluosilicate hexahydrate

The EPR of Mn²⁺ in cobalt fluosilicate hexahydrate has been studied at room temperature. An axial spin-hamiltornian explained the observed spectrum. The presence of a single Mn²⁺ site in an octahedral oxygen environment was confirmed. A phase transition at ?55°C was observed.     

Structure of naphazoline nitrate

2-(l-Naphthylmethyl)-2-imidazoline nitrate, C₁₄H₁₅N₃O₃,M _r =273.29, orthorhombic,Pbca, a=12.033(4),b=14.387(4),c=15.913(4)Å,V=2754.9(4)Å₃,Z=8,D _m=1.32(3) (flotation),D _x=1.318 Mgm^–3, (CuK)=1.5418 Å,=7.45 cm^–1,F(000)=1152,T=296K, finalR=0.078,wR=0.058 for 1397 reflections withI> 2(I). The naphthalene ring exhibits orientational disorder. The N-HO hydrogen bonds involving both the nitrogen atoms of the imidazoline ring serve to form infinite chains of alternating naphazoline cations and nitrate anions.DCB Contribution No. 811.     

Estimation of pioglitazone hydrochloride and metformin hydrochloride in tablets by derivative spectrophotometry and liquid chromatographic methods

Two simple and accurate methods of analysis to determine pioglitazone hydrochloride (PIO) and mefformin hydrochloride (MET) in combined dosage forms were developed using second-derivative spectrophotometry and reversed-phase liquid chromatography (LC). PIO and MET in combined preparations (tablets) were quantified using the second-derivative responses at 227.55 nm for PIO and 257.25 nm for MET in spectra of their solutions in a mixture of methanol and acetonitrile (30 + 70). The calibration curves were linear [correlation coefficient (r) = 0.9984 for PIO and 0.9986 for MET] in the concentration range of 8-40 microg/mL for PIO and 4-12 microg/mL for MET. In the LC method, analysis was performed on a Hypersil ODS-C18 column with 5 microm particle size using the mobile phase acetonitrile-water-acetic acid (75 + 25 + 0.3), adjusted to pH 5.5 with liquor ammonia, at a flow rate of 0.5 mL/min. Measurement was made at a wavelength of 230 nm. Both the drugs were well resolved on the stationary phase, and the retention times were 8.5 min for PIO and 16.0 min for MET. The calibration curves were linear (r = 0.9933 for PIO and 0.9958 for MET) in the concentration range of 4-20 microg/mL for PIO and MET. Both methods were validated, and the results were compared statistically. They were found to be accurate, precise, and specific. The methods were successfully applied to the estimation of PIO and MET in combined tablet formulations.