X-ray diffraction,optical birefringence,dielectric and phase transition properties of the long homologous series of nematogens 4-(trans -4′- n -alkylcyclohexyl) isothiocyanatobenzenes

The temperature dependence of density, refractive indices, apparent molecular length and intermolecular distance of 11CHBT, are reported, together with the static dielectric permittivities, ε∥, ε┴, ε _iso of 11CHBT and 12CHBT; the effect of chain length on various physical properties of the CHBT series is also discussed. All the temperatures T _m, T _NI and T _NCr show an odd-even (OE) effect, but transition enthalpies ΔH _m and ΔH _c show no such behaviour. T _m, T _NI and T _NCr and ΔH _m are found to increase with chain length, while ΔH _c shows a maxima at n = 6. At the common reduced temperature T* = 0.98 T_NI, the density of the compounds are found to decrease with increasing chain length while the polarizability parameters α_e, α_o and α increase. However, the volume expansion coefficient, polarizability anisotropy and normalized polarizability anisotropy show a distinct OE effect. Similarly, n _e decreases smoothly with chain length but n _o and Δn show an OE effect like ε┴ and Δε. The ratio ln ?P ₂? /ln ? P ₄? remains closer to Faber theory than MS theory. Effective dipole moments are found to be approximately constant in the series; antiparallel association is observed in all the members. Kirkwood correlation factors g┴ and Δg are found to exhibit an OE effect like ε∥ and ε∥, but g∥ and ε∥ show no such effect. The effects of substitution in the core and end polar group on these properties are also discussed.     

A nematic phase created in mixtures of polar smectics The effect of smectic layer properties

Phase diagrams of binary mixtures composed of compounds with the NCS terminal group (n-DBT, n-PBT, n-TPB (smectic A₁) or n-BT (smectic E₁)) and n-OCB, n-CB (smectics A_d) are presented. It is shown that the width of the nematic gap that separates the A₁ or E₁ phase region from the smectic A_d phase is related to the interaction energy of the molecules in the smectic layers and to the difference in the smectic layer spacings.     

Amplitude and phase fluctuation modes in the smectic Cα* phase of an antiferroelectric compound

Dielectric measurements have been carried out on the chiral smectic C_α (SmC_α*) phase of a MHPOBC analogous compound. Two relaxation modes have been observed in this phase for planar orientation of the molecules. One process has been observed at frequency lower than that of the soft mode of the chiral smectic A (SmA*) phase. This relaxation process is connected with the helicity of the SmC_α* phase. In the high‐frequency region, another relaxation process has been observed in the SmC_α* phase for which bias field dependence is similar to that of the soft mode at the SmA*–SmC* phase transition. The experimental observations are in agreement with a recently proposed dielectric theory for the SmC_α* phase and theoretical dielectric results obtained by numerical simulations. Thus, we report here experimental verification of two theoretically predicted dielectric modes in the SmC_α* phase.     

Subwavelength resonant dielectric nanoparticles with high refractive indices

This paper aims at understanding the nature of the subwavelength resonant frequencies of dielectric particles with high refractive indices. It is proved that for an arbitrary shaped particle, these subwavelength resonant frequencies can be expressed in terms of the eigenvalues of the Newtonian potential associated with its shape. The enhancement of the scattered field at the resonant frequencies is shown. The hybridization of the subwavelength resonant frequencies of a dimer consisting of high refractive index dielectric nanoparticles is also characterized.     

Structural and magnetic study of RFe0.5V0.5O3 (R=Y, Eu, Nd, La) perovskite compounds

B-site disordered RFe_0.5V_0.5O₃ compounds, with R=La, Nd, Eu and Y, have been prepared by solid-state reaction technique and their structures and magnetic properties have been investigated through X-ray powder diffraction, time-of-flight neutron powder diffraction and magnetization measurements at temperatures ranging from 5 to 700 K. The four compounds can be described as distorted perovskites with space group symmetry Pbnm and a⁺b⁻b⁻ tilt system. The studied compounds also show antiferromagnetic ordering with Neel temperatures of 299, 304, 304, and 335 K respectively. The magnetic structures of R=La, Nd and Y compounds were determined from the neutron powder diffraction as G_z with observed magnetic moments of 2.55, 2.54 and 2.69μ_B at 30, 40 and 40 K, respectively.     

Porous xerogels with a bifunctional surface layer of the composition ≡Si(CH<Subscript>2</Subscript>)<Subscript>3</Subscript>SH/≡Si(CH<Subscript>2</Subscript>)<Subscript>2</Subscript>H<Subscript>3</Subscript>

The sol-gel method with ethanol as a solvent and fluoride ion as a catalyst was used to prepare polysiloxane xerogels containing both 3-mercaptopropyl and n-propyl groups in the surface layer. An increase in the relative amount of n-propyltriethoxysilane in the initial reaction solution was found to result in the formation of xerogels with developed porous structures, which was accompanied by an increase in the specific surface area from 370 to 550 m²/g; simultaneously, other porous structure parameters such as sorption volume and pore size exhibited a tendency to increase. Atomic-force microscopy was used to show that the xerogels synthesized comprised aggregates of mean size 30 nm. An analysis of the IR and ¹³C cross-polarization magic angle spinning NMR data led us to conclude that the surface layer of bifunctional xerogels contained not only 3-mercaptopropyl and n-propyl groups but also silanol groups, part of nonhydrolyzed alkoxy groups, and H-bonded water molecules. The ²⁹Si cross-polarization magic angle spinning NMR spectra revealed the presence of structural units of the compositions T¹ [(≡SiO)Si(OR’)₂(CH₂CH₂CH₃) and/or (≡SiO)Si(OR’)₂(CH₂)₃SH, R’ = H, OCH₃, or OC₂H₅], T² [(≡SiO)₂Si(OR’)(CH₂CH₂CH₃) and (≡SiO)₂Si(OR’)(CH₂)₃SH], and T³ [(≡SiO)₃SiCH₂CH₂CH₃ and (≡SiO)₃Si(CH₂)₃SH] in the xerogels synthesized.     

Synthesis, photophysical studies and anticancer activity of a new halogenated water-soluble porphyrin

A water-soluble halogenated porphyrin, namely 5,10,15,20-tetrakis(2-chloro-3-sulfophenyl)porphyrin (TCPPSO(3)H), was prepared and evaluated as sensitizer for photodynamic therapy (PDT). Photophysical properties of TCPPSO(3)H, such as high photostability, long triplet lifetime and high singlet oxygen quantum yield suggest high effectiveness of this class of halogenated porphyrins in PDT. TCPPSO(3)H is non-toxic in the dark and causes a significant photodynamic effect examined against MCF7 (human breast carcinoma), SKMEL 188 (human melanoma) and S91(mouse melanoma) cell lines upon red light irradiation (cutoff < 600 nm) at low light doses. Time-dependent cellular uptake of TCPPSO(3)H reached plateau at 120 min and was the highest for S91, 20% lower for MCF7 and 70% lower for SKMEL 188. Our results show that this halogenated water-soluble porphyrin is an efficient photosensitizer and reveal the potential of this class of compounds as PDT agents.     

Structural,optical and dynamical properties of a high birefringence laterally fluorinated terphenyl isothiocyanate

A doubly fluorinated isothiocyanato butyl terphenyl compound exhibiting a broad range of the nematic and a narrow range of smectic phase has been investigated by X-ray, dielectric and optical methods and compared with the properties of singly and doubly fluorinated ethyl homologues to see the effect of fluorination and chain flexibility. Contrary to common perception, weak antiparallel correlation of molecules is observed in each compound both from X-ray and dielectric studies. Observed dielectric anisotropy is strong enough to ensure a driving voltage suitable for thin film transistor-based liquid crystal display. Measured splay elastic constant suggests that the present compound will exhibit the fastest response. Flip-flop mode relaxations are observed in a few hundred kHz to MHz range. All the compounds exhibit high birefringence (0.373–0.331). They also show high order parameters at low temperatures. These compounds are expected to be suitable for formulating high birefringence nematic mixtures for fast switching displays.     

Fullerene derived molecularly imprinted polymer for chemosensing of adenosine-5′-triphosphate (ATP)

For molecular imprinting of oxidatively electroactive analytes by electropolymerization, we used herein reductively electroactive functional monomers. As a proof of concept, we applied C₆₀ fullerene adducts as such for the first time. For that, we derivatized C₆₀ to bear either an uracil or an amide, or a carboxy addend for recognition of the adenosine-5′-triphosphate (ATP) oxidizable analyte with the ATP-templated molecularly imprinted polymer (MIP-ATP). Accordingly, the ATP complex with all of the functional monomers formed in solution was potentiodynamically electropolymerized to deposit an MIP-ATP film either on an Au electrode of the quartz crystal resonator or on a Pt disk electrode for the piezoelectric microgravimetry (PM) or capacitive impedimetry (CI) determination of ATP, respectively, under the flow-injection analysis (FIA) conditions. The apparent imprinting factor for ATP was ∼4.0. After extraction of the ATP template, analytical performance of the resulting chemosensors, including detectability, sensitivity, and selectivity, was characterized. The limit of detection was 0.3 and 0.03 mM ATP for the PM and CI chemosensor, respectively. The MIP-ATP film discriminated structural analogues of ATP quite well. The Langmuir, Freundlich, and Langmuir–Freundlich isotherms were fitted to the experimental data of the ATP sorption and sorption stability constants appeared to be nearly independent of the adopted sorption model.     

The molecular and crystal structure of a polar mesogen 4-cyanobiphenyl-4′-hexylbiphenyl carboxylate

The crystal structure of the compound 4-cyanobiphenyl-4′-hexylbiphenyl carboxylate (6CBB), which exhibits both monolayer smectic A and nematic phases, has been determined by direct methods using single crystal X-ray diffraction data. The structure is triclinic with the space group P-1 and Z=2. The unit cell parameters are a=9.3511(7)?Å, b=11.2456(7)?Å, c=13.1417(6)?Å, α=85.872(4)°, β=76.258(5)° and γ=70.697(5)°. The molecule is found to be slightly bow-shaped although the alkyl chain is in all-trans conformation. The phenyl rings in 6CBB are non-coplanar. The packing of the molecules in the crystalline state is found to be a precursor to the smectic A phase structure. Comparison of crystal structures and packing of the four-ring 6CBB with those of the two-ring nCB or nOCB compounds has been made to explain the observed phase behaviour.