Transformation of a kinetically controlled nematic phase of a linear polymer into one which is thermodynamically controlled via cyclization [1]

The synthesis and characterization of cyclic main chain liquid-crystalline oligomers based on 1-(4-hydroxy-4'-biphenyl)-2-(4-hydroxyphenyl)butane (TPB) with 1,7-dibromoheptane (TPB-7(c)] are described. These oligomers were synthesized by the phase transfer catalysed polyetherification of TPB with 1,7-dibromoheptane under high dilution conditions and separated by column chromatography. Their cyclic structure was confirmed by 200 MHz ¹H NMR spectroscopy. The mesomorphic behaviour of TPB-7(c) was characterized by differential scanning calorimetry and polarized optical microscopy. The cyclic dimer is only crystalline, while the cyclic trimer, tetramer and pentamer exhibit an enantiotropic nematic mesophase. The high molecular weight linear homologue TPB-7(1) exhibits a nematic mesophase which has an isotropization transition temperature located in the very close proximity of its glass transition temperature. Therefore, this nematic phase is kinetically controlled. Due to the higher rigidity of cyclics versus linear structures the cyclic trimer, tetramer and pentamer exhibit higher isotropization transition temperatures than their linear homologue. Subsequently, the kinetically controlled nematic mesophase of the linear homologue is transformed into a thermodynamically controlled phase via cyclization.     

Novel memory effect found in nematic liquid crystal/fine particle system

Novel liquid crystalline composites composed of a nematic two-frequency-addressing liquid crystal and organized clay mineral (about 1 wt %) have been prepared. The particles of clay mineral were dispersed homogeneously in the liquid crystal. The composite cells became transparent within 50ms when a 60 Hz electric field was applied. The transparent state was maintained after the field was switched off. It transformed into a turbid light scattering state by applying 1.5 kHz electric field which caused dynamic scattering in the cell. The light transmittance of both memory states did not change after 20 h without the electric field.     

Resolution enhancement of pump–probe microscope with an inverse-annular filter

Optical Review - Optical pump–probe microscopy can provide images by detecting changes in probe light intensity induced by stimulated emission, photoinduced absorbance change, or...     

Deciphering UV-induced DNA Damage Responses to Prevent and Treat Skin Cancer

Ultraviolet (UV) radiation is among the most prevalent environmental factors that influence human health and disease. Even 1 h of UV irradiation extensively damages the genome. To cope with resulting deleterious DNA lesions, cells activate a multitude of DNA damage response pathways, including DNA repair. Strikingly, UV-induced DNA damage formation and repair are affected by chromatin state. When cells enter S phase with these lesions, a distinct mutation signature is created via error-prone translesion synthesis. Chronic UV exposure leads to high mutation burden in skin and consequently the development of skin cancer, the most common cancer in the United States. Intriguingly, UV-induced oxidative stress has opposing effects on carcinogenesis. Elucidating the molecular mechanisms of UV-induced DNA damage responses will be useful for preventing and treating skin cancer with greater precision. Excitingly, recent studies have uncovered substantial depth of novel findings regarding the molecular and cellular consequences of UV irradiation. In this review, we will discuss updated mechanisms of UV-induced DNA damage responses including the ATR pathway, which maintains genome integrity following UV irradiation. We will also present current strategies for preventing and treating nonmelanoma skin cancer, including ATR pathway inhibition for prevention and photodynamic therapy for treatment.     

Synthesis of nylon 6–clay hybrid by montmorillonite intercalated with ϵ-caprolactam

It was found that montmorillonite was intercalated with ?-caprolactam. X-ray diffraction revealed that the chain axes of the ?-caprolactam were parallel to the montmorillonite plates. The intercalated montmorillonite was swollen by molten ?-caprolactam at 200°C. ?-Caprolactam and 6-aminocaproic acid (accelerator) were polymerized with the intercalated montmorillonite at 260°C for 6 h, yielding a nylon 6-clay hybrid. X-ray diffraction and transmission electron micrography revealed that the silicate layers of the hybrid were uniformly dispersed in the nylon 6 matrix. Mechanical properties of the hybrid were improved. The strength and the modulus of the hybrid increased compared with the previously reported nylon 6 clay-hybrid (NCH) synthesized by montmorillonite intercalated with 12-aminolauric acid. The heat distortion temperature (HDT) of the hybrid was 164°C, which was 12°C higher than that of NCH. © 1993 John Wiley & Sons, Inc.     

Flow behaviours of liquid crystal droplets on polyimide alignment layers

The flow behaviours of liquid crystal droplets on polyimide alignment layers and during assembling between two substrates have been directly observed. The droplet shape became elliptical with time on the rubbed polyimide layer, where the major axis of the elliptical droplet was parallel to the rubbing direction. Rubbing enhanced the wettability between the liquid crystal and the polyimide layer. During the assembling process, the liquid crystal droplets elliptically splayed out between two substrates assembled antiparallel. The liquid crystal molecules preferentially flowed parallel to the rubbing direction in a two-step flow mode; the droplet diameter slowly increased at the first step, and then it rapidly increased at the second step. The two-step flow of the droplet proved to be due to the thickness of the droplet dependent on the rubbing strength.     

Viscoelastic properties of dilute nematic mixtures containing cyclic and hyperbranched liquid crystal polymers dissolved in a nematic solvent

The twist and bend viscosities of dilute solutions of cyclic and hyperbranched liquid crystal polymers (LCP) dissolved in low molar mass nematic solvents were determined via dynamic light scattering analysis. These results were compared to those of linear chains with similar chemical repeat structures. The nematic solvent used was 4′-pentyloxy-4-cyanobiphenyl (50CB). The cyclic LCP oligomers, Cy TPB10, have a mesogenic group, 1-(4-hydroxy-4′-biphenyl)-2-(4-hydroxyphenyl) butane, separated by flexible decamethylene spacers. The twist viscosity of the cyclic Cy-TPB10 oligomers increases with molecular weight more strongly than the linear, TPB-10, suggesting that the hydrodynamic behavior of Cy-TPB10 is closer to that of a rigid rod than TPB10. Surprisingly, the intrinsic bend viscosity [η_bend] of Cy-TPB10 decreases with molecular weight, in contrast to the positive dependence for linear TPB10. This may reflect the higher strain energy in the smaller ring sizes. The hyperbranched LCP, TPD-b-8, is also based on the mesogen 10-bromo-1-(4-hydroxy-4′-biphenyl)-2(4-hydroxyphenyl) decane but with octyl groups at the chain ends. We compare the viscoelastic behavior of dilute nematic solutions of TPD-b-8 in 50CB against that of a linear main-chain LCP, TPB7, with the same mesogenic group but with heptamethylene spacers. The viscometric properties of TPD-b-8/50CB and TPB7/50CB are quite different. The results suggest that each chain is prolate (i. e., R_∥ > R_⊥) but that TPD-b-8 has a smaller chain anisotropy than that of TPB7. © 1995 John Wiley & Sons, Inc.     

Change of zonal flow spectra in the JIPP T-IIU tokamak plasmas

When Ohmically heated low-density plasmas are additionally heated by higher-harmonics ion-cyclotron-range-of frequency heating, heated by neutral beam injection, or strongly gas puffed, the intensity of zonal flows in the geodesic acoustic mode frequency range in the tokamak core plasma decreases sharply and that of low-frequency zonal flow grows drastically. This is accompanied by a damping of the drift wave propagating in the electron diamagnetic drift direction, turbulence by trapped electron mode (TEM), and the increase of the mode propagating to ion diamagnetic drift direction (ITG). In the half-radius region, TEM and high-frequency zonal flows remain intense in both OH and heated phases. ITG and low-frequency zonal flows grow in heated plasmas, suggesting a strong coupling between ITG and low-frequency zonal flow.