Texture changes inside smectic-C droplets in azobenzene Langmuir monolayers

Preparation of Langmuir monolayers of a mixture of trans- and cis-isomers of an azobenzene derivative, 4-[4-[(4-octylphenyl)azo]phenoxy]butanoic acid, results in the segregation of birefringent trans-isomer domains embedded in an isotropic medium of cis-isomers. Brewster angle microscopy observations allow us to identify different textures inside the domains depending on surface pressure, temperature, and domain size. The evolution of the monolayer in the dark, from initial droplets formed after spreading to a stable stripe texture, is described. The dynamics of domain coalescence and some morphological transitions induced by temperature and surface pressure changes are also discussed. A simple theoretical model is included to supplement some of these experimental observations.     

Sterically and electrosterically stabilized emulsion polymerization. Kinetics and preparation

The principal subject discussed in the current paper is the radical polymerization in the aqueous emulsions of unsaturated monomers (styrene, alkyl (meth)acrylates, etc.) stabilized by non-ionic and ionic/non-ionic emulsifiers. The sterically and electrosterically stabilized emulsion polymerization is a classical method which allows to prepare polymer lattices with large particles and a narrow particle size distribution. In spite of the similarities between electrostatically and sterically stabilized emulsion polymerizations, there are large differences in the polymerization rate, particle size and nucleation mode due to varying solubility of emulsifiers in oil and water phases, micelle sizes and thickness of the interfacial layer at the particle surface. The well-known Smith-Ewart theory mostly applicable for ionic emulsifier, predicts that the number of particles nucleated is proportional to the concentration of emulsifier up to 0.6. The thin interfacial layer at the particle surface, the large surface area of relatively small polymer particles and high stability of small particles lead to rapid polymerization. In the sterically stabilized emulsion polymerization the reaction order is significantly above 0.6. This was ascribed to limited flocculation of polymer particles at low concentration of emulsifier, due to preferential location of emulsifier in the monomer phase. Polymerization in the large particles deviates from the zero-one approach but the pseudo-bulk kinetics can be operative. The thick interfacial layer can act as a barrier for entering radicals due to which the radical entry efficiency and also the rate of polymerization are depressed. The high oil-solubility of non-ionic emulsifier decreases the initial micellar amount of emulsifier available for particle nucleation, which induces non-stationary state polymerization. The continuous release of emulsifier from the monomer phase and dismantling of the non-micellar aggregates maintained a high level of free emulsifier for additional nucleation. In the mixed ionic/non-ionic emulsifiers, the released non-ionic emulsifier can displace the ionic emulsifier at the particle surface, which then takes part in additional nucleation. The non-stationary state polymerization can be induced by the addition of a small amount of ionic emulsifier or the incorporation of ionic groups onto the particle surface. Considering the ionic sites as no-adsorption sites, the equilibrium adsorption layer can be thought of as consisting of a uniform coverage with holes. The de-organization of the interfacial layer can be increased by interparticle interaction via extended PEO chains--a bridging flocculation mechanism. The low overall activation energy for the sterically stabilized emulsion polymerization resulted from a decreased barrier for entering radicals at high temperature and increased particle flocculation.     

Osteoarthritis subjects have differentiated lower extremity thermal skin response after the concurrent acute training session

Journal of Thermal Analysis and Calorimetry - This study investigated the thermal skin (Tsk) response of lower limbs in older adults with or without osteoarthritis before and after a concurrent...     

X-ray structural analysis and antitumor activity of new salicylic acid derivatives

Tetrakis-, tris-, bis-, and mono salicylic acid derivatives 1–4 were synthesized by reaction of methyl 2-hydroxy benzoate (methyl salicylate) with 2,2-bis (hydroxymethyl) propane-1,3-diol (pentaerythritol) in the presence of sodium. Yields of different salicyloyloxy derivatives were changed by varying the molar ratios of reactants. For compounds 2 and 3, X-ray structure analysis was performed, as well as molecular energy minimization, to define their conformation in terms of their energy minima. Comparison of crystal and energy minimized structures for these two compounds (2 and 3) revealed that the intramolecular hydrogen bonds play an important role, stabilizing conformation of the most part of the molecule. The antioxidant activity and cytotoxicity of the synthesized derivatives were evaluated in a series of in vitro tests, as well as 17β-hydroxysteroid dehydrogenase type 2 inhibition potency. Tetrakis salicyloyloxy derivative 1 expressed the highest antioxidant potency, tris salicyloyloxy derivative 2 was the best inhibitor of 17βHSD2 enzyme, while bis salicyloyloxy derivative 3 showed strong cytotoxicity against prostate and breast cancer cells with no cytotoxicity against healthy cells.     

Interfacial Chiral Selection by Bulk Species

A chiral selection process in a self‐assembled soft monolayer of an achiral amphiphile as a consequence of its interaction with chiral species dissolved in the aqueous subphase, is reported. The extent of the chiral selection is statistically measured in terms of the enantiomorphic excess of self‐assembled submillimeter domains endowed with well‐defined orientational chirality that is unambiguously resolved using optical microscopy. Our results show that the emergence of chirality is mediated by electrostatic interactions and significantly enhanced by hydrophobic effects. This chiral chemical effect can be suppressed and even reversed by opposing a macroscopic physical influence, such as vortical stirring. This result gives evidence for the crucial role of hydrodynamic effects in supramolecular aggregation.     

Production of biologically inert Teflon thin layers on the surface of allergenic metal objects by pulsed laser deposition technology

Allergic-type diseases are current nowadays, and they are frequently caused by certain metals. We demonstrated that the metal objects can be covered by Teflon protective thin layers using a pulsed laser deposition procedure. An ArF excimer laser beam was focused onto the surface of pressed PTFE powder pellets; the applied fluences were 7.5–7.7 J/cm². Teflon films were deposited on fourteen-carat gold, silver and titanium plates. The number of ablating pulses was 10000. Post-annealing of the films was carried out in atmospheric air at oven temperatures between 320 and 500 °C. The thickness of the thin layers was around 5 μm. The prepared films were granular without heat treatment or after annealing at a temperature below 340 °C. At 360 °C a crystalline, contiguous, smooth, very compact and pinhole-free thin layer was produced; a melted and re-solidified morphology was observed above 420 °C. The adhesion strength between the Teflon films and the metal substrates was determined. This could exceed 1–4 MPa depending on the treatment temperature. It was proved that the prepared Teflon layers can be suitable for prevention of contact between the human body and allergen metals and so for avoidance of metal allergy. Received: 12 June 2002 / Accepted: 13 June 2002 / Published online: 4 November 2002 RID="*" ID="*"Corresponding author. E-mail: bhopp@physx.u-szeged.hu     

Comparative time-resolved study of solid-state and liquid ablation of polyethylene-glycol 1000: temperature, viscosity and surface tension dependence

Comparative study of solid and liquid phase ablation on the same sample by time-resolved investigations is presented in this paper. Polyethylene-glycol (PEG) 1000 having relatively low melting point (35 °C) was used in our experiments. By varying the sample temperature in the 20–80 °C range we could study the ablation mechanism in both solid and liquid (below and above the melting point) state of matter. An ArF excimer laser (λ=193 nm, FWHM=20 ns) was used for ablation at 1.95 J/cm² fluence. Ablation processes were observed by transmission fast photographic arrangement. It was demonstrated that plasma development and expansion (primer ablation, in 0–50 ns time range), formation and propagation parameters of shock wave and contact front did not depend on sample temperature and state of matter. The secondary material ejection (between 1–100 μs) showed a strong temperature dependence. Material ejection in the case of solid target occurred in the form of dense material cloud, and in the form of splashing for liquid (molten) sample. The ejection velocity of splashed jets depended on the sample temperature, significantly. This can be due to the change of molten PEG 1000 viscosity. Received: 1 November 1999 / Accepted: 17 April 2000 / Published online: 5 July 2000     

Generation of frequency-chirped laser pulses by an electro-optic amplitude modulator

We propose a single electro-optic amplitude modulator to modulate both the intensity and the phase of the light of a diode laser to produce frequency-chirped light pulses in the nanosecond time range. The two-in-one property of the Mach–Zehnder type electro-optic amplitude modulator is used to create a specific device available for experiments with cooled atoms. The phase induced in each optical path of the Mach–Zehnder interferometer and the phase-to-intensity modulation ratio, the intrinsic chirp parameter of the device is determined by generating high order optical harmonics.     

Collective molecular precession induced by rotating illumination in photosensitive langmuir monolayers

Langmuir monolayers of an amphiphilic azobenzene derivative exhibit easily perturbable mesophases with long-range orientational order that couples strongly to linearly polarized light, resulting in symmetric photoaligned textures. Controlled rotation of the polarization plane induces continuous collective precession of the molecular field, which reveals the shear-thinning nature of the surface rotational viscosity. The dynamics is controlled by a balance between the strength of the optical coupling and viscous dissipation so that an increase in the rotational velocity results in a dampening of the synchronous anharmonic oscillations of the orientational field, as revealed by a space-time analysis of the Brewster angle microscopy images.     

Nanocrystalline alloys of Fe-Cu-Nb-Si-B after neutron irradiation

Transmission Mössbauer spectroscopy was used to study changes induced by irradiation of amorphous and nanocrystalline samples. In an as-cast sample neutrons mostly affect the orientation of a net magnetic moment. The average hyperfine field decreases towards higher neutron fluencies. In the case of the nanocrystalline samples a new disordered structure is created in the amorpous remainder corresponding to boride phases as it is shown in the samples isothermally heated from 1 to 8 hours. The structural changes of the amorphous remainder depend on the stage of crystallization and total neutron fluencies.