Intermolecular interactions of polymethacrylic acid with nonylphenoxypoly(ethoxy)ethanol in water solutions

On the basis of concentration pH dependences of binary solutions of anionic polyelectrolyte, polymethacrylic acid, and nonionic surfactant, nonylphenoxypoly(ethoxy)ethanol the role of hydrophobic interaction in the development of associative and aggregative processes was shown. It is established that the criterion of evaluation of the preferred contribution of hydrophobic interaction is the inflection point on the dependence of pH difference of the individual solutions of nonylphenoxypoly(ethoxy)ethanol and binary solutions of polymethacrylic acid and nonylphenoxypoly(ehoxy)ethanol on the logarithm of ratio of their concentrations.     

Dielectric relaxation by intramolecular motion in chain molecules

The internal dipolar correlation function for substituted ethanes is calculated by analysis of the rate of interconversion of rotational isomeric states. The states are defined by the location of the molecule on a tetrahedral lattice. The result differs from that of Beevers and Williams due to differences in the models. Reasons for preferring the present model are advanced. Procedures for applying the formalism to longer chains are outlined.     

Dielectric relaxation of liquid crystal molecules in anisotropic confinements

Abstract

The dielectric relaxation of the liquid crystal 4-n-pentyl-4′-cyanobiphenyl (K15) in the presence of an anisotropic network has been studied. Anisotropic networks containing K15 molecules were prepared by in situ polymerisation of liquid-crystalline diacrylate molecules in a mixture containing K15. By changing the network concentration, the effect of the network molecules on the behaviour of the K15 molecules, which were not chemically attached to the network, was investigated. With increasing network concentration it was found that the mean relaxation times of K15 molecules shifted to lower temperatures and that their distribution became broader. The activation energy associated with the relaxation, however, remained almost constant before showing some increase at high network concentrations.     

Dielectric relaxation of liquid crystal molecules in anisotropic confinements

The dielectric relaxation of the liquid crystal 4-n-pentyl-4'-cyanobiphenyl (K15) in the presence of an anisotropic network has been studied. Anisotropic networks containing K15 molecules were prepared by in situ polymerisation of liquid-crystalline diacrylate molecules in a mixture containing K15. By changing the network concentration, the effect of the network molecules on the behaviour of the K15 molecules, which were not chemically attached to the network, was investigated. With increasing network concentration it was found that the mean relaxation times of K15 molecules shifted to lower temperatures and that their distribution became broader. The activation energy associated with the relaxation, however, remained almost constant before showing some increase at high network concentrations.     

An isotopic effect in the dielectric spectra of Ark. 9/water systems

Dielectric spectra of H₂O and D₂O molecules in the L_α liquid crystalline phase of nonylphenoxy-poly(ethylenoxy)ethanol(Ark. 9)/water lyotropic systems have been investigated by dielectric time domain spectroscopy in the frequency range from 10 MHz to 10 GHz. By fitting the Cole-Cole formula to the dielectric spectra, obtained at different temperatures the dielectric increments, the relaxation times and the distribution parameters have been calculated. A strong retardation of water molecules has been found for the lamellar phase with low water content, i.e. 10 water molecules (H₂O or D₂O) per one Ark. 9 molecule. The relaxation times obtained at room temperature for the light and heavy water are 63 and 93 ps, respectively. It means that the retardation factor for D₂O molecules in the L_α phase is close to 1.5 and higher than that found for pure heavy water (1.25). Any decomposition of the dielectric spectra obtained seems to be unsubstantiated. The temperature dependences of the relaxation times acquired for both kinds of water obey the Arrhenius behaviour.     

Dielectric relaxation spectroscopy in poly(ethylene oxide)/water systems

The dielectric properties of poly(ethylene oxide) (PEO) are studied by dielectric relaxation spectroscopy measurements in wide ranges of frequency (5–2×10⁹ Hz) and temperature (193 − 300 K). PEO/water systems are also studied in a wide range of water content h (0 − 0.85 grams of water per grams of dry PEO). The measurements allow to distinguish between the dipolar secondary mechanism γ and effects related to free charge motion. The data are analyzed within the formalisms of permittivity, ϵ*, and electric modulus, M*. The water has been found to plasticize the dipolar process and to affect strongly the conduction process. A critical water content h_c, h_c = 0.13, has been found for the mechanism of charge transport.     

Dielectric relaxation spectroscopy in poly(hydroxyethyl acrylates)/water hydrogels

The electrical and dielectric properties of poly(hydroxyethyl acrylate), PHEA, hydrogels were studied by means of dielectric relaxation spectroscopy in wide ranges of frequencies (5–2 × 10⁹ Hz), temperatures (173–363 K) and water contents (0.065–0.46, g of water per gram of dry material). The secondary dipolar mechanisms (γ and β_sw) and the dc conductivity mechanism were studied in detail by analyzing the dielectric susceptibility data within the complex permittivity formalism, the modulus formalism, and the complex impedance formalism. For both mechanisms molecular mobility was found to increase with increasing temperature or increasing water content (T-f-h superposition principle). The energy parameters and the shape parameters of the response were determined for both mechanisms at several water contents and temperatures. The temperature dependence of dc conductivity was found to change from Vogel-Tamman-Fulcher (VTF) type to Arrhenius type at water contents of ca. 0.30. At water contents lower than about 0.30 the hydrogels are homogeneous whereas at higher water contents a separate water phase appears. In terms of the strong/fragile classification scheme our results suggest that the PHEA hydrogels are fragile systems. ©1995 John Wiley & Sons, Inc.     

Dielectric relaxation spectroscopy of macroporous IER beads suspensions dispersed in primary alcohols and water–ethanol mixtures

Dielectric measurements were first carried out on suspensions of ion-exchange resin beads dispersed in primary alcohols and water–ethanol mixtures in the frequency range 40 Hz–110 MHz. Due to the large bead radius, only Maxwell–Wagner (M–W) dielectric relaxations were observed. Regular dielectric behaviors were observed and phase parameters concerning constituent phases’ properties were determined through dielectric analysis, which revealed that the properties and the dispersing state of the bead are strongly dependent on the properties of dispersion medium. It is also found that dry beads cannot be completely soaked by alcohols with long aliphatic chain, and that suspension in water-rich mixture has similar dielectric behavior as in pure water due to the mixture's molecular construction. Then the dielectric behaviors of the following suspensions were measured as a function of time: suspensions of beads that have been equilibrated with water/ethanol redispersed in ethanol/water. The dielectric behaviors showed remarkable time dependency, characterized by distinct transitions on the curves of time dependent relaxation parameters. Based on the above understandings, the time dependent dielectric behaviors were analyzed in detail. It is showed that the time dependency directly reflected such processes as ion diffusion, solvent diffusion and solvent uptake that the systems undergo.     

Dielectric relaxation of some rigid polar molecules in a polystyrene matrix

Dielectric absorption studies have been carried out on solutions of twelve polar solutes dispersed in an atactic polystyrene matrix over a range of temperatures in the frequency region 50 to 10⁵Hz and in one case also in the range of 10⁴ to 10⁷Hz. Rigid molecules of varying size and molecular dipole moments halobenzenes, p-halotoluenes, p-halobiphenyls, p-nitrobiphenyl and p-bromoethylbenzene - have been examined. All these solute molecules have in common the fact that the molecular dipole moment lies along the main principal axis. The relaxation times and energy barrier parameters for molecular dipole relaxations are determined. The Eyring enthalpy of activation, ΔH_E, is found to range from 9 for fluorobenzene to 102 kJ mol⁻¹ for p-iodobiphenyl. Relaxation data of these molecules indicate a linear correlation between enthalpy and entropy of activation, and the former is found to depend upon the volume needed for the reorientation of molecules. Present results for halobenzenes and p-halotoluenes reveal a linear dependence of log (relaxation time) on the mean moment of inertia. The enthalpy data for these rigid molecules are useful in the study of flexible molecules when a decision has to be made as to whether the absorption is to be ascribed to molecular or intramolecular or overlap of the two relaxation processes.     

Dielectric relaxation processes in water mixtures of tripropylene glycol

Broadband dielectric measurements for anhydrous tripropylene glycol (3PG) and 96, 92, 84, 80, 74, 71, and 68 wt % 3PG-water mixtures are performed in the frequency range of 10(-2)-10(7) Hz and in the temperature range of 123-243 K. We examined the effect of adding water into anhydrous 3PG on relaxation dynamics. Apart from the two well-known relaxation processes, i.e., alpha and beta for anhydrous 3PG we observed new relaxation peak (beta') for all aqueous mixtures of 3PG. In addition we found the critical mole fraction of water x(w)=0.67 in which relaxation dynamics changes its behavior. According to the Sudo approach [S. Sudo et al., J. Non-Cryst. Solids 307-310, 356 (2002)], the behavior of relaxation processes was interpreted assuming the existence of three kinds of cooperative domains (CDs): containing only 3PG molecules, including only water molecules, and including both 3PG and water molecules, which molecules of each kind CD are bound by hydrogen bonds.     

Radiotracer studies on ion-selective electrode membranes containing metal complexes of a nonylphenoxypoly(ethyleneoxy)ethanol in poly(vinyl chloride) matrices

Radiotracer studies with (133)Ba, (45)Ca and (36)Cl are reported for PVC matrix membranes containing 2-nitrophenyl phenyl ether and the tetraphenylborate of a barium (or calcium) complex with a nonylphenoxypoly(ethyleneoxy)ethanol (NP), Antarox CO880. The results show that there is very limited permeation of radioactive barium and calcium ions through the membrane systems. However, the continued uptake (with time) of radioactive barium ions by the membranes (the uptake of calcium ion is less) suggests that in relation to selective electrode response the stabilization of ions by the NP ligand within the membrane is important in addition to the simple availability of membrane pathways for primary-ion transport through the membrane. Permselectivity to counter-ions is indicated by the non-permeation of radioactive chloride ions.     

Dielectric relaxation of poly(ester-ether-carbonate) multiblock terpolymers

The dielectric properties of a series of poly(ester-ether-carbonate) multiblock terpolymers have been investigated as a function of ether and carbonate composition in the frequency range of 10³–10⁶ Hz. The degree of polymerization of the samples was determined by viscosimetry measurements. The weight fraction, degree of crystallinity, and melting temperatures were characterized by means of x-ray diffraction and DSC methods. Dielectric behavior has been discussed in terms of Havriliak-Negami formulation. The variation of the dielectric properties with temperature has been associated with two relaxation processes: a) the -relaxation process observed at low temperature, which is associated to local motion of polar groups attached to both the soft and the hard segments, and b) the process assigned to long-range molecular motions above the glass transition temperature.     

Dielectric relaxation in concentrated solutions of poly(methyl methacrylate)

Measurements of dielectric relaxation have been made for a series of solutions of poly(methyl methacrylate) in toluene. A range of concentrations between 2% and 20% was used for a number of polymers of differing molecular weights. The dispersion was studied over the frequency range 10³-10⁶ Hz for temperatures between ?90°C and +20°C. It has been found that both the distribution of relaxation times and the activation energy increase with increasing concentration. The magnitudes of the effects vary with molecular weight. A significant observation is that the increase in dielectric constant with concentration is not linear.     

Dielectric relaxation of LC-thermotropic poly(ester imide)s

Two different series of poly(ester imide)s, which are distinguished from each other in the orientation of the ester linkages and show well-differentiated thermotropic behavior, are investigated by means of model calculations and dielectric relaxation spectroscopy. Model calculations show that the orientation of the ester linkages has a strong influence on the rotational energy barriers. The dielectric relaxation spectra of both series shows three relaxation regions in the temperature range between 100 and 400 K that have been identified as the α-, β- and γ-relaxation processes. A difference of about two orders of magnitude between the characteristic rates of the γ-relaxation is the main feature observed in the dielectric response. However, the β-relaxation shows very similar behavior for both series. The differences in the relaxation behavior in the solid state are interpreted on the basis of the rotational barriers deduced from the model calculation results. © 1997 John Wiley & Sons, Inc.     

Dielectric relaxation and molecular motion in poly(vinylidene fluoride)

The dielectric properties of poly(vinylidene fluoride) have been studied in the frequency range 10 Hz to 100 kHz at temperatures between ?196 and 150°C. Three dielectric relaxations were observed: the α relaxation occurred near 130°C, the β near 0°C, and the γ near ?30°C at 100 kHz. In the α relaxation the magnitude of loss peak and the relaxation times increased not only with increasing lamellar thickness, but also with decrease of crystal defects in the crystalline regions. In the light of the above results, the α relaxation was attributed to the molecular motion in the crystalline regions which was related to the lamellar thickness and crystal defects in the crystalline phase. In the β relaxation, the magnitude of the loss peak increased with the amount of amorphous material. The relaxation times were independent of the crystal structure and the degree of crystallinity, but increased slightly with orientation of the molecular chains by drawing. The β relaxation was ascribed to the micro-Brownian motions of main chains in the amorphous regions. The Arrhenius plots were of the so-called WLF type, and the “freezing point” of the molecular motion was about ?80°C. The Cole-Cole distribution parameter of the relaxation time α increased almost linearly with decreasing temperature in the temperature range of the experiment. The γ relaxation was attributed to local molecular motions in the amorphous regions.     

Exciton fission and fusion in bis(tetracene) molecules with different covalent linker structures

Bichromophoric molecules can support two spatially separated excited states simultaneously and thus provide novel pathways for electronic state relaxation. Exciton fission, where absorption of a single photon leads to two triplet states, is a potentially useful example of such a pathway. In this paper, a detailed study of exciton fission in three novel phenylene-linked bis(tetracene) molecules is presented. Their spectroscopy is analyzed in terms of a three-state kinetic model in which the singlet excited state can fission into a triplet pair state, which in turn undergoes recombination on a time scale longer than the molecule's radiative lifetime. This model allows us to fit both the prompt and delayed fluorescence decay data quantitatively. The para-phenylene linked bis(tetracene) molecules 1,4-bis(tetracen-5-yl)benzene (1) and 4,4'-bis(tetracen-5-yl)biphenylene (2) show intramolecular exciton fission with yields of approximately 3%, whereas no delayed fluorescence is observed for tetracene or the meta-linked molecule 1,3-bis(tetracen-5-yl)benzene 3. Analysis of the temperature-dependent fluorescence dynamics yields activation energies for fission of (10.0 +/- 0.6) kJ/mol for 1 and (4.1 +/- 0.5) kJ/mol for 2, with Arrhenius prefactors of (1.48 +/- 0.04) x 10(8) s(-1) for 1 and (1.72 +/- 0.02) x 10(7) s(-1) for 2. The observed trends in activation energies are reproduced by ab initio calculations of the independently optimized singlet and triplet energies. The calculations indicate that electronic coupling between the two tetracene units is primarily through-bond, allowing differences in fission rates to be qualitatively explained in terms of the linker structure as well. Our results show that it is important to consider the effects of the linker structure on both energy relaxation and electronic coupling in bichromophoric molecules. This study provides insight into the structural and energetic factors that should be taken into account in the design of exciton fission molecules for possible solar cell applications.     

Internal water molecules and magnetic relaxation in agarose gels

Agarose gels have long been known to produce exceptionally large enhancements of the water 1H and 2H magnetic relaxation rates. The molecular basis for this effect has not been clearly established, despite its potential importance for a wide range of applications of agarose gels, including their use as biological tissue models in magnetic resonance imaging. To resolve this issue, we have measured the 2H magnetic relaxation dispersion profile from agarose gels over more than 4 frequency decades. We find a very large dispersion, which, at neutral pH, is produced entirely by internal water molecules, exchanging with bulk water on the time scale 10(-8)-10(-6) s. The most long-lived of these dominate the dispersion and give rise to a temperature maximum in the low-frequency relaxation rate. At acidic pH, there is also a low-frequency contribution from hydroxyl deuterons exchanging on a time scale of 10(-4) s. Our analysis of the dispersion profiles is based on a nonperturbative relaxation theory that remains valid outside the conventional motional-narrowing regime. The results of this analysis suggest that the internal water molecules responsible for the dispersion are located in the central cavity of the agarose double helix, as previously proposed on the basis of fiber diffraction data. The magnetic relaxation mechanism invoked here, where spin relaxation is induced directly by molecular exchange, also provides a molecular basis for understanding the water 1H relaxation behavior that governs the intrinsic magnetic resonance image contrast in biological tissue.     

Dielectric properties of water clusters containing CO and NO molecules. Computational experiment

The absorption of CO and NO molecules by (H₂O)₂₀ clusters was studied by the method of molecular dynamics. In general, the clusters containing CO molecules are more stable mechanically, while the clusters with NO molecules are more stable against heating. The mobility of NO molecules in such clusters is higher than that of CO molecules. The total dipole moment, the static dielectric permeability, the number of active electrons in the clusters, and the specific number of hydrogen bonds between water molecules possess peak values when the number of doping molecules i = 6. IR absorption spectra mostly acquire a smooth shape at i > 6. Capture of CO and NO molecules by water cluster operates as anti-greenhouse effect.     

Dielectric relaxation in bulk and cylindrically confined octylcyanobiphenyl (8CB)

The dielectric relaxation spectrum over the frequency range 10² to 1.8×10⁹ Hz of 4-octyl-4'-cyanobiphenyl, 8CB, in bulk and confined to 200 nm diameter cylindrical pores is reported. We used matrices with parallel cylindrical pores, obtaining different alignments of the molecular director depending on the treatment. Results show that there are two relaxations in the isotropic phase and in the mesophases for parallel alignment and three for perpendicular alignment. The molecular origin of theses modes and the effect of the confinement on their dynamics are discussed. To compare properly the results for bulk and confined 8CB, a re-scaling of the experimental data is proposed.