Relationship between Hansen Solubility Parameters and Lewis Acid–Base Parameters of Polymers

Hansen solubility parameters and Lewis acid–base parameters are two groups of parameters that are used to characterize solvents, polymers, and the interactions between polymer matrix and additives. Although their definitions are very different, they can well explain the interactions in polymer composites. Therefore, some relations should exist between them. In this paper, the Lewis acid–base parameters of three polymers (PET, PS, and PVA) were measured by IGC technique. Including five other polymers (PE, PMMA, PC, PVC, and PVDF), the relationship between total Lewis acid–base intensity (K _a+K _b) and total polar intensity (δ² _p+δ² _h) of the eight kinds of polymers are discussed, where δ_p and δ_h are the polar components of the Hansen parameters. It is found that these polymers are all Lewis base polymers according to the values of K _b/K _a. Generally, a polymer with a larger (K _a+K _b) value possesses a higher (δ² _p+δ² _h) value.     

Influence of the nematic order on the rheology and conformation of stretched comb-like liquid crystalline polymers

We have studied the rheology and the conformation of stretched comb-like liquid-crystalline polymers. Both the influence of the comb-like structure and the specific effect of the nematic interaction on the dynamics are investigated. For this purpose, two isomers of a comb-like polymetacrylate polymer, of well-defined molecular weights, were synthesized: one displays a nematic phase over a wide range of temperature, the other one has only an isotropic phase. Even with high degrees of polymerization N, between 40 and 1000, the polymer chains studied were not entangled. The stress-strain curves during the stretching and relaxation processes show differences between the isotropic and nematic comb-like polymers. They suggest that, in the nematic phase, the chain dynamics is more cooperative than for a usual linear polymer. Small-angle neutron scattering has been used in order to determine the evolution of the chain conformation after stretching, as a function of the duration of relaxation t _r. The conformation can be described with two parameters only: , the global deformation of the polymer chain, and p, the number of statistical units of locally relaxed sub-chains. For the comb-like polymer, the chain deformation is pseudo-affine: is always smaller than (the deformation ratio of the whole sample). In the isotropic phase, has a constant value, while pincreases as tr. This latter behavior is not that expected for non-entangled chains, in which p varies as t _r ^1/2 (Rouse model). In the nematic phase, decreases as a stretched exponential function of t _r, while p remains constant. The dynamics of the comb-like polymers is discussed in terms of living clusters from which junctions are produced by interactions between side chains. The nematic interaction increases the lifetime of these junctions and, strikingly, the relaxation is the same at all scales of the whole polymer chain. Received 5 May 1999 and Received in final form 18 October 1999     

The permittivities of PVDF/PMMA blends at hydrostatic pressure

The complex permittivities of poly(vinylidene fluoride)/poly(methyl methacrylate) (PVDF/PMMA) blends have been measured under variation of temperature T(20°-60°C), frequency v(5 Hz-300 kHz), and hydrostatic pressure p (0-260 MPa). The values can be represented by a master curve with the shift factors △p/△ log (v/Hz) = ?140 MPa at room temperature and △ (1 /T) /△ log (v/Hz) = ?2. 10^?4 K^?1 at atmospheric pressure. The dependence of the activation energy △E _A on pressure p is then given by △E _A=(100 + 0.02 MPa^?1 p) kJ/mol. Furthermore, the results indicate that the β-relaxation of PVDF is due to motions in the crystal-amorphous interphase. The interactions between the two polymers, which are miscible at all compositions, disturb the correlations between the PVDF monomer units at that location as well as the mobility of the PMMA side group.     

The Role of Specific Side Groups and pH in Magnetization Transfer in Polymers

The nature of water–macromolecule interactions in aqueous model polymers has been investigated using quantitative measurements of magnetization transfer. Cross-linked polymer gels composed of 94% water, 3%N,N′-methylene-bis-acrylamide, and 3% functional monomer (acrylamide, methacrylamide, acrylic acid, methacrylic acid, 2-hydroxyethyl-acrylate, or 2-hydroxyethyl-methacrylate) were studied. Water–macromolecule interactions were modified by varying the pH and specific functional group on the monomer. The magnitudes of the interactions were quantified by measuring the rate of proton nuclear spin magnetization exchange between the polymer matrix and the water. This rate was highly sensitive to the presence of carboxyl side groups on the macromolecule. However, the dependence of the rate on pH was not consistent with simple acid/base-catalyzed chemical exchange, and instead, the data suggest that multiequilibria proton exchange, a wide distribution in surface group pKvalues, and/or a macromolecular structural dependence on pH may play a significant role in magnetization transfer in polymer systems. These model polymer gels afford useful insights into the relevance of chemical composition and chemical dynamics on relaxation in tissues.     

Specific radiation damage to acidic residues and its relation to their chemical and structural environment

Intense synchrotron radiation produces specific structural and chemical damage to crystalline proteins even at 100 K. Carboxyl groups of acidic residues (Glu, Asp) losing their definition is one of the major effects observed. Here, the susceptibilities to X‐ray damage of acidic residues in tetrameric malate dehydrogenase from Haloarcula marismortui are investigated. The marked excess of acidic residues in this halophilic enzyme makes it an ideal target to determine how specific damage to acidic residues is related to their structural and chemical environment. Four conclusions are drawn. (i) Acidic residues interacting with the side‐chains of lysine and arginine residues are less affected by radiation damage than those interacting with serine, threonine and tyrosine side‐chains. This suggests that residues with higher pK_a values are more vulnerable to damage than those with a lower pK_a. However, such a correlation was not found when calculated pK_a values were inspected. (ii) Acidic side‐chains located in the enzymatic active site are the most radiation‐sensitive ones. (iii) Acidic residues in the internal cavity formed by the four monomers and those involved in crystal contacts appear to be particularly susceptible. (iv) No correlation was found between radiation susceptibility and solvent accessibility.     

MOLECULAR STRUCTURE OF HETEROCYCLES: 17O NMR CHEMICAL SHIFTS: TORSION ANGLE RELATIONSHIPS IN 3-ALKYL SUBSTITUTED 4,5-DIHYDROISOXAZOLES AND ISOXAZOLES†

A quantitative relationship between the ¹⁷O substituent chemical shifts (SCS) of γ-alkyl substituents and the torsion angles calculated by the AM1 method is reported. A series of 3-alkyl substituted 5-trichloromethyl-5-hydroxy-4,5-dihydroisoxazoles and 5-trichloromethyl isoxazoles [where 3-alkyl substituents are Me, Et, n-Pr, iso-Bu, BrCH₂, iso-Pr, Br₂CH and tert-Bu] as model compounds were used.

     

A Pascal's triangle-like approach for the determination of characteristic polynomial coefficients of reciprocal graphs

Characteristic polynomial coefficients of three classes of graph, namely L_n + n(p), C_n + n(p) and K _1,n-1 + n(p), which are known to have reciprocal pairs of eigenvalues, have been shown to be generated by simple manipulation of the Pascal's triangle.     

Molecular Dynamics Simulations of Adsorption of Polymer Chains on the Surface of B<Subscript>m</Subscript>N<Subscript>n</Subscript> Graphyne-Like Monolayers

Molecular dynamics simulations are used here to study the interactions between B_mN_n graphyne-like monolayers and four different polymer chains. BN, B₁N₉, and B₂N₈ graphyne-like monolayers are selected from the family of B_mN_n graphyne-like monolayers. It is observed that increasing the number of B atoms in the structure of B_mN_n graphyne-like monolayers results in larger interaction energies of nanosheet/polymer systems. It is also shown that the polymer chains with the linear adsorbed configurations on the nanosheets have larger interaction energies with the nanosheets. Investigating the effect of number of polymer repeat units on the polymer/nanosheet interaction energy, it is observed that increasing the number of repeat units of polymers leads to enhancing the polymer/nanosheet interaction energy.     

Discovery of a narrow resonance state of the system K S K S at mass 1520 MeV

Data are presented which indicate the existence of a previously unknown narrow resonance near mass 1520 MeV, discovered while analyzing the system K _S K _S . The data were obtained at ITEP using the 6-m magnetic spectrometer in a beam of 40-GeV negative particles. The resonance is observed in π⁻ p and K ⁻ p interactions with a total statistical confidence of not less than 5 standard deviations. The width of this state is comparable to the mass resolution of the spectrometer (∼5 MeV). The mass is 1521.5±2.5 MeV. Estimates of the product σ·BR (K _S K _S ) give ∼5.0 nb in π⁻ p interactions and ∼250 nb in K ⁻ p interactions. From the fact that the production cross section of this resonance in the K ⁻ beam is approximately 50 times greater than the production cross section in the π⁻ beam, it can be concluded that this new state belongs to a system of mesons with hidden strangeness. Pis’ma Zh. éksp. Teor. Fiz. 70, No. 4, 242–246 (25 August 1999)     

The immunity of polymer-microemulsion networks

The concept of network immunity, i.e., the robustness of the network connectivity after a random deletion of edges or vertices, has been investigated in biological or communication networks. We apply this concept to a self-assembling, physical network of microemulsion droplets connected by telechelic polymers, where more than one polymer can connect a pair of droplets. The gel phase of this system has higher immunity if it is more likely to survive (i.e., maintain a macroscopic, connected component) when some of the polymers are randomly degraded. We consider the distribution p(σ) of the number of polymers between a pair of droplets, and show that gel immunity decreases as the variance of p(σ) increases. Repulsive interactions between the polymers decrease the variance, while attractive interactions increase the variance, and may result in a bimodal p(σ).     

Electronic interactions in two-dimensional polymers of the C60 fullerene

The electronic structure of tetragonal and rhombohedral polymers of the C₆₀ fullerene is investigated using x-ray emission spectroscopy. It is found that, compared to the C₆₀ molecular crystals, the formation of intermolecular covalent bonds in two-dimensional layers of the C₆₀ fullerene polymers leads to a broadening of the maxima in the CK _α x-ray emission spectra, a decrease in the density of high-energy states, and an increase in the width of the valence band of the polymer. The experimental data are interpreted by analyzing the results of the calculations performed within the density functional theory for the C₆₀ fullerene cage forming eight and twelve covalent bonds. It is shown that the electronic interactions between C₆₀ molecules in the polymerized layers are provided by two types of molecular orbitals located at energies 0.5–3.0 and ∼5.0 eV below the energy of the Fermi level.     

Observation of K+d correlations from pA collisions

Results of a first experiment on (K^+p) and (K^+d) correlations from proton-carbon (pC) and proton-deuteron (pd) interactions at beam energies above and much below the threshold for elementary kaon production in nucleon-nucleon reactions ( T _NN = 1580 MeV) are discussed. These data, obtained with the ANKE spectrometer at COSY-Jülich, provide first direct evidence for K⁺ production via the two-step mechanism and an indication for a cluster mechanism. It is shown that both processes contribute significantly in pC collisions at 1200 MeV, while they are strongly suppressed at 2300 MeV and also in pd-interactions at 1344 MeV. It is emphasized that the underlying kinematics can be exploited to distinguish between these reaction mechanisms. Received: 26 November 2002 / Accepted: 26 March 2003 / Published online: 20 May 2003     

Organic–inorganic polymer hybrids prepared by the sol-gel method

This review focuses on some aspects of organic-inorganic hybrid materials prepared by the sol-gel method. This field has been studied worldwide as one of the nanotechnologies, and is now of current interest for both organic and inorganic scientists. The elaboration of organic–inorganic polymer hybrid materials using the sol-gel process can be accomplished by various approaches. The simplest method is increasing the compatibility by using physical interactions, covalent bonding and compatibilizer between organic polymer and silica gel. Other novel approaches, such as an in-situ method, NHSG (Non- Hydrolysis Sol-Gel) process, and use of reactive polymer hybrids resulted in the preparation of novel transparent organic–inorganic polymer hybrid materials. Stimulus responsive polymer hybrids are also mentioned. Furthermore, nano-structured organic–inorganic polymer hybrids are created by using supermolecular and self-assembly of organic molecules or polymers recently. The obtained nano-structured hybrid materials showed unique properties that could not be found in amorphous hybrid materials. The possibilities and applications of organic–inorganic polymer hybrid materials are also described in this review.     

An analysis of absorption-desorption of volatile organic compounds by molecularly imprinted polymer films

A theoretical analysis of the experimental data on absorption (desorption) of volatile organic compounds by (from) molecularly imprinted polymer films was performed. The theoretical time dependences of the amount of absorbed analyte in a film were calculated using a system of equations with four kinetic parameters (Γ, K, K _sur , and C _eq ), which were determined by theoretically approximating the experimental data. The special features of the absorption-desorption process in a polymer film were suggested to be described using a parameter called the specificity coefficient. Specificity coefficients were determined for all the polymers and analytes studied. The specificity coefficients obtained from the chromatographing data were compared with the imprinting factors of chromatograms calculated from the experimental retention time values. An empirical linear dependence of specificity coefficients on imprinting factor values was obtained.     

Sensitive interferometer for determination of optical and thermal properties

A very sensitive interferometric technique is presented. It allows direct measurement of optical and thermal properties. The experimental set-up is very simple and acts essentially as an unfocused Fabry-Perot interferometer giving rise only to a central fringe. Measurement of (∂n/∂T)_p up to 10^-7 K^-1 is possible. Determination of (∂n/∂T)_p for some liquids, particularly for water and deuterium oxide, has been already performed and others, for ionic crystals, are under way.     

Analogs of Gallagher-Moszkowski bands in IBFFM — A relation to spectrum-generating supersymmetry?

The quantal analogs of the Gallagher-Moszkowski bands in the Interacting boson-fermion-fermion model (IBFFM) withSU (3) boson core are associated with the exact quantum numberKj _p+j_n and approximate quantum numberK-¦j _p-j_n¦ of IBFFM. For characteristic ratiosГ/δ it is shown that theK _c=0 band in even-even IBM system, theK=j _p andK=j _n bands in the corresponding odd-even (IBFM) systems and theK=j _p+j band in the corresponding odd-odd IBFFM system exhibit the supermultiplet pattern.     

Real-space renormalization group investigation of pure and disordered mixed spin Ising models ond-dimensional lattices

The mixed spin Ising model (spins =1/2 andS=1) ond-dimensional hypercubic lattices with nearest-neighbour exchange interactions is studied via a renormalization group transformation in position space. The phase diagrams in (L, K) space, i.e. in dependence of the bilinear (K) and the biquadratic (L) interaction coefficients, are qualitatively different ford=2 andd>2. For any dimensiond however it is found that all transitions are of second order. At zero-temperature (K=,L=), the ferromagnetic order disappears at (L/K)₀=2, which does not depend ond. Using an extension of this real-space renormalization group analysis we study the two-dimensional random disordered version of the above model.L is kept homogeneous and the bilinear interactionsK _ij are assumed to be independent random variables with distributionP(K _ij )=p(K _ij –K)+(1–p)(K _ij –K); whereK>0. The phase diagrams for different values ofp are obtained. At zero temperature, it is found that in the bond diluted model (=0) the value (L/K)₀ depends continuously onp, whereas in the random ±K interactions (=–1) (L/K)₀ is unique and does not depend onp.Supported by the agreement of cooperation between the DFGW. Germany and the CNR-Maroc     

Attenuation characteristics of a light attenuator combined by polarizers with different extinction ratios

This paper deals with a systematical analysis and an algorithm of attenuation characteristics of a light attenuator combined by n pieces of polarizers (n-LACP) whose extinction ratios are different from each other.The attenuation ratio expression of a two-LACP is deduced.We find that the monotonic attenuation interval depends on the first polarizer and that the attenuation range depends on the second one.For the three-LACP,a method for obtaining a monotonic attenuation interval is proposed.Moreover,the attenuation ratio expression is demonstrated.Analysis and experiment show that when the initial status of the three-LACP is at the maximum output,if the second or third polarizer rotates alone,the minimum attenuation ratios can reach K-1 2 and K-1 3,respectively,and if the first polarizer rotates,a minimum attenuation ratio of K-1 2 K-1 3 can be obtained (K 1,K 2 and K 3 represent the extinction ratios of the three polarizers in turn).Furthermore,the attenuation ratio expression of n-LACP and the relevant attenuation characteristics are proposed.The minimum attenuation ratio of an n-LACP is (K 2 K 3 ··· K n)-1.     

Temperature dependent photoluminescence down to 4.2 K in EuTFC

The temperature dependence of photoluminescence in Europium tris[3-(trifluoro-methylhydroxymethylene)-(+)-camphorate] (EuTFC) embedded in polymer films has been examined from 40 K down to 4.2 K with the goal of preparing sensor films for low-temperature thermal imaging. The behavior of EuTFC showed significant difference when based on polystyrene compared to poly(n-alkyl methacrylate)s. In poly(n-alkyl methacrylate)s prepared by standard methods for imaging applications, the photoluminescence is fully saturated below 30 K, whereas in polystyrene films there is a strong temperature dependence even down to 4.2 K. By optimizing the preparation procedure for films made of poly(butyl methacrylate) (PBMA) and poly(methyl methacrylate), also these polymers became very sensitive down to liquid helium temperature. The maximum temperature sensitivity of EuTFC in PBMA is found to be 1.0%/K at 4.2 K. The problem of delamination and cracking of the polymer film at cryogenic temperature is also avoided by the special preparation method.     

Structural role of polyethylene glycol in the formation of anatase nanocrystalline titania at low temperature

Anatase nanocrystalline TiO₂ thin films were obtained by a sol–gel dip‐coating method, in which the nanocrystallization is effected by a simple hot water treatment of the deposited films at temperatures below 90 °C under atmospheric pressure for 1 h. The dip‐coating sol was prepared by reacting titanium tetra‐n‐butoxide [Ti(OⁿBu)₄] with polyethylene glycol (PEG) in ethanol. Films obtained from a sol that do not contain PEG show no sign of crystallization, demonstrating the importance of PEG in the crystallization process. Raman studies of reaction dynamics show that PEG undergoes a nucleophilic substitution reaction replacing butoxy groups in Ti(OⁿBu)₄. Stoichiometric reactions of Ti(OⁿBu)₄ with PEG in polar and nonpolar solvents were performed, and they yielded different titanium–PEG hybrid polymers, which were isolated and characterized by various spectroscopic techniques such as IR, Raman, solid‐state NMR and MALDI‐TOF‐MS. NMR studies evidenced the location and the way in which PEG is bonded with titanium atoms in the titanium–PEG hybrid polymers. On the basis of these studies, we have proposed structures for these polymers. It is demonstrated that the structure of the obtained polymers plays an important role in the formation of anatase TiO₂ nanoparticles in hot water at temperatures below 90 °C under atmospheric pressure. Copyright © 2009 John Wiley & Sons, Ltd.