Determination of ionizable groups of proteins by potentiometric titration in concentrated solutions of guanidine hydrochloride

A linearization method based on modified Gran functions, and a general nonlinear regression program were used to study potentiometric titration curves of denatured ovalbumin and lysozyme in 6 mol L^–1 guanidine hydrochloride medium with the aim of determining the ionizable species. With both numerical techniques it was possible to determine the sum of the carboxylic groups, the imidazol, the α-amine, and the sum of ɛ-amine, phenolic and sulfhydryl groups, if the protein is completely denatured, and assumes a randomly coiled conformation. A total of 87.8 ± 2.5 and 20.7 ± 0.6 groups per mol were determined in the ovalbumin and lysozyme, respectively. These values are very close to the 88 and 21 groups expected by aminoacid composition of both proteins, indicating that all ionizable groups were exposed to the solvent. For ovalbumin the distribution of groups was very similar to that expected by the aminoacid composition, but for lysozyme some anomalies were observed, suggesting the existence of interactions between ionizable groups, altering the dissociation constants. Received: 9 December 1996 / Revised: 27 February 1997 / Accepted: 4 March 1997     

Magnetic behaviour of γ-Fe2O3 nanoparticles by mössbauer spectroscopy and magnetic measurements

-Fe₂O₃ nanoparticles with varying state of dispersion in a polymer have been investigated by Mössbauer spectroscopy, static magnetic measurements at low applied field, and alternative susceptibility measurements over a large range of frequencies (2×10^–2–10⁴ Hz). The dynamical behaviour was characterized through the variation of the blocking temperature with the characteristic time of the measurement. The Mössbauer blocking temperature was determined according to a procedure described. For quasi-isolated particles an Arrhenius law is demonstrated. Effects of interparticle interactions in concentrated and aggregated systems are satisfactorily explained by the previous model. Dependence of the superparamagnetic susceptibility on the experimental conditions interpreted using the Lorentz or Onsager fields is mentioned.     

Two-player simultaneous location game: Preferential rights and overbidding

Competitive location problems can be characterized by the fact that the decisions made by others will affect our own payoffs. In this paper, we address a discrete competitive location game in which two decision-makers have to decide simultaneously where to locate their services without knowing the decisions of one another. This problem arises in a franchising environment in which the decision-makers are the franchisees and the franchiser defines the potential sites for locating services and the rules of the game. At most one service can be located at each site, and one of the franchisees has preferential rights over the other. This means that if both franchisees are interested in opening the service in the same site, only the one that has preferential rights will open it. We consider that both franchisees have budget constraints, but the franchisee without preferential rights is allowed to show interest in more sites than the ones she can afford. We are interested in studying the influence of the existence of preferential rights and overbidding on the outcomes for both franchisees and franchiser. A model is presented and an algorithmic approach is developed for the calculation of Nash equilibria. Several computational experiments are defined and their results are analysed, showing that preferential rights give its holder a relative advantage over the other competitor. The possibility of overbidding seems to be advantageous for the franchiser, as well as the inclusion of some level of asymmetry between the two decision-makers.     

Flexible cellulose derivative PDLC type cells

In this work we perform a study of 250 ≈ μm thick flexible electro-optical PDLC type cells made from a biocompatible cellulose derivative film and several conductive substrates. The deposition of an ITO layer by reactive thermal evaporation on a polymeric substrate was referred to in the literature very recently and this type of coated substrate was used in the present work. In order to consider the influence of the substrates on the electro-optical behaviour of the cells, five cells were made using different substrates (three flexible polymers and two glass for comparison). Three of the substrates were coated under the same conditions, and the other two were commercially available substrates.     

Two negative minima of the first normal stress difference in a cellulose‐based cholesteric liquid crystal: Helix uncoiling

The shear rate dependence of material functions such as shear viscosity (η) and the first normal stress difference (N₁) were given and interpreted earlier by Kiss and Porter. Their widely accepted work revealed the possibility of having a negative minimum of N₁ for polymeric liquid crystals. In this work, we disclose for the first time the evidence of two negative N₁ minima on a sheared cellulosic lyotropic system. The lower shear rate minimum is ascribed to the uncoiling of the cholesteric helix, as theoretically predicted earlier. Our findings contribute also to the understanding of the other minimum already reported in the literature and attributed to the nematic director tumbling mode. Moreover, the elastic change that the LC‐HPC sample undergoes during the helix unwinding of the cholesteric structure is also by means of oscillatory measurements. This study is a contribution for the understanding of the structure‐properties relationship linked with the complex rheological behavior of chiral nematic cellulose‐based systems and may help to improve their further processing. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 821–830     

Shear‐induced lamellar phase of an ionic liquid crystal at room temperature

The phase behaviour of a number of N‐alkylimidazolium salts was studied using polarizing optical microscopy, differential scanning calorimetry and X‐ray diffraction. Two of these compounds exhibit lamellar mesophases at temperatures above 50°C. In these systems, the liquid crystalline behaviour may be induced at room temperature by shear. Sheared films of these materials, observed between crossed polarisers, have a morphology that is typical of (wet) liquid foams: they partition into dark domains separated by brighter (birefringent) walls, which are approximately arcs of circle and meet at “Plateau borders” with three or more sides. Where walls meet three at a time, they do so at approximately 120° angles. These patterns coarsen with time and both T1 and T2 processes have been observed, as in foams. The time evolution of domains is also consistent with von Neumann's law. We conjecture that the bright walls are regions of high concentration of defects produced by shear, and that the system is dominated by the interfacial tension between these walls and the uniform domains. The control of self‐organised monodomains, as observed in these systems, is expected to play an important role in potential applications.     

Electro‐optical cells using a cellulose derivative and cholesteric liquid crystals

A cellulose derivative/liquid crystal composite‐type electro‐optical cell using a commercial cholesteric liquid crystal (CLC) was investigated. The electro‐optical properties of the system were examined, i.e. the dependence on applied voltage of the reflected wavelength and the minimum and maximum transmissions. A thin film of the CLC was dispersed with a cross‐linked cellulose film of 25 µm thickness. In the voltage dependence of the reflected wavelength it was verified that there is a hysteresis in the reflected wavelength. The variation of the reflected wavelength with temperature was also determined. The results are analysed in the framework of similar systems described in the literature for CLC dispersed in a polymer matrix.     

Magnetic nanoscale aggregates of cobalt and nickel in MgO single crystals

The magnetic properties of Co and Ni nanosized aggregates formed after implantation of nickel and cobalt ions in magnesium oxide single crystals were investigated. The influence of the implantation energy and annealing treatments was characterized. The particle size distribution was determined from the combined analysis of the magnetic moment dependence on both magnetic field and temperature, and used to determine the magnetic anisotropy constant of the aggregates. The results for nickel aggregates indicate the presence of an antiferromagnetic layer after the annealing treatments.     

EPR spectroscopy of protein microcrystals oriented in a liquid crystalline polymer medium

Correlation of the g-tensor of a paramagnetic active center of a protein with its structure provides a unique experimental information on the electronic structure of the metal site. To address this problem, we made solid films containing metalloprotein (Desulfovibrio gigas cytochrome c(3)) microcrystals. The microcrystals in a liquid crystalline polymer medium (water/hydroxypropylcellulose) were partially aligned by a shear flow. A strong orientation effect of the metalloprotein was observed by EPR spectroscopy and polarizing optical microscopy. The EPR spectra of partially oriented samples were simulated, allowing for molecular orientation distribution function determination. The observed effect results in enhanced sensitivity and resolution of the EPR spectra and provides a new approach towards the correlation of spectroscopic data, obtained by EPR or some other technique, with the three-dimensional structure of a protein or a model compound.