Quantitative model of the phase behavior of recombinant pH-responsive elastin-like polypeptides.

Quantitative models are required to engineer biomaterials with environmentally responsive properties. With this goal in mind, we developed a model that describes the pH-dependent phase behavior of a class of stimulus responsive elastin-like polypeptides (ELPs) that undergo reversible phase separation in response to their solution environment. Under isothermal conditions, charged ELPs can undergo phase separation when their charge is neutralized. Optimization of this behavior has been challenging because the pH at which they phase separate, pHt, depends on their composition, molecular weight, concentration, and temperature. To address this problem, we developed a quantitative model to describe the phase behavior of charged ELPs that uses the Henderson-Hasselbalch relationship to describe the effect of side-chain ionization on the phase-transition temperature of an ELP. The model was validated with pH-responsive ELPs that contained either acidic (Glu) or basic (His) residues. The phase separation of both ELPs fit this model across a range of pH. These results have important implications for applications of pH-responsive ELPs because they provide a quantitative model for the rational design of pH-responsive polypeptides whose transition can be triggered at a specified pH.

Gas-liquid two phase flow through a vertical 90deg elbow bend

Pressure drop data are reported for two phase air-water flow through a vertical to horizontal 90° elbow bend set in 0.026 m i.d. pipe. The pressure drop in the vertical inlet tangent showed some significant differences to that found for straight vertical pipe. This was caused by the elbow bend partially choking the inflow resulting in a build-up of pressure and liquid in the vertical inlet riser and differences in the structure of the flow regimes when compared to the straight vertical pipe. The horizontal outlet tangent by contrast gave data in general agreement with literature even to exhibiting a drag reduction region at low liquid rates and gas velocities between 1 and 2 m s -1. The elbow bend pressure drop was best correlated in terms of le/d determined using the actual pressure loss in the inlet vertical riser. The data showed a general increase with fluid rates that tapered off at high fluid rates and exhibited a negative pressure region at low rates. The latter was attributed to the flow being smoothly accommodated by the bend when it passed from slug flow in the riser to smooth stratified flow in the outlet tangent. A general correlation was presented for the elbow bend pressure drop in terms of total Reynolds numbers. A modified Lockhart-Martinelli model gave prediction of the data.

New catanionic surfactants based on 1-alkyl-3-methylimidazolium alkylsulfonates, [C(n)H(2n+1)mim][CmH2m+1SO3]: mesomorphism and aggregation

Anionic and cationic alkyl-chain effects on the self-aggregation of both neat and aqueous solutions of 1-alkyl-3-methylimidazolium alkylsulfonate salts ([C(n)H(2n+ 1)mim][CmH2m+1SO3]; n = 8, 10 or 12; m = 1 and n = 4 or 8; m = 4 or 8) have been investigated. Some of these salts constitute a novel family of pure catanionic surfactants in aqueous solution. Examples of this class of materials are rare; they are distinct from both mixed cationic-anionic surfactants (obtained by mixing two salts) and gemini surfactants (with two or more amphiphilic groups bound by a covalent linker). Fluorescence spectroscopy and interfacial tension measurements have been used to determine critical micelle concentrations (CMCs), surface activity, and to compare the effects of the alkyl-substitution patterns in both the cation and anion on the surfactant properties of these salts. With relatively small methylsulfonate anions (n = 8, 10 and 12, m = 1), the salts behave as conventional single chain cationic surfactants, showing a decrease of the CMC upon increase of the alkyl chain length (n) in the cation. When the amphiphilic character is present in both the cation and anion (n = 4 and 8, m = 4 and 8), novel catanionic surfactants with CMC values lower than those of the corresponding cationic analogues, and which exhibited an unanticipated enhanced reduction of surface tension, were obtained. In addition, the thermotropic phase behaviour of [C(8)H(18)mim][C8H18SO3] (n = m = 8) was investigated using variable temperature X-ray scattering, polarising optical microscopy and differential scanning calorimetry; formation of a smectic liquid crystalline phase with a broad temperature range was observed.

[Ag(NH3)(2)]ClO4: Crystal structures, phase transition, and vibrational spectra

[Ag(NH3)(2)](ClO4) is obtained from a solution of AgClO4 in cone. ammonia as colourless single crystals (orthorhombic, Pnmn, Z = 4, a = 795.2(1) pm, b 617.7(1) pm, c = 1298.2(2) pm, R-all = 0.0494). The structure consists of linearly coordinated cations, [Ag(NH3)(2)](+), stacked in a staggered conformation and of tetrahedral (ClO4)(-) anions. A first order phase transition was observed between 210 and 200 K and the crystal structure of the low-temperature modification (monoclinic. P2/m, Z = 4, a = 789.9(5) pm, b = 604.1(5) pm, c = 1290.4(5) pm, beta = 97.436(5)degrees, at 170 K, R-all = 0.0636) has also been solved. Spectroscopic investigations (IR/Raman) have been carried out and the assignment of the spectra is discussed.

On visco-elastic modelling of polyethylene terephthalate behaviour during multiaxial elongations slightly over the glass transition temperature

The mechanical response of Polyethylene Terephthalate (PET) in elongation is strongly dependent on temperature, strain and strain rate. Near the glass transition temperature Tg, the stress-strain curve presents a strain softening effect vs strain rate but a strain hardening effect vs strain under conditions of large deformations. The main goal of this work is to propose a viscoelastic model to predict the PET behaviour when subjected to large deformations and to determine the material properties from the experimental data. To represent the non–linear effects, an elastic part depending on the elastic equivalent strain and a non-Newtonian viscous part depending on both viscous equivalent strain rate and cumulated viscous strain are tested. The model parameters can then be accurately obtained trough a comparison with the experimental uniaxial and biaxial tests. The in?uence of the temperature on the viscous part is also modelled and an evaluation of the adiabatic self heating of the specimen is compared to experimental results.

Disorder-induced phase transition in a one-dimensional model of rice pile

We propose a one-dimensional rice-pile model which connects the 1D BTW sandpile model (Phys. Rev. A 38 (1988) 364) and the Oslo rice-pile model (Phys. Rev. Lett. 77 (1997) 107) in a continuous manner. We found that for a sufficiently large system, there is a sharp transition between the trivial critical behaviour of the 1D BTW model and the self-organized critical (SOC) behaviour. When there is SOC, the model belongs to a known universality class with the avalanche exponent tau = 1.53. (C) 1999 Elsevier Science B.V. All rights reserved.

Photon Production from the Vacuum Close to the Superradiant Transition: Linking the Dynamical Casimir Effect to the Kibble-Zurek Mechanism

The dynamical Casimir effect (DCE) predicts the generation of photons from the vacuum due to the parametric amplification of the quantum fluctuations of an electromagnetic field. The verification of such an effect is still elusive in optical systems due to the very demanding requirements of its experimental implementation. We show that an ensemble of two-level atoms collectively coupled to the electromagnetic field of a cavity, driven at low frequencies and close to a quantum phase transition, stimulates the production of photons from the vacuum. This paves the way to an effective simulation of the DCE through a mechanism that has recently found experimental demonstration. The spectral properties of the emitted radiation reflect the critical nature of the system and allow us to link the detection of the DCE to the Kibble-Zurek mechanism for the production of defects when crossing a continuous phase transition.

Electronically Scanned Rotman Lens Antenna with Liquid Crystal Phase Shifters

The performance of a Rotman lens, which forms fixed beams at 0°, ±15° and ±30°, is augmented using liquid crystal phase shifters to simultaneously steer each beam by up to ±7.5°. Measured results are used to demonstrate that the true time delay property of the antenna and voltage controlled phase shifters can be exploited to provide continuously scanned beams with full coverage over an angular range of ±37.5°, and with operation over the band 6-10 GHz.

Elucidation of a mechanism of cell lysis by chorhexidine : a biophysical approach

Chlorhexidine is an effective antiseptic used widely in disinfecting products (hand soap), oral products (mouthwash), and is known to have potential applications in the textile industry. Chlorhexidine has been studied extensively through a biological and biochemical lens, showing evidence that it attacks the semipermeable membrane in bacterial cells. Although extremely lethal to bacterial cells, the present understanding of the exact mode of action of chlorhexidine is incomplete. A biophysical approach has been taken to investigate the potential location of chlorhexidine in the lipid bilayer. Deuterium nuclear magnetic resonance was used to characterize the molecular arrangement of mixed phospholipid/drug formulations. Powder spectra were analyzed using the de-Pake-ing technique, a method capable of extracting both the orientation distribution and the anisotropy distribution functions simultaneously. The results from samples of protonated phospholipids mixed with deuterium-labelled chlorhexidine are compared to those from samples of deuterated phospholipids and protonated chlorhexidine to determine its location in the lipid bilayer. A series of neutron scattering experiments were also conducted to study the biophysical interaction of chlorhexidine with a model phospholipid membrane of DMPC, a common saturated lipid found in bacterial cell membranes. The results found the hexamethylene linker to be located at the depth of the glycerol/phosphate region of the lipid bilayer. As drug concentration was increased in samples, a dramatic decrease in bilayer thickness was observed. Differential scanning calorimetry experiments have revealed a depression of the DMPC bilayer gel-to-lamellar phase transition temperature with an increasing drug concentration. The enthalpy of the transition remained the same for all drug concentrations, indicating a strictly drug/headgroup interaction, thus supporting the proposed location of chlorhexidine. In combination, these results lead to the hypothesis that the drug is folded approximately in half on its hexamethylene linker, with the hydrophobic linker at the depth of the glycerol/phosphate region of the lipid bilayer and the hydrophilic chlorophenyl groups located at the lipid headgroup. This arrangement seems to suggest that the drug molecule acts as a wedge to disrupt the bilayer. In vivo, this should make the cell membrane leaky, which is in agreement with a wide range of bacteriological observations.

Caractérisation et modélisation de l’aimant organique NIT-2Py

L'aimant organique NIT-2Py a été caractérisé expérimentalement et ses propriétés ont été simulées numériquement à partir de la théorie de la fonctionnelle de la densité. Le magnétisme dans ce matériau provient de la présence d'un électron non apparié sur chaque molécule qui a ainsi un moment magnétique non nul. Ceci a été confirmé par des simulations sur une molécule isolée. Les molécules de NIT-2Py cristallisent dans le groupe d'espace P21/c avec huit molécules par maille élémentaire pour former la structure cristalline Alpha étudiée dans ce document. Le moment effectif de la susceptibilité et l'entropie magnétique totale montre que ce matériau est un système de spins 1/2 avec un spin par molécule. Les mesures de chaleur spécifique ont mis en évidence la présence de deux phases magnétiques ordonnées à basse température qui sont séparées par un plateau en aimantation. Une première phase est observée à des champs magnétiques inférieurs à 2.2 T et a une température de transition de 1.32 K en champ nul. Les mesures de susceptibilité magnétique et d'aimantation ont permis d'établir que cette phase ordonnée est antiferromagnétique. Ceci est confirmé par les simulations numériques. La deuxième phase est induite par le champ magnétique avec une température de transition de 0.53 K à 6 T. L'information disponible sur cette phase est limitée et l'étude du système à l'extérieur des phases ordonnées en donne une meilleure compréhension. Un modèle de spins S=1/2 isolés et de dimères S=0 isolés reproduit bien les mesures d'aimantation et de chaleur spécifique au-dessus de 3 K. L'application d'un champ magnétique réduit l'écart d'énergie entre le singulet et le triplet du dimère jusqu'au croisement qui se produit à 6 T. La phase induite émerge précisément à ce croisement et on spécule l'existence d'un condensat de Bose-Einstein des états triplets.

Electrical conductivity, dielectric properties and phase transition in ethylenediammonium sulphate single crystals

D.C. and a.c. electrical conductivities, dielectric constant and dielectric loss factor in single crystals of ethylenediammonium sulphate, (H3NCH2CH2NH3)(SO4), have been measured axiswise as a function of temperature. Anomalous variations in all the above properties at 480 K indicate the occurrence of a phase transition in the above material at this temperature. The existence of such a phase transition is also confirmed by DSC measurements. Electrical conductivity results are analysed and the activation energies of conduction at different temperature regions have been evaluated from the logσ vs 103T−1 plot. Possible mechanisms for the electrical conduction process are discussed, the available results being in favour of a proton transport model.

Temperature dependent polarized Raman spectra of nonaaqualanthanoid (Pr) single crystal

Polarized Raman spectral changes with respect to temperature were investigated for Pr(BrO3)3·9H2O single crystals. FTIR spectra of hydrated and deuterated analogues were also recorded and analysed. Temperature dependent Raman spectral variation have been explained with the help of the thermograms recorded for the crystal. Factor group analysis could propose the appearance ofBrO3 ions at sites corresponding to C3v (4) and D3h (2). Analysis of the vibrational bands at room temperature confirms a distorted C3v symmetry for the BrO3 ion in the crystal. From the vibrations of water molecules, hydrogen bonds of varying strengths have also been identified in the crystal. The appearance υ1 mode of BrO3− anion at lower wavenumber region is attributed to the attachment of hydrogen atoms to the BrO3− anion. At high temperatures, structural rearrangement is taking place for bothH2Omolecule and BrO3 ions leading to the loss ofwater molecules and structural reorientation of bromate ions causing phase transition of the crystal at the temperature of 447 K.

Temperature- and Pressure-induced Proton Transfer in the 1:1 Adduct Formed between Squaric Acid and 4,4 '-Bipyridine

We have applied a combination of spectroscopic and diffraction methods to study the adduct formed between squaric acid and bypridine, which has been postulated to exhibit proton transfer associated with a single-crystal to single-crystal phase transition at ca. 450 K. A combination of X-ray single-crystal and very-high flux powder neutron diffraction data confirmed that a proton does transfer from the acid to the base in the high-temperature form. Powder X-ray diffraction measurements demonstrated that the transition was reversible but that a significant kinetic energy barrier must be overcome to revert to the original structure. Computational modeling is consistent with these results. Modeling also revealed that, while the proton transfer event would be strongly discouraged in the gas phase, it occurs in the solid state due to the increase in charge state of the molecular ions and their arrangement inside the lattice. The color change is attributed to a narrowing of the squaric acid to bipyridine charge-transfer energy gap. Finally, evidence for the possible existence of two further phases at high pressure is also presented.

Liquid crystal phase formation by biopolymers

This review discusses liquid crystal phase formation by biopolymers in solution. Lyotropic mesophases have been observed for several classes of biopolymer including DNA, peptides, polymer/peptide conjugates, glycopolymers and proteoglycans. Nematic or chiral nematic (cholesteric) phases are the most commonly observed mesophases, in which the rod-like fibrils have only orientational order. Hexagonal columnar phases are observed for several systems (DNA, PBLG, polymer/peptide hybrids) at higher concentration. Lamellar (smectic) phases are reported less often, although there are examples such as the layer arrangement of amylopectin side chains in starch. Possible explanations for the observed structures are discussed. The biological role of liquid crystal phases for several of these systems is outlined. Commonly, they may serve as a template to align fibrils for defined structural roles when the biopolymer is extruded and dried, for instance in the production of silk by spiders or silkworms, or of chitin in arthropod shells. In other cases, liquid crystal phase formation may occur in vivo simply as a consequence of high concentration, for instance the high packing density of DNA within cell nuclei.

Measurement of molecular orientation in thermotropic liquid crystalline polymers

Procedures for obtaining molecular orientational parameters from wide angle X-ray scattering patterns of samples of thermotropic liquid crystalline polymers are presented. The methods described are applied to an extrusion-aligned sample of a random copolyester of poly(ethylene terephthalate) (PET) and p-acetoxybenzoic acid. Values of the orientational parameters are obtained from both the interchain and intrachain maxima in the scattering pattern. The differences in the values so derived suggest some level of local rotational correlation