Equivalent Chain Research Articles

From National Service to Global Player: Transforming the Organizational Logic of a Public Broadcaster

abstractWe present organizational logics as a meso‐level construct that lies between institutional theory's field‐level logics and the sense‐making activities of individual agents in organizations. We argue that an institutional logic can be operationalized empirically using the concept of a discourse – that is, a coherent symbolic system articulating what constitutes legitimate, reasonable, and effective conduct in, around, and by organizations. An organization may, moreover, be simultaneously exposed to several institutional logics that make up its broader ideational environment. Taking these three observations together enables us to consider an organizational logic as a spatially and temporally localized configuration of diverse discourses. We go on to show how organizational logics were transformed in the Australian Broadcasting Corporation between 1953 and 1999 by examining the changing discourses that appeared in the Corporation's annual reports. We argue that these discourses were modified through three main forms of discursive agency: (1) undertaking acts of ironic accommodation between competing discourses; (2) building chains of equivalence between the potentially contradictory discourses; and (3) reconciling new and old discourses through pragmatic acts of ‘bricolage’. We found that, using these forms of discursive agency, a powerful coalition of actors was able to transform the dominant organizational logic of the ABC from one where the Corporation's initial mission was to serve national interests through public service to one that was ultimately focused on participating in a globalized media market. Finally, we note that discursive resources could be used as the basis for resistance by less powerful agents, although further research is necessary to determine exactly how more powerful and less powerful agents interact around the establishment of an organizational logic.

MESOSCOPIC SIMULATION ON THE PHASE STRUCTURE OF PLURONIC P105 AQUEOUS SOLUTION

The mesoscopic dynamic simulation (MesoDyn) has been carried out to investigate the phase structure and the aggregate properties of triblock copolymers (ethylene oxide)37 (propylene oxide)56 (ethylene oxide)37 (P105) in aqueous solution. A Gaussian chain model is successfully built according to the equivalent chain method and the Flory–Huggins interaction parameters, χ, used for determining the repulsions between different chain segments are computed. Simulation results show that P105 can form several microstructures including spherical micelles, ellipsoid micellar cluster, worm-like micelles, defective bicontinuous phase, and bicontinuous phase with increasing concentration. A special transition phase structure of P105 is found in the spherical micellar region. The dynamic evolution processes of spherical micelles are investigated by observing the induction time before phase separation and the changing of isosurface during phase separation. The influence of P105 concentration on the density of micelles at equilibrium state is also discussed, which shows that the increase of P105 concentration will lead to the decrease of micelles' amount. Two kinds of growth mechanisms during phase separation are discussed by MesoDyn simulation.

The Voronoi volume and molecular representation of molar volume: Equilibrium simple fluids

The Voronoi volume of simple fluids was previously made use of in connection with volume transport phenomena in nonequilibrium simple fluids. To investigate volume transport phenomena, it is important to develop a method to compute the Voronoi volume of fluids in nonequilibrium. In this work, as a first step to this goal, we investigate the equilibrium limit of the nonequilibrium Voronoi volume together with its attendant related molar (molal) and specific volumes. It is proved that the equilibrium Voronoi volume is equivalent to the molar (molal) volume. The latter, in turn, is proved equivalent to the specific volume. This chain of equivalences provides an alternative procedure of computing the equilibrium Voronoi volume from the molar volume/specific volume. We also show approximate methods of computing the Voronoi and molar volumes from the information on the pair correlation function. These methods may be employed for their quick estimation, but also provide some aspects of the fluid structure and its relation to the Voronoi volume. The Voronoi volume obtained from computer simulations is fitted to a function of temperature and pressure in the region above the triple point but below the critical point. Since the fitting function is given in terms of reduced variables for the Lennard-Jones (LJ) model and the kindred volumes (i.e., specific and molar volumes) are in essence equivalent to the equation of state, the formula obtained is a reduced equation state for simple fluids obeying the LJ model potential in the range of temperature and pressure examined and hence can be used for other simple fluids.

Rational Design of Interleukin-21 Antagonist through Selective Elimination of the γC Binding Epitope

The cytokine interleukin (IL)-21 exerts pleiotropic effects acting through innate as well as adaptive immune responses. The activities of IL-21 are mediated through binding to its cognate receptor complex composed of the IL-21 receptor private chain (IL-21Ralpha) and the common gamma-chain (gammaC), the latter being shared by IL-2, IL-4, IL-7, IL-9, and IL-15. The binding energy of the IL-21 ternary complex is predominantly provided by the high affinity interaction between IL-21 and IL-21Ralpha, whereas the interaction between IL-21 and gammaC, albeit essential for signaling, is rather weak. The design of IL-21 analogues, which have lost most or all affinity toward the signaling gammaC chain, while simultaneously maintaining a tight interaction with the private chain, would in theory represent candidates for IL-21 antagonists. We predicted the IL-21 residues, which compose the gammaC binding epitope using homology modeling and alignment with the related cytokines, IL-2 and IL-4. Next we systematically analyzed the predicted binding epitope by a mutagenesis study. Indeed two mutants, which have significantly impaired gammaC affinity with undiminished IL-21Ralpha affinity, were successfully identified. Functional studies confirmed that these two novel hIL-21 double mutants do act as hIL-21 antagonists.

Sacrificial Violence and Targeting in International Humanitarian Law

International humanitarian law (IHL) does not prohibit military action resulting in the loss of civilian life at large. As long as its rules on the protection of civilians and their property are followed, the incidental causation of civilian loss is legal. Why is this so? The not-so-naive answer is that contemporary military operations would be made difficult, if they were to be carried out under legal norms leaving no room for civilian casualties whatsoever. Such severe constraints were as undesirable for states developing ius in bello through history as the total absence of constraints. That apart, incidental and lawful civilian losses within the framework of IHL could be seen as indispensable signs in a symbolic order fettering violent conflicts in communities. With this text, I would like to outline how this possibility might be researched in a future, more comprehensive project. In choosing targeting as an area, I believe that I am close to an archetypical norm on the fettering of violence in the laws of war. The present text features two distinct steps.First, I explore central norms on targeting in contemporary IHL, as the ultimate point of a historically grown body of thought on the lawful killing of certain civilians. This reading of the law emphasises its central ambiguities, and tries to lay bare the chains of equivalence between military objective and civilian death it constructs. A central concern is the open question of civil-political objective to be pursued through IHL-abiding war. All this will be done in the consecutive Section 2.Second, to argue that casualties are perceived as necessary preconditions for peace in an international community, I introduce a theory explaining how the causation of incidental death of civilians, rather than the willed death of enemy combatants, plays a pacifying role in the symbolic order of international law. I wish to explore targeting norms as part of a contemporary victimisation ritual, offering the civilian casualty in exchange for divine appeasement of an international community. This approach draws on the work of Rene Girard explaining how communal violence is contained through ritual acts of sacrificial killings. This projection of Girardian theory on IHL norms will be performed in Section 3. A brief conclusion will be drawn in Section 4.

Ekhidna lutea gen. nov., sp. nov., a member of the phylum Bacteroidetes isolated from the South East Pacific Ocean

A novel aerobic, heterotrophic bacterium, designated BiosLi39(T), was isolated from the South East Pacific Ocean. Cells were Gram-negative gliding rods forming yellow colonies on marine agar. The isolate was oxidase-, catalase- and alkaline phosphatase-positive and β-galactosidase-negative. Strain BiosLi39(T) grew at 20-37°C (optimum 30°C), at pH7.0-9.0 (optimum pH8.0) and with 20-60 g NaCl l(-1) (optimum 30-50 g NaCl l(-1)). The fatty acids (>1 %) comprised iso-C(14 : 0), iso-C(15 : 1) G, iso-C(15 : 0), anteiso-C(15 : 0), C(15 : 1) G, C(15 : 0), iso-C(15 : 0) 2-OH, iso-C(16 : 1) G, iso-C(16 : 0), iso-C(16 : 0) 3-OH, iso-C(16 : 0) 2-OH, iso-C(17 : 0) 3-OH, C(17 : 0) 2-OH and three unidentified components with equivalent chain lengths of 17.87, 18.10 and 18.71. A significant proportion of the hydroxylated fatty acids are amide-linked. The lipid pattern indicated the presence of phosphatidylethanolamine, two unidentified aminolipids and three unidentified polar lipids. The strain contained menaquinone 7 as the sole respiratory lipoquinone and did not produce flexirubin-type pigments. The G+C content of the genomic DNA was 37.2 mol%. Comparative 16S rRNA gene sequence analysis indicated that strain BiosLi39(T) was distantly related to all of the representatives of the phylum Bacteroidetes. Its closest relative was Marinoscillum furvescens IFO 15994(T), with which it shared 92.5 % 16S rRNA gene sequence similarity. On the basis of genotypic, phenotypic and chemotaxonomic characteristics, we propose a novel genus and species, Ekhidna gen. nov., sp. nov., with type strain BiosLi39(T) (=DSM 19307(T) =CIP 109600(T) =OOB 398(T)).

Structural Models for Interactions between the 20S Proteasome and Its PAN/19S Activators

Proteasome activity is regulated by sequestration of its proteolytic centers in a barrel-shaped structure that limits substrate access. Substrates enter the proteasome by means of activator complexes that bind to the end rings of proteasome alpha subunits and induce opening of an axial entrance/exit pore. The PA26 activator binds in a pocket on the proteasome surface using main chain contacts of its C-terminal residues and uses an internal activation loop to trigger gate opening by repositioning the proteasome Pro-17 reverse turn. Subunits of the unrelated PAN/19S activators bind with their C termini in the same pockets but can induce proteasome gate opening entirely from interactions of their C-terminal peptides, which are reported to cause gate opening by inducing a rocking motion of proteasome alpha subunits rather than by directly contacting the Pro-17 turn. Here we report crystal structures and binding studies of proteasome complexes with PA26 constructs that display modified C-terminal residues, including those corresponding to PAN. These findings suggest that PA26 and PAN/19S C-terminal residues bind superimposably and that both classes of activator induce gate opening by using direct contacts to residues of the proteasome Pro-17 reverse turn. In the case of the PAN and 19S activators, a penultimate tyrosine/phenylalanine residue contacts the proteasome Gly-19 carbonyl oxygen to stabilize the open conformation.

Contracting in Supply Chains: A Laboratory Investigation

The coordination of supply chains by means of contracting mechanisms has been extensively explored theoretically but not tested empirically. We investigate the performance of three commonly studied supply chain contracting mechanisms: the wholesale price contract, the buyback contract, and the revenue-sharing contract. The simplified setting we consider utilizes a two-echelon supply chain in which the retailer faces the newsvendor problem, the supplier has no capacity constraints, and delivery occurs instantaneously. We compare the three mechanisms in a laboratory setting using a novel design that fully controls for strategic interactions between the retailer and the supplier. Results indicate that although the buyback and revenue-sharing contracts improve supply chain efficiency relative to the wholesale price contract, the improvement is smaller than the theory predicts. We also find that although the buyback and revenue-sharing contracts are mathematically equivalent, they do not generally result in equivalent supply chain performance.

Trichroic infrared analysis of the strain-induced structural changes in the PA6 layer of PA6/PE multilayer films under biaxial drawing

This work deals with the structural evolution under biaxial drawing of PA6/tie/PE multilayer films as a function of composition. The occurrence of plastic instabilities in the PA6 layer in the multilayers is strongly reduced with respect to the PA6 monolayer film and the maximum biaxial drawability of PA6 is considerably improved with increasing PE layer thickness. Quantitative evaluation by trichroic infrared analysis of the various crystal forms of the PA6 component shows that the strain-induced β–α crystalline phase transition is delayed in the multilayers, i.e. equivalent level of phase transformation is reached at higher strains. Similar phenomenon is observed regarding the orientation within the film plane of the PA6 chains in the strain-induced α-crystals, i.e. equivalent chain orientation is reached at higher strains in the multilayers. The deformation synergism between the PA6 and PE layers is discussed in terms of benefiting effect from the PE layer that prevents plastic instabilities and promotes homogeneous deformation accompanied with orthotropic extension of the chains in the PA6 layer. This is the driving force to the delay of the detrimental β–α phase transition of PA6, the mechanically anisotropic α-crystals being highly crack-prone in contrast to the ductile isotropic β-crystals. Film rupture is shown to occur when the PA6 strain-induced α-crystals reach a constant content of about 10%, irrespective of film composition and draw temperature in the range 80–110°C. This kind of critical phenomenon is assigned to a percolation process of the crack-prone α-crystals.

Simulation of dilute solutions of linear and star-branched polymers by dissipative particle dynamics

A most promising off-lattice technique in order to simulate not only static but in addition dynamic behavior of linear and star-branched chains is the dissipative particle dynamics (DPD) method. In this model the atomistic representation of polymer molecules is replaced by a (coarse-grained) equivalent chain consisting of beads which are repulsive for each other in order to mimic the excluded volume effect (successive beads in addition are linked by springs). Likewise solvent molecules are combined to beads which in turn are repulsive for each other as well as for the polymer segments. The system is relaxed by molecular dynamics solving Newton's laws under the influence of short ranged conservative forces (i.e., repulsion between nonbonded beads and a proper balance of repulsion and attraction between bonded segments) and dissipative forces due to friction between particles, the latter representing the thermostat in conjunction with proper random forces. A variation of the strength of the repulsion between different types of beads allows the simulation of any desired thermodynamic situation. Static and dynamic properties of isolated linear and star-branched chains embedded in athermal, exothermal, and endothermal solvent are presented and theta conditions are examined. The generally accepted scaling concept for athermal systems is fairly well reproduced by linear and star-branched DPD chains and theta conditions appear for a unique parameter independent of functionality as in the case of Monte Carlo simulations. Furthermore, the correspondence between DPD and Monte Carlo data referring to the shape of chains and stars is fairly well, too. For dilute solutions the Zimm behavior is expected for dynamic properties which is indeed realized in DPD systems.

Estimation of the Center of Mass: From Humanoid Robots to Human Beings

This paper presents a new technique for estimating the center of mass of articulated rigid body systems. This estimation technique uses the statically equivalent serial chain, a serial chain representation of any multilink branched chain whose end-effector locates directly the center of mass. This technique works based on a knowledge of only the kinematic architecture of the system and does not require the total mass, or any of the individual body's mass or length properties. This constitutes an advance in center of mass estimation, providing an alternative to techniques requiring continuously a force plate. A comparison of these estimation techniques is presented. The modeling and estimation technique is then implemented on a human subject.

Aggregation of a network of conjugated polymer chains: symmetry of the excitonic states and spectral features

In this paper, we have theoretically studied the nature of symmetry of the interchain excitonic states for a conjugated polymer aggregate system consisting of N equivalent polymer chains. This approach is applied to show that for any such N-mer aggregate, the 0–0 emission peak is absent at low temperature. The system is studied beyond the nearest-neighbour approximation considering both the electronic and vibrational degrees of freedom. For example, for equivalent tetramer aggregates with square planar (2D) and tetrahedral (3D) structures, the permutation symmetry approach is an appropriate general recipe to classify the symmetry of the eigenstates of both the tetramer systems. The absorption and emission spectra for different classes of aggregates, over a wide range of temperatures, are explained in terms of the symmetry properties of the coupled excitonic states.

Poly- l-lysines and poly- l-arginines induce leakage of negatively charged phospholipid vesicles and translocate through the lipid bilayer upon electrostatic binding to the membrane

Poly- l-lysines (PLL) and poly- l-arginines (PLA) of different polymer chain lengths interact strongly with negatively charged phospholipid vesicles mainly due to their different electrical charges. 1-Palmitoyl-2-oleoyl- sn-glycero-3-phosphoglycerol (POPG), 1,2-dipalmitoyl- sn-glycero-3-phosphoglycerol (DPPG) and their mixtures (1/1 mol/mol) with the respective phosphatidylcholines of equivalent chain length were chosen as model membrane systems that form at room temperature either the fluid L α or the gel phase L β lipid bilayer membranes, respectively. Leakage experiments revealed that the fluid POPG membranes are more perturbed compared to the gel phase DPPG membranes upon peptide binding. Furthermore, it was found that pure PG membranes are more prone to release the vesicle contents as a result of pore formation than the lipid mixtures POPG/POPC and DPPG/DPPC. For the longer polymers (≥ 44 amino acids) maximal dye-release was observed when the molar ratio of the concentrations of amino acid residues to charged lipid molecules reached a value of R P = 0.5, i.e. when the outer membrane layer was theoretically entirely covered by the polymer. At ratios lower or higher than 0.5 leakage dropped significantly. Furthermore, PLL and PLA insertions and/or translocations through lipid membranes were analyzed by using FITC-labeled polymers by monitoring their fluorescence intensity upon membrane binding. Short PLL molecules and PLA molecules of all lengths seemed to translocate through both fluid and gel phase lipid bilayers. Comparison of the PLL and PLA fluorescence assay results showed that PLA interacts stronger with phospholipid membranes compared to PLL. Isothermal titration calorimetry (ITC) measurements were performed to give further insight into these mechanisms and to support the findings obtained by fluorescence assays. Cryo-transmission electron microscopy (cryo-TEM) was used to visualize changes in the vesicles' morphology after addition of the polypeptides.

A comparative assessment of octanol-water partitioning and distribution constant estimation methods for perfluoroalkyl carboxylates and sulfonates

AbstractNew experimental data is available in the literature regarding the octanol-water distribution behavior of representative straight chain perfluoroalkyl carboxylate (PFCA) and sulfonate (PFSA) congeners. The current study provides the first investigation into the predictive ability of various software programs for estimating the corresponding octanol-water partitioning (log P) and distribution (log D) constants of PFCAs and PFSAs. Wide predictive variation was found within and between the various methods. Several programs were able to accurately estimate the log P/D fragmental contributions of a -CF~2~- group for PFCAs, as well as the associated Gibbs free energies for partitioning into octanol from water due to the hydrophobic character of the perfluoroalkyl chain (Δ~hydrophobic~G~ow~). Only the SPARC log D method accurately predicted the electrostatic contributions of the carboxylate head group (Δ~electrostatic~G~ow~) towards octanol-water partitioning for PFCAs. Similar log D values and organic carbon normalized sediment-water partitioning coefficients (K~oc~) for PFCAs and PFSAs having equivalent perfluoroalkyl chain lengths suggests potentially equivalent Δ~electrostatic~G~ow~ and Δ~hydrophobic~G~ow~ contributions towards lipophilic partitioning for these two contaminant classes at near neutral pH values, regardless of head group identity. In contrast, there are potentially different Δ~electrostatic~G~ow~ and Δ~hydrophobic~G~ow~ contributions towards proteinophilic partitioning under biologically relevant conditions.

Abstract: P175 HEPATIC GENE EXPRESSION IN PRAGUE HEREDITARY HYPERCHOLESTEROLEMIC (PHHC) AND WISTAR RATS

Fatty acid order parameter profiles were determined by2H-NMR in order to characterize the arrangement and behaviour of the hydrophobic region of glycosphingolipids (GSLs) dispersed as minor components in phosphatidylcholine/cholesterol membranes. Direct comparison was made amongst species with important fatty acid structural features found in natural glycosphingolipids. Galactosyl ceramides (GalCer) were prepared by partial synthesis having 18:0[d35], D-α-OH 18:0[d34],l-α-OH 18:0[d34], 18:1[d33], and 24:0[d47] fatty acids. Unsonicated multilamellar liposomes of the common natural phospholipid, 1-palmitoyl-2-oleoylphosphatidylcholine (POPC), containing 23% cholesterol, were employed as host matrix. Smoothed profiles of the order parameter, SCD, for 18:0[d35] GalCer proved to be very similar to profiles known for 16:0 and 18:0 fatty acids of glycerolipids in cholesterol-containing bilayers. In general, order along the GSL chain was slightly higher than anticipated for equivalent chain segments in phospholipids. Order parameter profiles for the GSL 18-carbon saturated fatty acids were strikingly similar. However, small quantitative differences were found for glycolipids havingl- andl-α-hydroxylation at C-2 — thed-stereoisomer being marginally more ordered in the plateau region. Although order profiles have not been reported for unsaturated glycerolipid fatty acids in cholesterol-rich membranes, spectra of 18:1[d33] GalCer appeared to be assignable by applying known ordering effects of cholesterol to existing data for unsaturated glycerolipids. The unsaturated chain was found to be less ordered than saturated 18-carbon chains toward the membrane surface, but more ordered in the region of the bilayer midplane. The ordering may result from cholesterol-induced restriction of isomerisation at the cis-double bond, and represents an apparent exaggeration of a phenomenon known for glycerolipids. Addition of an ‘extra’ 6 carbons to the fatty acid (24:0[d47] GalCer) produced no significant effect on the order profile to a membrane depth of C-12C-13. These results suggest that fluid membrane area requirements for GSLs with saturated fatty acids are not strongly influenced by the nature of that fatty acid when the GSL is a minor component. Order parameter profiles for the very long chain GSL deviated to higher order below this point, and formed a second ‘plateau’ of reduced negative slope toward the methyl terminus: this is characteristic of profiles for very long chain GSLs. These features were essentially unchanged over a range of temperatures providing different degrees of spatial constraint.

A comparative assessment of octanol-water partitioning and distribution constant estimation methods for perfluoroalkyl carboxylates and sulfonates

AbstractNew experimental data is available in the literature regarding the octanol-water distribution behavior of representative straight chain perfluoroalkyl carboxylate (PFCA) and sulfonate (PFSA) congeners. The current study provides the first investigation into the predictive ability of various software programs for estimating the corresponding octanol-water partitioning (log P) and distribution (log D) constants of PFCAs and PFSAs. Wide predictive variation was found within and between the various methods. Several programs were able to accurately estimate the log P/D fragmental contributions of a -CF~2~- group for PFCAs, as well as the associated Gibbs free energies for partitioning into octanol from water due to the hydrophobic character of the perfluoroalkyl chain (Δ~hydrophobic~G~ow~). Only the SPARC log D method accurately predicted the electrostatic contributions of the carboxylate head group (Δ~electrostatic~G~ow~) towards octanol-water partitioning for PFCAs. Similar log D values and organic carbon normalized sediment-water partitioning coefficients (K~oc~) for PFCAs and PFSAs having equivalent perfluoroalkyl chain lengths suggests potentially equivalent Δ~electrostatic~G~ow~ and Δ~hydrophobic~G~ow~ contributions towards lipophilic partitioning for these two contaminant classes, regardless of head group identity. In contrast, there are potentially different Δ~electrostatic~G~ow~ and Δ~hydrophobic~G~ow~ contributions towards proteinophilic partitioning.

Analysis of insect triacylglycerols using liquid chromatography‐atmospheric pressure chemical ionization‐mass spectrometry

AbstractAn HPLC non‐aqueous reversed‐phase separation system was adapted for analyzing insect triacylglycerols (TAG). The method uses two conventional Nova‐Pak C18 columns connected in series, for a total length of 45 cm. The mobile phase gradient is mixed from acetonitrile and 2‐propanol, and the flow rate is programmed from 1.0 to 0.7 mL/min. TAG are detected by atmospheric pressure chemical ionization‐mass spectrometry. The method ensures efficient separation of isomers and analysis of high‐molecular‐weight TAG with equivalent chain lengths up to 72. The method performance is demonstrated on analysis of TAG isolated from the fat body of the bumblebee Bombus lucorum.

High-pressure phase transformation in LiFeGe2O6 pyroxene

A synthetic pyroxene with composition LiFeGe 2 O 6 and space group P 2 1 / c at ambient conditions was investigated by single-crystal X-ray diffraction using a diamond anvil cell. The unit-cell parameters and crystal structure were determined at eight different pressures up to 8.7 GPa. Between 4.16 and 4.83 GPa, the sample shows a strongly first-order phase transition as indicated by a drastic drop in a , c , β, and unit-cell volume. The transition is marked by the disappearance of b -type reflections ( h + k = odd) forbidden in a C -centered lattice. The volume bulk modulus of the P 2 1 / c phase is estimated to be 110 GPa as compared to 147 GPa of the C 2/ c one. The crystal structure evolution as a function of pressure is mainly influenced by the kinking of tetrahedral chains; the A and B non-symmetry equivalent chains of the P 2 1 / c phase undergo strong deformations up to 4.16 GPa (A chain ~2%, B chain ~5.3%). At the transition, the two chains become symmetry equivalent and the single tetrahedral chain of the C 2/ c phase shows only minor deformations with pressure (~1.9%) due to its already strong kinking (~130°). Such behavior is the main reason for the strong difference in compressibility between the low- and high-symmetry forms.

An experimental evaluation of the behaviour of mono and polydisperse polystyrenes in Cross-Slot flow

The behaviour of a number of mono and polydisperse polystyrenes are probed experimentally in complex extensional flow within a Cross-Slot geometry using flow-induced birefringence. Polystyrenes with similar molecular weight (M w) and increasing polydispersity (PD) illustrated the effect of PD on the principal stress difference (PSD) pattern in extensional flow. Monodisperse materials exhibited only slight asymmetry at moderate flowrates, although increased asymmetry and cusping was observed at high flowrates. The response of monodisperse materials of different M w at various flowrates is presented and characterised by Weissenberg numbers for both chain stretch and orientation using a theory for linear entangled polymers. The comparison of stress profiles against Weissenberg number for each process is used to determine whether the PSD pattern observed is independent of M w and elucidate which relaxation mechanism is dominant in the flow regimes probed. For monodisperse materials, at equivalent chain orientation Weissenberg number (We τd), different molecular weight materials were seen to exhibit similar steady state PSD patterns independent of We τR (chain stretch We). Whilst no obvious critical Weissenberg number (We) was found for the onset of increased asymmetry and cusping, it was found to occur in the “orientating flow without chain stretch” regime.

Designing Amphotropic Smectic Liquid Crystals Based on Phosphonium Salts for Partial Ordering of Solutes as Monitored by NMR Spectroscopy

The ordering parameters of selected solutes from NMR spectroscopic measurements have been assessed in the thermotropic and amphotropic smectic liquid-crystalline phases of a wide structural range of phosphonium salts with three equivalent long n-alkyl chains, one shorter chain, and various anions. The nature of the added liquids that convert the salts to amphotropic phasesalcohols and other small organic moleculesand their concentrations have been determined. These factors are correlated with the NMR-derived parameters in order to understand how the phases can be optimized to maximize information about the solutes. The various salts cover a range of liquid crystallinity from -40 to 100 degrees C. The phosphonium salts are easily aligned in the strong magnetic fields of the spectrometers. In several of the systems, a coexistence of isotropic and anisotropic phases is observed over a wide range of temperatures. The order parameters of the amphotropic liquid-crystalline phases vary from high to very low values, and some of the systems provide good spectral resolution for the solute molecules. Also, structural and orientational parameters of a model molecule, (13)C-enriched acetonitrile, have been calculated in various systems in order to evaluate more precisely the applicability of the host systems for determining solute structures by NMR. The results, in toto, indicate that several of the phosphonium salts are very promising as hosts to determine solute structures.