Poly(hexamethylene terephthalate)—I. Interpretation of its diffraction patterns

X-ray diffraction, electron microscopy and electron diffraction studies of poly(hexamethylene terephthalate) reveal a variety of structures and morphologies. Polymer micro-single crystals, grown from nitrobenzene-hexane or nitrobenzene-decane solutions exist in three crystal structures. Two forms are triclinic, the third is monoclinic. The single chain triclinic unit-cell (form I) has dimensions $\text{a = 5.217, b = 5.284, c = 15.738}\text{A}\text{?}\text{(}\text{fibre axis}\text{) α = 129.4, β = 97.6, γ = 95.6°}$. The double chain triclinic unit-cell, (form II), has all dimensions and angles equal to those of form I but for b which is twice as large. There are six chains in the monoclinic unit-cell (form III) with dimensions $\text{a = 9.100, b = 17.560, c = 15.74}\text{A}\text{?}\text{(}\text{fibre axis}\text{), α = 127.8°}$. All three forms have a common value of the fibre repeat, $\text{c = 15.74}\text{A}\text{?}$, indicating that in all three forms the polyester presents itself in a fully extended conformation. The differences between the various polymorphs arise from different packing modes of the chains. In the fibre, both the monoclinic and the triclinic forms coexist.     

Halogénures Alcalins: Un Modèle Incluant une Délocalisation à Courte Distance Application à la Stabilité Relative des Divers Arrangements Cristallins

The introduction of symmetry-adapted hybrid atomic orbitals on the metallic atoms allows us to divide the crystal into elementary cells which contain 8 valence electrons each. These cells are described by linear combinations of the halogen valence shell s and p orbitals and the hybrid orbitals of the nearest metallic atoms which point to the halogen. The electronic delocalization of the halogen ions is very weak (?0.02) for: LiF, NaF, KF, LiCl, NaCI, and KCI. The cell energy in the crystal is obtained by using a first-order perturbative treatment. In agreement with experiment, the f.c.c. type is found more stable than the b.c.c. or the blende type.     

Effect of actin concentration on the structure of actin-containing liposomes

Liposomes encapsulating monomeric actin (G-actin) were produced via extrusion through 400 and 600 nm pore diameter polycarbonate membranes in low ionic strength buffer (G-buffer). After actin-containing liposomes were subjected to high ionic strength polymerization buffer (F-buffer), morphological changes in the structure of actin-containing liposomes were studied using asymmetric flow field-flow fractionation (AFFF) coupled with multiangle static light scattering (MASLS). The general shape of these liposomes was initially determined by fitting three form factors, which describe the angular distribution of scattered light from a spherical thin shell, thin disk, and thin rod, to the experimentally measured light scattering spectra to regress the dimensions of the liposomes corresponding to the proposed geometry. Light scattering spectra that yielded a best fit to the thin disk model were analyzed further and fit to the ellipsoidal of revolution form factor to regress both the major and minor axis dimensions. The results of this analysis showed that actin-containing liposomes extruded through 400 and 600 nm pore diameter membranes in F-buffer, at a low actin concentration (0.1 mg/mL), assumed a spherical shape, which is also the case for plain liposomes (no actin present) in G-buffer and F-buffer. When the actin concentration was increased to 1 mg/mL, the polymerizing actin filaments stretched the initially spherical liposome into a disklike shape. However, when the actin concentration was further increased to 5 mg/mL, the liposomes reverted back to a spherical shape.     

Synthesis and characterization of novel anionic siloxane polymers as pseudostationary phases for electrokinetic chromatography

Four novel siloxane polymeric pseudostationary phases with three different ionic head groups have been synthesized and characterized for electrokinetic chromatography. Siloxane polymers are of interest in this application because of the wide range of chemistries that can be developed based on these backbones, including much of the chromatographic stationary phase chemistry developed in the last thirty years. All four of the siloxanes studied were synthesized by modification of a single methylhydrosiloxane polymer with highly acidic anionic functionalities. One of the siloxanes had both ionic groups and alkane chains attached to the siloxane backbone. The electrophoretic mobilities varied from being somewhat less than sodium dodecyl sulfate (SDS) to being much greater than SDS. The siloxanes substituted with ionic groups at all of the silicon sites showed significant nonequilibrium band broadening, severely limiting the efficiencies of these polymers. Substitution of 20% of the silicon sites with an alkyl group improved the efficiency of the separations and the peak symmetry. The chemical selectivities of the siloxane polymers are very different from SDS, but are similar to each other.     

Step-scan FTIR time-resolved spectroscopy study of excited-state dipole orientation in soluble metallopolymers

Step-scan FTIR time-resolved spectroscopy (S2FTIR TRS) in acetonitrile-d3 has been used to probe the acceptor ligand in metal-to-ligand charge transfer (MLCT) excited states of amide-substituted polypyridyl complexes of RuII and in analogues appended to polystyrene. On the basis of ground-to-excited state shifts in v(C = O) of -31 cm-1 for the amide group in [RuII(bpy)2(bpyCONHEt')]2+ (bpyCONHEt' = 4'-methyl-2,2'-bipyridine-4-carboxamide-Et'; Et' = -CH2CH2BzCH2CH3) (1) and in the derivatized polystyrene abbreviated [PS-[CH2-CH2NHCObpy-RuII(bpy)2]20]40+ (3), the excited-state dipole is directed toward the amide-containing pyridyl group in the polymer side chain. Smaller shifts in v(C = O) of -17 cm-1 in [RuII(4,4'-(CONEt2)2bpy)2-(bpyCONHEt')]2+ (2) and in the derivatized polystyrene abbreviated [PS-[CH2CH2NHCObpy-RuII(4,4'-(CONEt2)2bpy)2]20]40+ (4) indicate that the excited-state dipole is directed toward one of the diamide bpy ligands. The nearly identical results for 1 and 3 and for 2 and 4 show that the molecular and electronic structures of the monomer excited states are largely retained in the polymer samples. These conclusions about dipole orientation in the polymers are potentially of importance in understanding intrastrand energy transfer dynamics. The excited-state dipole in 3 is oriented in the direction of the covalent link to the polymer backbone, and toward nearest neighbors. In 4, it is oriented away from the backbone.     

An alternative model for partly diffusion controlled cage recombination

We proposed a simple kinetc model in which a diffusional physical process and a chemical process of reaction in a cage occur simultaneously. Good agreement between experimental results and the kinetic model are found.

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Dissociation quotients of succinic acid in aqueous sodium chloride media to 225°C

The first and second molal dissociation quotients of succinic acid were measured potentiometrically with a hydrogen-electrode, concentration cell. These measurements were carried out from 0 to 225°C over 25° intervals at five ionic strengths ranging from 0.1 to 5.0 molal (NaCl). The dissociation quotients from this and two other studies were combined and treated with empirical equations to yield the following thermodynamic quantities for the first acid dissociation equilibrium at 25°C: log K_1a=–4.210±0.003; H _1a ⁰ =2.9±0.2 kJ-mol^–1; S _1a ⁰ =–71±1 J-mol^–1-K^–1; and C _p1a ⁰ =–98±3 J-mol^–1-K^–1; and for the second acid dissociation equilibrium at 25°C: log K_2a=–5.638±0.001; H _2a ⁰ = –0.5±0.1 kJ-mol^–1; S _2a ⁰ =–109.7±0.4 J-mol^–1-K^–1; and C _p2a ⁰ = –215±8 J-mol^–1-K^–1.     

Improvement and simplification of synthesis of 3-aryloxy-1,2-epoxypropanes using solvent-free conditions and microwave irradiations. Relation with medium effects and reaction mechanism

Some 3-aryloxy-1,2-epoxypropanes, interesting as potential synthons in β-adrenergic receptor antagonists preparation, were obtained in excellent yields (65-96% within 2-17 min) by microwave activation (monomode system) using solid-liquid solvent-free phase transfer catalysis (PTC). The best results for the O-alkylation of some phenols with epichlorohydrin were obtained using TBAB and NaOH/K₂CO₃ (1:4 mol/mol) as phase transfer catalyst and more acceptable basic system, respectively. These new procedure is compared with classical methods. Significant specific microwave effect (non-purely thermal) was evidenced in all cases. They were discussed in terms of reaction medium and mechanism, taking into account the variations in polarity of the systems.     

A study of the production of high-p t π0 at the CERN intersecting storage rings

The inclusive cross-section for π⁰ production near 90° inpp collisions at the CERN Intersecting Storage Rings has been studied for thep _T range 3<p _T <16GeV/c at four different centre-of-mass energies ( \(\sqrt s = 30.6\) , 44.8, 52.7, and 62.8 GeV). In this experiment the two photons from the π⁰→yy decay were resolved and measured separately forp _T values up to 10 GeV/c. Results indicate an agreement with thep _T ^?8 behaviour for the lower values ofp _T and a slower decrease of the cross-section for the higher values ofp _T . The high-p _T data deviate from the scaling expressionp _T ^?n F(x _T ), which holds for the lowerp _T values (p _T <8GeV/c).