Gas permeability and n‐butane solubility of poly(1‐trimethylgermyl‐1‐propyne)

The gas permeability and n‐butane solubility in glassy poly(1‐trimethylgermyl‐1‐propyne) (PTMGP) are reported. As synthesized, the PTMGP product contains two fractions: (1) one that is insoluble in toluene and soluble only in carbon disulfide (the toluene‐insoluble polymer) and (2) one that is soluble in both toluene and carbon disulfide (the toluene‐soluble polymer). In as‐cast films, the gas permeability and n‐butane solubility are higher in films prepared from the toluene‐soluble polymer (particularly in those films cast from toluene) than in films prepared from the toluene‐insoluble polymer and increase to a maximum in both fractions after methanol conditioning. For example, in as‐cast films prepared from carbon disulfide, the oxygen permeability at 35 °C is 330 × 10^?10 cm³ (STP) cm/(cm² s cmHg) for the toluene‐soluble polymer and 73 × 10^?10 cm³ (STP) cm/(cm² s cmHg) for the toluene‐insoluble polymer. After these films are conditioned in methanol, the oxygen permeability increases to 5200 × 10^?10 cm³ (STP) cm/(cm² s cmHg) for the toluene‐soluble polymer and 6200 × 10^?10 cm³ (STP) cm/(cm² s cmHg) for the toluene‐insoluble polymer. The rankings of the fractional free volume and nonequilibrium excess free volume in the various PTMGP films are consistent with the measured gas permeability and n‐butane solubility values. Methanol conditioning increases gas permeability and n‐butane solubility of as‐cast PTMGP films, regardless of the polymer fraction type and casting solvent used, and minimizes the permeability and solubility differences between the various films (i.e., the permeability and solubility values of all conditioned PTMGP films are similar). © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2228–2236, 2002     

Correlation effects in the electronic coupling between π electrons through a cyclohexane spacer

The electronic coupling between symmetrically placed π electrons through a cyclohexane spacer is calculated using ab initio methods. In particular we have performed a multiconfigurational configuration interaction study involving the broken symmetry Hartree—Fock solutions. The value of Δ, in a simplified model the splitting between the symmetric and antisymmetric π orbitals, is moderately changed compared to the Koopmans theorem value. The influence of the basis set on the calculated splittings is also analyzed.     

Energy transport in one-dimensional thermoelectric systems

The efficiency of thermoelectric power generators and the coefficient of performance of thermoelectric refrigerators increase rapidly in the region of small ZT, and then level off to a flat curve in the region of large ZT, where ZT is the figure of merit. Therefore, simply because one-dimensional thermoelectric materials have high ZT predicted theoretically does not imply that efficient thermoelectric devices can be built with such one-dimensional systems. Our numerical analysis, based on the fundamental thermodynamics which is independent of material systems, with emphasis on energy transport has confirmed this conjecture.     

Minimum detection efficiency for a loophole-free atom-photon bell experiment

In Bell experiments, one problem is to achieve high enough photodetection to ensure that there is no possibility of describing the results via a local hidden-variable model. Using the Clauser-Horne inequality and a two-photon nonmaximally entangled state, a photodetection efficiency higher than 0.67 is necessary. Here we discuss atom-photon Bell experiments. We show that, assuming perfect detection efficiency of the atom, it is possible to perform a loophole-free atom-photon Bell experiment whenever the photodetection efficiency exceeds 0.50.     

Influence of non-singular stress terms and specimen geometry on small-scale yielding at crack tips in elastic-plastic materials

The plane strain elastic-plastic state at a crack tip is determined for compact tension, bend, double edge-cracked and centre-cracked specimens using a finite element method with triangular constant-strain elements. The solutions are found to differ by 10 to 30 per cent at the ASTM-limit as regards fracture surface displacement, normal stress and plastic zone size. In order to bring the boundary layer solution for the crack problem into agreement with the solution for a specific specimen one has to modify this solution. The modification consists of an addition to the boundary tractions for the boundary layer problem of tractions corresponding to the non-singular, constant second term in a series expansion of the normal stress parallel to the crack plane.     

Low-Energy Collisions of Protonated Enantiopure Amino Acids with Chiral Target Gases

Here we report on the gas-phase interactions between protonated enantiopure amino acids (l- and d-enantiomers of Met, Phe, and Trp) and chiral target gases [(R)- and (S)-2-butanol, and (S)-1-phenylethanol] in 0.1–10.0 eV low-energy collisions. Two major processes are seen to occur over this collision energy regime, collision-induced dissociation and ion-molecule complex formation. Both processes were found to be independent of the stereo-chemical composition of the interacting ions and targets. These data shed light on the currently debated mechanisms of gas-phase chiral selectivity by demonstrating the inapplicability of the three-point model to these interactions, at least under single collision conditions.

Open image in new window

Graphical Abstract

     

Instability and failure of internally pressurized ductile metal cylinders

Forlong, ductile, thick-walled tubes under internal pressure instabilities and final failure modes are studied experimentally and theoretically. The test specimens are closed-end cylinders made of an aluminum alloy and of pure copper and the experiments have been carried out for a number of different initial external radius to internal radius ratios. The experiments show necking on one side of the tubes at a stage somewhat beyond the maximum internal pressure. All tubes, except for one aluminum alloy tube, failed by shear fracture under decreasing pressure. The aluminum alloy tubes exhibited localized shear deformations in the neck region prior to fracture and also occasionally surface wave instabilities. The numerical investigation is based on an elastic-plastic material model for a solid that develops a vertex on the yield surface, using representations of the uniaxial stress-strain curves found experimentally. In contrast to the simplest flow theory of plasticity this material model predicts shear band instabilities at a realistic level of strain. A rather sharp vertex is used in the material model for the aluminum alloy, while a more blunt vertex is used to characterize copper. The theoretically predicted bifurcation into a necking mode, the cross-sectional shape of the neck, and finally the initiation and growth of shear bands from the highly strained internal surface in the neck region are in good agreement with the experimental observations.     

Crystallographic analysis of metal-ion binding to human ubiquitin

The metal-binding ability of human ubiquitin (hUb) towards a selection of biologically relevant metal ions and complexes has been probed. Different techniques have been used to obtain crystals suitable for crystallographic analysis. In the first type of experiments, crystals of hUb have been soaked in solutions containing copper(II) acetate and two metallodrugs, Zeise salt (K[PtCl(3)(η(2)-C(2)H(4))]·H(2)O) and cisplatin (cis-[PtCl(2)(NH(3))(2)]). The Zeise salt is used in a test for hepatitis, whereas cisplatin is one of the most powerful anticancer drugs in clinical use. The Zeise salt readily reacts with hUb crystals to afford an adduct with three platinum residues per protein molecule, Pt(3)-hUb. In contrast, copper(II) acetate and cisplatin were found to be unreactive for contact times up to one hour and to cause degradation of the hUb crystals for longer times. In the second type of experiments, hUb was cocrystallized with a solution of copper(II) or zinc(II) acetate or cisplatin. Zinc(II) acetate gives, at low metal-to-protein molar ratios (8:1), crystals containing one metal ion per three molecules of protein, Zn-hUb(3) (already reported in previous work), whereas at high metal-to-protein ratios (70:1) gives crystals containing three Zn(II) ions per protein molecule, Zn(3)-hUb. In contrast, once again, copper(II) acetate and cisplatin, even at low metal-to-protein ratios, do not give crystalline material. In the soaking experiment, the Zeise anion leads to simultaneous platination of His68, Met1, and Lys6. Present and previous results of cocrystallization experiments performed with Zn(II) and other Group 12 metal ions allow a comprehensive understanding of the metal-ion binding properties of hUb with His68 as the main anchoring site, followed by Met1 and carboxylic groups of Glu16, Glu18, Glu64, Asp21, and Asp32, to be reached. In the case of platinum, Lys6 can also be a binding site. The amount of bound metal ion, with respect to that of the protein, appears to be a relevant parameter influencing crystal packing.