Room-temperature post-yield creep

Post-yield creep of smooth specimens at room temperature in nine different metals was studied. Significant creep was observed in eight of the nine metals tested. The average creep strain from all tests was equal to nearly half of the total strain after one hour at constant load. Creep strains of significant magnitude were also found to occur within plastic enclaves of otherwise elastically deformed notched members. The characteristics of localized creep in the notched members strongly parallel the creep behavior observed in unnotched members. The need to consider time-dependent deformation in experimental mechanics is discussed. Post-yield time-dependent deformation as a cause of failure, as a cause of residual-stress relaxation affecting fatigue life, and as a primary feature of inelastic deformation needing to be modeled, are also discussed.     

Applications of proton transfer reaction time-of-flight mass spectrometry for the sensitive and rapid real-time detection of solid high explosives

Using recent developments in proton transfer reaction mass spectrometry, proof-of-principle investigations are reported here to illustrate the capabilities of detecting solid explosives in real-time. Two proton transfer reaction time-of-flight mass spectrometers (Ionicon Analytik) have been used in this study. One has an enhanced mass resolution (m/Δm up to 8000) and high sensitivity (～50 cps/ppbv). The second has enhanced sensitivity (～250 cps/ppbv) whilst still retaining high resolution capabilities (m/Δm up to 2000). Both of these instruments have been successfully used to identify solid explosives (RDX, TNT, HMX, PETN and Semtex A) by analyzing the headspace above small quantities of samples at room temperature and from trace quantities not visible to the naked eye placed on surfaces. For the trace measurements a simple pre-concentration and thermal desorption technique was devised and used. Importantly, we demonstrate the unambiguous identification of threat agents in complex chemical environments, where multiple threat agents and interferents may be present, thereby eliminating false positives. This is of considerable benefit to security and for the fight against terrorism.     

β-d-Xylosidase from Selenomonas ruminantium: Role of Glutamate 186 in Catalysis Revealed by Site-Directed Mutagenesis, Alternate Substrates, and Active-Site Inhibitor

β-d-Xylosidase/α-l-arabinofuranosidase from Selenomonas ruminantium is the most active enzyme known for catalyzing hydrolysis of 1,4-β-d-xylooligosaccharides to d-xylose. Catalysis and inhibitor binding by the GH43 β-xylosidase are governed by the protonation states of catalytic base (D14, pK _a 5.0) and catalytic acid (E186, pK _a 7.2). Biphasic inhibition by triethanolamine of E186A preparations reveals minor contamination by wild-type-like enzyme, the contaminant likely originating from translational misreading. Titration of E186A preparations with triethanolamine allows resolution of binding and kinetic parameters of the E186A mutant from those of the contaminant. The E186A mutation abolishes the pK _a assigned to E186; mutant enzyme binds only the neutral aminoalcohol $ \left( {{\text{pH}} - {\text{independent}}\;K_{\text{i}}^{\text{triethanolamine}} = 19\,{\text{mM}}} \right) $ , whereas wild-type enzyme binds only the cationic aminoalcohol $ \left( {{\text{pH}} - {\text{independent}}\;K_{\text{i}}^{\text{triethanolamine}} = 0.065\,{\text{mM}}} \right) $ . At pH 7.0 and 25°C, relative kinetic parameter, $ k_{\text{cat}}^{\text{4NPX}}/k_{\text{cat}}^{\text{4NPA}} $ , for substrates 4-nitrophenyl-β-d-xylopyranoside (4NPX) and 4-nitrophenyl-α-l-arabinofuranoside (4NPA) of E186A is 100-fold that of wild-type enzyme, consistent with the view that, on the enzyme, protonation is of greater importance to the transition state of 4NPA whereas ring deformation dominates the transition state of 4NPX.     

Proton transfer reaction mass spectrometry for the sensitive and rapid real-time detection of solid high explosives in air and water

Relying on recent developments in proton transfer reaction mass spectrometry (PTR-MS), we demonstrate here the capability of detecting solid explosives in air and in water in real time. Two different proton transfer reaction mass spectrometers have been used in this study. One is the PTR-TOF 8000, which has an enhanced mass resolution (m/Δm up to 8,000) and high sensitivity (~50 cps/ppbv). The second is the high-sensitivity PTR-MS, which has an improved limit of detection of about several hundreds of parts per quadrillion by volume and is coupled with a direct aqueous injection device. These instruments have been successfully used to identify and monitor the solid explosive 2,4,6-trinitrotoluene (TNT) by analysing on the one hand the headspace above small quantities of samples at room temperature and from trace quantities not visible to the naked eye placed on surfaces (also demonstrating the usefulness of a simple pre-concentration and thermal desorption technique) and by analysing on the other hand trace compounds in water down to a level of about 100 pptw. The ability to identify even minute amounts of threat compounds, such as explosives, particularly within a complex chemical environment, is vital to the fight against crime and terrorism and is of paramount importance for the appraisal of the fate and harmful effects of TNT at marine ammunition dumping sites and the detection of buried antipersonnel and antitank landmines.

Intramolecular aromatic 1,5-hydrogen transfer in free radical reactions III. Reactivity of diaryl ketones,ethers, thioethers,sulfoxydes, and sulfones. An experimental and theoretical study

[reaction: see text] Experiments show that free radical hydrogen shift is significant in the Pschorr cyclization of diphenyl ethers (X = O) and thioethers (X = S) and does not take place with sufoxides (X = SO) and sulfones (X = SO(2)). DFT calculations of the product ratios, activation energies, rate constants for H-transfers, and ring-closings at the UB3PW91/6-31G(d,p) level are in excellent agreement with the experimental results reported here and elsewhere in the literature.     

The electrochemically-tuneable interactions between flavin-functionalised C60 derivatives and 2,6-diethylamidopyridine

We report the electrochemically-tuneable interactions between flavin-functionalised C60 derivatives and a diamidopyridine derivative.     

Stabilization of zwitterions in solution: phosphinic and phosphonic acid GABA analogues

The influence of treatment of electron correlation, size of basis set and choice of solvation model on the predicted stabilization of zwitterionic phosphinic and phosphonic acid gamma-aminobutyric acid (GABA) analogues is investigated using ab initio molecular orbital methods and density functional theory. Density functional theory with the B3LYP functional and a composite basis set composed of the 6-31+G(2df) basis for phosphorus atoms and the 6-31+G(d,p) basis set for all other atoms is found to give an acceptable tradeoff between accuracy and computational expense. Either directly optimizing zwitterionic conformers within the conductor-like screening solvation model (COSMO) or pre-optimizing as dihydrates and then applying the COSMO solvation model give an acceptable treatment of solvation in terms of determining stable solvated structures, although directly optimizing within COSMO is simpler and less computationally expensive. With this protocol, cis-constrained phosphinic and phosphonic acid GABA analogues, which exhibit lower affinities for GABAC receptors, are found to possess only folded, intramolecularly hydrogen bonded low energy conformers. Trans-constrained analogues, on the other hand, exhibit higher affinities for GABAC receptors and are found to exist only as partially folded stable conformers. Conformationally flexible analogues can attain folded, partially folded or fully extended conformations and also have high biological activity. These results imply that the partially folded conformation is likely to be the most biologically active.     

Fixed node diffusion Monte Carlo using a genetic algorithm: a study of the CO-(4)He(N) complex, N = 1…10

The diffusion Monte Carlo (DMC) method is a widely used algorithm for computing both ground and excited states of many-particle systems; for states without nodes the algorithm is numerically exact. In the presence of nodes approximations must be introduced, for example, the fixed-node approximation. Recently we have developed a genetic algorithm (GA) based approach which allows the computation of nodal surfaces on-the-fly [Ramilowski and Farrelly, Phys. Chem. Chem. Phys., 2010, 12, 12450]. Here GA-DMC is applied to the computation of rovibrational states of CO-(4)He(N) complexes with N≤ 10. These complexes have been the subject of recent high resolution microwave and millimeter-wave studies which traced the onset of microscopic superfluidity in a doped (4)He droplet, one atom at a time, up to N = 10 [Surin et al., Phys. Rev. Lett., 2008, 101, 233401; Raston et al., Phys. Chem. Chem. Phys., 2010, 12, 8260]. The frequencies of the a-type (microwave) series, which correlate with end-over-end rotation in the CO-(4)He dimer, decrease from N = 1 to 3 and then smoothly increase. This signifies the transition from a molecular complex to a quantum solvated system. The frequencies of the b-type (millimeter-wave) series, which evolves from free rotation of the rigid CO molecule, initially increase from N = 0 to N～ 6 before starting to decrease with increasing N. An interesting feature of the b-type series, originally observed in the high resolution infra-red (IR) experiments of Tang and McKellar [J. Chem. Phys., 2003, 119, 754] is that, for N = 7, two lines are observed. The GA-DMC algorithm is found to be in good agreement with experimental results and possibly detects the small (～0.7 cm(-1)) splitting in the b-series line at N = 7. Advantages and disadvantages of GA-DMC are discussed.     

Interaction of the anionic surfactant SDS with a cellulose thin film and the role of electrolyte and poyelectrolyte. 2 Hydrophilic cellulose

The interaction of the anionic surfactant, sodium dodecylsulfate (SDS), with the hydrophilic surface of a thin cellulose film and the role of electrolyte (0.1 M NaCl) and the polyelectrolyte, poly(dimethyldiallyl ammonium chloride) [polydmdaac], have been studied by neutron reflectivity (NR). The thin cellulose films were prepared by Langmuir-Blodgett (LB) deposition of trimethylsilyl-cellulose (TMSC) on silicon, and the hydrophilic surface was produced by the cleaving of the terminal methyl groups of the TMSC by HCl vapor. Despite both the surfactant and cellulose surfaces being nominally anionic, SDS adsorption and swelling of the cellulose film occurred during adsorption. The results show that the nature of the adsorption and the extent of the penetration into the cellulose film can be controlled by the addition of electrolyte, NaCl, and cationic polyelectrolyte, polydmdaac.