Preparation, properties, and crystal structures of organometallic ionic liquids comprising 1-ferrocenyl-3-alkylimidazolium-based salts of bis(trifluoromethanesulfonyl)amide and hexafluorophosphate

Bis(trifluoromethanesulfonyl)amide (TFSA), hexafluorophosphate (PF(6)(-)), and iodide salts of 1-ferrocenyl-3-alkylimidazolium were prepared and their thermal and physical properties, including the dependence on alkyl chain length (methyl-hexadecyl), were investigated. The TFSA salts were highly viscous ionic liquids with melting points around room temperature. 1-Ferrocenyl-4-methyltriazolium salts were also prepared for comparison. The ferrocenylimidazolium and ferrocenyltriazolium cations showed redox waves for both the ferrocenyl moiety and the azolium moiety and exhibited corresponding charge-transfer bands at around 330 nm, which were analyzed using the Marcus-Hush model. Crystal structure determinations at low temperature revealed that the PF(6) and iodide salts form layerlike structures composed of ionic layers of the charged moieties. The TFSA salt exhibited short hydrogen-bond-like intermolecular contacts between the hydrogen atoms of the cation and oxygen atoms of the anion.     

Two chitinase-like proteins abundantly accumulated in latex of mulberry show insecticidal activity

Background  

Plant latex is the cytoplasm of highly specialized cells known as laticifers, and is thought to have a critical role in defense against herbivorous insects. Proteins abundantly accumulated in latex might therefore be involved in the defense system.     

The contact stress in a bolted joint with a threaded bolt

The contact stress of a bolted joint, in which a clamped part was fastened to a body with a threaded bolt, was measured using sensitive pins, sensitive films and ultrasonic waves. The contact stress distribution was analyzed as a contact problem by an axisymmetrical theory of elasticity. Numerical calculations were performed. The experimental results were in fairly good agreement with the analytical results.Paper was presented at the 1992 SEM International Congress held in Las Vegas on June 9, 1992.     

Modeling gas permeation through membranes by kinetic Monte Carlo: applications to H2, O2, and N2 in hydrated Nafion®

We present a simulation tool in order to predict gas permeation through heterogeneous, microphase separated structures. The method combines dissipative particle dynamics (DPD) with kinetic Monte Carlo (KMC). Morphologies obtained from DPD are mapped onto a high density grid on which gas diffusion takes place. Required input parameters for the KMC calculations are the gas solubility and gas diffusion constant within each of the pure phase components. Our method was tested and validated for permeation of H(2), O(2), and N(2) gasses through hydrated Nafion membranes at various temperatures and water contents. We predict that membranes that contain an equal volume fraction of water, those with the highest ion exchange capacity exhibit the largest N(2) and O(2) permeation rates. For membranes of the same ion exchange capacity the H(2), O(2), and N(2) and permeability increases approximately linearly with Bragg spacing. We also predict that O(2) gas permeation depends much more on bottleneck phenomena within the phase separated morphologies than H(2) gas permeation. Overall, the calculated H(2) and O(2) permeability is found to be slightly lower than experimental values. This is attributed to the robustness of DPD resulting in ～7% larger Bragg spacing as compared with experiment and∕or increased gas solubility within the polymer phase with water uptake.     

Theoretical prediction of maxima in association constants for complex formation between flavin mononucleotide and indoleacetate in the presence of polyelectrolytes

The effects of ionene polymers (6,3-ionene, 6,6-ionene, 6,8-ionene, and 6,12-ionene) with various charge densities upon association constants K for the complexation between flavin mononucleotide and indoleacetate have been studied. Except for 6,12-ionene, K increases with increasing polymer concentration then passes through a maximum, and declines at high polymer concentrations. The value of the maximum K increases in the order 6,8-ionene > 6,3-ionene > 6,6-ionene. In contrast, 6,12-ionene gives only a monotone increasing curve with increasing polymer concentration. These curves are analyzed using the theory of the partition coefficient proposed in the previous paper. The types of the curves that the theory predicts are classified in greater detail than in the previous paper, and examples are given. © 1993 John Wiley & Sons, Inc.     

Dendritic Macromolecules as Inhibitors to Protein-Protein Binding

Summary: Our initial studies into protein binding using a series of dendrimers as size selective inhibitors have been described. Two different proteins, cytochromo-c and chymotrypsin have been selected for these binding experiments.     

Preferential intramolecular ring closure of aminoalcohols with diethyl carbonate to oxazolidinones

The closure by cyclization with diethyl carbonate (EtO)(2)CO from aminoalcohols 1 as starting material can lead to the oxazolidinones 2a, b and 2c, respectively. In the reaction of trans-isomer (6) and (EtO)(2)CO, isolated products were also only 5-membered oxazolidinone derivative (7), containing its dehydrated derivative 8. The preferential formation of the 5-membered oxazolidinone ring system apparently indicated that this process (5-Exo-Trig ring closure) is more favorable than that of 6- or 7-membered ring derivative (3 or 9) by 6- or 7-Exo-Trig ring closure.     

Structure of the electrical double layer on the aqueous solution side of the polarized interface between water and a room-temperature ionic liquid, tetrahexylammonium bis(trifluoromethylsulfonyl)imide

The structure of the electrical double layer on the aqueous solution side has been studied by measuring electrocapillary curves at the polarized interface between a room-temperature ionic liquid (RTIL), tetrahexylammonium bis(trifluoromethylsulfonyl)imide, and water (W) at different concentrations of LiCl. Thermodynamic analysis of the electrocapillary curves indicates that Li+ ions negatively adsorb at the point of zero charge. The adsorption of Li+ and Cl- ions in the polarized potential window of about 200 mV can be explained by the Gouy's double layer model, and the specific adsorption of Li+ and Cl- ions at the RTIL|W interface is negligible within the polarized potential window.