Enhanced rate of arene hydrogenation with imidazolium functionalized bipyridine stabilized rhodium nanoparticle catalysts

The imidazolium functionalized bipyridine compounds, {4,4'-bis[7-(2,3-dimethylimidazolium)heptyl]-2,2'-bipyridine}(2+) ([BIHB](2+)) and {4,4'-bis[(1,2-dimethylimidazolium)methyl]-2,2'-bipyridine}(2+) ([BIMB](2+)), were prepared and used as Rh nanoparticle stabilizers. The dispersed Rh nanoparticles were used as catalysts in the biphasic hydrogenation of various arene substrates. The catalytic activity was strongly influenced by the stabilizer employed and followed the trend [BIHB](2+) > bipy > [BIMB](2+). The steric and electronic characteristics of the imidazolium functionalized bipyridine ligands were assessed via the synthesis of rhenium carbonyl complexes, which facilitated the rationalization of the catalytic properties of the nanoparticles.     

Low frequency mechanical modes of viral capsids: an atomistic approach

We present a method for the calculation of the low frequency vibrational modes and frequencies of viral capsids, or other large molecules, where the modes are modeled with atomic detail. Extending ideas from electronic structure theory, an energy functional is used to find modes of a classical dynamical matrix below a fixed (pseudo-Fermi) level. The icosahedral satellite tobacco necrosis virus is modeled as an example. We find that atoms around the C5 and C3 axis have small relative displacement while the beta sheet body shows gliding motion.     

Competitive reactions among three monomers over a catalytic surface

We studied in this work a three-monomer reaction model on one- and two-dimensional lattices. We have taken different reactivity rates among pairs of monomers and the reaction between two selected monomers was forbidden. We have employed the mean field and the pair approximation to decouple the equations of motion for the densities of single and pairs of monomers. We found the stationary states and the phase diagram of the model. We have shown that, in two dimensions and within the pair approximation, there is a first-order transition line between active and poisoned steady states.     

4-Cyanopyridine and amide-N and amide-O linkage isomers of 4-pyridinecarboxamide on trans-chloro(1,4,8,11-tetraazacyclotetradecane)ruthenium(II/III)

The synthesis, UV-vis spectra, and electrochemical behavior of the nitrile-bonded trans-[Ru(II)Cl(cyclam)(4-NCpyH(+))](BF(4))(2) (4-Ncpy = 4-cyanopyridine; cyclam = 1,4,8,11-tetraazacyclotetradecane) and of trans-[Ru(III)Cl(cyclam)(NHC(O)-4-pyH(+))](2+) are described. The UV-vis spectrum of the Ru(II) nitrile complex shows a MLCT band at 548 nm at pH 1, which is shifted to 440 nm at pH approximately 6, for the unprotonated species. trans-[Ru(II)Cl(cyclam)(4-NCpyH(+))](2+) was electrolytically oxidized (+600 mV vs Ag/AgCl) at pH 1 to Ru(III), followed by hydrolysis (k = 0.25 s(-1)) of the coordinated nitrile to give trans-[Ru(III)Cl(cyclam)(NHC(O)-4-pyH(+))](2+), in which the amide is deprotonated and coordinated through nitrogen. The identity of the species is pH dependent, the nitrogen-bonded amide prevailing at low pH (< 7), but the oxygen-bonded amide is formed through linkage isomerization at higher pH (>8). Reduction of trans-[Ru(III)Cl(cyclam)(NHC(O)-4-pyH)](2+) in acidic media does not result in fast aquation (k = approximately 2.4 x 10(-5) s(-1)) as for other amides on ruthenium(II) pentaammine, but instead linkage isomerization occurs, resulting in the oxygen-bonded species, with an estimated rate constant of approximately 2 x 10(-2) s(-1), smaller than in the pentaammine analogues.     

New Methodologies for Fracture Detection of Automotive Steels in Tight Radius Bending: Application to the VDA 238–100 V-Bend Test

Background

The VDA 238–100 tight radius V-bend test can be used to efficiently characterize the bendability and fracture limits of sheet metals in severe plane strain bending. Material performance in plane strain bending is critical for the selection of advanced high strength steels for energy absorbing structural components.

Objective

The detection of failure based upon a reduction in the punch force can lead to erroneous predictions of failure for ductile or thin gage alloys in the VDA 238–100 test. New failure criteria were proposed and evaluated across a range of automotive steels.

Methods

Four detection methods in the V-bend test were evaluated based upon the load drop, bending moment, novel stress metric and the strain rate for seven steels with strength levels from 270 to 1500 MPa. The appropriate failure threshold was identified from visual inspection of the surface during bending.

Results

The vertical punch force will decrease as a consequence of the mechanics in the V-bend test at intermediate bend angles even without fracture. The novel stress-based metric accounts for sheet thinning and could successfully identify “false positives” and punch lift-off when considering the strain-rate evolution.

Conclusions

Failure detection using the VDA load threshold method may significantly under-report the bend performance of alloys with intermediate-to-high bendability or thin gauges. The proposed stress-based metric can reliably detect fracture for bend angles in excess of 160° and be readily calculated using the existing data. The VDA load threshold for failure can work well for materials that exhibit significant cracking.