Infrared investigation of the reactions of rhodiumcarbonyl halides and carbon monoxide at elevated pressures

Infrared spectral results at elevated carbon monoxide pressures suggest that rhodiumdicarbonyl halides and carbon monoxide exist in an equilibrium with the corresponding rhodiumtricarbonyl halides.     

On the rate and activation energy of the Br + Br2 ataom-exchange reaction

The Br + Br₂ atom-exchange reaction has been studied using quasiclassical trajectories and a semi-empirical potential-energy surface with shallow, long-range wells. The computed reaction rate coefficient is in good agreement with experiment. The computed reaction activation energy is ? 1 kcal/mole.     

Connecting pairwise and positional election outcomes

General conclusions relating pairwise tallies with positional (e.g., plurality, antiplurality (“vote-for-two”)) election outcomes were previously known only for the Borda Count. While it has been known since the eighteenth century that the Borda and Condorcet winners need not agree, it had not been known, for instance, in which settings the Condorcet and plurality winners can disagree, or must agree. Results of this type are developed here for all three-alternative positional rules. These relationships are based on an easily used method that connects pairwise tallies with admissible positional outcomes; e.g., a special case provides the first necessary and sufficient conditions ensuring that the Condorcet winner is the plurality winner; another case identifies when there must be a profile whereby each candidate is the “winner” with some positional rule.     

SYNTHESIS AND PROPERTIES OF SOME NEW,STABLE THIETES (THIACYCLOBUTENES)

Abstract

Simple alkyl substituted thietes are liquids which decompose at room temperature presumably via electrocyclic ring opening to give polymeric material.     

Metal‐Templated,Tight Loop Conformation of a Cys‐X‐Cys Biomimetic Assembles a Dimanganese Complex

With the goal of generating anionic analogues to MN₂S₂ ? Mn(CO)₃Br we introduced metallodithiolate ligands, MN₂S₂^2? prepared from the Cys‐X‐Cys biomimetic, ema^4? ligand (ema=N,N′‐ethylenebis(mercaptoacetamide); M=Ni^II, [V^IV≡O]²⁺ and Fe^III) to Mn(CO)₅Br. An unexpected, remarkably stable dimanganese product, (H₂N₂(CH₂C=O(μ‐S))₂)[Mn(CO)₃]₂ resulted from loss of M originally residing in the N₂S₂^4? pocket, replaced by protonation at the amido nitrogens, generating H₂ema^2?. Accordingly, the ema ligand has switched its coordination mode from an N₂S₂^4? cavity holding a single metal, to a binucleating H₂ema^2? with bridging sulfurs and carboxamide oxygens within Mn‐μ‐S‐CH₂‐C‐O, 5‐membered rings. In situ metal‐templating by zinc ions gives quantitative yields of the Mn₂ product. By computational studies we compared the conformations of “linear” ema^4? to ema^4? frozen in the “tight‐loop” around single metals, and to the “looser” fold possible for H₂ema^2? that is the optimal arrangement for binucleation. XRD molecular structures show extensive H‐bonding at the amido‐nitrogen protons in the solid state.     

Harnessing selenocysteine reactivity for oxidative protein folding

Although oxidative folding of disulfide-rich proteins is often sluggish, this process can be significantly enhanced by targeted replacement of cysteines with selenocysteines. In this study, we examined the effects of a selenosulfide and native versus nonnative diselenides on the folding rates and mechanism of bovine pancreatic trypsin inhibitor. Our results show that such sulfur-to-selenium substitutions alter the distribution of key folding intermediates and enhance their rates of interconversion in a context-dependent manner.