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.     

A Mild Method for the Preparation of Functionalised,Unsymmetrical Ketene Acetals

A variety of functionalised β-iodoacetals have been prepared, and their elimination reaction to give ketene acetals conducted under mild conditions.     

THE REACTIONS OF SOME 2-NITROPHENYL SULPHIDES IN 98% SULPHURIC ACID

Abstract

The coloured solutions of 2-nitrobenzenesulphenyl derivatives in 98% sulphuric acid have previously been suggested to contain either the conjugate acid of the sulphenyl derivative¹ or the sulphenium ion in equilibrium with the starting material. ¹⁹F n.m.r. studies on solutions of 4-trifluoromethyl-2-nitrobenzenesulphenyl derivatives show that these compounds react in sulphuric acid to give the corresponding 2-amino- and 2-nitro-benzenesulphonic acids together with other products.     

Gouy Interferometry: Properties of Multicomponent System Omega (Ω) Graphs

We consider the properties of Ω graphs (Ω versus f(z)) obtained from Gouy interferometry on multicomponent systems with constant diffusion coefficients. We show that they must have (a) either a maximum or else a minimum between f(z)=0 and f(z)=1 and (b) an inflection point between the f(z) value at the extremum and f(z)=1. Consequently, an Ω graph cannot have both positive and negative Ω values.