Steric effects on nascent vibrational distributions of the HCN product produced in CN radical reactions with ethane, propane and chloroform

Time-resolved IR emission spectroscopy (TRIES) has been used to study infrared emission in the 3400–3100 cm⁻¹ region from HCN molecules produced when CN radicals abstract a hydrogen atom from ethane, propane, and chloroform. From these observations the nascent vibrational distributions of the HCN produced were derived. The nascent vibrational population distributions of the product HCN in all of the reactions are non-statistical and inverted in both the pure CH stretch (00p) and CH stretch—bend (0np) series.     

NMR study of the stoichiometry,stability and exchange kinetics of complexation reaction between Pb2+ ion and 18-crown-6 in binary acetonitrile-water mixtures

Proton NMR was used to study the complexation reaction between lead ion and 18-crown-6 in a number of binary acetonitrile-water mixtures. Formation constant for the resulting 11 complexes in different solvent mixtures was determined by computer fitting of the chemical shift-mole ratio data. There is an inverse relationship between the complex stability and amount of water in the mixed solvent. The dissociative kinetics of the complex was studied by proton line-shape analysis. The Arrhenius plots showed a distinct isokinetic temperature at about 25°C at which the decomplexation rate is more or less independent of the solvent composition. the complexation rate and the activation parameters E _a , H and S, for the exchange have been determined and found to be strongly solvent dependent. There is actually a linear relationship between the mole fraction of acetonitrile in the mixed solvent and logarithm of the stability constant as well as activation parameters.     

Six-coordinate dinuclear hexaazamacrocyclic complexes of nickel(II), copper(II) and zinc(II) with tetraamide group ligands

Summary A series of 20–24 membered macrocyclic dinuclear transition metal complexes [M₂L¹X₄]-[M₂L⁴X₄] (M = Ni^II, Cu^II or Zn^II; X = Cl or NO₃) have been synthesized by template condensation of diethylenetriamine with dicarboxylic acids. The bonding and stereochemistry of the complexes have been characterized by i.r.,¹H-n.m.r., e.p.r. and electronic spectral studies, magnetic susceptibility and conductivity measurements. The Ni and Zn complexes exhibit octahedral geometry around the metal ion, whereas the Cu complexes possess a distorted octahedral geometry. Each metal ion is coordinated by two amide nitrogens and two secondary nitrogens of the diethylenetriamine moiety; the fifth and sixth coordination sites are occupied by the anions.     

TEAD–YAP Interaction Inhibitors and MDM2 Binders from DNA-Encoded Indole-Focused Ugi Peptidomimetics

DNA-encoded combinatorial synthesis provides efficient and dense coverage of chemical space around privileged molecular structures. The indole side chain of tryptophan plays a prominent role in key, or “hot spot”, regions of protein–protein interactions. A DNA-encoded combinatorial peptoid library was designed based on the Ugi four-component reaction by employing tryptophan-mimetic indole side chains to probe the surface of target proteins. Several peptoids were synthesized on a chemically stable hexathymidine adapter oligonucleotide “hexT”, encoded by DNA sequences, and substituted by azide-alkyne cycloaddition to yield a library of 8112 molecules. Selection experiments for the tumor-relevant proteins MDM2 and TEAD4 yielded MDM2 binders and a novel class of TEAD-YAP interaction inhibitors that perturbed the expression of a gene under the control of these Hippo pathway effectors.