Solid-Phase Synthesis of an Insect Pyrokinin Analog Incorporating an Imidazoline Ring as Isosteric Replacement of a trans Peptide Bond

A facile solid-phase synthetic method for incorporating the imidazoline ring motif, a surrogate for a trans peptide bond, into bioactive peptides is reported. The example described is the synthesis of an imidazoline peptidomimetic analog of an insect pyrokinin neuropeptide via a cyclization reaction of an iminium salt generated from the preceding amino acid and 2,4-diaminopropanoic acid (Dap).     

Janis Stradins: An outstanding electrochemist and expert in the history of science

Journal of Solid State Electrochemistry - Janis Stradins (10.12.1933 – 29.11.2019) was a well-known expert in molecular electrochemistry, ESR spectroscopy and physical organic chemistry, as...     

Correction to: Effects of environmental factors on key kinetic parameters relevant to pitting corrosion

Journal of Solid State Electrochemistry -     

Silver as a capturing material for iodine released from lead–bismuth eutectic in various conditions

Journal of Radioanalytical and Nuclear Chemistry - The usage of silver as a filtering material for removal of iodine from the gas phase of a lead–bismuth eutectic based nuclear reactor was...     

Analytical and statistical studies of Rodriguez–Velazquez indices

Journal of Mathematical Chemistry - In this work we perform analytical and statistical studies of the Rodríguez–Velázquez (RV) indices on graphs G. The topological RV(G) indices,...     

Secondary Metabolites of Clinacanthus nutans

Chemistry of Natural Compounds -     

Secondary Metabolites of Mahonia bealei

Chemistry of Natural Compounds -     

Optical Emission Spectroscopy Study of Plasma-Precursor Interactions in TiO2 Suspension Plasma Spray

Plasma Chemistry and Plasma Processing - The influence of plasma power on liquid precursor decomposition in suspension plasma spray (SPS) is studied with optical emission spectroscopy (OES). The...     

Acetylene Derivatives of Cationic Diazaoxatriangulenes and Diaza [4]Helicenes - Access to Red Emitters and Planar Chiral Stereochemical Traits

Cationic triangulenes, and related helicenes, constitute a rich class of dyes and fluorophores, usually absorbing and emitting light at low energy, in the orange to red domains. Recently, to broaden the scope of applications, regioselective late-stage functionalizations on these core moieties have been developed. For instance, with the introduction of electron-donating groups (EDGs), important bathochromic shifts are observed pushing absorptions towards or in the near-infrared (NIR) spectral domain while emissive properties disappear essentially completely. Herein, to upset this drawback, acetylene derivatives of cationic diazaoxa triangulenes (DAOTA) and [4]helicenes are prepared (16 examples). Contrary to other EDG-functionalized derivatives, C≡C− functionalized products remain broadly fluorescent, with red-shifted absorptions (Δλ_abs up to 25 nm) and emissions (Δλ_em up to 73 nm, Φ_PL up to 51 %). Quite interestingly, a general dynamic stereoisomerism phenomenon is evidenced for the compounds derived from achiral DAOTA cores. At low temperature in ¹H NMR spectroscopy (218 K), N−CH₂ protons become diastereotopic with chemical shifts differences (Δδ) as high as +1.64 ppm. The signal coalescence occurs around 273 K with a barrier of ∼12 kcal mol⁻¹. This phenomenon is due to planar chiral conformations (S_p and R_p configurations), induced by the geometry of the alkyl (n-propyl) side-chains next to the acetylenic substituents. Ion pairing studies with Δ-TRISPHAT anion not only confirm the occurrence of the chiral conformations but evidence a moderate but definite asymmetric induction from the chiral anion onto the cations. Finally, DFT calculations offer a valuable insight on the geometries, the corresponding stereodynamics and also on the very large difference in NMR for some of the diastereotopic protons.