Synthesis of a stable crystalline nitrene

Science, Journal Year: 2024, Volume and Issue: 385(6706), P. 318 - 321

Published: June 13, 2024

Nitrenes are a highly reactive, yet fundamental, compound class. They possess monovalent nitrogen atom and usually short life span, typically in the nanosecond range. Here, we report on synthesis of stable nitrene by photolysis arylazide M

Language: Английский

---

Multifunctionalized Carbon Dots as an Active Nanocarrier for Drug Delivery to the Glioblastoma Cell Line

ACS Omega, Journal Year: 2024, Volume and Issue: 9(12), P. 13818 - 13830

Published: March 13, 2024

Nanoparticle-based nanocarriers represent a viable alternative to conventional direct administration in cancer cells. This advanced approach employs the use of nanotechnology transport therapeutic agents directly cells, thereby reducing risk damage healthy cells and enhancing efficacy treatment. By approving nanoparticle-based nanocarriers, potential for targeted, effective treatment is greatly increased. The so-called carbon-based nanoparticles, or carbon dots, have been hydrothermally prepared initiated by polymerization process. We synthesized characterized nanoparticles 2-acrylamido-2-methylpropanesulfonic acid, which showed biocompatibility with glioblastoma further, we tested them as carrier drug riluzole. obtained extensively techniques obtain exact composition their surface using Fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS), nuclear magnetic resonance (NMR) spectroscopy, well cryo-transmission electron microscopy. found that (NPs) covered mainly sulfonated, carboxylic, substituted amide groups. These functional groups make suitable carriers delivery Specifically, successfully utilized NPs system riluzole, has shown treating effect riluzole on was studied live-cell synchrotron-based FTIR microspectroscopy monitor

Language: Английский

---

Photoinduced Metallonitrene Formation by N₂ Elimination from Azide Diradical Ligands

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(42)

Published: Aug. 7, 2023

Transition-metal nitrides/nitrenes are highly promising reagents for catalytic nitrogen-atom-transfer reactivity. They typically prepared in situ upon optically induced N2 elimination from azido precursors. A full exploitation of their potential, however, requires in-depth knowledge the primary photo-induced processes and structural/electronic factors mediating loss with birth terminal metal-nitrogen core. Using femtosecond infrared spectroscopy, we elucidate here molecular-level mechanisms responsible formation a unique platinum(II) nitrene triplet ground state closed-shell azide precursor. The spectroscopic data combination quantum-chemical calculations provide compelling evidence that product initial occupation singlet excited an anionic diradical ligand is bound to low-spin d8 -configured PtII ion. Subsequent intersystem crossing generates Pt-bound diradical, which smoothly evolves into via near barrierless adiabatic dissociation. Our highlight importance productive, -releasing possessing ππ* character as design principle accessing efficient N-atom-transfer catalysts.

Language: Английский

---

CASPT2 Study of the Unimolecular Reactions of Nitromethane—A Look at the Roaming Reactions in the Decomposition of Nitromethane: An Exergonic Route at High Temperatures

Reactions, Journal Year: 2025, Volume and Issue: 6(1), P. 21 - 21

Published: March 12, 2025

In this work, we studied the main decomposition reactions on ground state of nitromethane (CH3NO2) with CASPT2 approach. The energetics elementary title molecule have been analyzed basis Gibbs free energies obtained from standard expressions statistical thermodynamics. addition, describe a mapping method (orthogonalized 3D representation) for potential energy surfaces (PESs) by defining an orthonormal consisting two Rn vectors (n, internal degrees freedom) that allows us to obtain set ordered points in plane (vector subspace) spanned such basis. Geometries and harmonic frequencies all species orthogonalized representations PESs computed It is found kinetically controlled are endergonic. For class reactions, dissociation into CH3 NO2 process lower activation barrier (ΔG); is, C-N bond cleavage most favorable process. contrast, there exists dynamically evolves through roaming reaction mechanism exergonic at high temperatures: CH3NO2 → [CH3…NO2]* [CH3ONO]* CH3O + NO. above assertions supported mappings classical trajectories “on-the fly” CASSCF molecular dynamics calculations.

Language: Английский

---

Experimental and theoretical investigation into the decomposition mechanism of 3,5-dimethyl-4-hydroxyphenylpentazole

Scientific Reports, Journal Year: 2025, Volume and Issue: 15(1)

Published: March 14, 2025

Language: Английский

---

Pyrolysis behavior and mechanism of high nitrogen compound 4,4’,6,6’-tetra(azido)-hydrazine-1,3,5-triazine

Energetic Materials Frontiers, Journal Year: 2025, Volume and Issue: unknown

Published: April 1, 2025

Language: Английский

---

UV-photoelectron spectroscopy and MS-CASPT2/CASSCF study of the thermolysis of azidoethyl-methyl sulfide: Characterization and mechanism of the formation of S-methyl-N-sulfenylethanimine

The Journal of Chemical Physics, Journal Year: 2025, Volume and Issue: 162(19)

Published: May 16, 2025

The thermal decomposition of azidoethyl methyl sulfide was studied by real-time UV-photoelectron spectroscopy (UV-PES) at temperatures ranging from 773 to 1023 K. Different ionization energies were obtained using density functional theory calculations assign UV-PES spectra. complete active space self-consistent field and multistate second-order perturbation methods used predict the formation different species present in process. N2 S-methyl-N-sulfenylethanimine are generated first step reaction is dissociation molecule into nitrene nitrogen. spin state (singlet or triplet) formed temperature-dependent. At low (T ≤ 650 K), both states with almost same probability; contrast, high ≥ 1000 singlet majority intermediate. From this nitrene, three stable products detected experiments: an imine derivative, a four-member cyclic sulfenyl derivative.

Language: Английский

---

Spectroscopic evidence for 1,2-diiminoethane – a key intermediate in imidazole synthesis

Chemical Communications, Journal Year: 2022, Volume and Issue: 58(61), P. 8484 - 8487

Published: Jan. 1, 2022

Finally characterized: Elusive 1,2-diiminoethane is spectroscopically characterized by infrared and UV/Vis spectroscopy for the first time. The diimine can be prepared through photochemical dinitrogen extrusion of explosive 1,2-diazidoethane.

Language: Английский

---

Glycine Imine—The Elusive α‐Imino Acid Intermediate in the Reductive Amination of Glyoxylic Acid

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(11)

Published: Jan. 19, 2023

Simple unhindered aldimines tend to hydrolyze or oligomerize and are therefore spectroscopically not well characterized. Herein we report the formation spectroscopic characterization of simplest imino acid, namely glycine imine, by cryogenic matrix isolation IR UV/Vis spectroscopy. Glycine imine forms after UV irradiation 2-azidoacetic acid N2 extrusion in anti-(E,E)- anti-(Z,Z)-conformation that can be photochemically interconverted. In pyrolysis experiments with cannot trapped as it further decarboxylates aminomethylene. aqueous solution is hydrolyzed hydroxy hydrated glyoxylic acid. At higher concentrations presence FeII SO4 a reducing agent undergoes self-reduction oxidative decarboxylation chemistry. may seen one key reaction intermediates connecting prebiotic amino sugar

Language: Английский

---

Understanding the reaction balances behind the viability PCR protocols based on photoreactive dyes

Journal of Microbiological Methods, Journal Year: 2023, Volume and Issue: 209, P. 106737 - 106737

Published: May 12, 2023

Language: Английский

---