Search results for "Theoretical Chemistry"

Angular Regioselectivity in the Reactions of 2-Thioxopyrimidin-4-ones and Hydrazonoyl Chlorides : Synthesis of Novel Stereoisomeric Octahydro[1,2,4]t…

2020

The regioselective synthesis of cis and trans stereoisomers of variously functionalized octahydro[1,2,4]triazolo[4,3-a]quinazolin-5-ones was performed. The 2-thioxopyrimidin-4-ones used in the synthesis reacted with hydrazonoyl chlorides in a regioselective manner to produce the angular regioisomers [1,2,4]triazolo[4,3-a]quinazolin-5-ones rather than the linear isomers [1,2,4]triazolo[4,3-a]quinazolin-5-ones. The synthesis process took place with electronic control. The angular regiochemistry of the products was confirmed by X-ray experiments and two-dimensional NMR studies.

Convergent results from experimental and theoretical DFT studies of the intramolecular rearrangement of Z-hydrazones of 3-acetyl-1,2,4-oxadiazoles

2004

A combined kinetic and theoretical study of the monocyclic rearrangements of heterocycles (MRH) has been carried out. The interconversion of the Z-hydrazone of 3-benzoyl-5-phenyl-1,2,4-oxadiazole into the corresponding triazole has been experimentally investigated in dioxane/water in the pS(+) range 5.5(5)-13.9. The uncatalyzed region has been examined at the DFT level using a model system formed by the Z-hydrazone of 3-formyl-1,2,4-oxadiazole and one or two water molecules. The environmental effect of the solvent has been emulated using a continuum model (COSMO) approach. The kinetic data suggest a concerted process where the magnitude of the activation barrier is determined by the interpl…

Identifying Vibrations that Control Non-adiabatic Relaxation of Polaritons in Strongly Coupled Molecule-Cavity Systems

2022

The strong light–matter coupling regime, in which excitations of materials hybridize with excitations of confined light modes into polaritons, holds great promise in various areas of science and technology. A key aspect for all applications of polaritonic chemistry is the relaxation into the lower polaritonic states. Polariton relaxation is speculated to involve two separate processes: vibrationally assisted scattering (VAS) and radiative pumping (RP), but the driving forces underlying these two mechanisms are not fully understood. To provide mechanistic insights, we performed multiscale molecular dynamics simulations of tetracene molecules strongly coupled to the confined light modes of an…

Quantitative EPR study of Mn(II)salen oxidation within zeolite Y

2000

Evidencias de un recubrimiento de magnetita artificial en el armamento íbero

2011

A metallographic study of two pre-roman Iberian arms, affected by a cremation process, revealed the presence of an outer magnetite layer, providing highly protective properties. This layer is extraordinarily tenacious and of very homogeneous thickness, indicating an intentional manufacturing process rather than an accidental formation during the severe heating/cooling cycles the artefact suffered. Up to date, the intentional production of these types of layers has been attributed to a welding process of three different metallic sheets, here an alternative model is proposed, allowing, as could be simulated in the laboratory, the virtually exclusive formation of a magnetite coating.<br>…

New Insight on Archaeological Metal Finds, Nails and Lead Sheathings of the Punic Ship from Battle of the Egadi Islands

2023

The wreck of the Punic ship exhibited at the Archaeological Park of Lilybaeum (Marsala, Italy) is a unique example in the world. In this paper, the investigation of some metal finds (30 nails and 3 fragments of sheathings) belonging to the wreck of the Punic ship is reported. Portable X-ray fluorescence and Raman spectroscopy allowed us to identify the elements and compounds constituting them and make some deductions about their composition. X-ray diffractometry, polarised optical microscopy and scanning electron microscopy of the collected micro-samples allowed us to explain the degradation that occurred in the underwater environment.

RNA-Binding Proteins as Epigenetic Regulators of Brain Functions and Their Involvement in Neurodegeneration.

2022

A central aspect of nervous system development and function is the post-transcriptional regulation of mRNA fate, which implies time- and site-dependent translation, in response to cues originating from cell-to-cell crosstalk. Such events are fundamental for the establishment of brain cell asymmetry, as well as of long-lasting modifications of synapses (long-term potentiation: LTP), responsible for learning, memory, and higher cognitive functions. Post-transcriptional regulation is in turn dependent on RNA-binding proteins that, by recognizing and binding brief RNA sequences, base modifications, or secondary/tertiary structures, are able to control maturation, localization, stability, and tr…

Spectroscopic and Structural Investigation of the Confinement of D and L Dimethyl Tartrate in Lecithin Reverse Micelles

2009

The confinement of D and L dimethyl tartrate in lecithin reverse micelles dispersed in cyclohexane has been investigated by FT-IR, polarimetry, electronic and vibrational circular dichroism (ECD and VCD), 1H NMR, and small-angle X-ray scattering (SAXS). Measurements have been performed at room temperature as a function of the solubilizate-to-surfactant molar ratio (R) at fixed lecithin concentration. The analysis of experimental data indicates that the dimethyl tartrate molecules are solubilized within reverse micelles in proximity to the surfactant head groups in the same way for the D and L forms. The encapsulation of dimethyl tatrate within lecithin reverse micelles involves changes in i…

Global analysis of the high resolution infrared spectrum of methane 12CH4 in the region from 0 to 4800 cm-1

2009

International audience; We report the global analysis of methane (12CH4) lines from high resolution rovibrational spectra including accurate line positions and intensities in the region 0–4800 cm−1. This covers four polyads: The Ground State Monad (rotational levels), the Dyad (940–1850 cm−1, 2 vibrational levels, 2 sublevels), the Pentad (2150–3350 cm−1, 5 vibrational levels, 9 sublevels) and the Octad (3550–4800 cm−1, 8 vibrational levels, 24 sublevels) and some of the associated hot bands (Pentad−Dyad and Octad−Dyad). New Fourier transform infrared (FTIR) spectra of the Pentad and Octad regions have been recorded with a very high resolution (better than 0.001 cm−1 instrumental bandwidth,…

Preliminary analysis of CH3D from 3250 to 3700 cm(-1)

2006

International audience; The infrared spectrum of CH3D from 3250 to 3700 cm(-1) was studied for the first time to assign transitions involving the nu(2) + nu(3), nu(2) + nu(5), nu(2) + nu(6), nu(3) + 2(nu 6) and 3 nu(6) vibrational states. Line positions and intensities were measured at 0.011 cm(-1) resolution using Fourier transform spectra recorded at Kitt Peak with isotopically enriched samples. Some 2852 line positions (involving over 900 upper state levels) and 874 line intensities were reproduced with RMS values of 0.0009 cm(-1) and 4.6%, respectively. The strongest bands were found to be nu(2) + nu(3) at 3499.7 cm(-1) and nu(2) + nu(6) at 3342.5 cm(-1) with integrated strengths, respe…