Люминесценция дитолуоилметаната дифторида бора. Образование J-агрегатов

The processes of the formation of J-aggregates during the dissolution 2,2-difluoro-4,6-di(4’-methylphenyl)-1,3,2-dioxaborine crystals (1) and their subsequent dissociation have been studied by absorption and luminescence spectroscopy and quantum-chemical modeling. It is shown that two luminescent centers are observed in the solution 1: monomeric luminescence and luminescence of J-aggregates (dual luminescence). Evolution of absorption, luminescence excitation and luminescence spectra is observed over time, indicating a slow dissociation of J-aggregates.

CH3-Terminated Carbon Chains in the GOTHAM Survey of TMC-1: Evidence of Interstellar CH3C7N

We report a systematic study of all known methyl carbon chains toward TMC-1 using the second data release of the GOTHAM survey, as well as a search for larger species. Using Markov Chain Monte Carlo simulations and spectral line stacking of over 30 rotational transitions, we report statistically significant emission from methylcyanotriacetylene (CH3C7N) at a confidence level of 4.6σ, and use it to derive a column density of ∼1011 cm−2. We also searched for the related species, methyltetraacetylene (CH3C8H), and place upper limits on the column density of this molecule. By carrying out the above statistical analyses for all other previously detected methyl-terminated carbon chains that have emission lines in our survey, we assess the abundances, excitation conditions, and formation chemistry of methylpolyynes (CH3C2n H) and methylcyanopolyynes (CH3C2n-1N) in TMC-1, and compare those with predictions from a chemical model. Based on our observed trends in column density and relative populations of the A and E nuclear spin isomers, we find that the methylpolyyne and methylcyanopolyyne families exhibit stark differences from one another, pointing to separate interstellar formation pathways, which is confirmed through gas–grain chemical modeling with nautilus.

Механизм люминесцентного хемосенсорного отклика в хелатах европия(III)

There were studied the luminescent chemosensory properties of Eu(III) carboxylatodibenzoylmethanates with acetic and acrylic acids while the interaction with ammonia vapors. Quantitative measurements of the optical response showed that with an increase in the analyte concentration in the range of 3-330 ppm, a linear increase in the luminescence intensity of europium(III) is observed. The reversibility of the luminescent response was established, the limit of detection of ammonia was 3 ppm. The mechanism of the optical effect is revealed by the method of quantum chemical modeling: the interaction of ammonia with the sensor leads to the formation of a rigid structural fragment of H2O–NH3, which blocks the quenching effect of high-frequency OH vibrations on luminescence. The studied chemosensors have high sensitivity and selectivity and, thus, can be promising for creating ammonia detection sensors for food safety control and environmental monitoring.

Hyteroatoms Si, P, S as possible factors for the formation of the structure of pyrolyzed carbon materials

The aim of the study was to investigate the effect of heteroatoms on the deformation of graphene, as well as on the formation of the Stone-Wallace defect. To date, research on processes involving nanocarbon materials is relevant. In particular, in the formation of fullerenes, nanoonions and a number of other carbon nanoforms, the five-membered carbon cycles (pentactagonis) of the hepatogenesis (pentactagon) play the most important role in the curvature of initially flat graphene sheets and the formation of fullerene-like structures in the form of closed, skeletal, macromolecular formations. It should be noted, however, that the Pentagon is not the only factor in distorting the flat structure of graphene sheets in layered carbon materials. Some other defects of the carbon lattice (in particular, seven-membered carbon cycles and heteroatoms of a number of nonmetals with covalent radii exceeding the radius of the carbon atom) may play a similar role to one degree or another. These heteroatoms (primarily Si, P, S) are usually part of the precursors of mineral or vegetable origin and can be embedded in the carbon lattice in the process of coal production. Stone-Wallace there is their mutual compensation and preservation of a flat structure. The calculations were performed using quantum chemical modeling of doped nanographs in clusters of different size, composition and morphology, using the theory of density functional (DFT) with exchange-correlation functional B3LYP, based on the extended valence-split basis 6-31G (d) with full optimism clusters using the Firefly software package. It has been found that heteroatoms of non-metals with covalent radii exceeding the radius of the C atom, which are usually present in the precursors of mineral or vegetable origin used to produce pyrolyzed carbon materials, can play a significant role in energy. a number of nanoforms of carbon, activated carbon and other pyrolyzed nanostructured carbon materials.

THEORETICAL AND EXPERIMENTAL STUDY OF MACROMOLECULAR NANOSTRUCTURES BASED ON HEPARIN AND LANTHANOIDS

Исследование синтетических и природных материалов пригодных для создания наноносителей и их модификация обеспечит прорыв в лечении многих заболеваний. Хорошим выбором для создания наноносителей являются гликозаминогликаны (гепарин и его производные), благодаря их уникальным биологическим и физико-химическим особенностям. Формирование композиций было исследовано методом pH -метрического титрования при 37 °С на фоне 0,15 М NaCl. С использованием программы NewDALSFEK определены значимые формы и химические равновесия. В диапазоне pH от 2,7 до 5 образуется комплекс вида {[LnHep]}, где Hep - мономерное звено макромолекулы гепарина. Получены данные об устойчивости нанокомпозиций: lgβ[PrHep] = 4,27 ± 0,04, lgβ[SmHep] = 4,28 ± 0,03 , lgβ[EuHep] = 4,28 ± 0,03. Методом M06-HF в сочетании с базисным набором CSDZ+* выполнено квантово-химическое моделирование комплексов. Study of synthetic and natural materials suitable for the creation of nanocarriers and their modification will provide a breakthrough in the treatment of many diseases. Glycosaminoglycans (heparin and its derivatives) are a good choice for creating nanocarriers due to their unique biological and physicochemical properties. The complexation of Pr (III), Sm (III), Eu (III) with heparin anions was studied by potentiometric titration at 37 °C and an ionic strength of 0,15 M NaCl. Significant forms and chemical equilibria were determined using the NewDALSFEK program. In the pH range from 2,7 to 5 , a complex of the type {[LnHep]} is formed, where Hep is a monomeric unit of the heparin macromolecule. Data on the stability of nanocompositions were obtained: lgβ[PrHep] = 4,27 ±0,04, lgβ[SmHep] = 4,28±0,03, lgβ[EuHep] = 4,28±0,03. The M06-HF method in combination with the CSDZ+* basic set was used to perform quantum chemical modeling of the complexes.

Pathways Toward High-Energy Li-Sulfur Batteries, Identified via Multi-Reaction Chemical Modeling

Here we present a 1D model of a Li-Sulfur battery with physically derived geometric parameters and thermodynamically consistent electrochemical kinetics. The approach enables straightforward comparison of proposed Li-S mechanisms and provides insights into the influence of polysulfide intermediates on battery discharge. Comparing predictions from multiple mechanisms demonstrates the need for both lithiated and non-lithiated polysulfide species, and highlights the challenge of developing parameter estimates for complex electrochemical mechanisms. The model is also used to explore cathode design strategies. Discharge performance and polysulfide concentrations for electrolyte/sulfur rations in the range 2 - 4 microleters per mg identifies trade-offs that limit battery energy and power density, and highlights the risk of polysulfide precipitation. New cathode and electrolyte approaches must limit polysulfide concentrations in the electrolyte, both to unlock better rate capabilities in Li-S technology and to prevent capacity fade due to polysulfide precipitation.

PMMA – C60 composite: thermal decomposition experiments in mass spectrometer and quantum chemical modeling

Mass-spectrometric thermal decomposition experiments with submicron films of neat polymethylmethacrylate (PMMA), and PMMA-fullerene composite (PMMA-C60) after UV irradiation are discussed. The experiment registers thermal desorption mass spectra (TDMS), that is the monomer desorption rate versus time upon gradual heating the PMMA films in a given heating regime. The spectra provide information on the amount of the monomer desorbed at different decomposition stages upon heating the given amount of film material as well as on the spectral shape changes. It is shown that both amount of monomer and the TDMS spectral shape are sensitive to the presence of fullerene and UV irradiation. The experimental results are discussed in terms of quantum chemical models of binding. The DFT/B3LYP-D3/def2/J RIJCOSX level of theory was used. The MMA-C60 structures which can yield different amounts of monomer have been compared.