Photoinduced Decarboxylative Borylation of -Hydroxyphthalimide Esters with Hypoboric Acid.

We developed a visible-light-driven photochemical transformation in which activated primary, secondary, and tertiary alkylcarboxylic acids were converted into the corresponding boronic esters in the absence of catechol and any added photocatalyst. The procedure relies on the utilization of hypoboric acid and redox-active esters of alkylcarboxylic acids to ensure a simple and economic procedure. Quantum chemical calculations and mechanistic considerations provide deeper insights into the mechanism of photochemical borylation reactions.

White and other fur colourations and hybridization in golden jackals (Canis aureus) in the Carpathian basin.

The golden jackal (Canis aureus) is a reoccurring species in the centre of the Carpathian basin, in Hungary. In total, 31 golden jackal tissue samples were collected, from 8 white-coated, 2 black-coated and one mottled animal across Hungary. Sequences and fragment length polymorphisms were studied for white colour (MC1R), and for black coat colouration (CBD103).

Prediction of Redox Power for Photocatalysts: Synergistic Combination of DFT and Machine Learning.

The accurate prediction of excited state properties is a key element of rational photocatalyst design. This involves the prediction of ground and excited state redox potentials, for which an accurate description of electronic structures is needed. Even with highly sophisticated computational approaches, however, a number of difficulties arise from the complexity of excited state redox potentials, as they require the calculation of the corresponding ground state redox potentials and the estimation of the 0-0 transition energies ().

Isocyanonaphthol Derivatives: Excited-State Proton Transfer and Solvatochromic Properties.

Fluorescent probes that exhibit solvatochromic or excited-state proton-transfer (ESPT) properties are essential tools for the study of complex biological or chemical systems. Herein, the synthesis and characterization of a novel fluorophore that reveals both features, 5-isocyanonaphthalene-1-ol (ICOL), are reported. Various solvatochromic methods, such as Lippert−Mataga and Bilot−Kawski, together with time-dependent density functional theory (TD-DFT) and time-resolved emission spectroscopy (TRES), were applied to gain insights into its excited-state behavior.

Multiscale Modeling of Electronic Spectra Including Nuclear Quantum Effects.

Theoretical prediction of electronic absorption spectra without input from experiments is no easy feat, as it requires addressing all of the factors that affect line shapes. In practice, however, the methodologies are limited to treat these ingredients only to a certain extent. Here, we present a multiscale protocol that addresses the temperature, solvent, and nuclear quantum effects as well as anharmonicity and the reconstruction of the final spectra from individual transitions.

Kinetically Equivalent Functionality and Reactivity of Commonly Used Biocompatible Polyurethane Crosslinking Agents.

In this paper, the kinetics of the reaction of phenyl isocyanate with crosslinking agents such as sucrose, sorbitol, and glycerol are reported. Crosslinking agents were used in high molar excess to isocyanate to obtain pseudo-first-order rate dependencies, and the reaction products were separated by high-performance liquid chromatography and detected by UV spectroscopy and mass spectrometry. It was found that the glycerol's primary hydroxyl groups were approximately four times reactive than the secondary ones.

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Recently, a new approach of converting (hetero)aryl ethers to C-C coupled products via a photoinduced intramolecular rearrangement has been reported. Although this reaction is photocatalyst-free, it requires excitation in the ultraviolet (UV) range. To help refine this process, three different 2-(hetero)aryloxybenzaldehydes are selected from the available substrate scope in which the general mechanism based on experimental results is evaluated using density functional theory calculations.

The mechanism of monochloramine disproportionation under acidic conditions.

Monochloramine is a widely employed agent in water treatment technologies. However, its utilization has some drawbacks like the transformation of the active species into the undesired dichloramine. Although it is more pronounced in acidic solutions, the features of this reaction have still remained largely unexplored in the pH < 4 region.

Effect of the Substitution Position on the Electronic and Solvatochromic Properties of Isocyanoaminonaphthalene (ICAN) Fluorophores.

The properties of 1,4-isocyanoaminonaphthalene (1,4-ICAN) and 2,6-isocyanoaminonaphthalene (2,6-ICAN) isomers are discussed in comparison with those of 1,5-isocyanoaminonaphthalene (1,5-ICAN), which exhibits a large positive solvatochromic shift similar to that of Prodan. In these isocyanoaminonaphthalene derivatives, the isocyano and the amine group serve as the donor and acceptor moieties, respectively. It was found that the positions of the donor and the acceptor groups in these naphthalene derivatives greatly influence the Stokes and solvatochromic shifts, which decrease in the following order: 1,5-ICAN > 2,6-ICAN > 1,4-ICAN.

Amino-isocyanoacridines: Novel, Tunable Solvatochromic Fluorophores as Physiological pH Probes.

Amino-isocyanoacridines (ICAAcs), as first members of their class, turned out to be a novel, multifunctional acridine orange (AO) type dye family with a number of additional favorable properties. They have enhanced solvatochromic emission range, low quantum yields (Φ = 2.9-0.

DFT Study on the Mechanism of Hydrogen Storage Based on the Formate-Bicarbonate Equilibrium Catalyzed by an Ir-NHC Complex: An Elusive Intramolecular C-H Activation.

A novel iridium based, water-soluble phosphine-NHC (N-heterocyclic carbene) complex, Na[Ir( emim)(η-COD)( mtppts)] was previously developed in our research group. It was shown that it is a very effective catalyst for the reversible storage of hydrogen based on the formate-bicarbonate equilibrium. In this paper, we present a DFT investigation on the noninnocent behavior of the NHC ligand toward C-H activation of the N-ethyl side chain and its possible role in the hydrogen storage mechanism.