Triarylamines are demonstrated as novel, tunable electroactivated photocatalysts that use dispersion precomplexation to harness the full potential of visible photon (&gt;4.0 V <italic>vs.</italic> SCE) in anti-Kasha photo(electro)chemical super-oxidations arenes.

The emergence of single atom sites as a frontier research area in catalysis has sparked extensive academic and industrial interest, especially for energy, environmental chemicals production processes. Single catalysts (SACs) have shown remarkable performance variety catalytic reactions, demonstrating high selectivity to the products long lifespan, stability more importantly atomic metal utilization efficiency. In this review, we unveil depth insights on development achievements SACs,...

Abstract Electron‐deficient acridones and in situ generated acridinium salts are reported as potent, closed‐shell photooxidants that undergo surprising mechanisms. When bridging acyclic triarylamine catalysts with a carbonyl group (acridones), this completely diverts their behavior away from open‐shell, radical cationic, ‘beyond diffusion’ photocatalysis to closed‐shell, neutral, diffusion‐controlled photocatalysis. Brønsted acid activation of dramatically increases excited state oxidation...

The platination processes of DNA bases with second- and third-generation Pt(II) anticancer drugs have been investigated using density functional theory (DFT) combined the conductor-like dielectric continuum model (CPCM) approach, in order to describe their binding mechanisms obtain detailed data on reaction energy profiles. Although there is no doubt that a Pt-N7 bond forms during initial attack, energetic profiles for formation monofunctional adducts are not known. Herein, direct comparison...

Obtaining chemicals and fuels from the reduction of carbon dioxide (CO2) represents a promising strategy to mitigate growing greenhouse gas emissions. Because high thermodynamic stability CO2, real challenge is development efficient selective catalysts. In this regard, photocatalysis receiving much attention because it exclusively relies on energy input sunlight. Gallium nitride (GaN) semiconductors can effectively promote CO2 reduction. Moreover, addition semiconductor surfaces transition...

Based on our recent research experience, this review highlights the DNA binding of salen, salphen and salnaphen metal complexes, with a focus G‐quadruplex (G4) DNA, which is crucial in peculiar genomic regions cancer regulation. Such complexes have fact shown significant ability to bind stabilize G4 structures. We will point out role center ligand substituents affecting their selectivity toward G4s, supported by experimental computational studies.

Imparted with uniquely high and broad-scope bioactivity including antioxidant, anti-inflammatory, cardioprotective, neuroprotective, antimicrobial anticancer properties, the IntegroPectin bioconjugate obtained from citrus processing waste via hydrodynamic cavitation (HC) was investigated Density Functional Theory computational approach. The main flavonoids of grapefruit (naringenin), orange (hesperidin), lemon (eriocitrin) were taken into account along a model structure for pectin RG-I...

Three‐component alkene difunctionalization reactions constitute an ideal platform to rapidly build molecular complexity, enabling the simultaneous introduction of two distinct, orthogonal functional groups into C=C bond in a single step. Herein, we report photoredox catalyzed Ritter‐type carboamidation electronically diverse styrenes harnessing non‐stabilized, nucleophilic primary radicals generated from readily‐accessible carboxylic acid‐derived redox active esters. Furthermore, it was...

Environmentally persistent free radicals (EPFRs) are toxic products deriving from incomplete combustion and able to generate DNA damage pulmonary dysfunction. They formed on particulate matter through interaction with aromatic hydrocarbons, catalyzed by transition metal oxides, produce reactive oxygen species (ROS) in aquatic media. The processes already described for substituted molecules, example, phenol, but not unsubstituted systems, such as benzene. This Article reports the reaction of...

We provide a comprehensive DFT investigation of the mechanistic details CO

Abstract GrafeoPlad‐Pd, a new metal‐organic alloy comprised of Pd nanoparticles doped with 3D‐entrapped graphene oxide, has promising applicative potential in sustainable synthetic organic chemistry. Besides hydrogenation, the metal nanopowder comprising material is also active and relatively stable cross‐coupling reactions carried out consecutively. X‐ray photoelectron spectroscopy (XPS) surface investigation density functional theory (DFT) calculations are applied to gain insight into...

A detailed theoretical investigation of the charge transport mechanism in poly(4-vinyl-imidazole) (P4VI), parent polymer a series N-heterocyclic-based membranes used as an electrolyte proton exchange membrane fuel cells, is presented. In particular, Density Functional Theory (DFT) results obtained for small model systems (protonated imidazole dimers and trimers) suggest that commonly accepted conduction mechanism, based on sequential transfer between moieties, could be impeded by geometrical...

Abstract DFT calculations were used to investigate the cycloaddition reaction of CO 2 styrene oxide for formation carbonate. The uncatalyzed process alongside reactions assisted by tetrabutylammonium bromide (TBAB), novel nonsymmetrical single‐center aluminum(III) salen–acac hybrid complex (salenac) (Al1cat) and binary Al1cat/TBAB system all investigated them optimized structures, rate‐determining steps, lowest energy barrier pathways intercepted both gas‐phase solvent environments. For...

The chemical shift (CS) values obtained by 1H NMR spectroscopy for the hydrogen atoms of a tetradentate N2O2-substituted Salphen ligand (H2L1) are differently shifted in its complexes nickel(II), palladium(II), platinum(II), and zinc(II), all bearing same charge on metal ions. To rationalize observed trends, DFT calculations have been performed implicit d6-DMSO solvent terms electronic effects induced ion nature strength metal-N metal-O bonds. Overall, results point out that, involving group...

Abstract Mg and Ca β‐diketiminato silylamides [HC{(Me)CN(2,6‐ i Pr 2 C 6 H 3 )} M(THF) n {N(SiMe ) }] (M=Mg, =0; M=Ca, =1) were studied as precatalysts for the dehydrogenation/dehydrocoupling of secondary amine–boranes R HNBH . By reaction with equimolar quantities amine–boranes, corresponding amidoborane derivatives are formed, which further react to yield dehydrogenation products such cyclic dimer [BH NMe ] DFT was used here explore mechanistic alternatives proposed on basis experimental...

NiOx has recently emerged as a robust catalyst with high catalytic activity for water oxidation reaction. Despite extensive studies, the origin of oxygen evolution reaction upon Fe doping is not fully solved, even one its simplest phases, β-Ni(OH)2. We present here density functional theory calculations using first time cluster approach to revisit electronic structure pure and Fe-doped First, our findings agree recent hypothesis that band gap case reduces doping. Second, in agreement earlier...

Photochemical reduction of carbon dioxide into methanol on bare and Mg-doped gallium nitrides. A detailed DFT study to shed light the photocatalytic activity this promising material.

Imparted with uniquely high and broad-scope bioactivity including antioxidant, anti-inflammatory, cardioprotective, neuroprotective, antimicrobial anticancer properties, the IntegroPectin phytocomplex obtained from citrus processing waste via hydrodynamic cavitation (HC) was investigated Density Functional Theory. The main flavonoids of grapefruit (naringenin), orange (hesperidin), lemon (eriocitrin) were taken into account along a model structure for pectin RG-I rhamnogalacturonan chains....

A quantum-chemical investigation of the dehydrocoupling reaction secondary amine-borane Me2HNBH3 assisted by phosphine chelating [Rh(Ph2P(CH2)n-PPh2)(C6H5F)]+ (n = 3–5) complexes to ultimately afford cyclic dimer [Me2NBH2]2 is reported. The hypothesis, proposed on basis experimental evidence, that catalytic efficiency such systems due formation Rh(III) dihydride complexes, which rapidly lose H2 and reform Rh(I) species, has been explored, together with influence structure ligand (namely,...

The utilization of CO2 as building block for the production cyclic carbonate is a promising route to simultaneously mitigate global warming issue and obtain valuable commercial chemicals. In this work, activity nicotinamidium halide catalysts towards conversion into has been explored by means density functional theory (DFT) calculations. DFT calculations support ability, suggested experimentally, pyridium α-C-H proton activate epoxide ring via hydrogen bond. Interestingly, underline...

The recently synthesized rhodium complex [Rh{P(C(5)H(9))(2)(η(2)-C(5)H(7))}(Me(2)HNBH(3))(2)]BAr(F)(4) (2), which incorporates two amine-boranes coordinated to the center with different binding modes, namely η(1) and η(2), has been used probe whether bis(σ-amine-borane) motifs are important in determining general course of dehydrocoupling reactions. DFT calculations have carried out explore mechanistic alternatives that ultimately lead formation amine-borane cyclic dimer [BH(2)NMe(2)](2) (A)...