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Pd-catalyzed C-H bond arylation applied to 2-(2,4-difluorophenyl)-5-(trifluoromethyl)pyridine (1) and 2-(3,5-difluorophenyl)-5-(trifluoromethyl)pyridine (5) allows the access to two families of Ir(III) complexes, charge-neutral and cationic species. The reaction is regioselective since only the C3- or C4-position of the fluorinated phenyl ring of 1 or 5 is readily functionalized – namely the C-H bond flanked by the two fluorine atoms which is the most acidic – which allows the electronic control of the reactive site. 2,2,2-Tribromoethanol in vivo A range of electron-withdrawing (CN, CO2Et, C(O)Me) substituents on the aryl group has been incorporated leading to the pro-ligands (1, Ar-2,4-dFppy; 2, Ar = p-C6H4-CN; 3, Ar = p-C6H4-CO2Et; 4, Ar = p-C6H4-C(O)Me; 5, and Ar-3,5-dFppy; 6, Ar = p-C6H4-CO2Et). The unsubstituted complexes F1/G1 and F1/G5 featuring 1 and 5, respectively, as C^N ligands are used as reference complexes. The families of five charge-neutral [Ir(C^N)2(N^O)] complexes (C^N is 2-(5-aryl-(4,6-difluorophenyl)-5-(trifluoromethy3- and C5-positions, emit in the green region of the visible spectrum. In all cases, a unitary photoluminescence quantum yield is found. The improvement of Φ might be explained by an increase of the radiative rate constant due to a higher degree of rigidity of these congested molecules, compared to the unsubstituted complex F1. The same trends are observed for the family of complexes G. Complexes G1-G4 exhibit blue photoluminescence, and G5 and G6 lead to a red-shifted emission band, as also found for the related complexes F5 and F6 due to the similar fluorine substitution pattern. Their emission quantum yields are remarkably high for charged complexes in the CH2Cl2 solution. These results showed that Pd-catalyzed C-H bond arylation is a valuable synthetic approach for designing efficient emitters with tunable photophysical properties.Mitochondrial dysfunction has been recognized as an essential contributor to many human diseases including neurodegenerative disorders. However, the exact pathological role of mitochondrial dysfunction, especially in mitochondrial reactive oxygen species-associated oxidative stress, remains elusive, partially due to the lack of chemical probes with well-defined mechanisms of action. Herein, we describe the characterization and discovery of a rationally designed small molecule ZCM-I-1 as a selective modulator of the production of reactive oxygen species from mitochondrial complex I that does not alter mitochondrial membrane potential and bioenergetics. Chemical biology studies employing photoaffinity probes derived from ZCM-I-1 demonstrated its novel mechanism of action of modulating complex I via interactions with the flavin mononucleotide site, proximal in the reaction pathway within complex I.The ethylene glycol (EG) molecule, HOCH2CH2OH, adopts a conformation where the central OCCO dihedral is exclusively gauche in the gaseous and crystalline states, but in the liquid state, for close to 20% of the molecules, the central OCCO adopts the energetically unfavorable trans conformation. Here we report calculations, based on ab initio molecular dynamics simulations, on the thermodynamics associated with hydrogen bond formation in the liquid state of EG between donor-acceptor pairs with different molecular conformations. We establish an operational, geometric definition of hydrogen bonds in liquid EG from an analysis of the proton NMR data and show that the key feature, irrespective of the conformation, is marked directionality with almost linear ∠HO···O angles. The free energy for hydrogen bond formation estimated as the potential of mean force for the reversible work associated with the passage from a hypothetical state where hydrogen bonding is absent and donor-acceptor pairs are randomly oriented to the hydrogen-bonded state where the pairs are oriented showed comparable magnitudes irrespective of the molecular conformation of either the donor or acceptor. The results suggest that the presence of the trans conformer in liquid EG would require an understanding of its role in the extended hydrogen-bonded network of the liquid.This work examines the electronic structure and apparent instability of ethylenedione (OCCO), including an analysis of the singlet and triplet potential energy surfaces along the bending vibrations. While the singlet state is inherently unstable due to the Renner-Teller effect, theory predicts the triplet state to have a stable minimum on the potential energy surface. The stability of the triplet state is examined in detail, taking into account spin-orbit interactions. Using multireference quantum chemical methods, the lifetime of the triplet state is estimated to be in the picosecond range, significantly lower than previously computed. A quasi-atomic molecular orbital (QUAO) analysis is also used to elucidate the nature of bonding along the potential energy surface in both the singlet and triplet states. These calculations confirm the transient nature of the OCCO molecule, although they do not fully explain the lack of experimental detection via spectroscopy, which is known have the capability to probe even shorter lifetimes.Although massive data is quickly accumulating on protein sequence and structure, there is a small and limited number of protein architectural types (or structural folds). This study is addressing the following question how well could one reveal underlying sequence-structure relationships and design protein sequences for an arbitrary, potentially novel, structural fold? In response to the question, we have developed novel deep generative models, namely, semisupervised gcWGAN (guided, conditional, Wasserstein Generative Adversarial Networks). To overcome training difficulties and improve design qualities, we build our models on conditional Wasserstein GAN (WGAN) that uses Wasserstein distance in the loss function. Our major contributions include (1) constructing a low-dimensional and generalizable representation of the fold space for the conditional input, (2) developing an ultrafast sequence-to-fold predictor (or oracle) and incorporating its feedback into WGAN as a loss to guide model training, and (3) exploiting sequence data with and without paired structures to enable a semisupervised training strategy.