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ed above the edge of the valence band, revealing an introduction of the p-type character.A variety of tetrahydroquinoline-fused bicycles bearing multiple stereocenters are prepared in good yields with high diastereoselectivity through Cu2O-catalyzed [4 + 2] cycloaddition of aza-ortho-quinone methides (ao-QMs) with bicyclic alkenes. Mechanistic studies reveal that the Cu(i) catalyst not only promotes the formation of ao-QMs through a radical process by single electron transfer but also accelerates [4 + 2] cycloaddition. The reaction was easily performed on gram scale and the obtained tetrahydroquinoline-fused bicycles can be converted to diverse tetrahydroquinoline scaffolds.Recently, re-purposing of cyanobacterial photoreceptors as optogentic actuators enabled light-regulated protein expression in different host systems. These new bi-stable optogenetic tools enable interesting new applications, but their light-driven working mechanism remains largely elusive on a molecular level. Here, we study the optogenetic cyanobacteriochrome Am1-c0023g2 with isotope labeling and two dimensional infrared (2D-IR) spectroscopy. Isotope labeling allows us to isolate two site-specific carbonyl marker modes from the overwhelming mid-IR signal of the peptide backbone vibrations. Unlike conventional difference-FTIR spectroscopy, 2D-IR is sensitive to homogeneous and inhomogeneous broadening mechanisms of these two vibrational probes in the different photostates of the protein. We analyse the 2D-IR line shapes in the context of available structural models and find that they reflect the hydrogen-bonding environment of these two marker groups.α-CF3-enamines can be prepared by the reaction of pyrrolidine with the corresponding haloalkenes. The prepared enamines react with 2-nitrobenzaldehydes to give ortho-nitro-substituted α,β-diaryl-CF3-enones highly stereoselectively in up to 88% yield. Subsequent reduction of the nitro-group by an Fe-AcOH system promotes intramolecular cyclization to afford 2-CF3-3-arylquinolines in up to 99% isolated yield. High synthetic utility of all synthetic steps of the sequence was shown. A one-pot procedure was developed to give the target trifluoromethylated quinolines directly from enamines or haloalkenes.Six-membered rings are common building blocks of many carbon structures. Recent studies have shown that penta-graphene composed of five-membered carbon rings have properties very different from that of graphene. This has motivated the search for new carbon structures. Among this is cp-graphyne, composed of carbon pentagons and bridged by acetylenic linkers. However, the bandgap of cp-graphyne, like that of graphene, is zero, making it unsuitable for applications in electronics. Herein, we show that a new two-dimensional (2D) carbon nitride structure formed by assembling the five-membered imidazole molecules with acetylenic linker can overcome this limitation. Named ID-GY, this new material not only has a direct band gap of 1.10 eV, but it is dynamically and mechanically stable and can withstand temperatures up to 1200 K. In addition, due to its porous and anisotropic geometry, the Young's modulus of ID-GY along the diagonal direction is lower than that of most 2D materials reported previously. Equally important, ID-GY exhibits strong refraction near infrared (IR) and has potential for applications in nanoelectronics and optical devices. These results, based on density functional theory, can stimulate experimental studies.Ribonucleases are useful as biomarkers and can be the source of contamination in laboratory samples, making ribonuclease detection assays important in life sciences research. With recent developments in DNA-based biosensing, several new techniques are being developed to detect ribonucleases. This review discusses some of these methods, specifically those that utilize G-quadruplex DNA structures, DNA-nanoparticle conjugates and DNA nanostructures, and the advantages and challenges associated with them.The first method for highly efficient asymmetric Michael-type Friedel-Crafts alkylation of naphthol and unsaturated pyrazolones has been accomplished under mild reaction conditions. In the presence of the chiral squaramide catalyst, a wide range of substrates are tolerated in excellent yields (up to 99%) with reasonable enantioselectivities (up to 96% ee).A Mn(ii)-catalyzed efficient C-H alkylation of imidazoheterocycles with methyl ketones has been developed via dehydrogenative C(sp3)-C(sp2) coupling which can serve as a novel approach toward hydrocarboxylated imidazolopyridines. The merit of this strategy is illustrated by excellent functional group tolerance and the use of cheap and readily available starting materials.We demonstrate here that the Ugi-Sonogashira protocol can be successfully used to obtain five new molecular rotors 10a-e with strong emission. They have been synthesized by combining multicomponent Ugi stators and several aromatic rotary components phenylene, p-xylene, naphthalene and anthracene. The synthesized conjugated rotors are highly fluorescent (Φf = 0.39 to Φf = 0.10), and changes in their emission were observed upon variations of the surrounding media. Particularly, we found that they are sensitive to aggregation (THF/water) or high viscosity (methanol/glycerol) conditions. This work paves the way to develop new emissive rotors with exciting photophysical properties.A convenient, "one-pot" synthesis of trisubstituted pyrroles via a Ru(ii)-catalyzed, Cu(ii)-mediated reaction of substituted isoxazoles with sulfonylhydrazones has been developed. A series of highly functionalized pyrroles are obtained via a synergistic formation of new C-C and C-N bonds. Mechanistic investigations were carried out to propose the plausible pathway. This protocol provides a facile and expeditious approach for the synthesis of various heterocyclic compounds bearing the pyrrole skeleton.In this study we report on the accurate computation of the biomolecular partial specific volume (PSV) from explicit-solvent molecular dynamics (MD) simulations. learn more The case of DNA is considered, and the predictions from two state-of-the-art biomolecular force fields, the CHARMM36 additive (C36) and Drude polarizable models, are presented. Unlike most of the existing approaches to assess the biomolecular PSV, our proposed method bypasses the need for the arbitrarily defined volume partitioning scheme into the intrinsic solute and solvent contributions. At the same time, to assess the density of the hydration layer water, we combine our simulation analysis approach with some of the existing fixed-size methods to determine the solute's intrinsic volume, and also propose our own approach to compute all required quantities exclusively from MD simulations. Our findings provide useful insights into the properties of the hydration layer, specifically its size and density, parameters of great importance to the variety of techniques used to model hydrodynamic and structural properties of biological molecules.