Base mediated synthesis of α-aminated aroyl/acetylnaphthalenes through [4+2] annulations

We have developed a base promoted simple, efficient and alternative approach for the synthesis of 4-amino-3-aroyl//heteroaroyl/acetyl-2-methylsulfanyl-naphthalene-1-carbonitriles by reaction of easily accessible 3,3-bis(methylthio)-1-aryl/heteroaryl/acetylprop-2-en-1-one and 2-cyanomethyl-benzonitrile. Reaction of 1-(2-halo/methoxy-phenyl)-3,3-bis(methylthio)prop-2-en-1-one and 2-cyanomethyl-benzonitrile under basic conditions also afforded 6-(methylthio)-7-oxo-7,12-dihydrobenzo[c]acridine-5-carbonitrile along with usual product. Structure of the synthesized product has been confirmed by single X-ray crystallography.     

Laser‐Induced Self‐Assembled Nanostructures on Electron‐Transparent Substrates

Currently, one of the challenges in high‐resolution transmission electron microscopy (TEM) studies of nanomaterials is to make contamination‐free materials in a simple and time‐efficient way. Here, a method is demonstrated that combines nanosecond‐pulsed laser dewetting of thin films with a film float‐off technique to realize nanostructures (NSs) on electron‐transparent substrates in a robust and rapid manner. NSs of metal (Ag) and bimetals (AgCo, AuCo) ranging from 20 to 150 nm are synthesized on thin carbon film deposited on mica substrates. The NS/carbon system is subsequently transferred onto TEM grids by a float‐off process resulting from debonding of the carbon from mica due to their contrasting hydrophobic nature. This process enables the fabrication of different NSs on flexible and electron‐transparent substrates.     

TDDFT Investigation of the Electronic Structures and Photophysical Properties of Fluorescent Extended Styryl Push-Pull Chromophores Containing Carbazole Unit

Push-pull chromophores attached to carbazole based π-conjugating spacers bearing N-alkylamino donors, cyanovinyl and carbethoxy acceptors have been studied by the means of UV-Visible measurements. The intramolecular charge transfer (ICT) of these π-conjugated systems has also been tested by investigating the ability of the solute molecules to undergo shifts in their fluorescence emission maxima with increasing solvent polarity. Density Functional Theory [B3LYP/6-31G(d)] and Time Dependent Density Functional Theory [TD-B3LYP/6-31G(d)] computations have been used to have more understanding of the structural, molecular, electronic and photophysical parameters of push-pull dyes. The largest wavelength difference between the experimental and computed electronic absorption maxima was 45 nm. For emission, a largest difference of 61 nm was observed. The ground state and excited state dipole moments in different solvents were determined using experimental solvatochromic data and computed Onsager radii. The dipole moments of the molecules in the excited state were observed to be higher than in the ground state.     

Synthesis, Photo-physical and DFT Studies of ESIPT Inspired Novel 2-(2′,4′-Dihydroxyphenyl) Benzimidazole, Benzoxazole and Benzothiazole

Novel ESIPT inspired benzimidazole, benzoxazole and benzothiazole were synthesized from 2,4-dihydroxy benzoic acid and 1,2-phenelenediamine, 2-aminophenol, and 2-aminothiophenol respectively. The synthesized 2-(2′,4′-dihydroxyphenyl) benzimidazole, benzoxazole and benzothiazole are fluorescent and the emission characteristic are very sensitive to the micro-environment. They show a single absorption and dual emission with large Stokes shift originating from excited state intramolecular proton transfer. The absorption-emission characteristics of all these compounds are studied as a function of pH. The change in the electronic transition, energy levels, and orbital diagrams of synthesized compounds were investigated by the molecular orbital calculation and were correlated with the experimental spectral emission. Experimental absorption and emission wavelengths are in good agreement with those predicted using the Density Functional Theory (DFT) and Time-Dependent Density Functional Theory (TD-DFT) [B3LYP/6-31G(d)].

Structures and photocatalytic performance of two d10 metal-based coordination polymers containing mixed building units

The linker 1,4-bis(2-methyl-imidazole-yl)-butane (bib) was used to construct two coordination polymers, specifically [Cd(bib)(ipa)]_n (1) and [Zn(bib)(tpa)]_n (2), in the presence of isophthalic acid (H₂ipa) and terephthalic acid (H₂tpa), respectively, under solvothermal conditions. Topological analyses reveal that the crystal of complex 1 consists of a 3D threefold interpenetrating network with Schläfli symbol {6⁵.8}, while complex 2 possesses a 2D wavelike layer structure with Schläfli symbol {6⁶}. The photocatalytic properties of both complexes for the degradation of methyl violet have been explored, revealing that complex 2 is a better photocatalyst than 1. A mechanism for the photocatalytic properties of the complexes is proposed, based on the results of density of states (DOS) and partial DOS calculations.

     

Conformational landscape of the HIV-V3 hairpin loop from all-atom free-energy simulations

Small beta hairpins have many distinct biological functions, including their involvement in chemokine and viral receptor recognition. The relevance of structural similarities between different hairpin loops with near homologous sequences is not yet understood, calling for the development of methods for de novo hairpin structure prediction and simulation. De novo folding of beta strands is more difficult than that of helical proteins because of nonlocal hydrogen bonding patterns that connect amino acids that are distant in the amino acid sequence and there is a large variety of possible hydrogen bond patterns. Here we use a greedy version of the basin hopping technique with our free-energy forcefield PFF02 to reproducibly and predictively fold the hairpin structure of a HIV-V3 loop. We performed 20 independent basin hopping runs for 500 cycles corresponding to 7.4 x 10(7) energy evaluations each. The lowest energy structure found in the simulation has a backbone root mean square deviation (bRMSD) of only 2.04 A to the native conformation. The lowest 9 out of the 20 simulations converged to conformations deviating less than 2.5 A bRMSD from native.