Liquid-like properties of cyclopentadienyl complexes of barium: molecular dynamics simulations of nanoscale droplets.

Cyclopentadienyl complexes of barium have great utility in materials science and engineering, in particular, as precursors in the atomic layer deposition processes, which are required to be fluidic as well as thermally stable and volatile. Here, we investigated the liquid-like properties of cyclopentadienyl barium complexes including (Me5C5)2Ba, (tBu3C5H2)2Ba, (iPr4C5H)2Ba, (iPr5C5)2Ba, and [(SiMe3)3C5H2]2Ba, using molecular dynamics simulations of nanoscale droplets. The compounds were modeled using a recently developed generic force field, GFN-FF. Nanoscale droplets with about 5.0 nm diameters were formed by aggregating 96 molecules of each compound. Simulation results reveal that substituting methyl groups of (Me5C5)2Ba with other alkyl and silyl moieties has a non-negligible effect on the intra- and intermolecular structure and dynamics. In particular, in contrast to more flexible (Me5C5)2Ba, the substitution with five iso-propyl groups to form (iPr5C5)2Ba adds rigidity to the complex with restricted orientational fluctuations for two cyclopentadienyl ligands and arranges molecules parallel to each other with greater probability. In addition, comparison between (tBu3C5H2)2Ba, with three tert-butyl groups, and its silyl analogue, [(SiMe3)3C5H2]2Ba, reveals that intermolecular interactions between the molecules with silyl groups are softer than those with tert-butyl groups and result in broader radial distribution functions, whereas the dynamic properties are similar for both compounds. This work suggests that molecular dynamics simulations contribute to molecular-level understanding of the effect of chemical substitution in organometallic compounds on the intra- and intermolecular properties of molecular liquids.

CTCF cooperates with CtIP to drive homologous recombination repair of double-strand breaks.

The pleiotropic CCCTC-binding factor (CTCF) plays a role in homologous recombination (HR) repair of DNA double-strand breaks (DSBs). However, the precise mechanistic role of CTCF in HR remains largely unclear. Here, we show that CTCF engages in DNA end resection, which is the initial, crucial step in HR, through its interactions with MRE11 and CtIP. Depletion of CTCF profoundly impairs HR and attenuates CtIP recruitment at DSBs. CTCF physically interacts with MRE11 and CtIP and promotes CtIP recruitment to sites of DNA damage. Subsequently, CTCF facilitates DNA end resection to allow HR, in conjunction with MRE11-CtIP. Notably, the zinc finger domain of CTCF binds to both MRE11 and CtIP and enables proficient CtIP recruitment, DNA end resection and HR. The N-terminus of CTCF is able to bind to only MRE11 and its C-terminus is incapable of binding to MRE11 and CtIP, thereby resulting in compromised CtIP recruitment, DSB resection and HR. Overall, this suggests an important function of CTCF in DNA end resection through the recruitment of CtIP at DSBs. Collectively, our findings identify a critical role of CTCF at the first control point in selecting the HR repair pathway.

Anti-solvent derived non-stacked reduced graphene oxide for high performance supercapacitors.

An anti-solvent for graphene oxide (GO), hexane, is introduced to increase the surface area and the pore volume of the non-stacked GO/reduced GO 3D structure and allows the formation of a highly crumpled non-stacked GO powder, which clearly shows ideal supercapacitor behavior.

A strategically designed porous iron-iron oxide matrix on graphene for heavy metal adsorption.

The iron oxide nanoparticles were transformed to a matrix of iron-iron oxide on the graphene surface at an elevated temperature in a H(2)/Ar atmosphere. The resultant iron-iron oxide dispersed graphene was highly porous, robust and attractive for a variety of potential applications.

Inhibiting olefin cis, trans-photoisomerization and enhancing electron-accepting ability of a diboryl compound by metal chelation.

To examine the impact of metal chelation on cis-trans olefin bond isomerization and the photo-stability of N,C-chelate photochromic boron compounds, a new π-conjugated molecule B-BPY that incorporates a 2,2'-bipy unit, two olefin bonds, and two BMes(2)(ppy) chromophores has been synthesized and found to stabilize the molecule toward olefin photoisomerization upon binding with a metal ion.

Single boryl isomerization in silyl-bridged photochromic diboryl dyes.

Silyl-bridged dimers of a ppy-BMes(2) (ppy = 2-phenylpyridine, Mes = mesityl) photochrome were found to undergo photochromic switching involving a single boryl unit only. A through-space intramolecular energy transfer was found to be responsible for the single-chromophore isomerization phenomenon and fluorescence quenching. Steric congestion in the diboryl molecules was found to have an impact on photoisomerization quantum efficiency.

Molecular design of near-IR harvesting unsymmetrical squaraine dyes.

The functionalized unsymmetrical benzothiazole squaraine organic sensitizers 5-carboxy-2-({3-[(3-hexylbenzothiazol-2(3H)-ylidene)methyl]-2-hydroxy-4-oxo-2-cyclobuten-1-ylidene}methyl)-1-hexyl-3,3-dimethyl-3H-indolium (hereafter named as SK-11) and 5-carboxy-2-({3-[(3-hexyl-5-methoxybenzothiazol-2(3H)-ylidene)methyl]-2-hydroxy-4-oxo-2-cyclobuten-1-ylidene}methyl)-1-hexyl-3,3-dimethyl-3H-indolium (coded as SK-12) are designed and developed to observe an intense and wider absorption band in the red/NIR wavelength region. DFT/TDDFT calculations have been performed on the two unsymmetrical squaraine sensitizers to gain insight into their electronic and optical properties. The utility of these dyes in solid state dye sensitized solar cells (SS-DSSCs) is demonstrated.

Steric and electronic influence on photochromic switching of N,C-chelate four-coordinate organoboron compounds.

A four-coordinate organoboron compound B(ppy)Mes(2) (1, ppy=2-phenylpyridyl, Mes=mesityl) was previously found to undergo reversible photochromic switching through the formation/breaking of a C-C bond, accompanied by a dramatic color change from colorless to dark blue. To understand this unusual phenomenon, a series of new four-coordinate boron compounds based on the ppy-chelate ligand and its derivatives have been synthesized. In addition, new N,C-chelate ligands based on benzo[b]thiophenylpyridine and indolylpyridine have also been synthesized and their boron compounds were investigated. The crystal structures of most of the new compounds were determined by X-ray diffraction analysis. UV/Vis, NMR, and electrochemical methods were used to monitor the photoisomerization process. DFT calculations were performed for all compounds to understand the photophysical and electronic properties of this class of molecules. The results of our study showed that the bulky mesityl group is necessary for photochromic switching. Electron-donating and electron-withdrawing groups on the ppy chelate have a distinct impact on the photoisomerization rate and the photochemical stability of the molecule. Furthermore, we have found that the non-ppy-based N,C-chelate ligands such as benzo[b]thiophenepyridyl can also promote photoisomerization of the boron chromophore in the same manner as the ppy chelate, but the product is thermally unstable.

Enhancing the photochemical stability of N,C-chelate boryl compounds: C-C bond formation versus C=C bond cis,trans-isomerization.

N,C-chelate boron compounds such as B(ppy)Mes(2) (ppy = 2-phenylpyridyl, Mes = mesityl) have been recently shown to undergo a facile and reversible C-C/C-B bond rearrangement upon irradiation with UV-light, quenching the emission of the sample and limiting their use in optoelectronic devices. To address this problem, four molecules have been synthesized in which the pi-conjugation is extended using either vinyl or acetylene linkers. These compounds, (ph-C[triple bond]C-ppy)BMes(2) (B1A), (ph-CH=CH-ppy)BMes(2) (B1), [p-bis(ppy-CH=CH)benzene](BMes(2))(2) (B2), and [1,3,5-tris(ppy-CH=CH)benzene](BMes(2))(3) (B3) have been fully characterized by NMR and single-crystal X-ray diffraction analyses. All four compounds are light yellow and emit blue or blue-green light upon UV irradiation. The acetylene compound B1A has been found to exhibit photochemical instability the same as that of the parent chromophore B(ppy)Mes(2). In contrast, all of the olefin-substituted compounds are photochemically stable, instead undergoing cis-trans isomerization exclusively upon exposure to UV light. Experimental and TD-DFT computational results establish that the presence of the olefinic bond in B1-B3 provides an alternate energy dissipation pathway for the B(ppy)Mes(2) chromophore, stabilizing the molecule toward photochromic switching via cis-trans isomerization. Furthermore, the incorporation of a cis-trans isomerization pathway may prove to be a useful strategy for the stabilization of photochemically unstable chromophores in other pi-systems as well.

Molecular engineering of organic sensitizers containing p-phenylene vinylene unit for dye-sensitized solar cells.

Three organic sensitizers containing bis-dimethylfluorenyl amino donor and a cyanoacrylic acid acceptor bridged by p-phenylene vinylene unit were synthesized. The power conversion efficiency was quite sensitive to the length of bridged phenylene vinylene groups. A nanocrystalline TiO2 dye-sensitized solar cell was fabricated using three sensitizers. The maximum power conversion efficiency of JK-59 reached 7.02%.

Generation and trapping reaction of an efficient 1,2-dehydrocarborane precursor, phenyl[o-(trimethylsilyl)carboranyl]iodonium acetate.

An efficient 1,2-dehydrocarborane precursor, phenyl[o-(trimethylsilyl)carboranyl]iodonium acetate, was readily prepared by reaction of [o-(trimethylsilyl)carboranyl]lithium and IPh(OAc)2. The facile 2+4 cycloaddition of with dienes such as anthracene, naphthalene, norborna-2,5-diene and 2,5-dimethylfuran gave high yields of the 1,2-dehydrocarborane adducts in the presence of a desilylating agent. The reaction of with a cyclic alkene and strained cycloalkynes afforded the adducts formed by the ene reaction and the 2+2 cycloaddition reaction. The reaction of with a bicyclopalladacycle yielded the cyclization product. The structures of compounds and were determined by single-crystal X-ray crystallography.