Self-organization of bent rod molecules into hexagonally ordered vesicular columns

Bent-shaped rigid-core molecules with flexible chiral dendrons grafted to the outer side of the bend were synthesized and characterized by circular dichroism, differential scanning calorimetry, X-ray scatterings, and transmission electron microscopy in solution and the solid state. The bent aromatic rods based on hepta- and nonaphenylene with nitrile groups at both ends self-assemble into well-ordered hollow tubular structures in aqueous solution, while the bent rod based on heptaphenylene without nitrile groups showed no apparent aggregations in aqueous solution. In the solid state, the rigid-flexible molecules based on heptaphenylene rod without the nitrile group self-assemble into a 2D oblique columnar structure with the columnar cross-section containing two interlocked molecules. Remarkably, the rigid flexible molecules based on hepta-, nona-, and undecaphenylene with nitrile groups self-assemble into a hexagonal columnar structure with weak 3D order. A model of vesicular channel structure is proposed based on small- and wide-angle X-ray diffraction on oriented fibers, density measurement, reconstruction and simulation of electron density maps, and molecular dynamics simulation. In contrast to the hollow tubular structure found in solution, in the solid both the outside and the interior of the columns are filled by the pendant aliphatic coils. Filling of the interior of these vesicular channels is made possible by some bent rod molecules turning their obtuse apex inward. One in 7, 2 in 8, and 4 in 10 molecules are thus inverted in a column slice in compounds with hepta-, nona-, and undecaphenylene cores, respectively. These are new examples of vesicular double-segregated columnar structures recently discovered in some dendrons.     

Determination and pharmacokinetics of [6]-gingerol in mouse plasma by liquid chromatography-tandem mass spectrometry

This study describes the development of a rapid and sensitive high‐performance liquid chromatography–electrospray ionization tandem mass spectrometry (LC‐MS/MS) assay for the quantification of [6]‐gingerol in mouse plasma and application to a pharmacokinetic study after dose ranging in mice. The assay involved a protein precipitation step with acetonitrile and an isocratic elution using a mobile phase consisting of acetonitrile and water containing 0.1% formic acid (80:20 v/v). The multiple reaction monitoring was based on the transition of m/z = 277.2 → 177.1 for [6]‐gingerol and 294.2 → 137.1 for nonivamide (internal standard). The assay was validated to demonstrate the specificity, linearity, recovery, accuracy, precision and stability. The calibration curves were linear over the wide concentration range of 10–10,000 ng/mL (r ≥ 0.9988). The lower limit of quantification was 10 ng/mL using a small volume of mouse plasma (20 μL). The method was successfully applied to a pharmacokinetic study in mice after intravenous injection of [6]‐gingerol at 1.5, 3 and 6 mg/kg doses. The pharmacokinetics of [6]‐gingerol were linear over the dose range studied as demonstrated by the linear increase in area under the concentration‐time curve (AUC_inf) with no significant change in the systemic clearance (Cl_s), volume of distribution (V_ss) and elimination half‐life (t_1/2) as a function of dose. Copyright © 2011 John Wiley & Sons, Ltd.     

Highly stable inverted poly (3-hexylthiophene):methano-fullerene [6,6]-phenyl C71-butyric acid methyl ester bulk heterojunction solar cell with thin oxide nano particle layer using solution process

We have investigated the inverted poly (3-hexylthiophene):methano-fullerene [6,6]-phenyl C71-butyric acid methyl ester (P3HT:PC₇₁BM) bulk heterojunction (IBHJ) solar cell with various n-type metal oxide nano particle layers on ITO and MoO₃ anode buffer layer underneath Al. The IBHJ solar cell with a tin oxide nano particle layer shows the power conversion efficiency (PCE) of 3.1% and better stability compared to conventional BHJ solar cell. The PCE of this cell decreases by 3% after 2 months in ambient air while the other cells show more degradation.     

Measuring relative grain-boundary energies in block-copolymer microstructures

The (relative) energies of symmetric tilt grain boundaries in a strongly segregated lamellar block copolymer are determined by analysis of the dihedral angles at grain-boundary triple junctions. The analysis reveals two regimes: at low and intermediate misorientations (corresponding to a tilt-angle range 0≤θ≤85°) the grain-boundary energy is found to depend on the tilt angle as E(θ)～θ(x), with 2.5>x≥0. At large misorientations the grain-boundary energy is found to be independent (within the experimental uncertainty) of the angle of tilt. The transition between the two scaling regimes is accompanied by the transition of the grain-boundary structure from the chevron to the omega morphology. Grain-boundary energy and frequency are found to be inversely related, thus suggesting boundary energy to be an important parameter during grain coarsening in block-copolymer microstructures, as it is in inorganic polycrystalline microstructures.     

Designed cyanide- and phenoxide-bridged Fe(III)Mn(III) single-molecule magnet constructed by highly blocked paramagnetic precursors

A tetranuclear Fe(III)(2)Mn(III)(2) compound was prepared using highly blocked precursors. The well-isolated molecular entity associated with appropriate magnetic anisotropy allows for single-molecule magnet behavior.     

Gold-catalyzed intramolecular hydroalkoxylation/cyclization of conjugated dienyl alcohols

Catalytic intramolecular additions of hydroxyl groups to tethered conjugated dienes are described. The reactions proceed smoothly at 60 °C in the presence of 5 mol % of (PPh₃)AuCl/AgOTf as a catalyst. A broad range of structurally diverse conjugated dienes produce substituted tetrahydrofurans and tetrahydropyrans in good yields. This reaction represents an atom-economic route to construct five- and six-membered cyclic ethers.     

Metal ion affinity purification of proteins by genetically incorporating metal-chelating amino acids

Affinity tags are efficient tools for protein purification. They allow simple one-step purification of proteins to high purity. However, in some cases the tags cause structural and functional changes in a protein, and need to be removed. Therefore, affinity tags that are readily introduced into proteins with minimal perturbation and have specific affinity for purification are desired. Herein, two metal-chelating amino acids derived from 2,2′-bipyridine and 8-hydroxyquinoline were genetically incorporated into glutathione S-transferase (GST) and the mutant proteins were purified by using the metal ion affinity of the unnatural amino acids. The purification of the GST mutants containing 2-amino-3-(8-hydroxyquinolin-3-yl)propanoic acid (HQA) showed that the proteins could be efficiently enriched in Ni–NTA by the metal ion affinity of the unnatural amino acid and purified to excellent purity. This method should be very useful for general protein affinity purification, especially for proteins whose structure or function is affected by affinity tags fused to N- or C-terminals.     

Beta‐decomposition for the volume and area of the union of three‐dimensional balls and their offsets

Given a set of spherical balls, called atoms, in three‐dimensional space, its mass properties such as the volume and the boundary area of the union of the atoms are important for many disciplines, particularly for computational chemistry/biology and structural molecular biology. Despite many previous studies, this seemingly easy problem of computing mass properties has not been well‐solved. If the mass properties of the union of the offset of the atoms are to be computed as well, the problem gets even harder. In this article, we propose algorithms that compute the mass properties of both the union of atoms and their offsets both correctly and efficiently. The proposed algorithms employ an approach, called the Beta‐decomposition, based on the recent theory of the beta‐complex. Given the beta‐complex of an atom set, these algorithms decompose the target mass property into a set of primitives using the simplexes of the beta‐complex. Then, the molecular mass property is computed by appropriately summing up the mass property corresponding to each simplex. The time complexity of the proposed algorithm is O(m) in the worst case where m is the number of simplexes in the beta‐complex that can be efficiently computed from the Voronoi diagram of the atoms. It is known in ?³ that m = O(n) on average for biomolecules and m = O(n²) in the worst case for general spheres where n is the number of atoms. The theory is first introduced in ?² and extended to ?³. The proposed algorithms were implemented into the software BetaMass and thoroughly tested using molecular structures available in the Protein Data Bank. BetaMass is freely available at the Voronoi Diagram Research Center web site. © 2012 Wiley Periodicals, Inc.     

Green water void fraction due to breaking wave impinging and overtopping

The present study uses laboratory measurements to investigate the void fraction of an overtopping flow on a structure. The overtopping flow, also called green water, was generated by the impingement of a plunging breaking wave on the structure following the Froude similarity of an extreme hurricane wave and a simplified offshore structure. The flow is multi-phased and turbulent with significant aeration. A fiber optic reflectometer (FOR) and bubble image velocimetry (BIV) were employed to measure the void fraction and velocity in the flow, respectively, and to determine the water level on the deck. Mean properties of void fraction and velocity were obtained by ensemble-averaging and time-averaging the repeated instantaneous measurements. The temporal and spatial distributions of void fraction reveal that the flow is very highly aerated near the front of green water and has relatively low aeration near the deck surface. The mean void fraction and velocity distributions were also depth-averaged for simplicity and potential use in engineering applications. Using the measured data, similarity profiles for depth-averaged void fraction, depth-averaged velocity, and water level were found. The study suggests that using only the velocity data is insufficient if the flow momentum or the flow rate is to be determined. The accuracy of the void fraction measurements was validated by comparing the directly measured water volume of the overtopping flow with the calculated water volume based on the measured velocity and void fraction.