Excitation-energy migration in self-assembled cyclic zinc(II)-porphyrin arrays: a close mimicry of a natural light-harvesting system

The excitation-energy-hopping (EEH) times within two-dimensional cyclic zinc(II)-porphyrin arrays 5 and 6, which were prepared by intermolecular coordination and ring-closing metathesis reaction of olefins, were deduced by modeling the EEH process based on the anisotropy depolarization as well as the exciton-exciton annihilation dynamics. Assuming the number of energy-hopping sites N = 5 and 6, the two different experimental observables, that is, anisotropy depolarization and exciton-excition annihilation times, consistently give the EEH times of 8.0 +/- 0.5 and 5.3 +/- 0.6 ps through the 1,3-phenylene linkages of 5 and 6, respectively. Accordingly, the self-assembled cyclic porphyrin arrays have proven to be well-defined two-dimensional models for natural light-harvesting complexes.     

Determination of PF‐04620110, a novel inhibitor of diacylglycerol acyltransferase‐1, in rat plasma using liquid chromatography–tandem mass spectrometry and its application in pharmacokinetic studies

In this study, we developed a method for the determination of PF‐04620110 (2‐{(1r,4r)‐4‐[4‐(4‐amino‐5‐oxo‐7,8‐dihydropyrimido[5,4‐f][1,4]oxazepin‐6(5H)‐yl)phenyl]cyclohexyl}acetic acid), a novel diacylglycerol acyltransferase 1 (DGAT‐1) inhibitor, in rat plasma and validated it using liquid chromatography–tandem mass spectrometry (LC‐MS/MS). Rat plasma samples were processed following a protein precipitation method by using acetonitrile and were then injected into an LC‐MS/MS system for quantification. PF‐04620110 and imipramine (internal standard) were separated using a Hypersil Gold C₁₈ column, with a mixture of acetonitrile and 10 mm ammonium formate (90:10, v/v) as the mobile phase. The ion transitions monitored in positive‐ion mode [M + H]⁺ of multiple‐reaction monitoring were m/z 397.0 → 260.2 for PF‐04620110 and m/z 280.8 → 86.0 for imipramine. The detector response was specific and linear for PF‐04620110 at concentrations within the range 0.05–50 µg/mL and the signal‐to‐noise ratios for the samples were ≥10. The intra‐ and inter‐day precision and accuracy of the method matched the acceptance criteria for assay validation. PF‐04620110 was stable under various processing and/or handling conditions. PF‐04620110 concentrations in the rat plasma samples could be measured up to 24 h after intravenous or oral administration of PF‐04620110, suggesting that the assay is useful for pharmacokinetic studies in rats. Copyright © 2013 John Wiley & Sons, Ltd.     

Structural and functional stabilities of artificially designed DNA ultra-thin films grown by silica Assistance

We report the structural and functional stabilities of artificially synthesized DNA ultra-thin films. Fully covered DNA ultra-thin films on a silica substrate were fabricated by the silica-assisted growth method and those samples were then incubated in various chemicals and physical conditions. The DNA ultra-thin films showed high maintainability under those harsh conditions and these results would aid to facilitate the use of artificial DNA ultra-thin films in advanced research areas such as biophotonics and bioelectronics.     

Refolding of Laccase in Dilution Additive Mode with Copper-Based Ionic Liquid

Ionic liquids (ILs) are molten salts which do not crystallize at room temperature. Tunable physicochemical properties of ILs including hydrophobicity and polarity facilitate their applications in many biological processes. In this study, a copper-based IL was employed in order to enhance the refolding efficiency of laccase from Trametes versicolor which requires copper as a cofactor. When 1-ethyl-3-methylimidazolium trichlorocuprate ([EMIM][CuCl₃]) was added to refolding buffer instead of urea, the laccase refolding yield was improved more than 2.7 times compared to the conventional refolding buffer which contains urea. When the refolding of laccase was carried out at different temperatures (4, 25, and 37 °C), the highest refolding yield was obtained at 25 °C. At low temperature, two conflicting effects, i.e., suppression of the aggregate formation and decrease of folding rate, influence the protein refolding. In contrast, a copper-based IL did not enhance the refolding of lysozyme, a non-copper-containing protein. From these results, we can conclude that this copper-based IL, [EMIM][CuCl₃], was exclusively effective on the refolding process of a copper-containing protein.     

Pd nanoparticles immobilized on PNIPAM–halloysite: highly active and reusable catalyst for Suzuki–Miyaura coupling reactions in water

Poly(N‐isopropylacrylamide)–halloysite (PNIPAM‐HNT) nanocomposites exhibited inverse temperature solubility with a lower critical solution temperature (LCST) in water. Palladium (Pd) nanoparticles were anchored on PNIPAM‐HNT nanocomposites with various amounts of HNT from 5 to 30 wt%. These Pd catalysts exhibited excellent reactivities for Suzuki–Miyaura coupling reactions at 50–70 °C in water. In particular, Pd anchored PNIPAM/HNT (95:5 w/w ratio) nanocomposites showed excellent recyclability up to 10 times in 96% average yield by simple filtration. Copyright © 2014 John Wiley & Sons, Ltd.     

Switched exponential state estimation of neural networks based on passivity theory

In this paper, a new exponential state estimation method is proposed for switched Hopfield neural networks based on passivity theory. Through available output measurements, the main purpose is to estimate the neuron states such that the estimation error system is exponentially stable and passive from the control input to the output error. Based on augmented Lyapunov–Krasovskii functional, Jensen’s inequality, and linear matrix inequality (LMI), a new delay-dependent state estimator for switched Hopfield neural networks can be achieved by solving LMIs, which can be easily facilitated by using some standard numerical packages. The unknown gain matrix is determined by solving delay-dependent LMIs. Finally, a numerical example is provided to demonstrate the effectiveness of the proposed method.     

Micromorphology of epicuticular wax structures of the garden strawberry leaves by electron microscopy: Syntopism and polymorphism

Ultrastructural aspects of leaf epicuticular wax structures were investigated in the garden strawberry Fragaria × ananassa by scanning and transmission electron microscopy. Both the adaxial and abaxial surfaces of two cultivars (Maehyang and Red Pearl) were collected and subjected to surface observations and ultrathin sections. The most prominent leaf epicuticular wax structures included membraneous platelets and angular rodlets. Most wax platelets were membraneous, and appeared to protrude from the surface at an acute angle. Angular rodlets were usually bent and had rather distinct facets in the abaxial surface of the two cultivars. Membraneous platelets were predominant on the adaxial surface of Maehyang, whereas the adaxial surface of Red Pearl was characterized by angular rodlets. However, both cultivars possessed angular rodlets on the abaxial surface, simultaneously. The combination of air-drying without vacuum and in-lens imaging of secondary electron signals with a field emission gun could impart the superb resolution at low electron dose with minimal specimen shrinkage. In vertical profiles of the leaf epidermis, epicuticular waxes were observed above the cuticle layer, and measured approximately as 50 nm in thickness. The natural epicuticular waxes were seemingly mixtures of electron-dense microfibrils, and heterogeneous in shape on ultrathin sections. Distinct crystal-like strata could be hardly discernable in the wax structures. These results suggest that the garden strawberry has the nature of syntopism within one plant and polymorphism within the same species in the formation and occurrence of leaf epicuticular waxes.