Site-selective guest inclusion in molecular networks of butadiyne-bridged pyridino and benzeno square macrocycles on a surface

We present here the formation of a modular 2D molecular network composed of two different types of square-shaped butadiyne-bridged macrocycles, having intrinsic molecular voids, aligned alternately at the solid-liquid interface. Site-selective inclusion of a guest cation took place at every other molecular void in the molecular network with two different recognition sites.     

Micropatterning of ZnO nanoarrays by forced hydrolysis of anhydrous zinc acetate

Micropatterns of ZnO nanoarrays were simply and successfully fabricated in an aqueous solution without any high-temperature treatment and/or expensive catalyst. In situ forced hydrolysis of patterned anhydrous zinc acetate, derived by ultraviolet irradiation with a photomask, resulted in heterogeneous nucleation and growth to form ZnO nanoarrays. Micropatterns of ZnO nanoarrays were characterized by FE-SEM and XRD. ZnO nanoarrays were well site-selectively deposited on anhydrous zinc acetate coated regions at 88 degrees C. HR-TEM clarified the formation mechanism in which anhydrous zinc acetate showed a tendency of forced hydrolyzation to ZnO nanocrystals at the initial stage in the reaction solution.     

Hidden electronic excited state of enhanced green fluorescent protein

Precise two-photon absorption spectra of the green fluorescent protein (GFP) and the mutants sapphire-GFP (T203I) and enhanced GFP (S65T/F64L), as well as a model compound for the chromophore, 4'-hydroxybenzylidene-2,3-dimethylimidazolinone (HBDI) were measured by multiplex two-photon absorption spectroscopy. The observed TPA bands of the anionic forms of enhanced GFP and HBDI were significantly shifted to the higher energy compared with the lowest-energy bands in one-photon absorption spectra. This result indicated the existence of a hidden electronic excited state in the vicinity of the lowest excited singlet (S1) state of the anionic form of the GFP chromophore, which is the origin of the blue shift of the two-photon absorption spectra as well as two-photon fluorescence excitation spectra.     

Molecular-Level Reinforced Adhesion Between Rubber and PTFE Film Treated by Atmospheric Plasma Polymerization

Extremely strong reinforced adhesion between a polytetrafluoroethylene (PTFE) film and butyl rubber is achieved using an atmospheric pressure plasma graft polymerization, involving argon and acrylic acid vapor. The treated PTFE film is then placed over a raw butyl rubber plate and hot-pressed under 157 N/cm² for 40 min at 150 °C or for 10 min at 180 °C. This procedure results in molecular-level or chemical adhesion between the butyl rubber and the PTFE film. The 180° peeling test results show that a high peeling strength of 3.9 N, per 1 mm sample width, is achieved. Adherend failure of the rubber sheet occurs when the peeling is enforced. From X-ray photoelectron spectroscopy analysis of the treated films, chemical bonds with fluorine atoms are absent from the surface. From scanning electron microscopy analysis, a transparent hydrophilic poly(acrylic acid) layer composed of nanoscale spherical particles is formed. This PTFE-rubber composite material is suitable for high-quality, prefilled medical syringe gaskets.     

Femtosecond Hydrogen Bond Dynamics of Bulk‐like and Bound Water at Positively and Negatively Charged Lipid Interfaces Revealed by 2D HD‐VSFG Spectroscopy

Interfacial water in the vicinity of lipids plays an important role in many biological processes, such as drug delivery, ion transportation, and lipid fusion. Hence, molecular‐level elucidation of the properties of water at lipid interfaces is of the utmost importance. We report the two‐dimensional heterodyne‐detected vibrational sum frequency generation (2D HD‐VSFG) study of the OH stretch of HOD at charged lipid interfaces, which shows that the hydrogen bond dynamics of interfacial water differ drastically, depending on the lipids. The data indicate that the spectral diffusion of the OH stretch at a positively charged lipid interface is dominated by the ultrafast (<～100 fs) component, followed by the minor sub‐picosecond slow dynamics, while the dynamics at a negatively charged lipid interface exhibit sub‐picosecond dynamics almost exclusively, implying that fast hydrogen bond fluctuation is prohibited. These results reveal that the ultrafast hydrogen bond dynamics at the positively charged lipid–water interface are attributable to the bulk‐like property of interfacial water, whereas the slow dynamics at the negatively charged lipid interface are due to bound water, which is hydrogen‐bonded to the hydrophilic head group.     

Experimental and theoretical studies on oligomer formation of N-confused porphyrin-zinc(II) complexes

Dimer formation of the N-confused porphyrin zinc(II), cadmium(II), and mercury(II) complexes was investigated experimentally as well as theoretically. The stable dimers were formed through coordination of the peripheral nitrogen atoms owing to flexible rotation of the confused pyrrole rings. The Z dimers were significantly more stable than the E dimers likely due to pi-pi interaction between the two confused pyrrole rings. The possible formation of higher oligomers such as trimers was suggested in the case of meso-unsubstituted derivatives.     

Study of compounds suppressing free radical generation from UV-exposed ketoprofen

Ketoprofen [(RS)-2-(3-benzoylphenyl)propanoic acid] is widely used for the treatment of inflammatory diseases and musculoskeletal injury. However, there is concern regarding its potential for photosensitization as a side effect. Free radicals and active oxygen species generated from ketoprofen on exposure to ultraviolet (UV) light have been implicated in phototoxicity and photosensitization. In this study, we examined the suppressing ability of some compounds for the free radicals and active oxygen species generated by the photodynamic reaction of ketoprofen, to determine a new resist of photosensitization by ketoprofen. Eight compounds, including six known free radical scavengers were individually mixed with ketoprofen, and the mixtures were exposed to UV. Then, the free radicals and the active oxygen species were determined by the electron spin resonance spectrometry to estimate suppressing and scavenging ability of compounds. The compounds that show promise in suppressing superoxide anion generation from UV-exposed ketoprofen were further evaluated using the on-line photo-irradiated superoxide anion detection system. It was confirmed that quercetin, a flavonoid, strongly suppresses the generation of free radicals and active oxygen species from UV-exposed ketoprofen. The experiments using the experimental formulation of an adhesive skin patch of ketoprofen containing quercetine and the Chemiluminescence analyzer (CLA) indicated that quercetin has high potential for use as an excipient in ketoprofen ointments to suppress phototoxicity and photosensitization by ketoprofen.     

Synthesis and isomerization of imino-fused N-confused porphyrin

[reaction: see text] A set of mutually interconvertable inner-bridged-type porphyrinoids, imino-fused N-confused porphyrins (IF-NCPs), which possess a [5.7.5] tricyclic ring in the core, were synthesized from a condensation reaction of 21-amino-substituted NCP and an arylaldehyde, and the structures were characterized by X-ray single-crystal analysis.