Synthesis,characterization, photo‐induced alignment,and surface orientation of poly(9,9‐dioctylfluorene‐alt‐azobenzene)s

Three types of bi‐functionalized copolymers ( P1FAz , P2FAz , and P3FAz ) with different numbers of fluorene units and an azobenzene unit were synthesized and characterized using UV–vis and polarized absorption spectroanalysis. The trans‐cis photoisomerization was conformed under 400 nm light irradiation for all copolymers in chloroform. However, in the film state, only the trans‐cis photoisomerization occurred by mono‐fluorene attached copolymer poly[(9,9‐di‐n‐octylfluorenyl‐2,7‐diyl)‐alt‐4,4′‐azobenzene)] ( P1FAz ). Photo‐induced alignment was achieved using the P1FAz film after irradiation with linear polarized 400 nm light and subsequent annealing at 60 °C. Surface orientation of a spin‐coating film of poly(9,9‐didodecylfluorene) ( F12 ) was achieved using the photo‐induced alignment layer of the P1FAz film after annealing at 90 °C. The photo‐induced alignment layer of P1FAz has potential application to the surface orientation technique for appropriate polymers, which will be useful for the fabrication of optoelectronics devices. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Analysis of the number of hydrogen bond groups of a multiwalled carbon nanotube probe tip for chemical force microscopy

In this paper, we describe a statistical method of quantification of the number of functional groups at the contact area of a probe tip for atomic force microscopy from the result of repetitive pull-off force measurements. We have investigated laboratory-made carbon nanotube (CNT) probe tips to apply them for chemical force microscopy because limited number of functional groups at the tip-end is expected. Using a CNT tip, we conducted repetitive pull-off force measurements against a self-assembled monolayer terminated with carboxyl group and analyzed them in terms of the number of hydrogen bond groups at the CNT tip. The elementary hydrogen bond rupture force quantum in n-decane medium was estimated to be 84.2 ± 0.5 pN in the present system. Thus it was revealed that only a couple of hydrogen bond groups of the CNT tip were participating in hydrogen bonding with the sample on an average in this experimental system.     

Illumination accelerates the decay of the O-intermediate of pharaonis phoborhodopsin (sensory rhodopsin II)

pharaonis phoborhodopsin (ppR, also called pharaonis sensory rhodopsin II [psRII]) is a member of the archaeal rhodopsin family and acts as a repellent phototaxis receptor of Natronobacterium pharaonis. Upon illumination, ppR is excited and undergoes a linear cyclic photoreaction, namely, a photocycle that constitutes photointermediates such as M- and O-intermediates (ppRM and ppRO, respectively). Under a constant background illumination (>600 nm) that irradiates ppRO, the decay rate of the flash-induced ppRO increased with an increase in the background light intensity, indicating the photoreactivity of ppRO. Azide did not influence the light-accelerated ppRO decay, but the time required for the cycle to be completed became shortened in an azide concentration-dependent manner because of acceleration of ppRM decay. Hence, the turnover rate of photocycling increased appreciably in the presence of both the background illumination and the azide. The observation reported previously (Schmies, G. et al. 2000, Biophys. J. 78:967-976) is discussed in connection with the present observations.     

Enhanced optical sensing of anions with amide-functionalized gold nanoparticles

A gold nanoparticle surface-modified with amide ligands shows enhanced optical sensing of anions: the detection limit is increased by about three orders of magnitude higher than that originally expected from the anion binding ability of neutral amide ligands.     

Siladenoserinols M–P,sulfonated serinol derivatives from a tunicate

Four new sulfonated serinol derivatives, siladenoserinols M–P (1–4), were isolated from a tunicate of the family Didemnidae collected in Indonesia. Their chemical structures were elucidated by the interpretation of NMR and mass spectroscopic data. Two of them (2 and 4) were revealed to be disulfonate serinol derivatives, and the others were monosulfonates. Siladenoserinols A (5) and B (6), which we previously isolated from the same tunicate, inhibited the p53–Hdm2 interaction with an IC₅₀ value of 2.0?μM. However, 1–4 did not inhibit the activity. The result suggested that the acetyl group in the bicyclic ketal unit and/or the glycerophospholipid moiety in 5 and 6 were responsible for the inhibition of the p53–Hdm2 interaction.     

Evaluation of the DNA Alkylation Properties of a Chlorambucil-Conjugated Cyclic Pyrrole-Imidazole Polyamide

Hairpin pyrrole-imidazole polyamides (hPIPs) and their chlorambucil (Chb) conjugates (hPIP-Chbs) can alkylate DNA in a sequence-specific manner, and have been studied as anticancer drugs. Here, we conjugated Chb to a cyclic PIP (cPIP), which is known to have a higher binding affinity than the corresponding hPIP, and investigated the DNA alkylation properties of the resulting cPIP-Chb using the optimized capillary electrophoresis method and conventional HPLC product analysis. cPIP-Chb conjugate 3 showed higher alkylation activity at its binding sites than did hPIP-Chb conjugates 1 and 2 . Subsequent HPLC analysis revealed that the alkylation site of conjugate 3 , which was identified by capillary electrophoresis, was reliable and that conjugate 3 alkylates the N3 position of adenine as do hPIP-Chbs. Moreover, conjugate 3 showed higher cytotoxicity against LNCaP prostate cancer cells than did conjugate 1 and cytotoxicity comparable to that of conjugate 2 . These results suggest that cPIP-Chbs could be novel DNA alkylating anticancer drugs.