Intensely Fluorescent Azobenzenes: Synthesis,Crystal Structures,Effects of Substituents,and Application to Fluorescent Vital Stain

2‐[Bis(pentafluorophenyl)boryl]azobenzenes bearing hydrogen, methoxy, dimethylamino, trifluoromethyl, fluoro, n‐butyl, and tert‐butyldimethylsiloxy groups at the 4′‐position or methoxy and bromo groups at the 4‐position have been synthesized. The 4‐bromo group of the 2‐boryl‐4‐bromoazobenzene derivative was converted to phenyl and diphenylamino groups by palladium‐catalyzed reactions. The absorption and fluorescence properties have been investigated using UV/Vis and fluorescence spectroscopy. The 2‐borylazobenzenes emitted an intense green, yellow, and orange fluorescence, in marked contrast to the usual azobenzene fluorescence. The 4′‐siloxy derivative showed the highest fluorescence quantum yield (0.90) among those reported for azobenzenes to date. The correlation between the substituent and the fluorescence properties was elucidated by studying the effect of the substituent on the relaxation process and from DFT and TD‐DFT calculations. An electron‐donating group at the 4′‐position was found to be important for an intense emission. Application of fluorescent azobenzenes as a fluorescent vital stain for the visualization of living tissues was also investigated by microinjection into Xenopus embryos, suggesting these compounds are nontoxic towards embryos.     

Chain‐growth condensation polymerization of 4‐aminobenzoic acid esters bearing tri(ethylene glycol) side chain with lithium amide base

Chain‐growth condensation polymerization of p‐aminobenzoic acid esters 1 bearing a tri(ethylene glycol) monomethyl ether side chain on the nitrogen atom was investigated by using lithium 1,1,1,3,3,3‐hexamethyldisilazide (LiHMDS) as a base. The methyl ester monomer 1a afforded polymer with low molecular weight and a broad molecular weight distribution, whereas the polymerization of the phenyl ester monomer 1b at ?20 °C yielded polymer with controlled molecular weight (M_n = 2800–13,400) and low polydispersity (M_w/M_n = 1.10–1.15). Block copolymerization of 1b and 4‐(octylamino)benzoic acid methyl ester ( 2 ) was further investigated. We found that block copolymer of poly 1b and poly 2 with defined molecular weight and low polydispersity was obtained when the polymerization of 1b was initiated with equimolar LiHMDS at ?20 °C and continued at ?50 °C, followed by addition of 2 and equimolar LiHMDS at ?10 °C. Spherical aggregates were formed when a solution of poly 1b in THF was dropped on a glass plate and dried at room temperature, although the block copolymer of poly 1b and poly 2 did not afford similar aggregates under the same conditions. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1357–1363, 2010     

The IR modulator utilizing light scattering effect with ferroelectric liquid crystal for gas analysis

Experimental infrared modulator elements have been fabricated utilizing the transient light scattering effect of ferroelectric liquid crystal with asymmetric waveform voltage drive. The new elements perform 80% modulation degrees at the 632.8nm. We have also achieved 30% modulation degrees in the 4 to 5µ m region where the strongest CO₂ absorption bands exist. A new type of analyzer which monitors ambient air quality has been developed. This analyzer uses non-dispersive infrared absorption method and composes of a double-beam, a single detector and a pair of liquid crystal light modulator as the IR chopper. The detection has achieved 10ppm noise equivalent concentration.     

A counter-example to a conjecture of Friedland

In 1982, S. Friedland proved that a bounded linear operator A on a Hilbert space is normal if and only if (αI + A + A*)² ≧ AA* − A*A ≧ −(αI + A + A*)² for all real α. And he conjectured the inequality (αI + A + A*)² ≧ AA* − A*A for all real α will imply that A*A − AA* ≧ 0, i.e., A is hyponormal. But his conjecture is incorrect. In this note I’ll give a counter-example for his conjecture.     

Uniform rotation of smectic layers of a ferroelectric liquid crystal in an asymmetric electric field

An asymmetric ac electric field with amplitudeE=10 V/μm gives rise to a matched rotation of the normal to the smectic layers, while a sinusoidal fieldE=1 V/μm is used to study the rotation in the method of modulation total internal reflection ellipsometry, which makes it possible to probe the region of a ferroelectric liquid crystal (FLC) next to the electrode (h≈0.7 μm). It is shown that the angle of rotation of the normal to the smectic layers near the surface of the electrode varies reversibly as a function of the polarity and number of electric pulses applied, just as in the interior region. The characteristic dynamic properties of thin layers of nematic liquid crystals, such as an anomalously long relaxation time and a high-frequency relaxation process, are observed in thin FLC layers.     

Direct transformation of N,N-disubstituted amides and isopropyl esters to nitriles

Various N,N-dimethyl amides, N-methoxy-N-methyl amides, and isopropyl esters were smoothly transformed into the corresponding nitriles in good to moderate yields by the treatment with diisobutylaluminium hydride, followed by treatment with molecular iodine in aq ammonia. The present reactions are novel one-pot and practical methods for the transformation of N,N-disubstituted amides and isopropyl esters into nitriles, through the formation of hemiaminal O-AlBu₂ and hemiacetal O-AlBu₂, respectively.     

A sensitive and quantitative technique for detecting autophagic events based on lysosomal delivery

We sought to develop a sensitive and quantitative technique capable of monitoring the entire flux of autophagy involving fusion of lysosomal membranes. We observed the accumulation inside lysosomal compartments of Keima, a coral-derived acid-stable fluorescent protein that emits different-colored signals at acidic and neutral pHs. The cumulative fluorescent readout can be used to quantify autophagy at a single time point. Remarkably, the technique led us to characterize an autophagy pathway in Atg5-deficient cells, in which conventional LC3-based autophagosome probes are ineffective. Due to the large Stokes shift of Keima, this autophagy probe can be visualized in conjunction with other green-emitting fluorophores. We examined mitophagy as a selective autophagic process; time-lapse imaging of mitochondria-targeted Keima and GFP-Parkin allowed us to observe simultaneously Parkin recruitment to and autophagic degradation of mitochondria after membrane depolarization.