Photoinduced bending and unbending behavior of crosslinked liquidcrystalline polymers containing azotolane moieties in side chains occurred upon irradiation with sunlight, according to the trans-cis photoisomerization of the azotolane moieties.
We performed second harmonic generation (SHG) measurements in the nematic liquid crystal
formed from polar aromatic polyester which comprises 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid
in a molar ratio of 73/27. The polymer is commercially available and called Vectra. The shear-oriented nematic
liquid crystal of Vectra shows strong SHG mostly along the n-director. Since no electric poling is made, the
observed SHG activity indicates that the polar ordering is spontaneously formed in the nematic liquid crystal.
From detailed analyses of the SHG intensity profiles measured with combinations of polarizer and analyzer
directions to the n-director, the nematic liquid crystal is found to possess the C
s
packing symmetry; in other
words, it is not uniaxial but biaxial, and the polarization arises in the symmetry plane. To search the origin of the
spontaneous polarization, we prepared a series of Vectra polymer with various degrees of polymerization (DP)
and two chemically modified Vectras. Of interest is that the DP of polymer significantly affects the polar structure.
When DP is decreased, the SHG activity in the nematic liquid crystal disappears completely. Since the dipole
moment increases with DP, the huge dipole moment of polymer is considered to be responsible for the polar
ordering. In one of the two chemically modified Vectras, terephthalic acid (TA) and biphenol (BP) in an equimolar
content are introduced. As expected from the dissipation of head−tail character in constituent polymer, the nematic
liquid crystals lose completely the SHG activity only with an incorporation of 5 mol % of TA and BP. In another
modified Vectra including 3-hydroxybenzoic acid (m-HBA), the head−tail character is not lost, but their liquid
crystallinity is destabilized because of kink conformation induced by the m-HBA unit. In this system, the SHG
is invariably observed for the nematic liquid crystals, but as one of the significant effects, polar biaxial nematic
liquid crystal of Vectra is altered to the polar uniaxial one by the introduction of m-HBA above 5 mol %.
N-linked glycosylation is one of the most important protein post-translational modifications. Despite the importance of N-glycans, the structural determination of N-glycan isomers remains challenging. Here we develop a mass spectrometry method, logically derived sequence tandem mass spectrometry (LODES/MSn), to determine the structures of N-glycan isomers that cannot be determined using conventional mass spectrometry. In LODES/MSn, the sequences of successive collision-induced dissociation are derived from carbohydrate dissociation mechanisms and apply to N-glycans in an ion trap for structural determination. We validate LODES/MSn using synthesized N-glycans and subsequently applied this method to N-glycans extracted from soybean, ovalbumin, and IgY. Our method does not require permethylation, reduction, and labeling of N-glycans, or the mass spectrum databases of oligosaccharides and N-glycan standards. Moreover, it can be applied to all types of N-glycans (high-mannose, hybrid, and complex), as well as the N-glycans degraded from larger N-glycans by any enzyme or acid hydrolysis.
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