wileyonlinelibrary.comand aggregation-enhanced emission (AEE) characteristics were reported in selected ACPs. [14][15][16] Therefore, it is of great interest to investigate ACPs in the aggregated state that are quite different from those the isolated chain state.The polymer nanosphere solution can be treated as an intermediate state between a solution state and a solid fi lm state because the polymer nanoparticles uniformly disperse in a solvent, similar to their behavior in solution, whereas the polymer chains aggregate with each other, similarly to their behavior in a solid fi lm. In other words, the polymer nanosphere solution can be regarded as a dispersed nano-ordered crystalline polymer system. This bilateral character of the nanosphere solution causes the polymer to exhibit high processability and fl uidity as well as aggregation effects. In addition, the polymer nanosphere solution enables quantitative analysis of the aggregated state of polymers from the spectroscopic point of view. Hence, the polymer nanosphere solution is useful for understanding the aggregation effect on ACPs as compared with the solution and solid fi lm states.Dynamic control of the fl uorescence of ACPs using an external light stimulus is of particular interest because such photoresponsive polymers are essential for next-generation optoelectronic materials. Dithienylethene (DE) derivatives [17][18][19][20] are one class of the most attractive photoresponsive materials because of their outstanding fatigue resistance, thermal stability, and ability to undergo conformational changes between open and closed forms via photoisomerization, and therefore they are regarded as promising materials for the fabrication of photodynamically controllable luminescent devices [ 21,22 ] as well as photodynamically color-tunable systems. [23][24][25][26][27] The DE derivatives are also known to display luminescent color changes via photoisomerization. [ 20,[28][29][30][31][32][33][34][35][36][37] Similarly, conjugated polymers that contain DE moieties in the polymer backbones exhibit photochromism. [ 20,[38][39][40][41] The chromism in both absorption and luminescence of the conjugated polymers is attributed to structural changes in the conjugated backbones resulting from the DE photoisomerization. Hence, it is necessary to properly design the molecular structure to realize the desired switching behavior and fl uorescent colors.It is well known that in ACP nanoparticles doped with luminescent dopants, the ACP fl uorescence is almost completely quenched and the fl uorescence of the dopant is mainly
catalysts, and chiral liquid crystal (LC) solvents. [13-15] In particular, the third method using a chiral LC solvent as an asymmetric reaction field is facile and versatile because it requires neither chiral monomers nor chiral catalysts, and furthermore, the helicity of the resultant conjugated polymer is strictly controlled by the chirality of the LC reaction field. [8,16] The preparation of a chiral LC is achieved by adding the chiral compound to an achiral host LC. If the chirality of the LC is inverted and/or controlled by an external stimulus, such as temperature [17-24] or photoirradiation, [25-34] only one LC with a chiroptical configuration is required. This condition significantly reduces the synthesis time and reduces the cost of reagents. Very recently, thermally invertible chiral LCs have been developed and used for interfacial chemical polymerizations of acetylene to afford helicity-controlled helical polyacetylene films. [35] However, no photoinvertible chiral LC exhibiting the chemical stability needed to serve as a solvent for chemical or electrochemical polymerization has been reported to date. [36-39] Previously, we synthesized a photoresponsive chiral compound by substituting two axially chiral binaphthyl moieties at both terminal sites of a photochromic dithienylethene moiety and used it as a chiral dopant to prepare a photocontrollable N*-LC. [26] Although the helical sense of the N*-LC was inverted by irradiation with UV and visible light, the fatigue resistance and helical twisting power (HTP) of the N*-LC were insufficient for the use of asymmetric polymerization. Meanwhile, poly(3,4-ethylenedioxythiophene) (PEDOT) is regarded as a versatile functional conjugated polymer because of its high conductivity due to its low bandgap, optical transparency, and electrochemiluminescence. [40-47] It is of keen interest to introduce helicity into PEDOT to develop uncultivated chiroptical properties and functions. In fact, helical PEDOT (H-PEDOT) is useful as a carbonization precursor for helical carbon and graphite bearing spiral morphology. [11,48] We previously reported the synthesis of H-PEDOT by electrochemical polymerization of EDOT in N*-LCs or LC-based ionic liquids that include ordinary chiral compounds. [11,48-50] However, two types of chiral compounds with opposite helicity were needed because these chiral compounds had neither thermally invertible nor photoinvertible helical senses. Photoinvertible chiral compounds are synthesized by linking a photoresponsive bisbenzothienylethene moiety with an axially chiral binaphthyl moiety and used as chiral dopants to prepare a photoinvertible chiral nematic liquid crystal (N*-LC) field. Subsequently, electrochemical polymerizations of ethylenedioxythiophene (EDOT) in the N*-LC field to synthesize helical poly(ethylenedioxythiophene)s (H-PEDOTs) are achieved. The H-PEDOTs show not only spiral morphologies resembling the fingerprinted texture of N*-LC in polarizing optical microscope but also bisignate Cotton effects in circular dichroism spectra, in...
Many electrophoretic variants of hemolymph inhibitors of proteases from Aspergillus melleus and pancreatic alpha-chymotrypsin were found using 126 silkworm strains. Six inhibitors of the fungal protease were detected and eight of chymotrypsin; the distribution of inhibitors among Japanese, Chinese, and European races was investigated. Comparison of electrophoretic patterns from F1 hybrids and parents showed that the offspring produce inhibitors of both parental types. Segregation in F2 and backcrossing suggest that the expression of each inhibitor is controlled in most cases by a pair of alleles which are responsible for strong and null bands. Two bands of fungal protease inhibitors C and D were controlled by codominant alleles. These results suggest that polymorphism of hemolymph protease inhibitors in the silkworm would be a useful experimental system for the study of the genetic control of protease inhibitors.
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