RESUMEN
Controlling the birefringence of optical films is imperative to fabricate thin birefringent optical devices. Here, new photoalignable liquid crystalline copolymers (PLCPs) with 4-formylphneyl benzoate (PA) and cinnamic acid (CA) side groups are synthesized, which attain high photoreactivity and controllability of the orientation direction. Additionally, the exposed films are treated with 2-aminofluorene (AF) for an in situ condensation of PA with AF to form a Schiff base with a high inherent birefringence. Birefringence of the photoaligned film can be controlled up to 0.45 without disturbing the photoinduced orientation structure.
RESUMEN
Copolymer films of photoalignable liquid crystalline (LC) copolymethacrylates comprised of a phenyl benzoate mesogen connected with N-benzylideneaniline end moiety (NBA2) and benzoic acid (BA) side groups exhibit a photoinduced reorientation behavior. Significant thermally stimulated molecular reorientation attains a dichroism (D) greater than 0.7 for all copolymer films and a birefringence of 0.113-0.181. In situ thermal hydrolysis of the oriented NBA2 groups decreases the birefringence to 0.111-0.128. However, the oriented structures of the film are maintained, demonstrating a photo-durability, even though the NBA2 side groups photo-react. The hydrolyzed oriented films show higher photo-durability without changing their optical properties.
RESUMEN
Polarized fluorescence of oriented N-salicylideneaniline (SA) derivatives is explored based on the thermally stimulated photoinduced molecular reorientation of liquid crystalline (LC) copolymethacrylate with N-benzylideneaniline derivative (NBA2) and benzoic acid (BA) side groups. The LC copolymer films show significant cooperative molecular reorientation of the NBA2 and BA side groups (D > 0.7). Subsequent thermal hydrolysis of the NBA2 side groups yields free phenylamine moieties. These moieties can form oriented SA derivatives via in situ condensation with 2-hydroxybenzaldehyde derivatives. The excited-state intermolecular proton transfer of the oriented SA molecules induces polarized fluorescence at 510-548 nm with a polarization ratio up to 6.2. Direct in situ exchange from the oriented NBA2 to SA derivatives achieves polarized fluorescence similar to that of the SA side groups.
RESUMEN
The influence of the annealing conditions on the thermally stimulated photoinduced molecular reorientation of a photoinactive liquid crystalline polymethacrylate with phenyl aldehyde and benzoic acid side groups (P1) doped with 4-methoxyaniline, which forms photoalignable 4-methoxy-N-benzylideneaniline (MNBA) side groups in situ, was investigated. Light exposure and subsequent thermal stimulation under a N2 atmosphere realized sufficient cooperative molecular reorientation (D > 0.7), but the simultaneous thermal hydrolysis of the MNBA groups under humid air lowered the molecular reorientation performance. By contrast, subsequent thermal hydrolysis of MNBA after molecular reorientation introduced different aromatic amines into the reoriented P1 film, which regulated the birefringence and photofunctionality of the oriented film.
RESUMEN
In this study, mechanochromic luminescence was induced in a complex of mechano-inactive compounds. Dye/acid complexes containing the same π-conjugated backbones were prepared. While the luminophore showed blue and red shifts in photoluminescence spectra when combined with different acids by grinding, it exhibited slight mechanoresponsiveness itself. Also, compounds with similar molecular backbones to the dye/acid complex were synthesized to clarify the color change mechanism. The compounds showed both blue and red shifts in photoluminescence and diffuse reflectance spectra upon grinding, indicating that mechanochromic luminescence in the hydrogen-bonded complex is like its monomeric analogue and that aggregation structure plays an important role in mechanoresponsive behavior rather than the π-conjugated structure. It was shown that a color change can be mechanically induced by imitating the solid-state aggregation structure of other mechanoresponsive compounds without synthetic modification.
RESUMEN
In situ formation of N-benzylideneaniline (NBA) side groups achieved photoinduced cooperative reorientation of photoinactive copolymers with phenylaldehyde (PA) and benzoic acid (BA) side groups doped with 4-methoxyaniline (AN) molecules. Thermally stimulated molecular reorientation of the side groups was generated due to the axis-selective photoreaction of the NBA moieties. Selective coating with AN on the copolymer film formed NBA moieties in the desired region, resulting in a photoinduced birefringent pattern. Additionally, postannealing at an elevated temperature for a long time attained photoinactivation of the reoriented film, and recoating with AN to form NBA achieved the multiple birefringent patterns and repatterning of the reoriented structures. The slow thermal hydrolysis of NBA, which was 50 times slower than the thermally stimulated self-organization of the side groups due to the presence of BA side groups, contributed to the photodurability of the reoriented film and multiple birefringent patterns.
RESUMEN
The application of a top-coating of 4-methoxy cinnamic acid (MCA) onto a photoinactive liquid crystalline polymeric film containing benzoic acid (BA) side groups (P6BAM) is shown to enable thermally stimulated, photoinduced reorientation of the polymer structure. Annealing the MCA-coated P6BAM films leads to H-bond formation between BA and MCA, which also effectively smooths the film surface. Exposure to linearly polarized (LP) UV light initiates axis-selective photoreaction of the MCA groups; subsequent thermal treatment in the LC temperature range of P6BAM amplifies molecular reorientation of the BA side groups, while simultaneously eliminating the MCA molecules. Selective inkjet coating of MCA provides a facile route for the fabrication of patterned, oriented, and rewritable P6BAM films with multiple controlled alignment directions.
RESUMEN
Adjusting the free-surface condition facilely controls the in-plane and out-of-plane orientations in liquid crystalline polymer (LCP) films. Top coating with aromatic molecules onto LC polymethacrylate films with N-benzylideneaniline (NBA) or 4-methoxybiphenyl (MB) side groups (PNBAM or PMBM) and subsequent annealing generate a random planar orientation while simultaneously removing the coated aromatic molecules, whereas annealing noncoated films induces a homeotropic orientation of the mesogenic side groups. Additionally, irradiating a top-coated PNBAM film with linearly polarized (LP) 365 nm light induces an in-plane molecular reorientation of the NBA side groups without changing the orientation in the homeotropically oriented region. Changes in the surface topology of the LCP films due to the reorientation processes are investigated in detail. Inkjet coating with aromatic molecules and LP 365 nm light exposure precisely controls the in-plane and out-of-plane alignment pattern in a PNBAM film.
RESUMEN
Facile fabrication of a photoalignable film from a nonphotoreactive polymethacrylate with 4-oxybenzaldehyde side groups (1) and a monomeric 4-methoxyaniline (2) composite is investigated. A 1/2 composite film fabrication and the annealing process form photoalignable N-benzylideneaniline (NBA) side groups, while the linearly polarized (LP) 365 nm light exposure to the resultant film induces sufficient molecular reorientation of NBA side groups. Furthermore, patterned coating of 2 on a 1 film and subsequent LP light exposure generate a patterned molecular orientation combined with controlled birefringence.
RESUMEN
Mechanoresponsive luminophores containing different substituted pyridine rings at the molecular terminus are synthesized and their photoluminescence properties are investigated. The solid chromophore with a 4-substituted pyridine ring exhibits a reversible photoluminescent color change, while the 2-substituted chromophore shows only a small change in luminescence, and the 3-substituted chromophore displays an irreversible photoluminescent color change with mechanical grinding. A change of the sample color in response to mechanical grinding is also achieved for a dye-dispersed poly(vinyl alcohol) film. Furthermore, a simultaneous acid and mechanoresponsive photoemission color change is achieved in the dye-dispersed film.
RESUMEN
Reversible addition-fragmentation chain transfer (RAFT) polymerization is used to synthesize diblock and random copolymers of poly[(2-trifluoroethyl methacrylate)-co-(methacrylic acid)]. Copolymer films doped with fluorene derivatives comprised of pyridine groups exhibit reversible photoluminescent (PL) color tuning by adjusting the location of fluorene derivatives in H-bonds or non-H-bonds environments. The composite films exhibit green and blue photoluminescence with and without effective H-bonding between the pyridine ring in the fluorene derivative and the carboxylic acid side group, respectively. At elevated temperatures, the H-bonded structure dissociates and the fluorene derivative migrates to the hydrophobic block in the diblock polymer, and they do not form H-bonds upon cooling. However, re-formation of H-bonds also occurs upon cooling random copolymers. Moreover, adjusting the annealing temperature and the solvent annealing reversibly tunes the PL color in the diblock copolymer composite films.
RESUMEN
We present a simple way to control the photoinduced bending direction of azobenzene-containing cross-linked liquid-crystalline polymers. By changing the location of the photoactive azobenzene moieties from cross-links to side-chains, the bending direction of the sample is reversed under identical irradiation conditions. In addition to providing a versatile route toward directionality control of the photoinduced macroscopic motions, this observation highlights the complicated nature of the photomechanical response of azobenzene-containing cross-linked liquid-crystalline polymers, showing that the photomobile behavior can be determined by seemingly small details on the materials design.
RESUMEN
The thymoproteasome is a recently discovered, specialized form of 20S proteasomes expressed exclusively in the thymic cortex. Although the precise molecular mechanism by which the thymoproteasome exerts its function remains to be elucidated, accumulating evidence indicates that it plays a crucial role in positive selection of T cells. In the present study, we analyzed the evolution of the ß5t subunit, a ß-type catalytic subunit uniquely present in thymoproteasomes. The gene coding for the ß5t subunit, designated PSMB11, was identified in the cartilaginous fish, the most divergent group of jawed vertebrates compared to the other jawed vertebrates, but not in jawless vertebrates or invertebrates. Interestingly, teleost fish have two copies of apparently functional PSMB11 genes, designated PSMB11a and PSMB11b, that encode ß5t subunits with distinct amino acids in the S1 pocket. BLAST searches of genome databases suggest that birds such as chickens, turkey, and zebra finch lost the PSMB11 gene, and have neither thymoproteasomes nor immunoproteasomes. In mammals, reptiles, amphibians, and teleost fishes, the PSMB11 gene (the PSMB11a gene in teleost fish) is located next to the PSMB5 gene coding for the ß5 subunit of the standard 20S proteasome, indicating that the PSMB11 gene arose by tandem duplication from the evolutionarily more ancient PSMB5 gene. The general absence of introns in PSMB11 and an unusual exon-intron structure of jawed vertebrate PSMB5 suggest that PSMB5 lost introns and duplicated in tandem in a common ancestor of jawed vertebrates, with PSMB5 subsequently gaining two introns and PSMB11 remaining intronless.
Asunto(s)
Endopeptidasas/genética , Evolución Molecular , Complejo de la Endopetidasa Proteasomal/genética , Timo/inmunología , Proteínas de Pez Cebra/genética , Pez Cebra/genética , Animales , Endopeptidasas/química , Endopeptidasas/inmunología , Genómica , Humanos , Modelos Moleculares , Datos de Secuencia Molecular , Filogenia , Complejo de la Endopetidasa Proteasomal/química , Complejo de la Endopetidasa Proteasomal/inmunología , Estructura Terciaria de Proteína , Pez Cebra/inmunología , Proteínas de Pez Cebra/química , Proteínas de Pez Cebra/inmunologíaRESUMEN
NKG2D is a major activating receptor of natural killer cells. Its ligands are major histocompatibility complex (MHC) class I-like molecules whose expression is induced by cellular stresses such as infections and tumorigenesis. Humans have two families of NKG2D ligands (NKG2DL): MHC class I-related chains (MIC) encoded in the MHC and UL16-binding proteins (ULBP) encoded outside the MHC. By contrast, mice have only the latter family of ligands; instead, they have non-MHC-encoded MILL molecules that are closely related to MIC, but do not function as NKG2DL. To gain insights into the origin and evolution of MIC, ULBP, and MILL gene families, we conducted comparative genomic analysis of NKG2DL family genes in five mammalian species. In the opossum MHC, we identified a ULBP-like gene adjacent to a previously described MIC-like gene, suggesting that ULBP genes were originally encoded in the MHC. The opossum genome also contained a transcribed MILL-like gene in a region syntenic to the rodent regions encoding MILL molecules. These observations indicate that MIC-, ULBP-, and MILL-like genes emerged before the divergence of placental and marsupial mammals. Comparison of the human, cattle, rat, mouse, and opossum genomes indicates that after emigration from the MHC, ULBP genes underwent extensive duplications in each species. In mice, some of the ULBP genes appear to have been translocated telomerically on the same chromosome, forming a major cluster of existent NKG2DL genes.