• Bulletin of the Korean Chemical Society
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• v.23 no.7
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• pp.957-963
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• 2002

We successfully synthesized the addition-type polynorbonenes (PNB) exhibiting photochromic properties and excellent thermal stability. Three norbornene-based monomers with different azobenzene moiety (R=NO2, H,OCH3) were synthesized by transesterification method. The corresponding PNB copolymers were synthesized by transition metal-catalyzed addition polymerization method, and characterized by GPC, UV-Vis spectroscopy, NMR, and thermal analysis. For comparison of the photochromic properties depending on the rigidity of polymer backbone, we prepared the polymethylmethacrylate (PMMA) copolymer with the corresponding azobenzene moiety. We investigated the photoisomerization behavior by means of optical muitichannel analyzer with Xe lamp as well as real-time UV-Vis spectroscopy with high-pressure mercury lamp. Among three PNB copolymers, a polymer with azobenzene (R=H) was the most adaptable for observation of photoisomerization behavior. It was found that the rate of photoisomerization and relaxation depended on the structure of azobenzene chromophore, rather than that of polymer backbone.

• Applied Chemistry for Engineering
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• v.23 no.1
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• pp.65-70
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• 2012

Structural changing materials which can induce the physical deformation of materials are interesting research topics with various potential applications. Particularly, light among many driving mechanisms is a non-contact energy source, hence the light-responsive system can be used where non-destructive, local irradiation, and remote control is needed. Here, a mainchain azobenzene polymer is synthesized and its physical and optical properties are observed and compared to that of a polymer having a light-responsive azobenzene moiety on its side chain. Further dispersion onto polyvinylalcohol hydrogel is made and its dual stability and actuation are observed upon UV-visible light irradiation. Extended azobenzene polymer blend films show an anisotropic light-actuation with non-polarized UV light at room temperature. This physical shape change is quite reversible and occurs at lower temperature than that of any other reported systems including liquid crystalline elastomers. It is successfully demonstrated that the simple physical azobenzene/polymer blending has a very good actuation compared to that of LCEs which need an elaborate chemical design and it can be further used in the areas requiring a dimensional shape change.

• Current Optics and Photonics
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• v.2 no.3
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• pp.221-225
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• 2018

We suggested the use of miniature hollow glass tubes having high ultraviolet (UV) transmission characteristics for the protection of optical-fiber-type UV sensors. We have recently proposed a highly sensitive optical sensor in the UV spectral range, using a fiber Bragg grating (FBG) coated with an azobenzene polymer as the photoresponsive material. In this study, we used UV-transparent miniature glass tubes to protect the etched FBG with the azobenzene polymer coating. This technique will be very useful for protecting various fiber-based UV sensors.

• Current Optics and Photonics
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• v.2 no.4
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• pp.303-307
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• 2018

We propose a simple ultraviolet (UV) sensor consisting of a conventional single-mode optical fiber capped with an azobenzene-moiety-containing polymer. The UV light changes the dimensions of the azobenzene polymer, as well as the refractive index of the material. Incident light with a wavelength of 1550 nm was reflected at the fiber/polymer and polymer/air interfaces, and interference of the reflected beams resulted in spectral interference that shifted the wavelength by 0.78 nm at a UV input power of $2.5mW/cm^2$. The UV sensor's response to wavelength is nonlinear and stable. The response speed of the sensor is limited by detection noise, which can be improved by modifying the insertion loss of the UV sensor and the signal-to-noise ratio of the detection system. The proposed compact UV sensor is easy to fabricate, is not susceptible to electromagnetic interference, and only reacts to UV light.

• Korean Journal of Optics and Photonics
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• v.22 no.2
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• pp.67-71
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• 2011

In the paper, we have demonstrated an azobenzene-coated fiber Bragg grating (FBG) for monitoring ultraviolet light (UV) intensity in remote measurement. The elasticity of the coated azobenzene polymer is changed by the UV light, which induces a center wavelength change corresponding to the change of the FBG's grating period. The wavelength shift resulting from both UV light and other light with the wavelength out of the UV range was about 0.18 nm. In order to improve the accuracy of the measurement, the center wavelength shift caused by radiant heat of the light source was sufficiently removed by using a thermal filter. The amount of the center wavelength shift was consequently reduced to 0.06 nm, compared to the result without the thermal filter. Also, the FBGs coated by using azobenzene polymer were produced by two different methods; thermal casting and UV curing. Considering temperature dependence, UV curing is more suitable than thermal casting in UV sensor application of the azobenzene-coated FBG. In addition, we have confirmed the wavelength dependence of the optical sensor by means of four different band pass filters. Thus, we found out that the center wavelength shift per unit intensity is 0.029 [arb. unit] as a maximum value at 370 nm wavelength region and that the absorption spectrum of the azobenzene polymer was very consistent with the wavelength dependence of the azobenzene-coated FBG.

• Polymer(Korea)
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• v.29 no.3
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• pp.308-313
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• 2005

The effects of molecular environments on photoisomerization of an azobenzene group were investigated using In-situ UV/Vis spectroscopy and optical anisotropy measurement technique. The reversible and repeatable photoisomeritation reactions of azobenzene were observed by irradiating the film containing 4-hydroxyazobenzene and by measuring absorption intensities of the characteristic bands of trans and cis isomers simultaneously. When the self-assembled monolayer with azobenzene groups was used as an alignment layer for a liquid crystal cell, the homeotropic alignment was induced due to their compact packing structures of azobenfene groups along the vertical direction of the substrate. By irradiating UV light on this cell, the trans-azobenzene groups change to cis-isomers through the photoisonlerieation and then resulting in the planar alignment of liquid crystal molecules.

• Elastomers and Composites
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• v.47 no.4
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• pp.282-291
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• 2012

Control of shape/volume, mechanical, optical, electrical, and chemical switching of materials by external stimuli such as light, temperature, pH, electric field, and pressure has attracted great attention. Among these materials, photo-responsive materials containing photochromic compounds such as azobenzene, spiropyran, and cinnamic acid groups have been the subject of intense interest in recent years. In this review, we describe the recent progress in the area of azobenzene containing polymer materials that can convert light energy into mechanical energy directly. Especially we focus our attention on light-driven actuators such as artificial muscle, motor, and valve. We summarize the photomechanical effects in liquid crystal elastomer, amorphous polymer, monolayer, and supramolecules containing azobenzene, respectively.

• Polymer(Korea)
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• v.24 no.6
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• pp.737-743
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• 2000

Polyquinonediimines (PQDI) which have stable structure on heat and contains mono-azobenzene in the side chain were synthesized by means of condensation polymerization under TiCl$_4$. The synthesized monomers and polymers were identified by FT-IR, $^1$H-NMR, and elementary analysis. Especially, PQDI was comfirmed by the double-bonding peak of >C=N appeared near 1625 $cm^{-1}$ / by means of FT-IR spectrum. PQDI containing mono-azobenzene group in both side chains wat not soluble in non-polar solvents at all but partially soluble in the polar solvents having small dielectric constant, and dissolved in the strong acid such as sulfuric acid and $CH_3$SO$_3$H. Molecular weight distribution of PQDI measured by GPC showed 1.74. It was confirmed through X-ray diffraction analysis that the polymer was partially crystalline at the low angle region, but amorphous after heat treatment at 1$25^{\circ}C$. The glass transition temperature (T$_{g}$ ) of synthesized polymer was measured as 1$25^{\circ}C$ by differential scanning calorimetry. The SHG value for $\chi$$^{(2)}$ after poling at 1$25^{\circ}C$ was 8.6 pm/V (λ=1.542 ${\mu}{\textrm}{m}$). The SHG value slowly decreased with time from the start but appeared temporal stability after 100 hours.

• Polymer(Korea)
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• v.25 no.4
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• pp.496-502
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• 2001

Thermally stable polyquinonediimines(PQDI) containing di-azobenzene in the side chain were synthesized by means of condensation polymerization under $TiCl_4$. The synthesized monomers and polymers were identified by FT-IR, $^1H-NMR$, and elemental analysis. Especially, the polymerization of PQDI was confirmed by the double-bonding peak of >C=N appearing near 1625cm$^{-1}$ in FT-IR spectrum. PQDI with di-azobenzene group in one side chain was insoluble in methanol, acetone and non-polar solvents having big dielectric constant, but had good solubility in polar solvents having small dielectric constant. Molecular weight distribution of PQDI measured by GPC was 1.38. It was confirmed to be amorphous polymer through X-ray diffraction by the appearance of the halo in case of PQDI containing di-azobenzene in the side chain. The glass transition temperature ($_g$) of synthesized polymer was measured to be 116$^{\circ}C$ by differential scanning calorimetry. The SHG value for ${\chi}^{(2)}$ was 1.2 pm/V (${\lambda}$ = 1.542 ${\mu}$m). The SHG value slightly decreased in an early stage but showed temporal stability after 20 hours.

• Applied Chemistry for Engineering
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• v.30 no.2
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• pp.219-225
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• 2019

Side-chain liquid crystalline polymers with various compositions of azobenzene and cholesteryl functional groups as the mesogenic moiety were synthesized by direct polycondensation, and their properties were investigated. The inherent viscosity values of synthesized polymers were between 0.32 and 0.38 dL/g in 1,1,2,2-tetrachloroethane. All polymers except the SP-A10C0 polymer containing only the azobenzene group were amorphous or exhibited very low crystallinity due to the presence of bulky mesogenic side chains. All synthesized polymers exhibited enantiotropic liquid crystallinity; the SP-A10C0 polymer having only the azobenzene group exhibited a nematic phase, and all other polymers showed a cholesteric phase. In particular, it was found that when the content of cholesteryl groups in the side chain of the polymer increases, the liquid crystallinity decreases due to the bulkiness of cholesteryl groups.