Azobenzene Polyesters Research Articles

Ionic conductivity probed in main chain liquid crystalline azobenzene polyesters

ABSTRACTThree main chain thermotropic liquid crystalline (LC) azobenzene polymers were synthesized using the azobenzene twin molecule (P4P) having the structure Phenylazobenzene‐tetraethyleneglycol‐Phenylazobenzene as the AA monomer and diols like diethylene glycol, tetraethylene glycol (TEG), and hexaethylene glycol as the BB comonomer. Terminal C(O)OMe units on P4P facilitated transesterification with diols to form polyesters. All polymers exhibited stable smectic mesophases. One of the polymers, Poly(P4PTEG) was chosen to prepare composite polymer electrolytes with LiCF3SO3 and ionic conductivity was measured by ac impedance spectroscopy. The polymer/0.3 Li salt complex exhibited a maximum ionic conductivity in the range of 10−5 S cm−1 at room temperature (25 °C), which increased to 10−4 S cm−1 above 65 °C. The temperature dependence of ionic conductivity was compared with the phase transitions occurring in the sample and it was observed that the glass transition had a higher influence on the ionic conductivity compared to the ordered LC phase. Reversible ionic conductivity switching was observed upon irradiation of the polymer/0.3 Li salt complex with alternate UV and visible irradiation. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 629–641

Influence of blue and red light illumination on the holographic storage in an azopolyester–PMMA blend

Volume holographic polarization gratings have been stored in thick films of blends of a side-chain azobenzene polyester and a poly(methyl methacrylate) (PMMA) homopolymers. The azobenzene content in the blend is 0.2wt%, and the holograms are recorded by using 2ms 4mJ/cm2 488nm light pulses. The dependence of holographic storage on the recording condition has been studied. No stable gratings can be recorded in thermally quenched films. The presence of cis isomers that can be induced by blue light irradiation seems to be necessary to store stable gratings. The cis isomer content and consequently the grating efficiency can be changed by blue and red light irradiation. By choosing appropriate conditions stable and rewritable polarization gratings have been recorded. Up to 20 gratings with diffraction efficiency values higher than 5×10−5 have been multiplexed.

Holographic storage and multiplexing in azopolyester blends using low energy pulses down to 2 ms

Three different blends containing side-chain azobenzene polyesters and poly(methyl methacrylate) homopolymers have been prepared for recording volume holographic polarization gratings using 488 nm light pulses. The final azo content in the blends has been decreased down to 0.2 wt. %, and their morphologies have been investigated by transmission electron microscopy. Stable and rewritable polarization gratings have been recorded, and 20 gratings have been multiplexed using 2 ms pulses of low energy (4 mJ/cm2). The equilibrium values of the diffraction efficiency were higher than 5 × 10−5.

Azobenzene Polyesters Used as Gate-Like Scaffolds in Nanoscopic Hybrid Systems

The synthesis and characterisation of new capped silica mesoporous nanoparticles for on-command delivery applications is reported. Functional capped hybrid systems consist of MCM-41 nanoparticles functionalised on the external surface with polyesters bearing azobenzene derivatives and rhodamine B inside the mesopores. Two solid materials, Rh-PAzo8-S and Rh-PAzo6-S, containing two closely related polymers, PAzo8 and PAzo6, in the pore outlets have been prepared. Materials Rh-PAzo8-S and Rh-PAzo6-S showed an almost zero release in water due to steric hindrance imposed by the presence of anchored bulky polyesters, whereas a large delivery of the cargo was observed in the presence of an esterase enzyme due to the progressive hydrolysis of polyester chains. Moreover, nanoparticles Rh-PAzo8-S and Rh-PAzo6-S were used to study the controlled release of the dye in intracellular media. Nanoparticles were not toxic for HeLa cells and endocytosis-mediated cell internalisation was confirmed by confocal microscopy. Furthermore, the possible use of capped materials as a drug-delivery system was demonstrated by the preparation of a new mesoporous silica nanoparticle functionalised with PAzo6 and loaded with the cytotoxic drug camptothecin (CPT-PAzo6-S). Following cell internalisation and lysosome resident enzyme-dependent gate opening, CPT-PAzo6-S induced CPT-dependent cell death in HeLa cells.

Biosynthesis of Liquid Crystalline Azo‐Polyesters

Main‐chain thermotropic liquid‐crystalline aromatic azobenzene polyesters containing rigid 4,4′‐dihydroxyazobenzene mesogens and flexible spacers with varying lengths were synthesized using a chemo‐enzymatic method. The enzyme‐catalyzed approach is based on immobilized candida antarctica lipase B. The resulting polyesters were characterized by 1H‐NMR, 13C‐NMR, differential scanning calorimetry (DSC), and polarized light optical microscopy (POM).

Polarisation-sensitive optical elements in azobenzene polyesters and peptides

In this article, we describe fabrication of polarisation holographic optical elements in azobenzene polyesters. Both liquid crystalline and amorphous side-chain polyesters have been utilised. Diffractive optical elements such as lenses and gratings that are sensitive to the polarisation of the incident light have been fabricated with polarisation holography. Computer-generated optical elements and patterns have also been written with a single polarised laser beam. Recording of polarisation defects enabling easy visualisation is also shown to be feasible in azobenzene polyesters.

Influence of UV irradiation on the blue and red light photoinduced processes in azobenzene polyesters

Birefringence induced in a series of liquid crystalline side-chain azobenzene polyesters with different substituent groups was investigated under irradiation with 488 and 633 nm linearly polarized lights. Two different initial conditions have been used: the effect of a previous irradiation with UV light that yields the films into the isotropic state at room temperature (RT) was compared with the quenching from temperatures above the isotropic transition temperature T i. UV–visible spectra of the thermally quenched films show the presence of aggregates when measured at RT. We have found that UV light irradiation creates a high concentration of cis isomers and breaks the aggregates, but they are formed again after a few days in dark at RT. Orientation of the chromophores perpendicular to the polarization of the 488 nm light and parallel to the polarization of the 633 nm light was confirmed by dichroism measurements.

Evanescent polarization holographic recording of sub-200-nm gratings in an azobenzene polyester.

I demonstrate high-resolution polarization holographic recording with evanescent waves in a thin film of an azobenzene polyester deposited directly on the hypotenuse of a highly refractive prism. A spatial frequency greater than 7000 lines/mm and diffraction efficiency greater than 1% have been achieved. It was found that diffraction efficiency increases in the dark after the writing beams have been switched off. The biphotonic effect found in other azobenzene polymers, which converts cis states of the azobenzene to trans states followed by an ordering process that is due to aggregation, is proposed as the reason for this increase in diffraction efficiency.

Photoinduced anisotropy in a family of amorphous azobenzene polyesters for optical storage.

We investigate parameters associated with optical data storage in a variety of amorphous side-chain azobenzene-containing polyesters denoted as E1aX. The polyesters possess a common cyano-substituted azobenzene chromophore as a side chain, but differ in their main-chain polyester composition. Seventeen different polymers from the E1aX family divided into four classes, depending on the type of the main-chain substituent (one-, two-, and three-ring aromatic or alicyclic) have been thoroughly investigated. Various parameters characterizing the photoinduced birefringence in these materials, such as the response time, thermal and light stability, and long-term stability under ambient light at room temperature have been measured. Each of these parameters is quantitatively represented and therefore it is possible to make a clear comparison between the properties of the polymers. The results indicate that the long-term stability at ambient temperature is closely related to the thermal stability of the photoinduced birefringence. A strong correlation has also been found between the response time and the stability of the induced anisotropy toward illumination with unpolarized white light. One of the classes of E1aX polymers characterized by two-ring aromatic substituent in the main chain is a good candidate for optical data storage media. A recording energy of approximately 2 J/cm2 is sufficient to induce high refractive-index modulations of deltan = 0.13 in these materials, which is retained even at elevated temperatures (>130 degrees C). Long-term stability of greater than one year for the induced anisotropy has also been achieved.

Polarization holographic and surface-relief gratings at 257 nm in an amorphous azobenzene polyester.

Polarization holographic and surface-relief gratings have been recorded in an amorphous azobenzene polyester by use of a frequency-doubled argon-ion laser beam at 257 nm. Higher excited states of azobenzene in the trans and cis configurations contribute to the formation of a diffraction grating in this experiment. A combination of right and left circularly polarized writing beams has been found to give the highest diffraction efficiency. The contributions to the total phase difference that arise from anisotropy and surface relief have been separated experimentally, and it is shown that the surface-relief grating contributes a larger phase difference than that which is due to anisotropy.

Saturation effect in azobenzene polymers used for polarization holography

The saturation behavior of diffraction efficiency has been experimentally studied and theoretically modeled in azobenzene polyesters by recording polarization gratings with two beams of orthogonal circular polarization. The model is an extension of the phenomenological expression of Kakichashvili, derived from the rate equations for photoanisotropic materials, taking into account the effect of saturation with time and intensity. The saturation model of the polyester material can be used for the computer simulation of a polarization holographic data storage system under development. The simulation is based on fast Fourier transforms, taking the parameters of the recording material and the optical processes into account. Agreement between measured and simulated results proves the applicability of the saturation model as an efficient tool in the optimization of the system.

Effect of heat and film thickness on a photoinduced phase transition in azobenzene liquid crystalline polyesters

The liquid crystal to isotropic phase transition induced with 488 nm light in films of liquid crystalline azobenzene polyesters has been studied as a function of temperature, light intensity, and film thickness. That phase transition is associated with the photoinduced trans–cis–trans isomerizations of azobenzene molecules and it has been found that the 488 nm light power needed to induce the transition to the isotropic state increases when the film thickness decreases. The irradiation with the laser beam heats the film up and this seems to be responsible for the observed thickness dependence. Optical absorption measurements show that azobenzene aggregates present in one of the polymers are broken down in the photoinduced phase transition. The birefringence induced with low power 488 nm light in films before and after undergoing that photoinduced phase transition has also been studied. Birefringence shows a faster growing rate in films which have undergone the transition.

Propagation of Polarized Light Through Azobenzene Polyester Films

When elliptically polarized light of appropriate wavelength corresponding to trans - cis - trans isomerisation process is incident on thin films of azobenzene polyesters, a helical structure is induced. We investigate the propagation of the exciting light beam (self-induced) as well as a probe light beam outside the absorption band through the polyester films. Investigations are carried out in one amorphous and one liquid crystalline polyester. We show that amorphous polyester after irradiation behaves like classical helical material.

Fabrication of narrow surface relief features in a side-chain azobenzene polyester with a scanning near-field microscope

Abstract We show that it is possible to fabricate topographic submicron features in a side-chain azobenzene polyester with a scanning near-field optical microscope. Through irradiation at a wavelength of 488 nm at intensity levels of 12 W/cm 2 , topographic features as narrow as 240 nm and as high as 6 nm have been reproducibly recorded in a thin film of the polyester. These observations are consistent with the fact that at low intensities peaks are produced evolving into formation of trenches at high intensities in the case of amorphous side-chain azobenzene polyesters. This may find applications in high-density optical storage and high-resolution lithography.

Physics and technology of optical storage in polymer thin films

We discuss different strategies for optical storage of information in polymeric films. An outline of the existing trends is given. The synthesis and characterization of side-chain azobenzene polyester films for holographic storage of information is described. A compact holographic memory card system based on polarization holography is described. A storage density of greater than 10MB/cm 2 has been achieved so far, with a potential increase to 100MB/cm 2 using multiplexing techniques and software correction. Finally the role of surface relief in azobenzene polymers on irradiation with polarized light is mentioned.

Surface relief measurements in side-chain azobenzene polyesters with different substituents

Light-induced surface modification of a series of liquid-crystalline side-chain azobenzene polyesters which have the same main- and side-chain structure but eleven different substituents on the azobenzene is investigated. Using a transmission mask as well as single focused beams we show that the formation of the surface relief is dependent on the substituents. In both experiments irradiation with p-polarized light generates peaks for the CN, CF3, CH3 and F substituents, while for a Cl substituent valleys are observed. Also s-polarized light is found to produce surface deformations. An amorphous azobenzene polyester was included in the study for comparison. The results point to a mechanism of the surface relief phenomenon, in which the architecture of the polyesters plays a crucial role.

Biphotonic holographic gratings in azobenzene polyesters: Surface relief phenomena and polarization effects

Biphotonic holographic gratings have been recorded in a side-chain azobenzene liquid crystalline polyester using a blue incoherent source and a He–Ne laser. Intensity gratings and the appearance of surface relief have been observed when two linearly polarized beams from a He–Ne laser are made to interfere on a film illuminated with blue light. Polarized holographic gratings are also created with two orthogonally circularly polarized He–Ne beams. All these gratings are stable in darkness but can be erased with blue light.

Determination of the response time of photoanisotropy in azobenzene side-chain polyesters

We present a method which allows the determination of the response time to polarized light of an azobenzene side-chain polyester. This method is based on the measurement of intensities in dependence on the delay time between a pump and a probe pulse. The described method does not need a very sophisticated time resolving measuring equipment. The time resolution is in the order 10 ps and is comparable with the laser pulse duration. The response time of the azobenzene side-chain polyester E1aP has determined to be about 40 ps.

An improved method for separating the kinetics of anisotropic and topographic gratings in side-chain azobenzene polyesters

The induction of anisotropy gratings in side-chain azobenzene polyesters is accompanied by the formation of surface relief. We introduce an improved holographic method to separate the contributions of the anisotropic and the topographic part to the diffraction efficiency by analyzing the polarization of the first-order diffracted beam. The main advantage of this method is that both parts can be determined simultaneously by only one measurement. Furthermore the displacement between both gratings can be determined in a similar manner. Experimental results obtained with two different polyesters are presented.

Photoinduced deformation of azobenzene polyester films

We investigate two types of azobenzene side-chain polyesters which have shown opposite behaviour in light-induced surface grating formation experiments. Thin films of these polymers prepared on a water surface undergo opposite changes of shape under the influence of polarized light. We propose this deformation to be responsible for the surface relief gratings.