Search Results (29)

Significant research endeavors have been devoted to developing adhesives with reversible switching capabilities, allowing them to activate adhesion in response to diverse environmental stimuli. Among these, photo-switchable adhesives stand out as particularly promising. The presence of a photo-reversible solid-to-liquid transition, characterized by a transition temperature (T_SL), in certain azobenzene-containing polymers offers a compelling avenue for creating such adhesives. The development of a method based on Atomic Force Microscopy to measure both the glass transition temperature (T_g) and T_SL provided an opportunity to investigate the impact of various structural parameters on the solid-to-liquid transition of azopolymers. Our findings revealed that increasing the molecular weight (Mn) from 3400 to 8100 g/mol needed to achieve a highly cohesive adhesive resulted in an elevation in T_SL (>10 °C), making the solid-to-liquid transition at room temperature more challenging. However, incorporating a highly flexible substituent at the para position of the azobenzene group proved effective in significantly reducing the T_SL value (from 42 °C to 0 °C). This approach allows for the creation of photo-switchable adhesives with intriguing properties. We believe that our results establish a pathway toward developing a robust room-temperature photo-switchable adhesive. Full article

Quantum dots (QDs) are emerging as promising candidates for innovative memristive materials, owing to their distinct surface, quantum size, and edge effects. Recent research has focused on tailoring QDs with specific organic molecules to fine-tune charge transfer states between the host and grafted species, as well as enhancing their dispersibility and processability. Violet phosphorus (VP), a newly discovered two-dimensional phosphorus allotrope, offers excellent carrier dynamics, predictable modifiability, and superior oxidation resistance, making it a promising contender in this domain. In this study, we synthesized a rich azobenzene-containing star-shaped polymer diazonium salt (AzoSPD) to functionalize violet phosphorus quantum dots (VPQDs), with the dual objectives of enhancing organic dispersibility and introducing photo-switching capabilities. The synthesized AzoSPD–VPQDs exhibit intramolecular charge transfer characteristics under electrical stimuli of ambient conditions, displaying significant non-volatile rewriteable memory properties and a substantial switching ratio exceeding 2 × 10³. Furthermore, the high resistance state (HRS) current can be enhanced by nearly 40 times under 465 nm illumination, enabling optoelectronic information sensing and storage within a single device. This work not only provides insights into enhancing the optoelectronic properties of QDs through functional organic molecular modification but also represents a pioneering exploration of the potential applications of VPQDs in novel memristors. Full article

One of the strategies to reduce the contents of low density lipoproteins (LDLs) in blood is a hemoperfusion, when they are selectively retracted from plasma by an adsorber located outside the patient’s body. Recently, a photo-controllable smart surface was developed experimentally, that is characterized by high selectivity and reusability. It comprises a nanocarrier functionalised by a brush of azobenzene-containing polymer chains. We present a mesoscopic model that mimics principal features of this setup and focus our study on the role played by the length and flexibility of the chains and grafting density of a brush. The model for LDL comprises a spherical core covered by a shell of model phospholipids. The model is studied via coarse-grained molecular dynamics simulation, performed with the aid of the GMBOLDD package modified for the case of soft-core beads. We examined the dependencies of the binding energy on both the length of polymer chains and the grafting density of a brush and established optimal conditions for adsorption. These are explained by competition between the concentration of azobenzenes and phospholipids in the same spatial region, flexibility of polymer chains, and excluded volume effects. Full article

In this paper, we report the first experimental results on capillary shear flows of a nematic liquid crystal 5CB (4-cyano-4′-pentylbiphenyl), arising due to interaction of the anisotropic liquid, correspondent to the continuous rotational symmetry, with photo-profiled polymer surfaces. The regular surface relief was obtained due to opto-mechanical deformation of azobenzene containing potoresponsive polymer film (PAZO) during irradiation with two-beam interference. Such surface treatment makes it possible to obtain a regular submicron profile with well-defined characteristics (direction, period, and height). The polarizing microscopy (PM) and dynamic light scattering (DLS) techniques were used to determine the direction of the surface orientation of LC and anchoring strength, which characterize the interaction of LC with the photo-profiled polymer surface. Two types of shear flows—spreading of LC droplets and capillary flow in a plane capillary, induced by the interaction of LC with one or two photo-profiled surfaces—were investigated for different directions of the flow relative to the direction of the relief. Strong anisotropy in the dynamics of the precursor film and contact line motion, as well as in the dynamical contact angle, was established. The experimental results were analyzed and compared with those previously obtained at the investigation of the spreading of LC droplets over a mechanically stamped submicron profile and capillary flows in plane capillaries with photo-aligned surfaces. Full article

Unlike azobenzene, the photoisomerization behavior of its ethylene-bridged derivative, diazocine, has hardly been explored in synthetic polymers. In this communication, linear photoresponsive poly(thioether)s containing diazocine moieties in the polymer backbone with different spacer lengths are reported. They were synthesized in thiol-ene polyadditions between a diazocine diacrylate and 1,6-hexanedithiol. The diazocine units could be reversibly photoswitched between the (Z)- and (E)-configurations with light at 405 nm and 525 nm, respectively. Based on the chemical structure of the diazocine diacrylates, the resulting polymer chains differed in their thermal relaxation kinetics and molecular weights (7.4 vs. 43 kDa) but maintained a clearly visible photoswitchability in the solid state. Gel permeation chromatography (GPC) measurements indicated a hydrodynamic size expansion of the individual polymer coils as a result of the Z→E pincer-like diazocine switching motion on a molecular scale. Our work establishes diazocine as an elongating actuator that can be used in macromolecular systems and smart materials. Full article

Recently, the realization of the spiral mass transfer of matter has attracted the attention of many researchers. Nano- and microstructures fabricated with such mass transfer can be used for the generation of light with non-zero orbital angular momentum (OAM) or the sensing of chiral molecules. In the case of metals and semiconductors, the chirality of formed spiral-shaped microstructures depends on the topological charge (TC) of the illuminating optical vortex (OV) beam. The situation is quite different with polarization-sensitive materials such as azopolymers, azobenzene-containing polymers. Azopolymers show polarization-sensitive mass transfer both at the meso and macro levels and have huge potential in diffractive optics and photonics. Previously, only one-spiral patterns formed in thin azopolymer films using circularly polarized OV beams and double-spiral patterns formed using linearly polarized OV beams have been demonstrated. In these cases, the TC of the used OV beams did not affect the number of formed spirals. In this study, we propose to use two-beam (an OV and a Gaussian beam with a spherical wavefront) interference lithography for realization spiral mass transfer with the desired number of formed spirals. The TC of the OV beam allows for controlling the number of formed spirals. We show the microstructures fabricated by the laser processing of thin azopolymer films can be used for the generation of OAM light at the microscale with the desired TC. The experimentally obtained results are in good agreement with the numerically obtained results and demonstrate the potential of the use of such techniques for the laser material processing of polarization-sensitive materials. Full article

Poly(N-isopropylacrylamide) PNIPAAm hydrogels were modified with a new azobenzene-containing co-monomer. In this work, light responsiveness as an additional functionality, is conceptualized to induce two phase transitions in the same material, which can be controlled by light. For a hydrogel with merely 2.5 mol% of this co-monomer, the lower critical solution transition temperature (LCST) was lowered by 12 °C (to 20 °C) compared to PNIPAAm (LCST at 32 °C), as analyzed by differential scanning calorimetry (DSC). The untreated unimodal endotherm split into a bimodal peak upon irradiation with UV-light, giving a second onset due to the switched (Z) isomer-rich regions, LCST*_H2.5%-(Z) = 26 °C. On irradiation with 450 nm, leading to the reverse (Z) to (E) isomerization, the endotherm was also reversible. Thus, a photo-switchable hydrogel whose LCST and structure are tunable with the hydrophobicity-hydrophilicity of the (E) and (Z) isomeric state of azobenzene was obtained. The influence of the increase in the mol% of azoacrylate on the LCST was evaluated via DSC, in combination with NMR studies, UV-vis spectroscopy and control experiments with linear polymers. The large light-driven modulation of the LCST adds bistability in thermoresponsive hydrogels, which may open diverse applications in the field of soft robotics actuators. Full article

Azobenzene-containing polymers (azo-polymers) have been a subject of extensive investigations during the last two and half decades, due to their remarkable ability to undergo pronounced alignment and deformation under irradiation with light. The molecular ordering and deformation in azo-polymers of various structures under irradiation with linearly polarized light was described in a series of theoretical works, based on the effect of the reorientation of azobenzene moieties due to the anisotropic character of the photoisomerization processes. In the present study, we generalize the previous orientation approach to describe the photo-alignment and deformation of azo-polymer networks under irradiation with elliptically polarized light. We demonstrate that, in general, the light-induced ordering and deformation have a biaxial symmetry defined by the polarization ellipse. Azobenzene chromophores have a tendency to align along the direction of light propagation, the orientation in the other two directions being dependent of the aspect ratio of the polarization ellipse. This causes deformation of azo-polymer networks along the direction of light propagation, the sign of which (expansion/contraction) is defined by a chemical structure of network strands. Theoretical results are in agreement with experiments and have a practical importance to predict the photo-mechanical response of azo-polymers depending on their structure and on the polarization of light. Full article

Here, we report our studies on photoresponsive poly(meth)acrylates containing azobenzene groups connected to a polymer backbone via a short methylene linker. A series of side-chain azobenzene polymers was synthesized via the atom transfer radical polymerization (ATRP) technique using several catalytic systems. The polymers synthesized under the optimized conditions were characterized by a narrow polydispersity (Đ ≤ 1.35), and they underwent a reversible transformation of their structure under light illumination. The fabricated polymers can store and release energy accumulated during the UV-light illumination by the thermal cis-trans isomerization of the chromophore groups. The enthalpy of the process (determined from DSC) was relatively high and equaled 61.9 J∙g⁻¹ (17 Wh∙kg⁻¹), indicating a high potential of these materials in energy storage applications. The liquid-crystalline behavior of the synthesized poly(meth)acrylates was demonstrated by the birefringent optical textures as observed in thin-films and X-ray scattering studies. Full article

Bio-inspiration relentlessly sparks the novel ideas to develop innovative soft robotic structures from smart materials. The conceptual soft robotic designs inspired by biomimetic routes have resulted in pioneering research contributions based on the understanding of the material selection and actuation properties. In an attempt to overcome the hazardous injuries, soft robotic systems are used subsequently to ensure safe human–robot interaction. In contrast to dielectric elastomer actuators, prolific efforts were made by understanding the photo-actuating properties of liquid crystalline elastomers (LCEs) containing azo-derivatives to construct mechanical structures and tiny portable robots for specific technological applications. The structure and material properties of these stimuli-responsive polymers can skillfully be controlled by light. In this short technical note, we highlight the potential high-tech importance and the photo-actuation behavior of some remarkable LCEs with azobenzene chromophores. Full article

Ionic complexation of azobenzene-containing surfactants with any type of oppositely charged soft objects allows for making them photo-responsive in terms of their size, shape and surface energy. Investigation of the photo-isomerization kinetic and isomer composition at a photo-stationary state of the photo-sensitive surfactant conjugated with charged objects is a necessary prerequisite for understanding the structural response of photo-sensitive complexes. Here, we report on photo-isomerization kinetics of a photo-sensitive surfactant in the presence of poly(acrylic acid, sodium salt). We show that the photo-isomerization of the azobenzene-containing cationic surfactant is slower in a polymer complex compared to being purely dissolved in aqueous solution. In a photo-stationary state, the ratio between the trans and cis isomers is shifted to a higher trans-isomer concentration for all irradiation wavelengths. This is explained by the formation of surfactant aggregates near the polyelectrolyte chains at concentrations much lower than the bulk critical micelle concentration and inhibition of the photo-isomerization kinetics due to steric hindrance within the densely packed aggregates. Full article

Recently, the design of novel supramolecular chiral materials has received a great deal of attention due to rapid developments in the fields of supramolecular chemistry and molecular self-assembly. Supramolecular chirality has been widely introduced to polymers containing photoresponsive azobenzene groups. On the one hand, supramolecular chiral structures of azobenzene-containing polymers (Azo-polymers) can be produced by nonsymmetric arrangement of Azo units through noncovalent interactions. On the other hand, the reversibility of the photoisomerization also allows for the control of the supramolecular organization of the Azo moieties within polymer structures. The construction of supramolecular chirality in Azo-polymeric self-assembled system is highly important for further developments in this field from both academic and practical points of view. The postpolymerization self-assembly strategy is one of the traditional strategies for mainly constructing supramolecular chirality in Azo-polymers. The in situ supramolecular self-assembly mediated by polymerization-induced self-assembly (PISA) is a facile one-pot approach for the construction of well-defined supramolecular chirality during polymerization process. In this review, we focus on a discussion of supramolecular chirality of Azo-polymer systems constructed by traditional postpolymerization self-assembly and PISA-mediated in situ supramolecular self-assembly. Furthermore, we will also summarize the basic concepts, seminal studies, recent trends, and perspectives in the constructions and applications of supramolecular chirality based on Azo-polymers with the hope to advance the development of supramolecular chirality in chemistry. Full article

In the search for novel smart multifunctional liquid crystalline materials, we report the synthesis, thermal and structural characterisation, and the conductivity, of a set of new block and statistical copolymers, containing light-responsive mesogenic groups (MeOAzB), polar sulfonic acids (AMPS), and methyl(methacrylate) groups (MMA). By using a cascade of reversible addition-fragmentation chain polymerisations, RAFT, we have tailored different side-chain polymeric structures by controlling monomer composition (MeOAzB/AMPS/MMA) and configuration. We have yielded simultaneous liquid crystalline behaviour and appreciable conductivity in polymers with low concentrations of polar acid groups, by the formation of smectic phases in narrow aggregates. The light-responsiveness of the polymers, via reversible trans-to-cis photoisomerization of azobenzene groups, and the local activation of conductivity at relatively low temperatures, opens the possibility to prepare polymer electrolytes for energy conversion and storage, whose conductivity could be controlled and optimised by external stimuli, including light irradiation. Full article

This paper describes the synthesis and characterization of new “T-type” azo poly(amide imide)s as well as guest-host systems based on the “T-type” matrices. The matrices possessed pyridine rings in a main-chain and azobenzene moieties located either between the amide or imide groups. The non-covalent polymers contained the molecularly dispersed 4-phenylazophenol or 4-[(4-methyl phenyl)diazinyl]phenol chromophores that are capable of forming intermolecular hydrogen bonds with the pyridine rings. The FTIR spectroscopy and the measurements of the thermal, optical and photoinduced optical birefringence were employed for the determination of the influence of H-bonds and the specific elements of polymer architecture on physicochemical properties. Moreover, the obtained results were compared to those described in our previous works to formulate structure-property relations that may be considered general for the class of “T-type” azo poly(amide imide)s. Full article

The photoinduced solid-to-liquid transitions property of azobenzene-containing polymers (azopolymers) enables azopolymers with various promising applications. However, a general lack of knowledge regarding the influence of structure of the azobenzene derivatives on the photoinduced liquefaction hinders the design of novel azopolymers. In the present study, a series of azopolymers with side chains containing azobenzene unit bearing alkyl electron-donating groups were synthesized. The photoisomerization and photoinduced liquefaction properties of newly synthesized azopolymers were investigated. Alkyl-based electron-donating group significantly facilitate the photoisomerization process of azopolymers in solution, as the electron-donating ability of substituents increased, the time required for photoisomerization of azopolymers continually deceased. Meanwhile, the electron-donating group can drastically accelerate photoinduced solid-to-liquid transitions of azopolymers, the liquefaction rate of obtained azopolymers gradually getting quicker as the electron-donating ability of substituents increased. This study clearly demonstrates that the electron-donating group that bearing in the azobenzene group of polymer side chain play an essential role on the photoinduced solid-to-liquid transitions of azopolymers, and hence, gives an insight into how to design novel azopolymers for practical applications. Full article