Photodeformable Azo Polymer Janus Particles Obtained upon Nonsolvent-Induced Phase Separation and Asynchronous Aggregation.

Photodeformable submicron Janus particles (JPs), containing an epoxy-based azo polymer (BP-AZ-CN) and poly(methyl methacrylate) (PMMA), were fabricated upon nonsolvent-induced phase separation. The formation of the JPs was induced by gradually adding deionized water into a tetrahydrofuran (THF) solution of both polymers. The results show that the two polymers start to precipitate from the solution at almost the same water content and immediately separate into two phases in each particle due to the strong incompatibility between the two components. After the nucleation, the sizes of the aggregates increase with increasing water content in the following growth stage. The amount of BP-AZ-CN molecules assembling into the aggregates is controlled by the water content in the medium, while the aggregation of PMMA molecules is a slow diffusion-controlled process due to the much higher molecular weight of this polymer. With a further increase in the water content in the dispersion medium, the swollen aggregates collapse to form JPs. Interestingly, when a dispersion with a water content of 50 vol % is diluted with a THF/H2O mixture with the same water content, the shapes of the JPs are significantly modified and vitrified after removal of THF through evaporation. By increasing the dilution multiples adopted to dilute the intermediate dispersions, JPs with more asymmetric shapes are obtained due to the enhanced asynchronous aggregation. Ternary phase diagrams calculated according to the Flory-Huggins theory provide a semi-quantitative description and rationalization of the phase separation behavior related to the thermodynamic factors. The differences in the transport behavior and aggregation dynamics of the two polymers are also proven to be critical for the formation of the asymmetric structures. Upon irradiation, the BP-AZ-CN compartments of JPs exhibit remarkable elongation along the electric vibrational direction of a linearly polarized laser beam at a wavelength of 488 nm.

Compartmentalized Janus droplets of photoresponsive cholesteric liquid crystals and poly(dimethylsiloxane)-based oligomers.

A new kind of Janus droplet containing photoresponsive cholesteric liquid crystals (CLCs) was fabricated for the first time and their formation, compartment structure, mesophase texture and function were thoroughly investigated. In the droplets, the CLC compartments included a typical nematic LC (4'-pentyl-4-biphenylcarbonitrile) doped with an azobenzene-containing chiral dopant, and the other compartments were formed of a poly(dimethylsiloxane)-based oligomer. Janus droplets were fabricated through microphase separation of the incompatible components in chloroform solution dispersed in an aqueous medium, induced by slow evaporation of chloroform. The mesophase structures of the CLC phase in Janus droplets, both suspended in aqueous medium and spreading on substrates, were controlled by the bulk elastic free energy of the CLC phase, surface anchoring and confining geometries. The helix pitch of the cholesteric phase in the droplets was determined by the doping concentration of the chiral dopant. For the suspended Janus droplets with the helix pitch obviously smaller than the droplet sizes, the CLC compartments mainly possessed a bipolar structure instead of the Frank-Pryce structure typically observed on CLC droplets. After the Janus droplets spread on the substrates, the CLC compartments changed to crescent shapes due to the different wettability characteristics of the two compartments, and the formed stable and metastable CLC configurations were distinctively different from those in the suspensions. Interestingly, when the Janus droplets spreading on substrates were irradiated with a laser beam (λ = 488 nm) of low intensity, the directors in the CLC compartments rearranged to form fingerprint structures with minimum total energy.

Triphasic Polymer Particles Assembled via Microphase Separation with Multiple Functions.

This work investigated a unique type of triphasic colloidal particles composed of an azo polymer (PCNAZO), a fluorescent pyrene-containing polymer [P(MMA-co-PyMA)], and a poly(dimethylsiloxane)-based polymer (H2pdca-PDMS), focusing on the synthesis, forming mechanism, morphology control, and functions. The triphasic particles with well-defined morphologies were assembled through the microphase separation of the components in dichloromethane (DCM) droplets in an aqueous medium, induced by the gradual evaporation of the organic solvent. The real-time fluorescence emission spectra of the pyrenyl moieties and in situ microscopic observations show that the formation of the triphasic particles undergoes the segregation of the PCNAZO-rich phase, separation between P(MMA-co-PyMA)-rich and H2pdca-PDMS-rich phases, coalescence, and solidification in the dispersed droplets. The structure formation is due to the strong phase separation of the polymers as revealed by the calculations based on the Flory-Huggins theory. The morphologies and phase boundaries of the particles are found to be controlled by the interfacial energy between the phases and processing conditions. The triphasic particles thus obtained possess a series of interesting functions stemming from the polymers and the triple-compartmentalized structures. After being deposited on a substrate, the H2pdca-PDMS parts can tightly adhere on the surface, caused by the spreading nature of the polymer when slightly swelled by DCM. Upon irradiation with a linearly polarized laser beam at 488 nm, the azo polymer compartments show a significant elongation along the electric vibration direction of the polarized light, accompanied by the cooperative deformation of the H2pdca-PDMS pads. When dispersed in water and adhered on the substrate surface, the triphasic particles exhibit tunable colors originating from the fluorescence of the pyrenyl fluorophores and light absorption of the azo chromophores. The real-time investigation methods developed here could lead to the deep understanding of the structure formation process in the confined volume and be applied in phase-separation study of other polymers as well.

Mussel-like Surface Adhesion and Photoinduced Cooperative Deformation of Janus Particles.

This study focused on mussel-like surface adhesion and photoinduced cooperative deformation of a unique type of Janus particles (JPs), composed of an isosorbide-based molecular glass bearing push-pull type azo chromophore (IAC-4) and a 2,6-pyridinedicarboxamide-containing poly(dimethylsiloxane) oligomer (H2pdca-PDMS). The JPs were obtained by the solvent evaporation method in an aqueous medium with the dispersed phase of a solution of IAC-4 and H2pdca-PDMS in dichloromethane (DCM). The JP formation and its mechanism were investigated by electron microscopy, in situ optical microscopy, and theoretical analysis. The results showed that the Janus structures form through gradual segregation between the two components in the droplets induced by the evaporation of DCM, which follows the ternary phase diagrams calculated according to Flory-Huggins theory. In the following stage, the gradual coalescence of small domains in droplets is controlled by dynamic factors. After being deposited on a substrate, the JPs exhibit unidirectional adhesion with the H2pdca-PDMS parts spreading on the substrate, while the IAC-4 parts orientate away from the substrate. The mussel-like adhesion is caused by the interfacial interaction of H2pdca-PDMS with the hard surfaces (i.e., glass and silicon substrates) and its strong ability to spread and wet the surfaces to increase the contact area with the surfaces. Upon irradiation with linearly and circularly polarized laser beams at 488 nm, respectively, a series of unique surface morphologies are observed because of the photoinduced deformation of the IAC-4 parts along the electric vibration direction of the polarized light and the cooperative deformation of the H2pdca-PDMS parts of the JPs. The cooperative deformation reveals the strong interfacial interaction and cohesiveness between the IAC-4 and the H2pdca-PDMS phases in JPs. No peeling-off from the substrate is observed after the large-scale deformation, which also indicates the strong adhesion of the JPs on the substrate surfaces. This study not only demonstrates the mussel-like adhesion and unique cooperative deformation behavior but also supplies new insights into the interfacial interaction in JPs as well as that with hard surfaces, thus opening a new avenue for surface modification and functionalization.

Multifunctional Janus Particles Composed of Azo Polymer and Pyrene-Containing Polymer.

This study investigated Janus particles (JPs) composed of an azo polymer and a pyrene-containing polymer, focusing on preparation, formation mechanism, photoinduced deformation behavior, and fluorescent properties as well as tunable colors of the dispersions. A methacrylate-based copolymer containing pyrenyl groups (P(MMA-co-PyMA)) and two azo polymers, i.e., a methacrylate-based polymer (PCNAZO) and an epoxy-based polymer (CH-TZ-NT) both bearing push-pull-type azo chromophores, were synthesized for this purpose. Two types of Janus particles, P(MMA-co-PyMA)/PCNAZO JPs and P(MMA-co-PyMA)/CH-TZ-NT JPs, were fabricated through microphase separation of the components in the droplets dispersed in aqueous media, induced by the evaporation of the organic solvent. The process of JP formation was thoroughly investigated by exploiting the function of pyrene moieties as a molecular probe through measuring the fluorescence emission spectra at different times during the structure evolution. The photoluminescent (PL) intensity, excimer emission, and vibrational fine structure of the fluorescence spectra were observed to give information about phase separation and solidification occurred in the dispersed droplets. The observations were rationalized by analysis with ternary phase diagrams calculated on the basis of the Flory-Huggins theory. Upon irradiation with a linearly polarized laser beam at 488 nm, the azo polymer parts in the P(MMA-co-PyMA)/PCNAZO JPs were observed to be elongated along the electric vibration direction of the polarized light and transformed into particles with unique morphologies. The dispersions of JPs with different compositions of the two types of the polymers showed highly tunable color changes originating from both fluorescence of the pyrenyl fluorophores and light absorption of the azo chromophores.

Shaping monodispersed azo molecular glass microspheres using polarized light.

Azo molecular glass (IAC-4) microspheres with a monodispersed diameter over ten microns were fabricated by microfluidics and unique shape manipulation was achieved based on their fascinating photoinduced deformation behaviour. After irradiation with a polarized laser beam (λ = 488 nm), the IAC-4 microspheres were transformed into uniform mushroom-like particles, and their three-dimensional (3D) asymmetric shapes were precisely manipulated by adjusting the irradiation time and the polarization state of light. By observing the particle morphology in three orthogonal views (top view, front view and side view) by scanning electron microscopy (SEM), the photoinduced deformation behaviour of the ten-micron-sized particles was comprehensively revealed in the 3D space for the first time. It was observed that the photoinduced deformation asymmetrically occurred on the upper part of the microspheres due to the strong optical absorption of the azo chromophores. Besides, the deformation manner of the upper part was decided by the direction of the electric vibration of the refracted light. This work not only depicts a clear picture of the photoinduced deformation behaviour of the ten-micron-sized azo particles upon polarized light irradiation, but also provides a new method to controllably manipulate the particle shape from spheres to complex 3D architectures.

Nitrogen-Doped Carbon Supported Nanocobalt Catalyst for Hydrogen-Transfer Dearomative Coupling of Quinolinium Salts and Tetrahydroquinolines.

A nitrogen-doped carbon supported nanocobalt catalyst was developed and successfully applied for the hydrogen-transfer coupling of quinolinium salts and tetrahydroquinoline compounds. The selective coupling of the C6 sites of tetrahydroquinolines (THQs) with the α sites of quinoline salts generated a series of 2-substituted N-alkyl-tetrahydroquinolines. This catalytic conversion method, which can be employed to synthesize various functionalized tetrahydroquinolines, has several advantages that include excellent hydrogen transfer selectivity, a reusable and inexpensive catalyst, and environmental friendliness.

Comparative study of photoinduced surface-relief-gratings on azo polymer and azo molecular glass films.

Photoinduced surface-relief-gratings (SRGs) on azo polymer and azo molecular glass films, caused by trans-cis isomerization of azo chromophores, have attracted wide interest for their intriguing nature and many possible applications in recent years. Understanding the mechanical properties of SRGs at the nanoscale is critically important for elucidating their formation mechanism and exploring their applications. In this work, a representative azo polymer (BP-AZ-CA) and a typical azo molecular glass (IAC-4) were comparatively studied for the first time concerning their properties related to SRG formation through a variety of methods. The results indicate that when inscribing SRGs on the films, IAC-4 shows a much higher efficiency for forming SRGs relative to that of BP-AZ-CA. The overall average moduli of SRGs measured by nanomechanical mapping techniques are obviously smaller compared with the moduli of the corresponding films of both materials. The moduli at different regions of SRGs are periodically varied along the grating vector direction for both BP-AZ-CA and IAC-4 gratings. The moduli at the trough regions of SRGs are always larger than those of the crests, while the moduli at the hillsides are the smallest. Distinct from BP-AZ-CA, even the moduli at the trough regions of IAC-4 SRG are smaller compared with that of the original film, and the ratio between the trough and crest moduli is significantly larger for IAC-4. These results provide deep understanding of the SRG formation mechanism and reveal the clear distinction between these two types of glassy materials for their SRG-forming behavior, which are important for future applications.