Supramolecular control over thermo-responsive systems with lower critical solution temperature behavior

Lower critical solution temperature(LCST)is the critical temperature below which the solution is miscible for all compositions and above which the solution becomes a suspension.The study of LCST properties has become a central research topic due to its profound impact on the applications of stimuli-responsive materials.Inspired by the marriage between materials science and supramolecular chemistry,the introduction of supramolecular pairs and interactions into polymeric LCST systems is increasingly practiced.Especially,supramolecular interactions provide precise control over LCST behavior in both water and organic solvents.Furthermore,supramolecular interactions not only control or adjust LCST behavior(supramolecular interaction controlled LCST),but also induce LCST phase behavior in species lack of thermo-sensitive properties(supramolecular interaction induced LCST).In this review,we summarize the applications of supramolecular interactions in LCST systems.By examining the relationship between supramolecular interactions and LCST changes,we further discuss the differences between supramolecular interaction controlled LCST and supramolecular interaction induced LCST.We hope this review will give our readers a snapshot on how the supramolecular interactions influence the LCST behavior in various systems,and benefit them with different applications.

Synthesis and Properties of Poly (N-isopropylacrylamide) and Poly (N-isopropylacrylamide-co-acrylamide) Hydrogels

The thermosensitive poly （ N-isopropylacrylamide ） （PNIPAAm） and poly （N-isopropylacrylamide-co-acrylamide） [ poly （NIPAAm-co-AAm） ] hydrogels with different acrylamide molar percentage are prepared by radiation polymerization using Co^60 γ-ray. Their swelling equilibrium data in the media of deionized water, NaCl aqueous solutions and different pH buffer solutions are determined. It appears that lower critical solution temperature （LCST） of the hydrogels will drop with the increase of ionic strength and increase with the rising of acrylamide content, A semi-empirical formula is set up with the experimental results. Moreover, it also indicates that this copolymer is pH-sensitive, which is similar to the homopolymer of PNIPAAm.

Temperature/pH dual-responsive reversible morphology evolution of block copolymer microparticles under three-dimensional confinement

Development of block copolymer(BCP)microparticles with switchable morphology in response to external stimuli is important for exploiting new intelligent materials.In this work,thermo/p H dual-responsive nanoparticles(NPs)were employed as a cosurfactant to modulate the self-assembly morphology of polystyrene-b-poly(2-vinylpyridine)(PS-b-P2VP)microparticles within confined emulsion droplets.The co-surfactant was synthesized by grafting poly(acrylic acid)-b-poly(N-isopropylacrylamide)onto the surface of Fe3O4NP.The introduction of the dual-responsive co-surfactant enabled thermo/p H dual-responsive reversible morphology transition of the PS-b-P2VP microparticles by tailoring the hydrophobicity and interfacial affinity of the cosurfactant.By using this strategy,the thermo-inert PS-b-P2VP self-assembled into pupa-like microparticles at T=10℃ and p H7.5,which could transform into tulip-like microparticles when T was increased to 50℃.When the p H value was increased to 11,the pupa-like particles turned into onion-like microparticles although the PS-b-P2VP was inert to alkali.However,the pupa-like microparticles remained unchanged when both T and p H were simultaneously increased.The PAA-b-PNIPAM-grafted Fe3O4NP surfactants showed obvious advantages over the linear PAA-b-PNIPAM surfactants in modulating the morphology transition,since the linear PAA-b-PNIPAM could not induce the reversible shape transition of microparticles.Our work provides an efficient strategy to achieve reversible shape transformation of BCP microparticles while the internal phase structure is preserved,which may be utilized to switch the structural color properties of BCP microparticles.

Controlling the gelation temperature of biomimetic polyisocyanides

Thermosensitive polymers show an entropy-driven transition from a well-solvated to a poorly solvated polymer chain, resulting in a more compact globular conformation. The transition at the lower critical solution temperature（LCST） is often sharp, which allows for a wide range of smart material applications.At the LCST, oligo（ethylene glycol）-substituted polyisocyanides（PICs） form soft hydrogels, composed of polymer bundles similar to biological gels, such as actin, fibrin and intermediate filaments. Here, we show that the LCST of PICs strongly depends linearly on the length of the ethylene glycol（EG） tails; every EG group increases the LCSTand thus the gelation temperature by nearly 30 ℃. Using a copolymerisation approach, we demonstrate that we can precisely tailor the gelation temperature between 10 ℃ and 60 ℃and, consequently, tune the mechanical properties of the PIC gels.

Tunable LCST-type phase behavior of [FeCl4]--based ionic liquids in water

In this work, 16 kinds of [FeCl4]--based magnetic ionic liquids （ILs） with different cation structures have been designed and synthesized, and their structures are characterized by IR and Raman spectroscopy. Then the lower critical solution temperature （LCST）-type phase behavior of these magnetic ILs in water is investigated as a function of concentration. It is shown that cat- ion structure, alkyl chain length and molar ratio of FeCl3/chloride IL have a significant influence on the LCST of the mixtures. The phase separation temperature can be tuned efficiently by these factors. Meanwhile, the LCST-type phase separation pro- cess is also investigated by dynamic light scattering. The results support the mechanism that the hydrogen bonds of the [Fefl4]- anion with water have been gradually disrupted to form ILs aggregates with increasing temperature. In addition, the stability of the ILs in water is also examined in some details. These LCST-type phase separation systems may have potential applications in extraction and separation techniques at room temperature.

Micromechanical properties of poly(N-isopropylacrylamide)hydrogel microspheres determined using a simple method

Temperature-responsive poly（N-isopropylacrylamide） （PNIPAM） hydrogel microspheres have attracted extensive attention because of their promising diverse biomedical applications. A quantitative understanding of the micromechanical properties of these microspheres is essential for their practical application. Here, we report a simple method for the characterization of the elastic properties of PNIPAM hydrogel microspheres. The results show that PNIPAM hydrogel microspheres exhibit elastic deformation and the obtained force-deformation experimental data fits the Hertz theory well. The moduli of elasticity of the PNIPAM hydrogel microspheres prepared under different conditions were systematically investigated in this work for the first time. The PN1PAM hydrogel microsphere composition significantly affects their micromechanical properties and their temperature sensitivity behavior. PNIPAM hydrogel microspheres with a larger equilibrium volume change have a lower modulus of elasticity. The modulus of elasticity of the PNIPAM hydrogel microspheres at body temperature （37 ℃, above the lower critical solution temperature （LCST） of PNIPAM） is much higher than that at room temperature （25 ℃, below the LCST of PNIPAM） because ofthermo-induced volume shrinkage and an increase in stiffness. These results provide valuable guidance for the design of smart materials for practical biomedical applications. Moreover, the simple microcompression method presented here also provides a versatile way to investigate the micromechanical properties of microscopic biomedical materials.

Supramolecular control over LCST behavior of hybrid macrocyclic system based on pillar[5]arene and crown ether

A hybrid system containing a pillar[5]arene unit and ten crown ether moieties was developed.The LCST behavior and thermo-responsive ness were successfully introduced into this pillar[5]arene-crown ether system.Both host-guest interactions and salting-out effect displayed great effects in realizing the supramolecular control over LCST properties and the rmo-re sponsiveness.Compa red with the individual macrocycles,this hybrid macrocycle system dramatically amplified the supramolecular control effect over LCST behavior.