Influence of poly(acrylic acid) grafting density on switchable protein adsorption/desorption of poly(2-methyl-2-oxazoline)/poly(acrylic acid) mixed brushes

Poly(dopamine) is employed as an anchor to obtain a series of poly(acrylic acid) (PAA) and poly(2-methyl-2-oxazoline) (PMOXA) mixed brush coatings by sequential grafting to methods with PAA chains longer than PMOXA chains. Then, the prepared mixed brush coatings are rigorously characterized. The results show that the grafting density of PAA in mixed brushes could be well adjusted by changing the concentration of PAA solution used for the preparation of mixed brush coatings and the amounts of lysozyme adsorbed on PMOXA/PAA mixed brushes increase with increasing the grafting density of PAA chains while the desorption amounts decrease significantly when the grafting density of PAA is higher than one-half of PMOXA chains. When the grafting density of PAA is about one-half of PMOXA chains, the mixed brush could absorb high amounts of lysozyme (898.4 ng cm⁻²), and then more than 90% of adsorbed proteins could be released sharply by changing pH and ionic strength (I). © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48135.     

A New Strategy to Prepare Poly(2‐methyl‐2‐oxazoline)‐Based Antifouling Coatings: Using UV‐Crosslinked Copolymer Anchors

A series of the copolymer, poly(styrene‐random‐glycidyl methacrylate) (P(St‐r‐GMA)), is synthesized by free radical polymerization, and characterized by ¹H NMR spectroscopy and gel permeation chromatography. The various substrates are then modified by P(St‐r‐GMA) under ultraviolet (UV) irradiation. Subsequently, the poly(2‐methyl‐2‐oxazoline) (PMOXA) based coatings are prepared by anchoring amino‐terminated PMOXA onto the P(St‐r‐GMA) modified surfaces through the reaction between the amino group of PMOXA and epoxy group of P(St‐r‐GMA). The results of ellipsometry, X‐ray photoelectron spectroscopy, atomic force microscopy, and water contact angle reveal that PMOXA‐based coatings can be prepared successfully on the substrates through UV‐crosslinked P(St‐r‐GMA) as anchoring coatings. Besides, the PMOXA‐based coatings display not only a superior antifouling property but long‐term stability as well. Furthermore, the location of the coating formed on the substrate can be well controlled through selecting the site of UV irradiation, which can be utilized for the selectivity of protein adsorption (or resistance) on special devices.     

Preparation and characterization of a poly(vinyl alcohol)/tetraethoxysilane ultrafiltration membrane by a sol–gel method

Using poly(vinyl alcohol) (PVA) with highly hydrophilic properties as membrane material and poly(ethylene glycol) (PEG) as an additive, we prepared PVA/tetraethoxysilane (TEOS) ultrafiltration (UF) membranes with good antifouling properties by a sol–gel method. The PVA/TEOS UF membranes were characterized by X‐ray diffraction patterns, Fourier transform infrared spectroscopy, scanning electron microscopy, and static contact angle of measurement of water. The hybridization of TEOS to PVA for preparing the PVA/TEOS UF membranes achieved the required permeation performance and good antifouling behaviors. The morphology and permeation performance of the PVA/TEOS membranes varied with the different TEOS loadings and PEG contents. The pure water fluxes (J_W) increased and the rejections (Rs) decreased with increasing TEOS loading and PEG content. The PVA/TEOS UF membrane with a PVA/TEOS/PEG/H₂O composition mass ratio of 10/3/4/83 in the dope solution had a J_W of 66.5 L m^?2 h^?1 and an R of 60.3% when we filtered it with 300 ppm of bovine serum albumin aqueous solution at an operational pressure difference of 0.1 MPa. In addition, the filtration and backwashing experiment proved that the PVA/TEOS membranes possessed good long‐term antifouling abilities. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4066–4074, 2013     

Peptide-Mimicking Poly(2-oxazoline)s Displaying Potent Antimicrobial Properties

Poly(2-oxazoline)s have excellent biocompatibility and have been used as FDA-approved indirect food additives. The inert property of the hydrophilic poly(2-oxazoline)s suggests them as promising substitutes for poly(ethylene glycol) (PEG) in various applications such as anti-biofouling agents. It was recently reported that poly(2-oxazoline)s themselves have antimicrobial properties as synthetic mimics of host defense peptides. These studies revealed the bioactive properties of poly(2-oxazoline)s as a new class of functional peptide mimics, by mimicking host defense peptides to display potent and selective antimicrobial activities against methicillin-resistant Staphylococcus aureus both in vitro and in vivo, without concerns about antimicrobial resistance. The high structural diversity, facile synthesis, and potent and tunable antimicrobial properties underscore the great potential of poly(2-oxazoline)s as a class of novel antimicrobial agents in dealing with drug-resistant microbial infections and antimicrobial resistance.     

Influence of electrochemically prepared poly(pyrrole-co-N-methyl pyrrole) and poly(pyrrole)/poly(N-methyl pyrrole) composites on corrosion behavior of copper in acidic medium

Poly(pyrrole-co-N-methyl pyrrole) copolymer and poly(pyrrole)/poly(N-methyl pyrrole) bilayer composites were electrochemically synthesized on copper by cyclic voltammetry from aqueous solution of 0.3 M oxalic acid and 0.1 M monomer. Synthesis of copolymers were performed with different monomer feed ratios (pyrrole:N-methyl pyrrole, 8:2, 6:4, 5:5, 4:6 and 2:8) and in order to determine the copolymer, which has the best corrosion performance, anodic polarization was applied to copolymer coated samples. It was found that the performance of coatings was strongly dependent to the monomer feed ratio and the copolymer synthesized with 8:2 concentration ratio showed the most protective property compared to others. Bilayer of poly(pyrrole)/poly(N-methyl pyrrole) was also synthesized to compare the anticorrosive properties. Polymer films were characterized by ATR-FTIR spectroscopy and SEM techniques. Corrosion behavior of polymer composites was investigated in 0.1 M H₂SO₄ solution by anodic polarization and electrochemical impedance spectroscopy. Different approaches such as phase angle at high frequency and areas under Bode plots were used to evaluate corrosion performances of the coatings. Copolymer and bilayer coatings were found to have higher protection effect than single polypyrrole coatings. Moreover, bilayer coating exhibited better protection efficiency than copolymer coating against corrosion of copper when the obtained results were compared.     

Outstanding antifouling performance of poly(vinylidene fluoride) membranes: Novel amphiphilic brushlike copolymer blends and one-step surface zwitterionization

In this study, we endowed a poly(vinylidene fluoride) (PVDF) membrane with outstanding antifouling ability by blending the hierarchical amphiphilic brushlike copolymer [poly(hydroxyethyl methacrylate)-b-polydimethylsiloxane-b-poly(hydroxyethyl methacrylate)]-g-poly(N,N-dimethylamino-2-ethyl methacrylate) with different initial monomer/initiator feed ratios and performing a one-step surface zwitterionization of spontaneously segregated poly(N,N-dimethyl aminoethyl methacrylate) segments. Interestingly, nanoscale granular micelles were formed on the surface during zwitterionization because of the migration and self-assembly of the amphiphilic copolymer; this contributed to the membrane hydrophilicity and antifouling ability. During the filtration of the model foulant bovine serum albumin (BSA) aqueous solution, the BSA rejection ratio and flux recovery ratio increased remarkably to 94.8 and 100.0%, respectively. Moreover, the modified membranes also possessed stable and durable antifouling properties after three cycles of BSA filtration. Thus, this study provided a versatile method for constructing a PVDF ultrafiltration membrane that could achieve high permeability and good antifouling properties in efficient wastewater treatment. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47637.     

Polymer brush coatings for combating marine biofouling

A variety of functional polymer brushes and coatings have been developed for combating marine biofouling and biocorrosion with much less environmental impact than traditional biocides. This review summarizes recent developments in marine antifouling polymer brushes and coatings that are tethered to material surfaces and do not actively release biocides. Polymer brush coatings have been designed to inhibit molecular fouling, microfouling and macrofouling through incorporation or inclusion of multiple functionalities. Hydrophilic polymers, such as poly(ethylene glycol), hydrogels, zwitterionic polymers and polysaccharides, resist attachment of marine organisms effectively due to extensive hydration. Fouling release polymer coatings, based on fluoropolymers and poly(dimethylsiloxane) elastomers, minimize adhesion between marine organisms and material surfaces, leading to easy removal of biofoulants. Polycationic coatings are effective in reducing marine biofouling partly because of their good bactericidal properties. Recent advances in controlled radical polymerization and click chemistry have also allowed better molecular design and engineering of multifunctional brush coatings for improved antifouling efficacies.     

A novel method of surface modification on thin-film composite reverse osmosis membrane by grafting poly(ethylene glycol)

A novel method of surface modification by grafting hydrophilic poly(ethylene glycol) (PEG) chains onto the surface of a thin-film composite (TFC) polyamide reverse osmosis (RO) membrane was performed. Aminopolyethylene glycol monomethylether (MPEG-NH₂) was used as grafting monomer. The membranes were characterized by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The changes in chemical composition and morphology of the membranes' surface indicated the successful grafting process. Furthermore, a preliminary experiment confirmed that the grafting of PEG chains improved membrane antifouling property.     

Effect of miscibility on migration of third component in star‐like co‐continuous and disperse‐within‐disperse mixed brushes

Novel ternary mixed‐brush single crystals were designed with disperse‐within‐disperse and star‐like co‐continuous morphologies based on poly(ethylene glycol) (PEG)‐b‐polystyrene (PS)/PEG‐b‐poly(methyl methacrylate) (PMMA)/PEG‐b‐polyaniline (PANI) and PEG‐b‐PS/PEG‐b‐PMMA/PEG‐b‐(poly(?‐caprolactone) (PCL) or poly(l ‐lactide) (PLLA)) block copolymers, respectively. In the disperse‐within‐disperse ternary mixed brushes, PANI nanorods were dispersed within the matrix (PS)–dispersed (PMMA) amorphous brushes. The flexibility and rigidity of brushes mainly affected the ultimate morphology and arrangement of amorphous coiled brushes in the vicinity of PANI nanorods. In addition, the migration of PCL and PLLA crystallizable brushes was evident into PMMA phases dispersed in the PS matrix, leading to star‐like co‐continuous patterns of PCL and PLLA brushes. This phenomenon was related to the miscibility of crystallizable PCL and PLLA brushes with the PMMA phase. The migration of crystallizable PCL and PLLA brushes increased the size of PMMA domains in the star‐like co‐continuous patterns. Despite the larger osmotic pressure of PLLA brushes, their higher miscibility with PMMA chains reflected the greater PMMA dispersal and wider PLLA star‐like branches. © 2017 Society of Chemical Industry     

Microwave dielectric relaxation and molecular dynamics in binary mixtures of poly(propylene glycol) 2000 and poly(ethylene glycol)s of varying molecular weight in dilute solution

Molecular dynamics of binary mixtures of poly(propylene glycol) (PPG) and poly(ethylene glycol)s (PEGs) of varying molecular weight due to molecular interactions, chain coiling and elongation in dilute solution under various conditions, ie varying number of monomer units of PEG, method of mixing of polymers and solvent environment, has been explored using microwave dielectric relaxation times. The average relaxation time τ_o, relaxation time corresponding to segmental motion τ₁ and group rotations τ₂, of a series of binary mixtures of poly(propylene glycol) 2000 and poly(ethylene glycol) of varying molecular weight (ie PPG 2000 + PEG 200, PPG 2000 + PEG 300, PPG 2000 + PEG 400, and PPG 2000 + PEG 600 mixed by equal volume in the pure liquid states, and PPG 2000 + PEG 1500, PPG 2000 + PEG 4000 and PPG 2000 + PEG 6000 mixed equal weights in solvent) have been determined in dilute solution in benzene and carbon tetrachloride at 10.10 GHz and 35 °C. A comparison of the results of these binary systems of highly associating molecules shows that the molecular dynamics corresponding to rotation of a molecule as a whole and segmental motion in dilute solutions are governed by the solvent density when the solutes are mixed in their pure liquid state. Furthermore, the molecular motion is independent of solvent environment when the polymers are added separately in the solvent for the preparation of binary mixtures. It has also been observed that there is a systematic elongation of the dynamic network of the species formed during mixing of pure liquid polymers in lighter environment of solvent with increasing PEG monomer units, while the elongation behaviour of the same species in the heavier environment of carbon tetrachloride solvent is in contrast to the elongation behaviour of the polymeric species formed in pure PEG. The role of rotating methyl side‐groups in the PPG molecular chain has been discussed in term of the breaking and reforming of hydrogen bonds in complex polymeric species for the segmental motion. In all these mixtures, the relaxation time corresponding to group rotations is independent of the solvent environment and constituents of the binary mixtures. The effect of chain flexibility and coiling in these binary mixtures is discussed by comparing the relaxation times of the mixtures with their individual relaxation times in dilute solutions measured earlier in this laboratory. © 2001 Society of Chemical Industry     

Preparation of waterborne polyurethanes using an amphiphilic diol for breathable waterproof textile coatings

The application of polyurethanes (PUs) on breathable waterproof fabric coatings requires a balance of water vapor permeability (WVP) and water resistance which can be achieved by tailoring hydrophilic and hydrophobic segments. PU prepolymers were prepared from isophorone diisocyanate, dimethylol butanoic acid, and a mixture of various ratios of amphiphilic PPG2050 (copolymer of ethylene oxide and propylene oxide with –OH end groups) and hydrophobic poly(tetramethylene ether glycol) (PTMEG). After neutralization with triethylamine, the prepolymers were chain-extended with ethylene diamine/1,4-butanediol (1:1 by molar). The WVP values of the fabric coatings prepared using various waterborne PUs were very similar (910–990 g/m² × 24 h). When waterborne PUs prepared using a mixture of PPG2050 and PTMEG were employed for the textile coatings, the resulting PU-coated textiles exhibited excellent waterproof properties (>10,000 mm H₂O). The textile coatings prepared from PPG2050/PTMEG-based waterborne PUs were significantly more waterproof than those prepared from poly(ethylene glycol) (PEG)/poly(propylene glycol) (PPG)/PTMEG-based waterborne PU. This is probably due to a more even distribution of hydrophobic segments in the PUs, even though the WVP values of the PEG/PPG/PTMEG-based PU coatings were considerably smaller than those of the PPG2050/PTMEG-based PU coatings.     

Synthesis and aggregation behavior of four types of different shaped PCL‐PEG block copolymers

Biodegradable, amphiphilic, linear (diblock and triblock) and star‐shaped (three‐armed and four‐armed) poly[(ethylene glycol)‐block‐(ε‐caprolactone)] copolymers (PEG–PCL copolymers) were synthesized by ring‐opening polymerization of ε‐caprolactone (CL) with stannous octoate as a catalyst, in the presence of monomethoxypoly(ethylene glycol) (MPEG), poly(ethylene glycol) (PEG), three‐armed poly(ethylene glycol) (3‐arm PEG) or four‐armed poly(ethylene glycol) (4‐arm PEG) as an initiator, respectively. The monomer‐to‐initiator ratio was varied to obtain copolymers with various PEG weight fractions in a range 66–86%. The molecular structure and crystallinity of the copolymers, and their aggregation behavior in the aqueous phase, were investigated by employing ¹H‐NMR spectroscopy, gel permeation chromatography and differential scanning calorimetry, as well as utilizing the observational data of gel–sol transitions and aggregates in aqueous solutions. The aggregates of the PEG–PCL block copolymers were prepared by directly dissolving them in water or by employing precipitation/solvent evaporation technique. The enthalpy of fusion (ΔH_m), enthalpy of crystallization (ΔH_crys) and degrees of crystallinity (χ_c) of PEG blocks in copolymers and the copolymer aggregates in aqueous solutions were influenced by their PEG weight fractions and molecular architecture. The gel–sol transition properties of the PEG–PCL block copolymers were related to their concentrations, composition and molecular architecture. Copyright © 2006 Society of Chemical Industry     

Preparation of waterborne polyurethanes using an amphiphilic diol for breathable waterproof textile coatings

The application of polyurethanes (PUs) on breathable waterproof fabric coatings requires a balance of water vapor permeability (WVP) and water resistance which can be achieved by tailoring hydrophilic and hydrophobic segments. PU prepolymers were prepared from isophorone diisocyanate, dimethylol butanoic acid, and a mixture of various ratios of amphiphilic PPG2050 (copolymer of ethylene oxide and propylene oxide with –OH end groups) and hydrophobic poly(tetramethylene ether glycol) (PTMEG). After neutralization with triethylamine, the prepolymers were chain-extended with ethylene diamine/1,4-butanediol (1:1 by molar). The WVP values of the fabric coatings prepared using various waterborne PUs were very similar (910–990 g/m² × 24 h). When waterborne PUs prepared using a mixture of PPG2050 and PTMEG were employed for the textile coatings, the resulting PU-coated textiles exhibited excellent waterproof properties (>10,000 mm H₂O). The textile coatings prepared from PPG2050/PTMEG-based waterborne PUs were significantly more waterproof than those prepared from poly(ethylene glycol) (PEG)/poly(propylene glycol) (PPG)/PTMEG-based waterborne PU. This is probably due to a more even distribution of hydrophobic segments in the PUs, even though the WVP values of the PEG/PPG/PTMEG-based PU coatings were considerably smaller than those of the PPG2050/PTMEG-based PU coatings.     

Inorganic precursor peroxides for antifouling coatings

Modern antifouling coatings are generally based on cuprous oxide (Cu₂O) and organic biocides as active ingredients. Cu₂O is prone to bioaccumulation, and should therefore be replaced by more environmentally benign compounds when technically possible. However, cuprous oxide does not only provide antifouling properties, it is also a vital ingredient for the antifouling coating to obtain its polishing and leaching mechanism. In this paper, peroxides of strontium, calcium, magnesium, and zinc are tested as pigments in antifouling coatings. The peroxides react with seawater to create hydrogen peroxide and highly seawater-soluble ions of the metal. The goals have been to establish the antifouling potency of an antifouling coating that releases hydrogen peroxide as biocide, and to investigate the potential use of peroxides as water-soluble polishing and leaching pigments. The investigations have shown that it is possible to identify particulates that, when applied as pigments in antifouling coatings, will provide polishing and leaching rates comparable to those of Cu₂O-based coatings. Furthermore, the combination of polishing and hydrogen peroxide leaching by a coating based on zinc peroxide in a suitable binder matrix provides antifouling properties exceeding those of a similar coating based entirely on zinc oxide.     

Antifouling effect of hydrogen peroxide release from enzymatic marine coatings: Exposure testing under equatorial and Mediterranean conditions

Hydrogen peroxide (H₂O₂) may be considered an environmentally friendly antifouling alternative to common biocides such as Cu₂O and various organic compounds. In this work, the efficiency of antifouling coatings releasing hydrogen peroxide via enzyme-mediated conversion of starch, under Mediterranean and equatorial climatic conditions, is investigated. During seawater exposure of the coatings, starch is first converted to glucose by glucoamylase (rate-controlling step) and subsequently glucose is rapidly oxidised by hexose oxidase in a reaction producing hydrogen peroxide.     

Molecular brushes with extreme grafted side chain densities

A series of densely grafted poly(n-butyl acrylate) (PBA) molecular brushes with four different grafting densities were synthesized by the “grafting-from” approach using atom transfer radical polymerization (ATRP). A novel monomer, isopropylidene-2,2-Bis(methoxy)propionic hydroxyethylmethacrylate (IMPHMA), was synthesized and copolymerized with methyl methacrylate (MMA) under different monomer feed ratios to yield a series of linear poly(methyl methacrylate-stat-IMAPA), [PMMA-s-(PIMPHMA)]. The resulting copolymers were deprotected and transformed to macroinitiators, [PMMA-s-(PHEMA-IMPHMA-Br)]. n-Butyl acrylate (BA) was grafted from these macroinitiators to yield a series of molecular brushes, [PMMA-s-{(PIMPHMA)-g-PBA}], with various side chain lengths. Molecular brushes were characterized by gel permeation chromatography (GPC) and ¹H NMR. PBA side chains were cleaved by acid hydrolysis, and the resulting linear PBA polymers were characterized by GPC to study initiation efficiency during the synthesis of molecular brushes. The initiation efficiency increased with polymerization time and decreased with macroinitiators that had more initiation sites. Atomic force microscopy (AFM) measurements demonstrated the characteristic molecular structure by resolving individual brush molecules.     

Microwave dielectric relaxation and molecular dynamics in binary mixtures of poly(vinyl pyrrolidone)–poly(ethylene glycol)s in non‐polar solvent

Dielectric relaxation study of binary mixtures of poly(vinyl pyrrolidone) (PVP) (M_w = 40 000 g mol^?1) and poly(ethylene glycol)s (PEGs) (M_n = 200, 400 and 600 g mol^?1) with concentration variation was carried out in dilute solutions of benzene at 10.1 GHz and 35 °C. The average relaxation time τ_o, corresponding to segmental motion τ₁ and group rotations τ₂ was determined for PVP–PEGs mixtures. A comparison of these mixtures relaxation times was made with the relaxation times of PEGs in benzene solvent. The evaluated τ_o values of PVP–PEGs mixtures in benzene solution are assigned to the reorientation of PEG molecules. It has been observed that the τ_o value of PVP–PEG200 mixtures increases with increasing concentration of PVP but their values are small in comparison with the τ_o value of PEG200 molecules. In the case of PVP–PEG400 and PVP–PEG600 mixtures, the evaluated values of τ_o are greater than the corresponding τ_o values of PEG400 and PEG600 molecules in benzene solvent. The variation in τ_o values in these systems has been discussed by considering the stretching effect in the PEGs molecular chains in PVP–PEGs mixtures in benzene solutions. The high value of distribution parameter α (≈0.4 to 0.7) suggests that in these mixtures there is a large contribution of segmental motion and group rotations to the relaxation processes. The nature of the formation of hydrogen‐bonded PVP–PEG complex heterogeneous network due to hydrogen bonding between carbonyl groups of PVP monomer units and terminal hydroxyl groups of PEGs is discussed. Furthermore, the elongation behaviour of PVP–PEG complex networks in benzene solvent and the molecular dynamics in the mixture due to breaking and reforming of hydrogen bonds has been explored by comparing the evaluated relaxation times and the Kirkwood correlation factor of pure PEG molecules for their possible use in drug control release systems. The relaxation times of these mixtures are independent of their viscosity, but the elongation of the mixture network is influenced by the PEG chain length and the number of hydroxyl groups in comparison with the number of carbonyl groups in the mixtures. Copyright © 2003 Society of Chemical Industry     

Cationic polymerization of 5-methyl-2-oxazoline and alkaline hydrolysis of product polymer to linear poly(propylenimine)

Summary A new monomer of 5-methyl-2-oxazoline(5-MeOZO) was prepared. It was found that 5-MeOZO underwent the cationic ring-opening isomerization polymerization to produce poly(N-formylpropylenimine) 1 of waxy or powdery materials. Alkaline hydrolysis of 1 gave linear poly(propylenimine) 2. Polymers 1 and 2 are the same as the respective polymers derived from 4-methyl-2-oxazoline.     

Preparation of functional reduced graphene oxide and its influence on the properties of polyimide composites

Homogeneous dispersion and strong filler–matrix interfacial interactions were vital factors for graphene for enhancing the properties of polymer composites. To improve the dispersion of graphene in the polymer matrix and enhance the interfacial interactions, graphene oxide (GO), as an important precursor of graphene, was functionalized with amine‐terminated poly(ethylene glycol) (PEG–NH₂) to prepare GO–poly(ethylene glycol) (PEG). Then, GO–PEG was further reduced to prepare modified reduced graphene oxide (rGO)–PEG with N₂H₄·H₂O. The success of the modification was confirmed by Fourier transform infrared spectroscopy, thermogravimetric analysis, and Raman spectroscopy. Different loadings of rGO–PEG were introduced into polyimide (PI) to produce composites via in situ polymerization and a thermal reduction process. The modification of PEG–NH₂ on the surface of rGO inhibited its reaggregation and improved the filler–matrix interfacial interactions. The properties of the composites were enhanced by the incorporation of rGO–PEG. With the addition of 1.0 wt % rGO–PEG, the tensile strength of PI increased by 81.5%, and the electrical conductivity increased by eight orders of magnitude. This significant improvement was attributed to the homogeneous dispersion of rGO–PEG and its strong filler–matrix interfacial interactions. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45119.     

Thermoresponsive Interplay of Water Insoluble Poly(2-alkyl-2-oxazoline)s Composition and Supramolecular Host–Guest Interactions

A series of water insoluble poly[(2-ethyl-2-oxazoline)-ran-(2-nonyl-2-oxazoline)] amphiphilic copolymers was synthesized and their solubility properties in the presence of different supramolecular host molecules were investigated. The resulting polymer-cavitand assemblies exhibited a thermoresponsive behavior that could be modulated by variation of the copolymer composition and length. Interestingly, the large number of hydrophobic nonyl units across the polymer chain induced the formation of kinetically-trapped nanoparticles in solution. These nanoparticles further agglomerate into larger aggregates at a temperature that is dependent on the polymer composition and the cavitand type and concentration. The present research expands the understanding on the supramolecular interactions between water insoluble copolymers and supramolecular host molecules.