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We report the effect of pH on the dynamics and structure of 3D networks formed by the temperature-dependent hydrophobic association of the end blocks of P(nBuMA18-co-TEGMA15)-b-PDMAEMA159-b-P(nBuMA...

Tunable electrostatic interactions in thin films from (C-co-D)-b-B-b-A-b-B-b-(C-co-D)-type pentablock quaterpolymers featuring hydrophobic end blocks as well as pH-responsive and hydrophilic midblo...

The present study reports on the development of a simple two-step process toward the isolation of nearly defect-free mono- and few-layer graphenes in various media. This was achieved by liquid phase pre-exfoliation of pristine graphite in the presence of an ionizable PSnP2VPn heteroarm star copolymer in an organic solvent and subsequent graphene shuttle between immiscible media, that is, organic solvent/water and water/ionic liquid. This polymer-assisted phase transfer of graphene sheets gave rise to enrichment of suspended nanostructures in monolayers, especially in an aqueous environment. The exfoliation efficiency was assessed through Raman and electron microscopy. Relatively high concentration suspensions of efficiently exfoliated graphene sheets of large size and in high solubilization yield, could be prepared in any kind of solvent, that is, organic low boiling point medium, aqueous environment, or ionic liquid, whereas the shuttle transfer was found to be a reversible process between organic and aq...

Here, we describe the preparation and characterization of organic/inorganic hybrid polymer multifunctional nanocarriers. Novel nanocomposites of gold nanoparticles using pH-responsive coordination pentablock terpolymers of poly(ε-caprolactone)-b-poly(ethylene oxide)-b-poly(2-vinylpyridine)-b-poly(ethylene oxide)-b-poly(ε-caprolactone), bearing or not bearing partially quaternized vinylpyridine moieties, were studied. The template morphology of the coordination pentablock terpolymer at physiological pH ranges from crew-cut to multicompartmentalized micelles which can be tuned by chemical modification of the central block. Additionally, the presence of 2VP groups allows the coordination of gold ions, which can be reduced in situ to construct gold@polymer nanohybrids. Furthermore, the possibility of tuning the gold distribution in the micelles, through partial quaternization of the central P2VP block, was also investigated. Various morphological gold colloidal nanoparticles such as gold@core-corona nanoparticles and gold@core-gold@corona nanoparticles were synthesized on the corresponding template of the pentablock terpolymer, first by coordination with gold ions, followed by reduction with NaBH4. The pentablock and gold@pentablock nanoparticles could sparingly accommodate a water-soluble drug, Tamoxifen (TAX), in their hydrophobic micellar cores. The nanostructure of the nanocarrier remarkably affects the TAX delivery kinetics. Importantly, the hybrid gold@polymer nanoparticles showed prolonged release profiles for the guest molecule, relative to the corresponding bare amphiphilic pentablock polymeric micelles. These Gold@pentablock terpolymer hybrid nanoparticles could act as a multifunctional theranostic nanoplatform, integrating sustainable pH-controlled drug delivery, diagnostic function and photothermal therapy.

Polysaccharide-based graft copolymers bearing thermo-responsive grafting chains, exhibiting LCST, have been designed to afford thermo-responsive injectable hydrogels. The good performance of the hydrogel requires control of the critical gelation temperature, Tgel. In the present article, we wish to show an alternative method to tune Tgel using an alginate-based thermo-responsive gelator bearing two kinds of grafting chains (heterograft copolymer topology) of P(NIPAM86-co-NtBAM14) random copolymers and pure PNIPAM, differing in their lower critical solution temperature (LCST) about 10 °C. Interestingly, the Tgel of the heterograft copolymer is controlled from the overall hydrophobic content, NtBAM, of both grafts, implying the formation of blended side chains in the crosslinked nanodomains of the formed network. Rheological investigation of the hydrogel showed excellent responsiveness to temperature and shear. Thus, a combination of shear-thinning and thermo-thickening effects provides the hydrogel with injectability and self-healing properties, making it a good candidate for biomedical applications.

Polylysine is a biocompatible, biodegradable, water soluble polypeptide. Thanks to the pendant primary amines it bears, it is susceptible to modification reactions. In this work Poly(L-lysine) (PLL) was partially modified via the effortless free-catalysed aza-Michael addition reaction at room temperature by grafting N-isopropylacrylamide (NIPAm) moieties onto the amines. The resulting PLL-g-NIPAm exhibited LCST-type thermosensitivity. The LCST can be tuned by the NIPAm content incorporated in the macromolecules. Importantly, depending on the NIPAm content, LCST is highly dependent on pH and ionic strength due to ionization capability of the remaining free lysine residues. PLL-g-NIPAm constitutes a novel biodegradable LCST polymer that could be used as “smart” block in block copolymers and/or terpolymers, of any macromolecular architecture, to design pH/Temperature-responsive self-assemblies (nanocarriers and/or networks) for potential bio-applications.

Sodium alginate grafted by a thermo-responsive copolymer of N-isopropylacrylamide, enriched with the hydrophobic N-tert-butylacrylamide monomer, (P(NIPAM-co-NtBAM)-NH2) was synthesized and its thermo- and shear-induced responsive capabilities were studied through rheology. The graft copolymer formed a 3D network through thermo-induced hydrophobic association of the thermo-responsive P(NIPAM-co-NtBAM) side chains in water. By applying the frequency-temperature superposition principle, the terminal relaxation time, τ and the shear viscosity, as a function of temperature were evaluated. Both parameters increased exponentially upon heating orders of magnitude, 15 °C above the onset of gelation (35 °C). It is shown that the thermo-induced thickening effect was mainly due to the slowdown of the P(NIPAM90-co-NtBAM10) associative side chains exchange dynamics. Moreover, combination of shear- and thermo-responsiveness provided excellent hydrogel injectability with instantaneous gelation at physiological temperature. The better insight of the thermo-thickening mechanism through oscillatory rheology allows precise tuning of the carbohydrate-based hydrogel properties towards potential bioapplications.

Graft copolymers of alginate backbone and N-isopropylacrylamide/N-tert-butylacrylamide random copolymer, P(NIPAMx-co-NtBAMy), side chains (stickers) with various NtBAM content were designed and explored in aqueous media. Self-assembling thermoresponsive hydrogels are formed upon heating, in all cases, through the hydrophobic association of the P(NIPAMx-co-NtBAMy) sticky pendant chains. The rheological properties of the formulations depend remarkably on the NtBAM hydrophobic content, which regulates the lower critical solution temperature (LCST) and, in turn, the stickers’ thermo-responsiveness. The gelation point, Tgel, was shifted to lower temperatures from 38 to 20 °C by enriching the PNIPAM chains with 20 mol % NtBAM, shifting accordingly to the gelation temperature window. The consequences of the Tgel shift to the hydrogels’ rheological properties are significant at room and body temperature. For instance, at 37 °C, the storage modulus increases about two orders of magnitude and the terminal relaxation time increase about 10 orders of magnitude by enriching the stickers with 20 mol % hydrophobic moieties. Two main thermo-induced behaviors were revealed, characterized by a sol–gel and a weak gel–stiff gel transition for the copolymer with stickers of low (0.6 mol %) and high (14, 20 mol %) NtBAM content, respectively. The first type of hydrogels is easily injectable, while for the second one, the injectability is provided by shear-thinning effects. The influence of the type of media (phosphate buffer (PB), phosphate-buffered saline (PBS), Dulbecco’s modified Eagle’s medium (DMEM)) on the hydrogel properties was also explored and discussed. The 4 wt % NaALG-g-P(NIPAM80-co-NtBAM20)/DMEM formulation showed excellent shear-induced injectability at room temperature and instantaneous thermo-induced gel stiffening at body temperature, rendering it a good candidate for cell transplantation potential applications.

This work is focused on the design and development of biocompatible self-assembling hydrogels which behave as soft gels at room temperature and as strong ones at the physiological temperature, suitable for potential bio-applications. A graft copolymer of sodium-alginate bearing 8 side chains of poly(N-isopropylacrylamide), enriched with the hydrophobic comonomer N-tertiary-butyl-acrylamide (NtBAM), [ALG-g-P(NIPAM-co-NtBAM)] were used as gelator. 5 wt % aqueous polymer solutions in the presence of various concentrations of Ca2+ cations were prepared and evaluated as thermoresponsive hydrogels. Rheological experiments revealed a twostep reversible gelation either upon heating or upon cooling . The divalent cations operate as cross-linking agent through ionic interactions inducing the formation of a network at low temperatures. Upon heating, an additional crosslinking develops through thermo-generated hydrophobic association of the thermo-responsive P(NIPAM-co-NtBAM) side chains above a critical temperature. The storage modulus, G’, increases with the cation concentration below and above the critical temperature. More importantly, the difference of G’ between 20 oC and 50 oC (ΔG’) increases linearly with the cation concentration, revealing a cooperative effect between the two-association mechanism, i.e. ionic and hydrophobic. In other words, the thermo-induced hydrogel elasticity is enhanced in the presence of the ionic bonds. Furthermore, the combination of thermo- and shear-responsiveness provides shelf-assembling systems as potential candidates for injectable strategies. Especially, the systems with lower cation concentration could be used for drug delivery, while the gelators with higher cation concentration could be used for cell transplantation, which require a weak gel to protect the cells during injection and an instantaneous gelation at physiological temperature after the injection to immobilize the created scaffold in the targeting position of the host tissue.

Steady shear properties and linear and nonlinear viscoelastic behaviors of a poly(methyl methacrylate)–poly(dimethyl amino ethyl methacrylate)–poly(methyl methacrylate) polymer, (PMMA–PDMAEMA–PMMA), telechelic polymers in salt-free aqueous solution have been investigated as a function of concentration and pH. Above a critical concentration, a transient physical network is formed through an association mechanism between hydrophobic end groups, leading to a gel-like behavior. The gel-like polymer solutions were shown to exhibit a peculiar flow behavior, associated with time fluctuation of the transient first normal stress difference, attributed to orientation effects of the stiff charged polymer chains. The viscoelastic behavior was shown to be governed by two pH dependent time scales: a short time scale controlled by the lifetime of the hydrophobic associative junctions and a long time scale corresponding to the network relaxation time. All rheological results show strong evidence that Coulomb interactions, which control both macromolecular chain rigidity and inter-chain interactions, lead to specific pH-tunable properties of great potential interest.

In the present study, a soil-derived mixed microbial consortium was developed for polyhydroxyalkanoates (PHAs) production via nutrient limitation. The enhanced consortium was then cultured continuously in sequential batch and the effect of different nitrogen to carbon ratios (N:C) on the yields and properties of produced PHAs and on the changes of the microbial population were investigated. In all cases, the produced polymers were identified as blends or co-polymers of 3-hydroxybutyrate (3HB) and 3-hydroxyvalerate (3HV) units, with 3HB being the dominant monomer. The degradation profile and the transition temperatures of the produced PHAs were further assessed and compared, as well as the molecular weights which ranged from 77.104 Da to 180.104 Da. In order to further investigate the effect of culturing conditions on the development and alteration of the microbial consortium, the Nile blue live staining was applied in the mixed cultures at the end of each operational period. Various fluorescent single colonies were selected based on differences in their morphology and were identified. Finally, the alterations in microbial diversity and community composition assessed via the RISA profiling method (rRNA Intergenic Spacer Analyses), resulted in the identification of a number of dominant organisms.

Heteroarm star-graft block quarterpolymers [PSn(P2VP-b-PAA-g-PNIPAM)n] with pH-sensitive weak polycationic/polyanionic arms and grafted thermoresponsive outer chains are integrated into hydrogen-bonded multilayers with morphologies distinct from those in traditional layer-by-layer assemblies. We discovered that block-specific swelling promotes heterogeneous partitioning of hydrophobic and hydrophilic reservoirs within the interior of the swollen multilayers. The molecular architecture and amphiphilicity balance governs the internal structure and is regulated via solution pH and temperature. In acidic/basic regimes, competing interactions between hydrophobic and ionized blocks favor compartmentalization of water to the hydrophilic pockets near the substrate surface. Heating the assemblies of star block quarterpolymers with high grafting densities above the lower critical solution temperature of the PNIPAM peripheries promotes the aggregation of the functional “soft nanoparticles” into star-like clusters wh...

The accumulation efficiency and the properties of polyhydroxyalkanoates (PHAs) produced from acidified waste glycerol (AWG) and its derivatives via an enriched microbial consortium derived from soil, were investigated in this study. AWG consisted mainly from short chain fatty acids, 1,3 propanediol and residual glycerol, which were also evaluated individually as substrates. Accumulation capacity and yields were estimated after solvent extraction and purification and PHAs were further analyzed in terms of their chemical structure, thermal properties, molecular masses and mechanical properties. The lowest accumulation capacity was noticed for non-acidified waste glycerol as carbon source which led to the generation of P(3HB), whereas for the other carbon sources co-polymers of 3HB with 3HV or 3HHx were produced. Average molecular mass weights were quite high in all cases reaching ~1.8 × 106 Da. The thermal properties and the mechanical behavior of PHAs were shown to be highly affected by their monomeric composition, whereas it was also concluded that DSC and DMA results were in good agreement.

We explore the self-assembly behavior of aqueous solutions of an amphiphilic, pH-sensitive poly(l-alanine)-b-poly(l-glutamic acid)-b-poly(l-alanine), (A5E11A5) triblock copolypeptide, end-capped by benzaldehyde through Schiff base reaction. At elevated concentrations and under physiological pH (7.4) and ionic strength (0.15M), the bare copolypeptide aqueous solutions underwent a sol-gel transition after heating and slow cooling thermal treatment, forming opaque stiff gels due to a hierarchical self-assembly that led to the formation of β-sheet-based twisted super fibers (Popescu et al. Soft Matter 2015, 11, 331-342). The conjugation of the N-termini with benzaldehyde (Bz) through a Schiff base reaction amplifies the copolypeptide pH-sensitivity within a narrow pH window relevant for in vivo applications. Specifically, the dynamic character of the imine bond allowed coupling/decoupling of the Bz upon switching pH. The presence of Bz conjugates to the N-termini of the copolypeptide resulted in enhanced packing of the elementary superfibers into thick and short piles, which inhibited the ability of the system for gelation. However, partial cleavage of Bz upon lowering pH to 6.5 prompted recovery of the hydrogel. The sol-gel transition triggered by pH was reversible, due to the coupling/decoupling of the benzoic-imine dynamic covalent bonding, endowing thus the gelling system with injectability. Undesirably, the gelation temperature window was significantly reduced, which however can be regulated at physiological temperatures by using a suitable mixture of the bare and the Bz-conjugated coplypeptide. This triblock copolypeptide gelator was investigated as a scaffold for the encapsulation of polymersome nanocarriers, loaded with a hydrophilic model drug, calcein. The polymersome/polypeptide complex system showed prolonged probe release in pH 6.5, which is relevant to extracellular tumor environment, rendering the system potentially useful for sustained delivery of anticancer drugs locally in the tumor.

Multicompartmental responsive microstructures with the capability for the pre-programmed sequential release of multiple target molecules of opposite solubility (hydrophobic and hydrophilic) in a controlled manner have been fabricated. Star block copolymers with dual-responsive blocks (temperature for poly(N-isopropylacrylamide) chains and pH for poly(acrylic acid) and poly(2-vinylpyridine) arms) and unimolecular micellar structures serve as nanocarriers for hydrophobic molecules in the microcapsule shell. The interior of the microcapsule can be loaded with water-soluble hydrophilic macromolecules. For these dual-loaded microcapsules, a programmable and sequential release of hydrophobic and hydrophilic molecules from the shell and core, respectively, can be triggered independently by temperature and pH variations. These stimuli affect the hydrophobicity and chain conformation of the star block copolymers to initiate out-of-shell release (elevated temperature), or change the overall star conformation and interlayer interactions to trigger increased permeability of the shell and out-of-core release (pH). Reversing stimulus order completely alters the release process.

Thermoresponsive polymers constitute an important class of materials for biomedical application due to their thermally reversible coil-to-globule transition which can be exploited in a multitude of biomedical applications spanning from triggered drug delivery systems in the form of bulk hydrogels and nanoparticles, “smart” cell culture setups, sensors and actuators, and separation technologies. In this perspective article we present the basic physicochemical properties of poly (N-isopropylacrylamide) (PNIPAM), which is the most widely studied thermoresponsive polymer with a lower critical solution temperature. We describe the basic thermodynamic and physicochemical parameters that affect the LCST and present selective applications that utilize thermoresponsive polymers in the form of nano-assemblies including micelles, polymersomes, microcapsules and microgels, as well as injectable hydrogels for biomedical applications.

We report the fabrication of polymersomes, using as building blocks star-graft quarterpolymers, composed of hydrophobic polystyrene and pH-sensitive poly(2-vinylpyridine)-b-poly(acrylic acid) (P2VP-b-PAA) arms, emanated from a common nodule, enriched by thermosensitive poly(N-isopropylacrylamide) grafts covalently bonded on the PAA block-arms. These multicompartmental polymersomes were evaluated as nanocarriers for the encapsulation and controlled co-delivery of doxorubicin (hydrophilic) and paclitaxel (hydrophobic) chemotherapeutic agents. The polymersomes can load these drugs in different compartments and can efficiently be internalized in the human lung adenocarcinoma epithelial cells, delivering their cargo and inducing high cell apoptosis. The release kinetics of both anticancer agents was controlled differently by the environmental conditions (pH and temperature). Enhanced release was observed at the acidic pH 6.0 and under physiological temperature (37 °C). At the same total drug level, co-delivery of these drugs with the polymersomes caused enhanced cytotoxicity and induced significantly higher cell apoptosis in the cancer cell line compared to the polymersomes loaded with either of the two drugs.

We report the synthesis and characterization of a C-b-(A-co-B)-b-C triblock terpolymer gelator, named telechelic polyampholyte, bearing a P(DEAEMA-co-MAA) statistical polyampholyte as the central long block, end-capped at both ends by PMMA blocks. This associative polymer forms 3D networks in aqueous media, composed of PMMA hydrophobic nanodomains, bridged by the hydrophilic P(DEA-co-MAA) ionogenic blocks. Thanks to the weak acid/base nature of the oppositely charged ionic moieties, the ionization degree of which are controlled by pH, the formed hydrogels exhibit unique pH-responsive behavior. The network structure and in turn the hydrogel rheological properties strongly depend on the preparation conditions, i.e. swelling film or direct dissolution in aqueous media.

We investigate the influence of ionic strength on the structural properties of stimuli-responsive hydrogels from triblock polyampholytes PAA-b-P2VP-b-PAA (PAA and P2VP are negatively charged poly(acrylic acid) and positively charged poly(2-vinylpyridine)). In our previous studies, we found that the transition behavior depends on the charge asymmetry which is controlled by pH and which alters the degree of ionization of the two types of blocks [Dyakonova Macromolecules 2014, 47, 7561]. The same triblock polyampholyte, but with chemically quaternized P2VP (QP2VP) instead of P2VP as the middle block, is highly positively charged, independently of pH. In the present investigation, PAA-b-P2VP-b-PAA at pH 3 and PAA-b-PQ2VP-b-PAA at pH 5 were chosen to investigate the influence of the ionic strength on the micellar network morphology by adding NaCl at concentrations in the physiological range. Computer simulations of the latter system show that salt addition results in the formation of larger complexes due to in...

Multifunctional star-graft quarterpolymers PSn[P2VP-b-(PAA-g-PNIPAM)]n with two different arm types, shorter PS arms and longer P2VP-b-PAA block copolymer arms with grafted PNIPAM chains, were studied in terms of their ability to form micellar structures at the air/water and air/solid interfaces. Because of the pH-dependent ionization of P2VP and PAA blocks, as well as thermoresponsiveness of PNIPAM chains, these multifunctional stars have multiple responsive properties to pH, temperature, and ionic strength. We observed that the molecular surface area of the stars is the largest at basic pH, when the PAA blocks are strongly charged and extended, and PNIPAM chains are spread at the interface. At acidic conditions, the molecular surface area is the smallest because the P2VP blocks submerge into the water subphase and the PAA blocks are contracted and form hydrogen bonding with grafted PNIPAM chains. The molecular surface area of the stars at the air/water interface gradually increases at elevated temperatu...

Hydrogels are three-dimensional (3D) soft materials that consist of a solid matrix (usually a three-dimensional network) entrapping high content of water (more than 90 wt%). This remarkable feature makes them suitable for many applications especially in medicine as drug carriers and tissue engineering scaffolds. As far as polymeric matrices are concerned, two main strategies for achieving 3D network structures can be distinguished. The first one relies on the covalent bonding of hydrophilic polymer chains, leading to hydrogels referred as chemical networks. The second approach deals with the self-assembly of tailor-made segmented macromolecules via reversible weak interactions, namely hydrophobic, ionic, π–π staking, and so on, that leads to the so-called self-assembling hydrogels. The use of reversible (physical) cross-links allows the design of “smart” soft materials that can response to their environment (e.g., pH, ionic strength, temperature, shear). This chapter is devoted to the self-assembling hydrogels arising from associative block copolymers bearing ionic or ionogenic blocks, namely polyelectrolytes or polyampholytes. This specific feature endows the hydrogels with responsiveness to pH and ionic strength which make them attractive soft materials for potential biomedical applications.

In this work, linear polystyrene-poly(2-vinylpyridine) (PS-b-P2VP) and heteroarm star PS_22P2VP_22 ionizable block copolymers were used as dispersing agents for the liquid-phase exfoliation of pristine graphene. Various strategies such as direct exfoliation, film hydration and phase transfer have been employed and compared. The best strategy involved a two-step process, namely, pre-exfoliation of graphite in polymer/CHCl3 solutions followed by phase transfer to acidified water. High concentrations of stable aqueous suspensions of graphene flakes, highly enriched in monolayer structures, were then obtained by using the star-shaped copolymers as stabilizers. The as-prepared graphene/copolymer hybrids were used as a filler material in order to prepare functional polymer composites for mechanical reinforcement. Such copolymer-modified graphene sheets have proven to be efficient reinforcing agents of PVA, as a significant increase of storage modulus (145% higher than that of neat PVA) was achieved even at a low graphene weight fraction of 0.1 wt%.

We report the rheological and structural properties of a suspension comprising poly(ethylene oxide)-polystyrene-poly(ethylene oxide) core-shell micellar nanoparticles dispersed in 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid. A liquid to soft solid transition was observed at a copolymer concentration of 10 wt % above which an elastic soft material was formed, which was composed of non-ordered jammed core-shell micellar nanoparticles. In the soft solid state, a significant reduction in the size of the nanoparticles, approaching hard sphere behavior, was observed by small-angle X-ray scattering which is attributed to compression of the soft poly(ethylene oxide) coronas. The nonvolatile ionic liquid-based glassy soft solid formed exhibited remarkable thermal stability with a melting temperature of 141 °C at 20 wt % copolymer, which renders it suitable for applications involving elevated temperatures and/or reduced pressure where water-based formulations are inappropriate.

In this work, the self-assembly behavior and pH responsiveness of a triblock copolypeptide in aqueous media are demonstrated. The copolypeptide was composed of a central pH responsive poly(l-glutamic acid) (PGA), flanked by two hydrophobic poly(l-alanine) blocks (PAla) (PAla5-PGA11-PAla5). This system showed a pH-responsive transition from short tapes to spherical aggregates by increasing the pH, as a result of deprotonation of the PGA block and a conformational change from α-helix to random coil. Increasing the ionic strength to physiological conditions (0.15 M) has triggered fibrillar self-assembly through intermolecular hydrogen bonding of PAla end-blocks that form β-sheet nanostructures, in conjunction with charge screening of the central random coil PGA segments. At elevated concentrations a thermo-responsive free supporting hydrogel was obtained, consisting of rigid β-sheet based twisted superfibers, resulting from hierarchical self-assembly of the copolypeptide. Yet, morphological transformation of this nanostructure was observed upon switching the pH from physiological conditions to pH 4. An unexpected morphology constituted of α-helix-based giant nanobelts was observed as a consequence of the secondary peptide transitions.

We investigate the influence of pH on the rheological and structural properties of hydrogels formed by hydrophobic association of the sticky ends of the triblock terpolymer poly(methyl methacrylate)-b-poly(2-(diethylamino)ethyl methacrylate-co-methacrylic acid)-b-poly(methyl methacrylate) (PMMA-b-P(DEA-co-MAA)-b-PMMA). The middle block is a weak polyampholyte having a pH dependent charge density and sign, which enables tuning of the rheological and structural properties by pH variation. Small-angle neutron scattering (SANS) studies of solutions in D2O at 0.05 wt% and pH 3.0 reveal clusters of interconnected spherical micelles having PMMA cores, stabilized by repulsive ionic interactions in the middle polyampholyte block. With increasing pH, the degree of ionization of the DEA units decreases, whereas the one of the MAA units increases, resulting in a complete loss of the correlation between these micelles. At a concentration of 3 wt% at low pH values, the system forms a gel with charged fuzzy spheres from PMMA interacting via a screened Coulomb potential. With increasing pH, the gel disintegrates due to the decrease in the effective charge on the micelles. At both concentrations, the hydrophobic aggregation of micelles is observed near the isoelectric point. At pH 3.0–7.4, the autocorrelation functions measured by rotational dynamic light scattering at 3 wt% exhibit a decay steeper than single exponential, which confirms that the gels are frozen, presumably due to the glassy PMMA cores and hydrophobic interpolyelectrolyte complexes. At pH 11, the diffusion of single micelles is observed in addition to the frozen dynamics.

We investigate the conformational properties of stimuli-responsive hydrogels from triblock polyelectrolytes PtBA-b-P2VP-b-PtBA (PtBA and P2VP are poly(tert-butyl acrylate) and poly(2-vinylpyridine)) and the corresponding polyampholytes PAA-b-P2VP-b-PAA (PAA is poly(acrylic acid)), the latter with nonquaternized or quaternized P2VP blocks. The block lengths are the same in all three polymers with relatively short end blocks and long middle blocks. The mechanical properties of the hydrogels have previously been found to depend strongly on the pH value and on the nature of the blocks (Polymer 2008, 49, 1249). Here, we present results from rheological studies and small-angle neutron scattering revealing the underlying hydrogel structures. The hydrogel structure of the polyampholyte depends on the charge asymmetry, controlled by the pH value, and reveals several transitions with increasing charge ratio. A low charge asymmetry causes the collapse of the chains into large globular structures due to the fluctuati...

The self-assembly of an amphiphilic pentablock terpolymer, consisting of a pH-sensitive poly(2-vinylpyridine) (P2VP) central block, bearing at both ends hydrophilic poly(ethylene oxide) (PEO) end-capped with hydrophobic poly(e-caprolactone) (PCL) blocks was investigated in aqueous media. When the polymer was transferred to aqueous medium through solvent exchange technique, micellar assemblies were obtained, with a morphological switch from “flower-like” crew-cut micelles to large compound vesicles upon partial quaternization of 2VP block. More importantly, well-defined polymer vesicles were formed when thin film hydration method was employed. Such polymersomes presented “flower-like” morphology, with a membrane composed of self-assembled P2VP hydrophobic central blocks shielded by PCL hydrophobic ends and surrounded by PEO looping chains at the inner and outer surfaces. The potential of the pentablock vesicles as drug delivery carriers was explored by encapsulation of calcein, a model hydrophilic drug, in the polymersomes and monitoring its release at different pH values simulating physiological environments. It is shown that the release profile of the nanoparticle formulations could be modulated by tuning the membrane permeability either through chemical (i.e. partial quaternization) and/or physical (i.e. pH variations) pathways.

We report the interfacial assembly of amphiphilic heteroarm star copolymers (PSnP2VPn and PSn(P2VP-b-PtBA)n (n = 28 arms)) on graphene oxide flakes at the air-water interface. Adsorption, spreading, and ordering of star polymer micelles on the surface of the basal plane and edge of monolayer graphene oxide sheets were investigated on a Langmuir trough. This interface-mediated assembly resulted in micelle-decorated graphene oxide sheets with uniform spacing and organized morphology. We found that the surface activity of solvated graphene oxide sheets enables star polymer surfactants to subsequently adsorb on the presuspended graphene oxide sheets, thereby producing a bilayer complex. The positively charged heterocyclic pyridine-containing star polymers exhibited strong affinity onto the basal plane and edge of graphene oxide, leading to a well-organized and long-range ordered discrete micelle assembly. The preferred binding can be related to the increased conformational entropy due to the reduction of interarm repulsion. The extent of coverage was tuned by controlling assembly parameters such as concentration and solvent polarity. The polymer micelles on the basal plane remained incompressible under lateral compression in contrast to ones on the water surface due to strongly repulsive confined arms on the polar surface of graphene oxide and a preventive barrier in the form of the sheet edges. The densely packed biphasic tile-like morphology was evident, suggesting the high interfacial stability and mechanically stiff nature of graphene oxide sheets decorated with star polymer micelles. This noncovalent assembly represents a facile route for the control and fabrication of graphene oxide-inclusive ultrathin hybrid films applicable for layered nanocomposites.

We present the layer-by-layer (LbL) assembly of amphiphilic heteroarm pH-sensitive star-shaped polystyrene-poly(2- pyridine) (PSnP2VPn) block copolymers to fabricate porous and multicompartmental microcapsules. Pyridine-containing star molecules forming a hydrophobic core/hydrophilic corona unimolecular micelle in acidic solution (pH 3) were alternately deposited with oppositely charged linear sulfonated polystyrene (PSS), yielding microcapsules with LbL shells containing hydrophobic micelles. The surface morphology and internal nanopore structure of the hollow microcapsules were comparatively investigated for shells formed from star polymers with a different numbers of arms (9 versus 22) and varied shell thickness (5, 8, and 11 bilayers). The successful integration of star unimers into the LbL shells was demonstrated by probing their buildup, surface segregation behavior, and porosity. The larger arm star copolymer (22 arms) with stretched conformation showed a higher increment in shell thickness due to the effective ionic complexation whereas a compact, uniform grainy morphology was observed regardless of the number of deposition cycles and arm numbers. Small-angle neutron scattering (SANS) revealed that microcapsules with hydrophobic domains showed different fractal properties depending upon the number of bilayers with a surface fractal morphology observed for the thinnest shells and a mass fractal morphology for the completed shells formed with the larger number of bilayers. Moreover, SANS provides support for the presence of relatively large pores (about 25 nm across) for the thinnest shells as suggested from permeability experiments. The formation of robust microcapsules with nanoporous shells composed of a hydrophilic polyelectrolyte with a densely packed hydrophobic core based on star amphiphiles represents an intriguing and novel case of compartmentalized microcapsules with an ability to simultaneously store different hydrophilic, charged, and hydrophobic components within shells.

We report the pH-controlled surface behavior of amphiphilic PS n (P2VP- b -PAA) n heteroarm star block terpolymers, ( n = number of arms, 9 and 22), bearing amphoteric diblock arms with varying polyvalent ionic charges (i.e. negative, positive, and zwitterionic) at the air–water and air–solid interfaces. We investigated the assembly of these pH-sensitive star terpolymers in Langmuir and Langmuir–Blodgett monolayers under different pH conditions of the subphase. The π-A isotherms acquired at variable pH conditions revealed a distinct aggregation behavior of surface micelles which is dependent on the ionization of the polyelectrolyte blocks and the number of arms. The star block copolymer with a small number of arms ( n = 9) was found to exhibit a strong pH-dependent phase transformation under compression. The pH responsive (zwitterionic) behavior results in changes in surface morphologies from circular micelles to complex labyrinth structures. In contrast, star polymers with a larger number of arms (22) and a crowded branched architecture show stable circular domain morphology without the internal reorganization under variable conditions. The observed variety of surface behaviors is attributed to the fine balance of intra molecular interactions caused by the highly branched chain architecture composed of both acidic and basic blocks. This study proposes a novel strategy for pH induced tunable surface assembly of responsive ultrathin films with multicompartments. We indeed demonstrated that the enhanced responsiveness of star polymers to wide pH range and their diverse morphology at the interface is enabled by coupling amphoteric concept and tailored molecular architecture.

We present a unique multisegmented, heteroarm star block terpolymer that can be used as an effective dispersing agent for multiwalled carbon nanotubes in aqueous media. The (polystyrene)22(poly(2-vinylpyridine)-b-poly(acrylic acid))22, PS22(P2VP-b-PAA)22, star terpolymer exhibits a pH responsive self-assembly behavior in aqueous solution, due to the ampholytic nature of its diblock copolymer arms. Depending on the pH of the medium, two different self-assemblies were observed. At a low pH (pH 2), core–shell unimolecular micelles, with a hydrophobic PS core and P2VP, PAA segments in the shell, as well as multicore large compound micelles were formed. At pH 8.5, the star was transformed from a bis-hydrophilic into a bis-hydrophobic state, leading to a network-like intermicellar assembly. This star terpolymer was capable of dispersing MWCNTs, through non-covalent interactions, thus leading to stable MWCNT–star nanohybrids in water. More importantly, the resulted MWCNT–star nanohybrids adopted the “smart” pH responsive properties of the physisorbed stars, i.e. the nanohybrids can be positively or negatively charged at low and high pH respectively, while at an intermediate pH window, phase separation occurs due to neutralization of the oppositely charged segments.

We report on the growth of gold nanoparticles in polystyrene/poly(2-vinyl pyridine) (PS/P2VP) star-shaped block copolymer monolayers. These amphiphilic PS(n)P2VP(n) heteroarm star copolymers differ in molecular weight (149,000 and 529,000 Da) and the number of arms (9 and 28). Langmuir-Blodgett (LB) deposition was utilized to control the spatial arrangement of P2VP arms and their ability to reduce gold nanoparticles. The PS(n)P2VP(n) monolayer acted as a template for gold nanoparticle growth because of the monolayer's high micellar stability at the liquid-solid interface, uniform domain morphology, and ability to adsorb Au ions from the water subphase. UV-vis spectra and AFM and TEM images confirmed the formation of individual gold nanoparticles with an average size of 6 ± 1 nm in the P2VP-rich outer phase. This facile strategy is critical to the formation of ultrathin polymer-gold nanocomposite layers over large surface areas with confined, one-sided positioning of gold nanoparticles in an outer P2VP phase at polymer-silicon interfaces.

This article is dealing with the design of novel segmented polymers comprising homopolymer and random copolymer building blocks designated as block-random. This type of polymeric materials can be prepared through macromolecular engineering by using controlled polymerization methods. By replacing a homopolymer block with a random one, in block copolymer topologies, further tuning of the copolymer properties can be achieved. The present article highlights the recent developments on block-random segmented macromolecules, bearing building blocks of tunable properties (e.g. thermo-sensitivity (LCST), hydrophobicity) and exhibiting responsive behavior in aqueous environments. Furthermore, preliminary novel results regarding pH-sensitive segmented macromolecules of various topologies, bearing random polyampholyte blocks among others, are also demonstrated and discussed.

In this communication an extended ‘‘in–out’’ polymerization method is presented, which leads to the synthesis of novel heteroarm star block terpolymers of the type An(B-b-C)n. A four step/one-pot synthetic procedure is pursued using anionic polymerization under an inert atmosphere. The resulted star-shaped terpolymer consists of a divinyl benzene nodule bearing pure polystyrene and poly(hexyl methacrylate)-block-poly(methyl methacrylate) diblock copolymer arms. It is shown that this kind of star terpolymers can self-assemble in the bulk forming lamellae mesophase by arm and block segregation. The mechanical properties of the terpolymer have been examined in detail. Finally, the proposed synthetic procedure can be easily employed in other controlled polymerization methods.

We report the surface behavior and morphologies of two series of pH-responsive amphiphilic heteroarm star block copolymers. In this respect, we studied polystyrene/poly(2-vinylpyridine)/poly(tert-butylacrylate), PSn(P2VP-PtBA)n, heteroarm star block terpolymers and their precursors, PSnP2VPn, star copolymers. These star block polymers differ in architecture (copolymer vs terpolymer), block topology, arm length (molecular weight of PtBA segments varies from 8 900 up to 15 250 Da), and number of arms (n = 9, 22, and 28). The π−A isotherms at different subphase pH (pH 5.8 and 2.0) exhibited strong pH dependence, leading to different limiting molecular area and surface micelle stability. Because of the pH-induced ionization of the P2VP block, the surface morphology of star copolymers bearing the free P2VP arms was strongly dependent on the pH of the subphase, whereas the star terpolymers containing the protonated hydrophilic P2VP block as midblocks maintained the same circular morphology at low pH and high pr...

This work is focused on the self-organization of an heteroarm star copolymer consisting of 5 polystyrene and 5 poly(2-vinylpyridine) (P2VP) arms emanated from a poly(divinyl benzene) core and the chemical stabilization of the resulting supramolecular nano-objects in the bulk and in solution. To tune various morphologies from the same star copolymer, selective and nonselective solvent media were used. Thepyridine moieties, forming distinct P2VP nanodomains in the copolymer nanostructures, were selectively crosslinked using 1,4-dibromobutane under mild conditions to yield stabilized polymeric “hairy” nano-objects, dispersible in hot tetrahydrofuran. The morphology of the resulting nanostructures was studied using scanning electron microscopy and was found to be strongly dependent on various factors, such as the self-assembly/casting conditions, the total time of the crosslinking reaction, and the dispersion procedure. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1636–1641, 2010

We report on the gelation capability of polystyrene/poly(2-vinyl pyridine) amphiphilic heteroarm polyelectrolyte stars in acidic salt-free aqueous media. The star polymers associate through hydrophobic interactions, by retraction of the stretched arms under no interdigitation conditions, in the dilute regime forming colloidal soft nanoparticles comprising about 6 stars, At concentrations significantly higher than the hydrodynamic overlap concentration (c > 40c∗), the crowding of the colloidal nanoparticles drives a jamming transition, leading to a colloidal gel. The intermediate overlap regime (c∗

The self-organization of the double hydrophilic triblock copolymer poly(ethylene oxide)-b-poly(2-vinylpyridine)-b-poly(ethylene oxide), PEO-b-P2VP-b-PEO, was investigated in dilute aqueous solution under several experimental conditions using turbidimetry, as well as static and dynamic light scattering. As a result of the temperature-sensitive properties of the end PEO blocks and the p H-responsive properties of the middle P2VP block, the formation of large star-like micellar nanostructures is observed at high p H, while at low p H, but in the presence of salt and at high temperature, flower-like micelles are formed. Moreover, the viscosimetric and dynamic light scattering studies at low p H revealed that micelle-like nanostructures are formed upon mixing the triblock copolymer with poly(acrylic acid), PAA, due to hydrogen bonding interpolymer complexation.

An asymmetric, amphiphilic, A n (B-b-C) n heteroarm star block terpolymer bearing polystyrene and poly(2-vinyl pyridine)-block-poly(acrylic acid) arms, was synthesized by anionic polymerization, using an extending "in-out" method and a post polymerization deprotection reaction. Due to the pH-dependent protonation/deprotonation equilibrium of the P2VP/PAA blocks, a rich phase behavior was observed as a function of pH. At pH = 2, the star terpolymers form a physical hydrogel through a solvent-induced sol/gel transition in a DMF/water solvent mixture. The gelation mechanism was attributed to a jamming effect mediated by increasing the dielectric permittivity of the medium.

A poly(methyl methacrylate)–poly(acrylic acid)–poly(2-vinyl pyridine)–poly(acrylic acid)–poly(methyl methacrylate) (PMMA–PAA–P2VP–PAA–PMMA), ABCBA pentablock terpolymer was synthesized by “living” anionic polymerization and was studied in aqueous media at different pH conditions in the presence of MeOH. By tuning the pH and/or the solvent selectivity and dielectric constant of the medium, reversible hydrogels of different nature were formed. At low pH the hydrogel is based on a three dimensional network comprising PMMA hydrophobic cores (physical crosslinks) interconnected by complex bridging (elastically active) chains constituted of positively charged P2VP and non-ionic PAA segments. At high pH the hydrogel is transformed reversibly to a negatively charged network the bridging chains of which comprise ionized PAA segments interrupted by hydrophobic P2VP blocks, swellable on MeOH addition. Furthermore, we found conditions for the formation of flower-like micelles of different topologies and nature like core–shell–corona micelles with positively charged corona (pH

A poly(methyl methacrylate)-block-poly(acrylic acid)-block-poly(2-vinyl pyridine)-block-poly (acrylic acid)-block-poly(methyl methacrylate) (PMMA-PAA-P2VP-PAA-PMMA), pentablock terpolymer has been synthesized by anionic polymerization with sequential addition of monomers and studied in aqueous media at low pH. The system exhibits combined properties and adopts the behavior of 'telechelic' polyelectrolytes and that of double hydrophilic polyampholytes. This complex behavior leads to the pentablock terpolymer forming a pH and temperature sensitive reversible hydrogel at very low polymer concentration.

We report on the diverse self-assembly of the poly(2-vinyl pyridine)-b-poly(acrylic acid)-b-poly(n-butyl methacrylate) (P2VP−PAA−PnBMA) ABC terpolymer in aqueous solutions. This has allowed us to fabricate a range of hierarchically organized nanostructured particles and hydrogels just by tuning both the pH and the concentration of polymer solutions. The multiresponsive molecule demonstrates a unique diversity of structural organizations caused by the combination of the P2VP and PAA building blocks. We found conditions for the formation of thermosensitive centrosymmetric core−shell−corona micelles, compact spheres, polyelectrolyte flowerlike micelles, a charged pH-sensitive 3D network, toroidal nanostructures, and finite size clusters (microgels). The transition between different micelles and the hydrogel was induced via the regulation of electrostatic and hydrophobic interactions in the system.

In this article, we highlight some recent developments in "smart" physical hydrogels achieved by self-assembling of block type macromolecules. More precisely we focus on two interesting types of gelators namely conventional ionic (or ionogenic) block copolymers and peptide-based polymers having as a common feature their responsiveness to pH and/or temperature which are the main triggers used for potential biomedical applications. Taking advantage of the immense skills of conventional block copolymer hydrogelators, namely macromolecular design, self-assembling mechanism, gel rheological properties, responsiveness to various triggers and innovative applications, the development of novel self-assembling gelators, integrating the new knowledge emerging from the peptide-based systems, opens new horizons towards bio-inspired technologies.

The current study summarizes the recent advances in design and synthesis of well-defined block polymers of various topologies prepared by different synthetic routes involving either only one polymerization mechanism or combination of different polymerization techniques, namely mechanistic transformations. A remarkable achievement in living/controlled polymerization methods has encouraged the synthesis of tailor-made block copolymers with specific macromolecular architecture, chemical composition/functionality, controlled molecular weight, low molecular polydispersity and corresponding minimized heterogeneity. Thus the chapter is focused on the methodologies involving living/controlled polymerization techniques for preparation of polymeric materials with desired fine properties.

Double-hydrophilic poly[(oligo(ethylene glycol) methacrylate)-co-methyl methacrylate]-b-poly(2-(diethylamino)ethyl methacrylate), P(EGMA-co-MMA)-b-PDEA, diblock terpolymers were designed and explored in aqueous media. Thanks to the thermosensitivity of the P(EGMA-co-MMA) statistical block and the pH sensitivity of the PDEA block, these terpolymers form two distinct micellar self-assemblies at different conditions of pH and temperature. The thermosensitivity of these terpolymers can be tuned by controlling the LCST of the statistical block through its monomer unit composition.