This review article highlights the recent advances in the pH and/or temperature responsive self-assembling hydrogels focusing on two types of gelators namely conventional block copolymers, bearing ionogenic repeating units, and polypeptide-based associative segmented (block) macromolecules.

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.

Star shaped segmented macromolecules constitute an interesting class of polymeric materials whose properties differ remarkably from those appearing in their linear counterparts. This review highlights the work done in the last decade, dealing with the self-assembly of star-shaped block copolymers and terpolymers of various topologies in aqueous media. This article focuses on a specific class of star shaped macromolecules designated as stimuli responsive. These stars bearblock/arms undergo sharp phase transitions upon responding to stimuli, such as temperature, pH, ionic strength and so forth. These transitions impose dramatic transformations on the morphology and, accordingly, in the functionality of the nanostructured associates. The number of arms, the specific functionality and topology of the different arm/blocks and the overall macromolecular architecture of the star polymer, significantly influence their behavior in terms of self-assembly and responsiveness.

Graft copolymers of alginate backbone and N-isopropylacrylamide/N-tert-butylacrylamide random copolymer, P(NIPAM_x-co-NtBAM_y), 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(NIPAM_x-co-NtBAM_y) 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, T_gel, 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 T_gel 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.