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New developments require innovative ecofriendly materials defined by their biocompatibility, biodegradability, and versatility. For that reason, the scientific society is focused on biopolymers such as chitosan, which is the second most abundant in the world after cellulose. These new materials should show good properties in terms of sustainability, circularity, and energy consumption during industrial applications. The idea is to replace traditional raw materials with new ecofriendly materials which contribute to keeping a high production rate but also reducing its environmental impact and the costs. The chitosan shows interesting and unique properties, thus it can be used for different purposes which contributes to the design and development of sustainable novel materials. This helps in promoting sustainability through the use of chitosan and diverse materials based on it. For example, it is a good sustainable alternative for food packaging or it can be used for sustainable agriculture. The chitosan can also reduce the pollution of other industrial processes such as paper production. This mini review collects some of the most important advances for the sustainable use of chitosan for promoting circular economy. Hence, the present review focuses on different aspects of chitosan from its synthesis to multiple applications.

The functionalization of smart polymers is opening a new perspective in catalysis, drug carriers and biosensors, due to the fact that they can modulate the response regarding conventional devices. This smart response could be affected by the presence of organometallic complexes in terms of interactions which could affect the physical chemical properties. In this sense, the thermoresponsive behavior of copolymers based on N -isopropylacrylamide (NIPAM) could be affected due to the presence of hydrophobic groups and concentration effect. In this work, the functionalization of a copolymer based on NIPAM and dopamine methacrylamide with different amounts of bis(cyclopentadienyl)titanium (IV) dichloride was carried out. The resulting materials were characterized, showing a clear idea about the mechanism of functionalization through FTIR spectroscopy. The thermoresponsive behavior was also studied for various polymeric solutions in water by UV-vis spectroscopy and calorimetry. The hydrophobic interactions promoted by the organometallic complex could affect the transition associated with the lower critical solution temperature (LCST), specifically, the segments composed by pure NIPAM. That fact would explain the reduction of the width of the LCST-transition, contrary to what could be expected. In addition, the hydrophobicity was tested by the contact angle and also DNA interactions.

Long-chain branched metallocene-catalyzed high-density polyethylenes (LCB-mHDPE) were solution blended to obtain blends with varying degrees of branching. A high molecular LCB-mHDPE was mixed with low molecular LCB-mHDPE at varying concentrations. The rheological behavior of those low molecular LCB-mHDPE is similar but their molar mass and molar mass distribution are significantly different. Those blends were characterized rheologically to study the effects of concentration, molar mass distribution, and long-chain branching level of the low molecular LCB-mHDPE. Owing to the ultra-long relaxation times of the high molecular LCB-mHDPE, the blends exhibited a clearly more long-chain branched behavior than the base materials. The thermorheological complexity analysis showed an apparent increase in the activation energies E a determined from G' , G″ , and especially δ. E a (δ), which for LCB-mHDPE is a peak function, turned out to produce even more pronounced peaks than observed for LCB-mPE with narrow molar mass distribution and also LCB-mPE with broader molar mass distribution. Thus, it is possible to estimate the molar mass distribution from the details of the thermorheological complexity.

The linear and nonlinear rheology of associative colloidal polymer assemblies with metallo-supramolecular interactions is herein studied. Polystyrene- b -poly( tert -butylacrylate) with a terpyridine ligand at the end of the acrylate block is self-assembled into micelles in ethanol, a selective solvent for the latter block, and supramolecularly connected by complexation to divalent metal ions. The dependence of the system elasticity on polymer concentration can be semi-quantitatively understood by a geometrical packing model. For strongly associated (Ni 2+ , Fe 2+ ) and sufficiently concentrated systems (15 w/v%), any given ligand end-group has a virtually 100% probability of being located in an overlapping hairy region between two micelles. By assuming a 50% probability of intermicellar crosslinks being formed, an excellent prediction of the plateau modulus was achieved and compared with the experimental results. For strongly associated but somewhat more dilute systems (12 w/v%) that still have significant overlap between hairy regions, the experimental modulus was lower than the predicted value, as the effective number of crosslinkers was further reduced along with possible density heterogeneities. The reversible destruction of the network by shear forces can be observed from the strain dependence of the storage and loss moduli. The storage moduli of the Ni 2+ and Zn 2+ systems at a lower concentration (12 w/v%) showed a rarely observed feature (i.e., a peak at the transition from linear to nonlinear regime). This peak disappeared at a higher concentration (15 w/v%). This behavior can be rationalized based on concentration-dependent network stretchability.

For the preparation of thermoresponsive copolymers, for e.g., tissue engineering scaffolds or drug carriers, a precise control of the synthesis parameters to set the lower critical solution temperature (LCST) is required. However, the correlations between molecular parameters and LCST are partially unknown and, furthermore, LCST is defined as an exact temperature, which oversimplifies the real situation. Here, random N-isopropylacrylamide (NIPAM)/dopamine methacrylamide (DMA) copolymers were prepared under a systematical variation of molecular weight and comonomer amount and their LCST in water studied by calorimetry, turbidimetry, and rheology. Structural information was deduced from observed transitions clarifying the contributions of molecular weight, comonomer content, end-group effect or polymerization degree on LCST, which were then statistically modeled. This proved that the LCST can be predicted through molecular structure and conditions of the solutions. While the hydrophobic DMA lowers the LCST especially the onset, polymerization degree has an important but smaller influence over all the whole LCST range.

An anomalous plasticizing effect was observed in polymer/ionic liquid (IL) solutions by applying broad range of rheological techniques. Poly(ethylene oxide)(PEO)/IL solutions exhibit stronger dynamic temperature dependence than pure PEO, which is in conflict with the knowledge that lower- T g solvent increases the fractional free volume. For poly(methy methacrylate)(PMMA)/IL solutions, the subtle anomaly was detected from the fact that the effective glass transition temperature T g,eff of PMMA in IL is higher than the prediction of the self-concentration model, while in conventional polymer solutions, T g,eff follows the original Fox equation. Observations in both solutions reveal retarded segmental dynamics, consistent with a recent simulation result ( Macromolecules , 2018, 51, 5336) that polymer chains wrap the IL cations by hydrogen bonding interactions and the segmental unwrapping delays their relaxation. Start-up shear and nonlinear stress relaxation tests of polymer/IL solutions follow a universal nonlinear rheological behavior as polymer melts and solutions, indicating that the segment-cation interaction is not strong enough to influence the nonlinear chain orientation and stretch. The present work may arouse the further theoretical, experimental, and simulation interests in interpreting the effect of complex polymer-IL interaction on the dynamics of polymer/IL solutions.

The thermoreversible sol-gel transition for an ionic liquid (IL) solution of isotactic-rich poly ( N -isopropylacrylamides) (PNIPAMs) is investigated by rheological technique. The meso-diad content of PNIPAMs ranges between 47% and 79%, and molecular weight ( M n ) is ~35,000 and ~70,000 g/mol for two series of samples. PNIPAMs are soluble in 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl) imide ([BMIM][TFSI]) at high temperatures but undergo a gelation with decreasing temperatures. The transition temperature determined from G'-G " crossover increases with isotacticity, consistent with the previous cloud-point result at the same scanning rate, indicating imide groups along the same side of backbones are prone to be aggregated for formation of a gel. The transition point based on Winter-Chambon criterion is on average higher than that of the G'-G" crossover method and is insensitive to tacticity and molecular weight, since it correlates with percolation of globules rather than the further formation of elastic network ( G' > G " ). For the first time, the phase diagram composed of both G'-G polymers for entropic reasons. The phase diagram composed of Winter-Chambon melting points, crossover points for melting, and clear points is similar with the gelation phase diagram, confirming the mechanism above." crossover points for gelation and cloud points is established in PNIPAM/IL mixtures. For low- M n PNIPAMs, the crossover-point line intersects the cloud-point line. Hence, from solution to opaque gel, the sample will experience two different transitional phases, either clear gel or opaque sol. A clear gel is formed due to partial phase separation of isotactic segments that could act as junctions of network. However, when the partial phase separation is not faster than the formation of globules, an opaque sol will be formed. For high- M n PNIPAMs, crossover points are below cloud points at all concentrations, so their gelation only follows the opaque sol route. Such phase diagram is attributed to the poorer solubility of high- M n polymers for entropic reasons. The phase diagram composed of Winter-Chambon melting points, crossover points for melting, and clear points is similar with the gelation phase diagram, confirming the mechanism above., Competing Interests: The authors declare no conflict of interest

We fabricated one fibrous-membrane type of flexible and lightweight supported catalyst via loading platinum-nickel nanoparticles (PtNi NPs) directly on the polydopamine-coated polymethylmethacrylate electrospun-fibers (PMMA@PDA). The polymer support with the PDA layer provided numerous active sites, leading to well-monodispersed and sized PtNi NPs on the nanofibers. Through the rational design of PtNi NPs, the resultant catalyst system exhibited 90% conversion for decomposing HCHO (10 ppm) at room temperature with only a low dosage (0.02 g), retaining the high activity for 100 hours. This superior catalytic performance stems from the formate oxidation, which was the key intermediate during HCHO decomposition, and was promoted by the existence of a sufficient Pt-OH-Ni interface in the PtNi NPs with an appropriate Pt/Ni ratio of 1:5. Such tailored Pt-based nanoparticles ideally work together with the polymer nanofibers as a support for catalytic reaction. Compared with classical catalysts, our system can handle a comparable efficiency with much lower air resistance and remarkably lower dosage. Furthermore, the membrane-like morphology provides easy handling and minimizes the leaching of catalyst nanoparticles., Competing Interests: The authors declare no conflict of interest.