Amphiphilic Block Copolymers PEG-b-PMTCs: Synthesis, Self-Assembly, Degradation Properties and Biocompatibility.

As a hydrophilic cyclic ketene acetal (CKA), 2-methylene-1,3,6-trioxocane (MTC) has recently attracted a lot of attention owing to its ability to promote a quicker (bio)degradation as compared to other heavily studied CKAs. Here, we prepared amphiphilic block copolymers based on poly-MTC with varying chain lengths by radical ring opening polymerization. Self-assemblies of these amphiphiles were performed in PBS buffer to generate nanoparticles with sizes from 40 to 105 nm, which were verified by dynamic light scattering, electron microscopy, and static light scattering (Zimm plots). Subsequently, fluorescence spectroscopy was applied to study the enzymatic degradation of Nile red-loaded nanoparticles. By performing a point-by-point comparison of fluorescence intensity decline patterns between nanoparticles, we demonstrated that lipase from Pseudomonas cepacia was very efficient in degrading the nanoparticles. Hydrolysis degradations under basic conditions were also carried out, and a complete degradation was achieved after 4 h. Additionally, cytotoxicity assays were carried out on HEK293 cells, and the results affirmed cell viabilities over 90% when incubated with up to 1 mg/mL nanoparticles for 24 h. These biodegradable and biocompatible nanoparticles hence hold great potential for future applications such as drug release.

Self-organization of metallo-supramolecular polymer networks by free formation of pyridine-phenanthroline heteroleptic complexes.

Nature employs spontaneous self-organization of supramolecular bonds to create complex matter capable of adaptation and self-healing. Accordingly, the self-sorting of unlike ligands towards a cooperative heteroleptic complex or narcistic homoleptic association in a mixed ligand system is frequently employed to form interchangeable stimuli-responsive complex geometries with a wide range of applications. This notion is however just rarely employed in the organization of polymer networks. In this paper, we report the free-formation of heteroleptic complexes between tetra-am poly(ethylene glycol) (tetraPEG) precursors functionalized either with pyridine (tetraPy) or phenanthroline (tetraEPhen). Among a wide range of studied metal ions, tetraPy could form a network only in combination with Pd2+, presumably with a square-planar geometry, highlighting the importance of complex strength and stability in forming gels with monodentate ligands. Also, mixed networks with tetraEPhen form only in combination with Pd2+ and Fe2+, with strengths surpassing those of individual components and stabilities incomparable to those of parent networks, indicative of heteroleptic complexation. Extensive rheological, UV-vis, and DFT simulation studies revealed the coexistence of different coordination geometries, with an octahedral arrangement prevailing in the presence of Fe2+ and a square-planar geometry in the presence of Pd2+. Therefore, this study offers new opportunities for the development of stimuli-responsive topology-switching polymer networks.

Defect-controlled softness, diffusive permeability, and mesh-topology of metallo-supramolecular hydrogels.

Hydrogels are polymer networks swollen in water; they are suitable materials for biomedical applications such as tissue engineering and drug delivery. In the latter, the controlled diffusion of small diffusants inside the network is essential, as it determines the release mechanism of the drug. In general, the diffusion inside a polymer network is controlled by its mesh-size. Here, we actively control the diffusivity and also the softness of metallo-supramolecular hydrogels via the network mesh-topology by introducing connectivity defects. A model polymer network is realized based on a 4-arm poly(ethylene glycol) (pEG) where each arm is capped with terpyridine moieties that are capable of forming metallo-supramolecular complexes with zinc ions. In this model network, we insert 8-arm pEG macromolecules that are functionalized with terpyridine at different ratios to create connectivity defects. With an increasing amount of 8-arm pEG, the polymer network forms more loops, as quantified by double quantum-NMR. This doped network shows an enhanced self-diffusivity of the building block molecules within the network, as examined by fluorescence recovery after photobleaching, and a higher softness, as investigated by oscillatory shear rheology. With these findings, we show that it is possible to tune the diffusivity and softness of hydrogels with defects in a rational fashion.

Metal-ligand complexation and clustering in mussel-inspired side-chain functionalized supramolecular hydrogels.

Byssus threads of mussels have high resistance against abrasion in wave-swept habitats because of their outer cuticle, which is rich in amino acid dopa complexes with Fe3+ ions. This stems from the transient nature of metal-ligand complexes that creates extra relaxation mechanisms. Inspired by this concept, in this work, supramolecular hydrogels based on poly(acrylic acid) functionalized with nitrocatechol groups are synthesized. Polymer chains are physically crosslinked via nitrocatechol-Fe3+ complexes. The hydrogels have different polymer volume fractions as well as different nitrocatechol : Fe3+ molar ratios. The strength of the supramolecular crosslinks strongly depends on the pH of the medium. The dynamics of these hydrogels are studied by stress relaxation experiments followed by calculation of the relaxation time spectrum. Generally, samples have three relaxation modes, including dissociation of distinct metal-ligand complexes, reptation of sticky polymer chains, and disengagement of network segments from supramolecular aggregates and clusters. Such clusters hinder the terminal relaxation and potentially increase the stability of supramolecular hydrogels.

Bridging Rigidity and Flexibility: Modulation of Supramolecular Hydrogels by Metal Complexation.

The combination of complementary, noncovalent interactions is a key principle for the design of multistimuli responsive hydrogels. In this work, an amphiphilic peptide, supramacromolecular hydrogelator which combines metal-ligand coordination induced gelation and thermoresponsive toughening is reported. Following a modular approach, the incorporation of the triphenylalanine sequence FFF into a structural (C3 EG ) and a terpyridine-functionalized (C3 Tpy ) C3 -symmetric monomer enables their statistical copolymerization into self-assembled, 1D nanorods in water, as investigated by circular dichroism (CD) spectroscopy and transmission electron microscopy (TEM). In the presence of a terpyridine functionalized telechelic polyethylene glycol (PEG) cross-linker, complex formation upon addition of different transition metal ions (Fe2+ , Zn2+ , Ni2+ ) induces the formation of soft, reversible hydrogels at a solid weight content of 1 wt% as observed by linear shear rheology. The viscoelastic behavior of Fe2+ and Zn2+ cross-linked hydrogels are basically identical, while the most kinetically inert Ni2+ coordinative bond leads to significantly weaker hydrogels, suggesting that the most dynamic rather than the most thermodynamically stable interaction supports the formation of robust and responsive hydrogel materials.

Hierarchy of relaxation times in supramolecular polymer model networks.

Supramolecular polymer gels are an evolving class of soft materials with a vast number of properties that can be tuned to desired applications. Despite continuous advances concerning polymer synthesis, sustainability or adaptability, a consistent understanding of the interplay between structure, dynamics, and diffusion processes within transient networks is lacking. In this study, the hierarchy of several relaxation processes is investigated, starting from a microscopic perspective of a single sticker dissociation event up to the center-of-mass diffusion of a star-shaped polymer building block on different length scales, as well as the resulting macroscopic mechanical response to applied external stress. In addition to that, a second focus is placed on the gel micro-structure that is analyzed by light scattering. Conversion of the dynamic light scattering (DLS) inverse length scale into real space allows for a combination of relaxation times with those obtained by forced Rayleigh scattering (FRS). For these investigations, a model-type metallo-supramolecular network consisting of narrowly dispersed tetra-arm poly(ethylene glycol)-terpyridine macromolecules that are interconnected via complexation with zinc ions is chosen. Assembling the obtained activation energies reveals that all complex dissociation-governed relaxation processes exhibit similar activation energies.

An Inverse Thermogelling Bioink Based on an ABA-Type Poly(2-oxazoline) Amphiphile.

Hydrogels are key components in several biomedical research areas such as drug delivery, tissue engineering, and biofabrication. Here, a novel ABA-type triblock copolymer comprising poly(2-methyl-2-oxazoline) as the hydrophilic A blocks and poly(2-phenethyl-2-oxazoline) as the aromatic and hydrophobic B block is introduced. Above the critical micelle concentration, the polymer self-assembles into small spherical polymer micelles with a hydrodynamic radius of approx 8-8.5 nm. Interestingly, this specific combination of hydrophilic and hydrophobic aromatic moieties leads to rapid thermoresponsive inverse gelation at polymer concentrations above a critical gelation concentration (20 wt %) into a macroporous hydrogel of densely packed micelles. This hydrogel exhibited pronounced viscoelastic solid-like properties, as well as extensive shear-thinning, rapid structure recovery, and good strain resistance properties. Excellent 3D-printability of the hydrogel at lower temperature opens a wide range of different applications, for example, in the field of biofabrication. In preliminary bioprinting experiments using NIH 3T3 cells, excellent cell viabilities of more than 95% were achieved. The particularly interesting feature of this novel material is that it can be used as a printing support in hybrid bioink systems and sacrificial bioink due to rapid dissolution at physiological conditions.

Cell Adhesion on UV-Crosslinked Polyurethane Gels with Adjustable Mechanical Strength and Thermoresponsiveness.

Temperature-responsive polyurethane (PU) hydrogels represent a versatile material platform for modern tissue engineering and biomedical applications. However, besides intrinsic advantages such as high mechanical strength and a hydrolysable backbone composition, plain PU materials are generally lacking bio-adhesive properties. To overcome this shortcoming, the authors focus on the synthesis of thermoresponsive PU hydrogels with variable mechanical and cell adhesive properties obtained from linear precursor PUs based on poly(ethylene glycol)s (pEG) with different molar masses, isophorone diisocyanate, and a dimerizable dimethylmaleimide (DMMI)-diol. The cloud point temperatures of the dilute, aqueous PU solutions depend linearly on the amphiphilic balance. Rheological gelation experiments under UV-irradiation reveal the dependence of the gelation time on photosensitizer concentration and light intensity, while the finally obtained gel strength is determined by the polymer concentration and spacing of the crosslinks. The swelling ratios of these soft hydrogels show significant changes between 5 and 40 °C whereby the extent of this switch increases with the hydrophobicity of the precursor. Moreover, it is shown that the incorporation of a low amount of catechol groups into the networks through the DMMI dimerization reaction leads to strongly improved cell adhesive properties without significantly weakening the gels.

Salt partitioning in ionized, thermo-responsive hydrogels: perspective to water desalination.

Charged hydrogels are capable of swelling in aqueous salt solutions, whereby part of the salt ions is repelled due to the presence of fixed charged groups inside the hydrogel. This effect creates a concentration gradient between the absorbed solution and the surrounding fluid known as salt partitioning, offering a potential for these materials to be employed to desalinate saltwater. If the charged hydrogels are thermo-sensitive as well, then the purer, absorbed solution can be recovered by shrinking the hydrogels upon temperature change. To tailor that potential in water-purification and desalination applications, the main parameters influencing the salt partitioning, the deswelling of the hydrogels, and the recovery of water must be understood. In this paper, we analyze these factors based on equations derived from the Donnan theory. In addition, hydrogels composed of N-isopropyl acrylamide and acrylic acid are synthesized, and their salt rejection efficiency in a model desalination experiment is studied. A comparison of the experimental and the theoretical results demonstrates that the charge density of the hydrogels at their equilibrium swelling and the degree of water recovery are two parameters controlling the salt rejection efficiency. These parameters are individually controlled by the content of the ionic groups and the degree of cross-linking of the gel polymer network. In addition, the prediction of the theory and the experimental results demonstrate that the salt rejection efficiency can be significantly improved if a second water recovery step is performed by a secondary increase in the temperature in the deswelling process.

"Dumb" pH-Independent and Biocompatible Hydrogels Formed by Copolymers of Long-Chain Alkyl Glycidyl Ethers and Ethylene Oxide.

The formation and rheological properties of hydrogels based on amphiphilic ABA triblock polyether copolymers are described, relying solely on the hydrophobic interaction of long-chain alkyl glycidyl ether (AlkGE)- based A-blocks that are combined with a hydrophilic poly(ethylene glycol) (PEG) midblock. Via anionic ring-opening copolymerization (AROP), ethylene oxide (EO) and long-chain alkyl glycidyl ethers (AlkGEs) were copolymerized, using deprotonated poly(ethylene glycol) (PEG) macroinitiators (Mn of 10, 20 kg mol-1). The polymerization afforded amphiphilic ABA triblock copolymers with molar masses in the range of 21-32 kg mol-1 and dispersities (D) of D = 1.07-1.17. Kinetic studies revealed random copolymerization of EO and AlkGE, indicating random spacing of the hydrophobic AlkGE units by polar EO units. Following this approach, the hydrophobicity of the apolar blocks of amphiphilic ABA triblock polyethers can be tailored. Detailed rheological measurements confirmed the successful formation of hydrogels at different pH values as a consequence of nonpolar interactions and alkyl chain crystallization. Hydrogel formation was also observed at different ionic strengths (i.e., varied salt concentration), based on the hydrophobic aggregates. This behavior is in contrast to other often-used supramolecular cross-linking strategies, such as Coulomb interactions, complexation, or hydrogen bonding. Micro-differential scanning calorimetry (µ-DSC) measurements of the hydrogels revealed crystalline hydrophobic domains with melting temperatures in the physiological temperature range. In 3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazoliumbromide (MTT) assays, diblock copolymers possessing structural analogy to the triblock copolymers were studied to assess the general cytotoxicity of amphiphilic polyethers bearing long alkyl chains at the polyether backbone, using splenic immune cells. At intermediate polymer concentrations, no cytotoxic effects were observed. This indicates that long-chain alkyl glycidyl ethers are promising for the introduction of highly hydrophobic as well as crystalline motifs at the polyether backbone in hydrogels for biomedical purposes.

Thermodynamic control over energy dissipation modes in dual-network hydrogels based on metal-ligand coordination.

Modern polymeric hydrogels use reversible bonds to mimic biological functionalities. However, true biological materials benefit from several supramolecular elements and deliver multiple functions at the same time. To approach similar creation and control of multiple different functional elements in a synthetic soft material, we develop a model dual-network hydrogel in which multiple energy dissipating modes are formed by metal-ligand coordination and regulated by their association thermodynamics. This idea is realized by using linear and tetra-arm poly(ethylene glycol) (PEG) precursors with complementary reactive end groups. The former also carries terpyridine ligands on both ends, which form metallo-supramolecular bonds upon addition of metal ions. Multiple relaxation modes are provided by a combination of different metal ions. The timescale and amplitude of energy dissipating elements are characterized by oscillatory shear deformation. These studies suggest that the composition of metal ions controls the contribution of the corresponding relaxation modes in a linear fashion. A molecular-level confirmation is provided by following the UV-vis absorbance of the linear precursor in combination with mixtures of metal ions, accompanied by a theoretical study on the kinetics of the reversible association process. These results show that the linearity of the aforementioned dependence holds for such systems in which the utilized combination of metal ions and ligands exclusively form stable bis-complexes. By contrast, in many other cases, especially when the ions may compete to form mono-, bis-, or tris-complexes with the ligand, deviation from linearity is expected.

Defects and defect engineering in Soft Matter.

Soft matter covers a wide range of materials based on linear or branched polymers, gels and rubbers, amphiphilic (macro)molecules, colloids, and self-assembled structures. These materials have applications in various industries, all highly important for our daily life, and they control all biological functions; therefore, controlling and tailoring their properties is crucial. One way to approach this target is defect engineering, which aims to control defects in the material's structure, and/or to purposely add defects into it to trigger specific functions. While this approach has been a striking success story in crystalline inorganic hard matter, both for mechanical and electronic properties, and has also been applied to organic hard materials, defect engineering is rarely used in soft matter design. In this review, we present a survey on investigations on defects and/or defect engineering in nine classes of soft matter composed of liquid crystals, colloids, linear polymers with moderate degree of branching, hyperbranched polymers and dendrimers, conjugated polymers, polymeric networks, self-assembled amphiphiles and proteins, block copolymers and supramolecular polymers. This overview proposes a promising role of this approach for tuning the properties of soft matter.

Efficiency range of the Belousov-Zhabotinsky reaction to induce the self-organization of transient bonds in metallo-supramolecular polymeric systems.

The periodic change of the oxidation state of the metal catalyst in the oscillating Belousov-Zhabotinsky (BZ) reaction has been reported to establish a periodic organization of metallo-supramolecular bonds in polymeric systems, which results in autonomous viscosity oscillations. To appraise the possible extent of quantitative control on the viscosity oscillation features, we assess how the kinetics of the BZ reaction affects the periodic self-organization of the metal-ligand coordination, and vice versa. Our model system includes mono-, bis-, and tetra-functional polyethyleneglycol (PEG) precursors end grafted with terpyridine ligands that are complexed with ruthenium ions, which oscillate between Ru2+ and Ru3+ oxidation states in the BZ reaction medium. The control parameters are divided into microscopic factors, which are responsible for the local reaction rate, and mesoscopic factors, which are responsible for the spatial distribution of the concentration patterns. The reactant concentrations are found to nonlinearly control the amplitude and periods of reduction and oxidation phases, independent of the precursor functionalization degree. An increased medium viscosity, and therewith cease of mixing, accelerates the reaction rate by localization of the reaction phases, even though the diffusion of reaction intermediates causes a periodic chemical wave with distinct harmonics. Time-course viscosity measurements of the tetra-arm precursors in the BZ medium demonstrate an initial overshoot followed by minor oscillations around a plateau that is significantly lower than the viscosity of an equivalent fully associated network. Apparently, the slow association kinetics of Ru2+-bis(terpyridine) limits the frequency and the extent of self-organization, and this way, avoids full establishment of the expected viscosity oscillation.

Origin of the low-frequency plateau and the light-scattering slow mode in semidilute poly(ethylene glycol) solutions.

A low-frequency plateau is often found in the rheological spectra of various kinds of semidilute solutions of polymers and other colloids; also, many such solutions have been reported to show slow-modes in their dynamic light scattering autocorrelation functions. Both these observations may lead to the hypothesis of weak associative network structures built by the dissolved polymer chains or colloidal building blocks. To challenge this hypothesis, we conduct a series of comparative studies on semidilute solutions of poly(ethylene glycol) by using classical rheology as well as passive microrheology based on dynamic light scattering, along with structural studies using static light scattering. Although we indeed find a low-frequency plateau using classical shear rheology, even at elevated temperatures where potential polymer aggregates should be broken, no such plateau is observed in any of our microrheology experiments. Also, dynamic and static light scattering studies on the polymer solutions do not confirm the presence of larger structural entities: no slow mode can be detected in the autocorrelation function of the scattering intensity signal, and this signal is angle independent if the samples are purified by a thorough procedure of filtration. Based on these findings, we conclude that the low-frequency plateau in classical rheology results is an instrument effect caused by erroneous recording of the phase angle, although the magnitude of the torque lies well within the resolution of the rheometer. We also conclude that slow modes in dynamic light scattering on solutions of poly(ethylene glycol) are impurity-based artifacts rather than due to actual associated structures.

Local dynamics in supramolecular polymer networks probed by magnetic particle nanorheology.

Transient supramolecular polymer networks are promising candidates as soft self-healing or stimuli-sensitive materials. In this paper, we employ a novel nanorheological approach, magnetic particle nanorheology (MPN), in order to better understand the local dynamic properties of model supramolecular networks from a molecular point of view. Hence, the bond strength between four-arm star-shaped polyethylene glycol (PEG) functionalized at the four extremities with terpyridine ligands is tuned by implementing different metal ions with variable complexation affinities for the ligand. We show that MNP allows for the evaluation of the strength and connectivity of the polymer networks by the estimation of relaxation times, mesh size, and also the viscoelastic properties of these materials. These results are compared and complemented to former outcomes on these systems that were obtained by macroscopic analytical methods. A clear dependence between the strength of the metal-ligand complex and the local dynamics of the polymeric network is observed by the nanorheological approach, which is in good agreement with previous predictions related to the complex formation constants.

Enhancement of metallo-supramolecular dissociation kinetics in telechelic terpyridine-capped poly(ethylene glycol) assemblies in the semi-dilute regime.

The dynamics of supramolecular polymer assemblies is governed by that of their polymeric building blocks and that of the transient bonds between them. Entrapment of such bonds by topological crowding often causes renormalization of the bond lifetimes towards prolonging. In the present study, by contrast, we show that this effect can also be inverse in the case of telechelic metallo-supramolecular polymers in semi-dilute solution. We focus on linear poly(ethylene glycols) capped by terpyridine binding motifs at both ends that can form metal-ligand coordinative bonds with various transition metal ions, thereby creating transient metallo-supramolecular assemblies of varying length and binding strength. Oscillatory shear rheology measurements along with theoretical modelling of the mechanical spectra of these samples reveals a pronounced enhancement of the complex dissociation kinetics that is dependent on the length of the polymeric chain segment, with longer segments yielding faster dissociation times up to six orders of magnitude shorter than described for the free complexes. This finding indicates that the dynamic activity of the polymer chain itself causes complex destabilization.

Dynamics-based assessment of nanoscopic polymer-network mesh structures and their defects.

Polymer-network gels often exhibit complex nanoscopic architectures. First, the polymer-network mesh topology on scales of 1-10 nm is usually not uniform and regular, but disordered and irregular. Second, on top of that, many swollen polymer networks display spatial inhomogeneity of their polymer segmental density and crosslinking density on scales of 10-100 nm. This multi-scale structural complexity affects the permeability, mechanical strength, and optical clarity of the polymer gels, which is of central relevance for their performance in popular applications. As a result, there is a need to characterize the polymer network structures on multiple scales. On the scale of the spatial inhomogeneity of crosslinking, 10-100 nm, scattering of neutrons, X-rays, and light has extraordinary utility and is well established. On the scale of the mesh topology, 1-10 nm, in contrast, experimental techniques are less established. This review intends to close this gap by reviewing two intrinsically dynamic methods that yield information on polymer network mesh structures. First, NMR-based assessment of residual dipolar proton-spin couplings, which arise upon the introduction of crosslinks into a liquidlike polymer system to impart partial solidlike characteristics, is suitable to quantitatively assess network meshes and local network defects. Second, diffusive penetration of molecular, macromolecular, and mesoscopic colloidal probes through a polymer gel provides insight into its obstructing network mesh structure and its potential irregularity. Either method is highly synergistic to scattering-based assessment of the network structures on larger scales, and in concert, a rich picture on the nano- and mesoscopic gel topology is obtained.

Secondary Structure-Driven Hydrogelation Using Foldable Telechelic Polymer-Peptide Conjugates.

The synthesis of ABA and ABA' triblock polyethylene glycol-and polysarcosine-peptide conjugates is reported. The A/A' peptides are based on phenylalanine(F)-histidine(H) pentapeptide sequences FHFHF, which promote pH-switchable ß-sheet self-assembly into nanorods in water. Only parallel ß-sheet-driven folding and intermolecular assembly using ABA triblock polymer-peptide conjugates leads to interstrand cross-linking and hydrogelation, highlighting the impact of supramolecular interactions-directed structure formation at the nano- and mesoscopic level.

Metallo-Polymer Chain Extension Controls the Morphology and Release Kinetics of Microparticles Composed of Terpyridine-Capped Polylactides and their Stereocomplexes.

Control over morphology and porosity of supramolecular complexed polylactide (PLA) microparticles can be achieved by manipulation of the supramolecular interactions between their constituent polymeric building blocks. It is expected that such modular systems are ideal candidates to serve as degradable delivery carriers. In view of this goal, this study reports about a modular fabrication of biodegradable microparticles from terpyridine (TPy) and bisterpyridine (bisTPy) end-functionalized PLAs that can be transiently extended by chain association through differently strong complexation to three metal cations: Ni2+ , Co2+ , or Fe2+ . Further influence on the morphology of the particles can be exerted by hydrogen-bonding association of enantiomeric l- and d-PLA chains in the form of stereocomplexes. Both effects cause different stabilization of phase-separating TPy and bisTPy PLA micrograins in a process of droplet-based microfluidic particle templating, resulting in different forms of microparticle porosity. If the resulting particles are tailored such to be highly porous, they exhibit a faster release of a model drug, (S)-(+)-4-(3-amino-pyrrolidino)-7-nitrobenzo-furazan, than if they have smooth surfaces. As a result, control over the synthetic parameters, and hence, the particle porosity, can be used to tune the release profiles of drugs from the PLA microspheres.

Effect of Supramolecular Interchain Sticking on the Low-Frequency Relaxation of Transient Polymer Networks.

Supramolecular polymer networks and gels often exhibit three effects in rheology as a function of increasing strength and extent of transient chain interlinkage: (i) the longest relaxation time increases, (ii) the elastic part of the complex shear modulus on timescales longer than that increases, and (iii) the frequency-dependent power-law scaling of this modulus gets shallower in this regime. In a recent report, these effects have been systematically assessed by comparing transient polymer networks derived from a common precursor modified with different extents of a common hydrogen-bonding supramolecular sticker. In this communication, complementary studies are discussed that are based on a set of polymers also derived from a common precursor but all modified with the same extent (4.8%) of very different supramolecular crosslinking motifs. This comparison reveals that effect (iii) can be rationalized by exacerbation of polydispersity effects to the relaxation time spectrum if supramolecular interchain sticking is present. In addition, effect (ii) is addressable to a simple thermodynamic argument that appraises the supramolecular sticking contribution to the elastic part of the shear modulus in the relaxation regime.