It has been observed previously that when permanently charged polyelectrolyte brushes are exposed to an external salt solution, they shrink when the salt level is high enough. In this study, we observed an enhanced swelling process before the salt concentration reached that limit. We systematically investigated a few strong polyelectrolyte brush systems, including sodium polystyrene sulfonate (PSSNa), poly([2-(methacryloyloxy)ethyl] trimethylammonium chloride) (PMETAC) and potassium poly(3-sulfopropyl methacrylate) (PSPMA) with different molecular weights and grafting density using a combination of methods, including ellipsometry, quartz crystal microbalance with dissipation (QCM-D) and atomic force microscope (AFM). The swelling enhancement is expressed by the thickening of the brush layer at moderate salt concentrations, accompanied by the decrease of refractive index, the increase of the amount of solvent inside the brushes and an increase in retardation time. A scenario is proposed in which the counterions penetrate into the brushes driven by the external salt ions, they disrupt and break up the previously formed multiplets due to the dipole-dipole interaction by the ion-pairs on the polymer chain. This process results in the release of the bound segments and the stretching of the polymer chains.

A study was made of the anti-polyelectrolyte effect of a model polyzwitterion at the single-chain level and from the point of view of comparison with inorganic salts and organic inner salts. A well-defined polymer of sulfobetaine was synthesized and fluorescently labeled. Fluorescence correlation spectroscopy was adopted to probe diffusion and chain size of polyzwitterion single chains in extremely dilute aqueous solutions over a broad concentration range of added salts. By the introduction of inorganic salts and organic inner salts, the single chains of polyzwitterions expanded with an increase of salt concentration. This observation indicates that the break-up of the dipole-dipole attraction between the zwitterion units is the mechanism of the anti-polyelectrolyte effect of polyzwitterions. The difference in the strength of the anti-polyelectrolyte effect induced by inorganic salts and organic inner salts also indicates the partial contribution from the asymmetric adsorption of ions onto polyzwitterion chains.

A self-healing hydrogel is prepared by crosslinking acrylamide with a host-guest macro-crosslinker assembled from poly(β-cyclodextrin) nanogel and azobenzeneacrylamide. The photoisomerizable azobenzene moiety can change its binding affinity with β-cyclodextrin, therefore the crosslinking density and rheology property of the hydrogel can be tuned with light stimulus. The hydrogel can repair its wound autonomously through the dynamic host-guest interaction. In addition, the wounded hydrogel will lose its ability of self-healing when exposed to ultraviolet light, and the self-healing behavior can be recovered upon the irradiation of visible light. The utilizing of host-guest macro-crosslinking approach manifests the as-prepared hydrogel reversible and light-switchable self-healing property, which would broaden the potential applications of self-healing polymers.

The molecular conformation of two typical polyelectrolytes, sodium polystyrene sulfonate (NaPSS) and quarternized poly-4-vinylpyridine (QP4VP), was studied in aqueous solutions without salt addition at the single molecular level. By fluorescence correlation spectroscopy, the hydrodynamic radius (R) of NaPSS and QP4VP with the molecular weight ranging more than one order of magnitude was measured. The scaling analysis of R exhibits scaling exponent of 0.70 and 0.86 for NaPSS and QP4VP in solutions without added salts, respectively, showing the conformation is much more expanded than random coil. Numerical fittings using the model of diffusion of a rod molecule agree with the data well, indicating that the polyelectrolyte chains take the rod-like conformation under the condition without salt addition. Further investigations by determining the electric potential of single PSS chains using the photon counting histogram technique demonstrate the enhanced counterion adsorption to the charged chain at higher molecular weight.

Recent advancements in electronics engineering require materials with the resiliency and sustainability to extend their life time. With this regard, we presented a sustainable multi-functional nanocomposites strategy by introducing dynamic imine bonds based polyazomethine (PAM) as molecular interconnects and Fe3O4-loaded multiwalled carbon nanotubes as electromagnetic (EM) wave absorbing units. Driven by the reversible dynamic imine bonds, our materials show robust spontaneous selfhealing with excellent healing efficiencies of 95 % for PAM and 90 % for nanocomposite, and an accelerated recovery under a moderate mechanical stimulus. By adding Fe3O4-loaded multiwalled carbon nanotubes, the hybrids show excellent EM wave absorbing properties with 50% increment on minimum reflection coefficient (-40.6 dB) than the reported value. We demonstrate a full degradability by decomposing a nanocomposite sheet of 100 mg in an acidic solution within 90 min at room temperature. The nanofillers and monomers after degradation can be re-used to synthesis nanocomposites. The testing results for recoverable nanocomposites show a good retention on mechanical property. This novel strategy may shed a light on the downstream applications in EM wave absorbing devices and smart structures with great potential to accelerate circular economy.

Aldrich) and palladium on activated carbon powder (Pd/C, 10%, Alfa Aesar) were used as received. Amino end-terminated polystyrene (PS) (M n = 120 × 10 3 g⋅mol −1 , M w /M n = 1.05) and amino end-terminated poly(N-isopropylacrylamide) (PNIPAM, M n = 7.1 × 10 3 g⋅mol −1 , M w /M n = 1.29) were purchased from Polymer Source (Quebéc, Canada). Water was purified with a Millipore system (18.2 MΩ•cm −1 ). All other chemical reagents were analytical grade and used as received without further purification. Spectral Characterizations:1 H nuclear magnetic resonance (NMR) spectra were measured with a Bruker DMX400 spectrometer with CDCl 3 or DMSO-d 6 as the solvent and tetramethylsilane (TMS) as the internal standard. A size exclusive chromatography (SEC) system equipped with a Waters 515 HPLC pump, three Waters Styragel columns (HT2, HT4, and HT5), a Rheodyne 7725i sampler, and a Waters 2414 refractive-index (RI) detector was adopted to determine the average molecular weights and molecular weight distribution of the polystyrene samples. Linear polystyrene standards were used to calibrate the SEC system. The eluent was DMF with 0.02 M LiBr at a flow rate of 1.0 mL⋅min −1 at 50 ºC. The pH value of the polymer solution was measured by a pH meter (Mettler-Toledo, Delta 320).

Thiol-terminated polymers poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC-SH), poly(N,N-isopropylacrylamide) (PNIPAM-SH), and poly(tert-butyl acrylate) (PtBA-SH) were synthesized, and the polymers were grafted on the gold surfaces of quartz crystal microbalance with dissipation (QCM-D) and surface plasmon resonance (SPR) sensor chips to form brushes. The grafting process of the polymer brushes as well as protein adsorption onto the brush layers was monitored by in situ QCM-D and SPR techniques. By examining the changes in frequency and dissipation factor as well as the value of ∂D/∂f from QCM-D measurements, different stages of the polymer grafting and protein adsorption are distinguished. The most interesting discovery is the conformation change of BSA protein adsorption from a weakly adsorbed native state to a strongly immobilized denatured state on the polymer brushes. The corresponding change in BSA adsorption from a reversible state to an irreversible state was confirmed by SPR measurements. The adsorption of protein on the polymer brushes' surface relies largely on interaction between the protein and the polymers, and the stronger hydrophilicity of the surfaces is proved to be more effective to suppress the protein adsorption. Analysis of the D-f plot of QCM-D measurements helps to characterize different binding strength of protein and the underlying polymer surface.

Using sodium polystyrene sulfonate (NaPSS) and quarternized poly 4-vinylpyridine (QP4VP) as model systems, the chain conformation of polyelectrolytes under finite salt concentrations is investigated at a single molecular level. By fluorescence correlation spectroscopy (FCS), the hydrodynamic radius (Rh) of the samples with the molecular weight ranging more than one order of magnitude was measured. The variations of Rh as a function of molecular weight reveal the molecular weight dependence: under moderate salt concentrations (such as 10−4 and 0.1M), the shorter chains of both NaPSS and QP4VP take the rod-like conformation, while the longer chains take the coiled conformation (random coil or swelled random coil conformation, respectively). At high enough salt levels, both the charged chains take the coiled conformations. Photon counting histogram (PCH) measurements of the local pH value at the vicinity of the NaPSS chain expose the higher extent of counterion adsorption for longer chains as well as higher salt concentrations, telling that the charge regularization process is the major governing factor.