Artificial macromolecules are well-defined synthetic polymers, with a relatively simple structure as compared to naturally occurring macromolecules. This review focuses on the ion specificities of artifical macromolecules. Ion specificities are influenced by solvent-mediated indirect ion–macromolecule interactions and also by direct ion–macromolecule interactions. In aqueous solutions, the role of water-mediated indirect ion–macromolecule interactions will be discussed. The addition of organic solvents to aqueous solutions significantly changes the ion specificities due to the formation of water–organic solvent complexes. For direct ion–macromolecule interactions, we will discuss specific ion-pairing interactions for charged macromolecules and specific ion–neutral site interactions for uncharged macromolecules. When the medium conditions change from dilute solutions to crowded environments, the ion specificities can be modified by either the volume exclusion effect, the variation of dielectric constant, or the interactions between ions, macromolecules, and crowding agents.

Like natural enzymatic systems, our study has demonstrated that the activity of the polymeric organocatalysts can be modulated by ion-specific effects via the combination of anion-specific salting-in/out effects and anion-specific polarization of hydrogen bonding induced stabilization of the transition state.

Both ion-specific interaction and carbon spacer length have strong effects on the properties of polyzwitterions. In this work, we have investigated the anion specificity of poly(sulfobetaine methacrylamide) (PSBMAm) brushes with different carbon spacer lengths. The effectiveness of anions to enhance the hydration of the PSBMAm brushes increases from kosmotropic to chaotropic anions. The interactions between the anions and the PSBMAm brushes are strongly influenced by carbon spacer length because the strength of inter/intrachain association of the PSBMAm brushes decreases with increasing carbon spacer length. The inter/intrachain association of the PSBMAm brushes with a longer carbon spacer is easier to break by the external anions in the high salt concentration regime. On the other hand, a longer carbon spacer is more favorable for the zwitterionic groups to form cyclic intramolecular structures. As a result, the addition of anions can more effectively enhance the hydration of the PSBMAm brushes with a medium-length carbon spacer compared with that of the PSBMAm brushes with a either shorter or longer carbon spacer in the low salt concentration regime, determined by the balance between the inter/intrachain association and the formation of cyclic intramolecular structures. Our study also demonstrates that both anion identity and carbon spacer length can be used to control protein adsorption on the surface of the PSBMAm brushes.

The electrolysis of aqueous solutions produces solutions that are supersaturated in oxygen and hydrogen gas. This results in the formation of gas bubbles, including nanobubbles ∼100 nm in size that are stable for ∼24 h. These aqueous solutions containing bubbles have been evaluated for cleaning efficacy in the removal of model contaminants bovine serum albumin and lysozyme from surfaces and in the prevention of the fouling of surfaces by these same proteins. Hydrophilic and hydrophobic surfaces were investigated. It is shown that nanobubbles can prevent the fouling of surfaces and that they can also clean already fouled surfaces. It is also argued that in practical applications where cleaning is carried out rapidly using a high degree of mechanical agitation the role of cleaning agents is not primarily in assisting the removal of soil but in suspending the soil that is removed by mechanical action and preventing it from redepositing onto surfaces. This may also be the primary mode of action of nanobubbles during cleaning.

Macromolecular crowding plays a significant role in the solubility and stability of biomacromolecules. In this work, the thermo-sensitive poly(N-isopropylacrylamide) (PNIPAM) has been employed as a model system to study the specific ion effects on the solubility of macromolecules in crowded environments of dextran and polyethylene glycol (PEG). Our study demonstrates that crowding agents can interact with either anions or PNIPAM chains. The chaotropic anion SCN− interacts with dextran but does not interact with PEG. Both Cl− and CH3COO− do not interact with dextran and PEG. On the other hand, dextran can interact with PNIPAM as a hydrogen-bond donor, whereas PEG interacts with PNIPAM as a hydrogen-bond acceptor. The salting-in effect exerted by SCN− on PNIPAM is weakened in the crowded environment of dextran but is strengthened in the crowded environment of PEG due to the distinct anion-crowder interactions. In parallel, the salting-out effect generated by Cl− and CH3COO− on PNIPAM is weakened by the crowding of dextran but is strengthened by the crowding of PEG because of the different macromolecule–crowder interactions. Our study reveals that the ion specificity of macromolecules is altered significantly changing from dilute solutions to crowded environments.

Protein adsorption is an important issue in biorelated fields. We have investigated the protein adsorption on the poly(ionic liquid) (PIL) brushes in the presence of different types of counterions. The protein adsorption is driven by a decrease in osmotic pressure within the brushes with an increase in entropy via the release of counterions. Our study demonstrates that counterion specificity has a significant influence on protein adsorption on the PIL brushes. There have been two different regimes for counterion-specific protein adsorption. When the released counterions cannot bind to the protein surface, the counterion-specific protein adsorption is dominated by the ion-specific counterion condensation within the PIL brushes. If the released counterions can bind to the protein surface, then counterion-specific protein adsorption is dominated by the ion-specific rebinding of released counterions on the protein surface. This work opens up a new opportunity for controlling protein adsorption on polyelectrolyte brushes.

We have investigated the interactions between the positively charged poly[2-(methacryloyloxy)ethyltrimethylammonium chloride] (PMETAC) brushes and the Hofmeister anions and the interactions between the negatively charged poly(3-sulfopropyl methacrylate potassium) (PSPMA) brushes and the Hofmeister cations using a combination of quartz crystal microbalance with dissipation and spectroscopic ellipsometry. A V-shaped anion series is observed in terms of the ion-specific interactions between the PMETAC brushes and the Hofmeister anions. We have found that the chaotropic and kosmotropic anions interact with the PMETAC brushes in different manners. The ion-specific interactions between the PMETAC brushes and the chaotropic anions are dominated by the direct interactions between the anions and the positively charged quaternary ammonium group via ion pairing mediated by ionic hydration strength or polarizability, whereas the ion-specific interactions between the PMETAC brushes and the kosmotropic anions are dominated by the competition for water molecules between the anions and the brushes. The ion-specific interactions between the PMETAC brushes and the anions have significant influences on both the hydration and the conformation of the brushes. The cations exhibit weaker specific ion effects on the PSPMA brushes in comparison with the specific anion effects on the PMETAC brushes.

A facile method to prepare a self-healing polymeric material with tunable mechanical properties is developed. The material has a remarkable self-healing efficiency via the formation of multiple dynamic hydrogen bonds. It can resist the corrosion of various organic solvents and can also be readily processed into a range of shapes.

We have investigated changes in the cation-specific conformational behavior of poly(sodium styrenesulfonate) (PSS) brushes as the solvent changes from water to methanol using a quartz crystal microbalance with dissipation (QCM-D). A solvation to desolvation transition of the grafted chains accompanied by swelling to the collapse transition of the brushes is observed for Na+. In the case of Cs+, the brushes undergo solvation to desolvation to resolvation accompanied by swelling to collapse to reswelling transitions. The resolvation and reswelling transitions for Cs+ are induced by the charge inversion of the brushes via van der Waals interactions between Cs+ and the brushes. All of the transitions for monovalent cations become less obvious as the methanol content increases. For divalent Ca2+ and trivalent La3+, a solvation to desolvation to resolvation transition of the grafted chains accompanied by a swelling to collapse to reswelling transition of the brushes can be observed. The resolvation and reswelling of the brushes for the multivalent cations are induced by the charge inversion of the brushes via charge-image charge interactions. The extent of the transitions for the PSS brushes in the presence of multivalent cations is only slightly influenced by the methanol content.

We have demonstrated that Hofmeister effect can be amplified by adding alcohols to aqueous solutions. The lower critical solution temperature behavior of poly(N-isopropylacrylamide) has been employed as the model system to study the amplification of Hofmeister effect. The alcohols can more effectively amplify the Hofmeister effect following the series methanol < ethanol < 1-propanol < 2-propanol for the monohydric alcohols and following the series d-sorbitol ≈ xylitol ≈ meso-erythritol < glycerol < ethylene glycol < methanol for the polyhydric alcohols. Our study reveals that the relative extent of amplification of Hofmeister effect is determined by the stability of the water/alcohol complex, which is strongly dependent on the chemical structure of alcohols. The more stable solvent complex formed via stronger hydrogen bonds can more effectively differentiate the anions through the anion–solvent complex interactions, resulting in a stronger amplification of Hofmeister effect. This study provides an alternative method to tune the relative strength of Hofmeister effect besides salt concentration.

Ethanol (EtOH) and dimethylsulfoxide (DMSO) are polar protic and aprotic organic solvents, respectively. In the present work, we have investigated the anion-specific lower critical solution temperature (LCST) and upper critical solution temperature (UCST) behaviors of poly(N-isopropylacrylamide) (PNIPAM) in the H2O–EtOH and H2O–DMSO mixtures. The turbidity and differential scanning calorimetry studies show that the LCST for the anions follows the Hofmeister series at the molar fraction of EtOH (xE) or DMSO (xD) of 6%. At xE of 26%, the UCST for the anions also follows the Hofmeister series because the dominating interactions for the UCST behavior are similar to that for the LCST behavior in the H2O–EtOH mixtures. In the H2O–DMSO mixture at xD of 70%, an inverted V-shaped anion series is observed for the UCST behavior of PNIPAM. Our studies demonstrate that the specific anion effect on the phase transition behaviors of PNIPAM is influenced not only by the anionic polarization of hydrogen bonding between solvent molecules and PNIPAM but also by the anion adsorption on the PNIPAM chain surface.

The conformation of polyzwitterionic brushes plays a crucial role in the adsorption/desorption of proteins on solid surfaces. By use of quartz crystal microbalance with dissipation (QCM-D) and surface plasmon resonance (SPR), we have systematically investigated the conformational behavior of poly(sulfobetaine methacrylate) (PSBMA) brushes as a function of ionic strength in the presence of different ions. The frequency change demonstrates that the effectiveness of anions to weaken the inter/intrachain association and to enhance the hydration of the grafted chains increases from kosmotrope to chaotrope in the low ionic strength regime, but the ordering of anions is almost reversed at the high ionic strengths. The dissipation change indicates that some heterogeneous structures are formed inside the brushes in the presence of chaotropic anions with the increase of ionic strength. In SPR studies, the change of resonance unit (ΔRU) with ionic strength is determined by the balance between the increase of thickness and the decrease of refractive index of the brushes. No anion specificity is observed in the SPR measurements because ΔRU is insensitive to the coupled water molecules inside the brushes. For the control of protein adsorption/desorption, our studies show that the brushes can more effectively resist the protein adsorption in the presence of a more chaotropic anion and a more chaotropic anion can also more effectively induce the protein desorption from the surface of the brushes. In addition, no obvious cation specificity can be observed in the conformational change of the brushes in either QCM-D or SPR measurements.

By use of a quartz crystal microbalance with dissipation (QCM-D), we have investigated the specific ion effect on the growth of poly(sodium 2-acrylamido-2-methylpropanesulfonate)/poly(diallyldimethylammonium chloride) multilayer at a salt concentration as low as 2.0 mM in water–methanol mixtures. QCM-D results demonstrate that specific ion effect can be observed in methanol and water–methanol mixtures though it is negligible in water. Moreover, the specific ion effect is amplified as the molar fraction of methanol (xM) increases from 0% to 75% but is weakened again with the further increase of xM from 75% to 100%. Nuclear magnetic resonance measurements reveal that the counterion–polyelectrolyte segment interactions may not account for the observed ion specificity. By extending the Collins’ concept of matching water affinities to methanol and water–methanol mixtures, we suggest that the ion–solvent interactions and the resulted counterion–charged group interactions are responsible for the occurrence of the specific ion effect. The conductivity measurements indicate that water and methanol molecules may form complexes, and the change of relative proportion of complexes with the xM causes the amplification or weakening of the specific ion effect.

In the present work, we have successfully fabricated a polyelectrolyte-tethered transparent surface on which superhydrophobicity and superhydrophilicity can be reversibly switched via counterion exchange between the chloride ion (Cl–) and perfluorooctanoate ion (PFO–). The stable superhydrophobic state can be obtained only when a certain extent of fluorine is chemically incorporated into the grafted polyelectrolyte. The counterion exchange does not have any influence on the transmittance of the transparent surface. The superhydrophobicity and superhydrophilicity can be reversibly switched on the surface for many cycles without any apparent damage to the wetting properties. Additionally, the transparent surface can be applied to prepare smart glass displays to hide and convey information by patterning the counterion distribution on the surface on the basis of the different antifogging properties between superphydrophobic and superhydrophilic surfaces.

Ethylene glycol (EG) and hydrogen peroxide (H2O2) can act as both hydrogen-bond donors and acceptors in the formation of solvent complexes with water molecules. In the present work, we have systematically investigated the ion-specific lower critical solution temperature (LCST) behavior of poly(N-isopropylacrylamide) (PNIPAM) in H2O–EG and H2O–H2O2 mixtures. The results obtained from turbidity measurements show that the specific anion effect is amplified with the increasing molar fraction of EG (xEG) but is independent of the molar fraction of H2O2 (xH2O2). The studies of Raman spectra and differential scanning calorimetry indicate that the discrepancy in amplification of specific anion effect between H2O–EG and H2O–H2O2 mixtures is due to the difference in the anion–solvent complex interactions rather than the anion–polymer or solvent–polymer interactions. On the other hand, the specific cation effect can also be amplified with the increasing xEG but changes only slightly with the xH2O2. The discrepancy in amplification of specific cation effect between the two types of solvent mixtures is attributed to the difference in the solvent–polymer interactions.

In the present study, by use of the atom transfer radical polymerization (ATRP) method, we have prepared well-defined 6-arm star-shaped poly[2-(dimethylamino)ethyl methacrylate] (PDEM) and poly(acrylic acid) (PAA) containing a fluorescent triphenylene core and have studied the pH and ion-species sensitive fluorescence properties of such two star polyelectrolytes. The results obtained by analytical ultracentrifugation indicate that the star PDEM molecules will aggregate together as the pH increases over the pKa but the star PAA molecules will keep a monomeric state over the whole pH range. For both PDEM and PAA, the fluorescence intensity decreases with increasing pH, indicating that the fluorescence intensities of PDEM and PAA are dominated by aggregation induced fluorescence quenching and the chain conformation controlled nonradiative relaxation, respectively. This suggestion is further confirmed by the fact that the star PDEM molecules can form excimers at high pHs and no excimer emission peak can be observed for the star PAA molecules. In the studies of ion-specific fluorescence properties at different pH, for both of the two polyelectrolytes, the ion specificity is determined by the counterion condensation for the charged chains, whereas nonelectrostatic ion adsorption governs the specific ion effect for the uncharged chains.

We have systematically investigated the effect of surface wettability on ion-specific adsorption of bovine serum albumin (BSA) by using quartz crystal microbalance with dissipation (QCM-D) and surface plasmon resonance (SPR). The changes in frequency (Δf) and resonance unit (ΔRU) show a nonmonotonous change of the adsorbed amount of BSA as a function of molar fraction of 1-dodecanethiol (xDDT) of the self-assembled monolayer at pH 3.8, while the amount of adsorbed protein gradually increases with the xDDT at pH 7.4. The small changes of dissipation (ΔD) indicate that BSA molecules form a quite rigid protein layer on the surfaces, which results in only a slight difference in the adsorbed mass between the mass-uptake estimations from the Sauerbrey equation and the Voigt model. The difference in the adsorbed mass between QCM-D and SPR measurements is attributed to the coupled water in the protein layer. On the other hand, specific anion effect is observed in the BSA adsorption at pH 3.8 with the exception of the surface at xDDT of 0%, but no obvious cation specificity can be observed at pH 7.4. The ΔD–Δf plots show that the BSA adsorption at pH 3.8 has two distinct kinetic processes. The first one dominated by the protein–surface interactions is an anion-nonspecific process, whereas the second one dominated by the protein structural rearrangements is an anion-specific process. At pH 7.4, the second kinetic process can only be observed at the relatively hydrophobic surfaces, and no cation specificity is observed in the first and second kinetic processes.

Poly(sodium 4-styrene sulfonate) (PSS) and poly(diallyldimethylammonium chloride) (PDDA) are flexible polyelectrolytes, whereas sulfated chitosan (SC) and cationic guar gum (CGG) are semiflexible polyelectrolytes. By use of a quartz crystal microbalance with dissipation (QCM-D), a zeta potential analyzer (ZPA), and atomic force microscopy (AFM), we have investigated the growth of PSS/PDDA, PSS/CGG, SC/PDDA, and SC/CGG multilayers as a function of NaCl concentration (CNaCl). For the same layer number, the changes of frequency (−Δf) and dissipation (ΔD) regarding PSS/PDDA multilayer increase with CNaCl, whereas −Δf and ΔD for SC/CGG multilayer increase at CNaCl < 0.1 M and decrease at CNaCl > 0.1 M as CNaCl increases. In the cases of PSS/CGG and SC/PDDA multilayer, for the same layer number, −Δf and ΔD increase with CNaCl in the range of CNaCl < 0.5 M, and they decrease with the increasing CNaCl in the case of SC/PDDA multilayer but slightly change for the PSS/CGG multilayer at CNaCl > 0.5 M. QCM-D studies indicate that the growth of multilayers as a function of salt concentration is determined by the delicate balance between the weakening of electrostatic repulsion between identically charged groups and the decrease of electrostatic attraction between neighboring layers. ZPA and AFM measurements demonstrate that the extent of surface charge overcompensation and the surface morphology of the multilayers are controlled by the chain conformation.

In the present work, we have for the first time systematically investigated the ion specific reentrant behavior of poly(N-isopropylacryamide) (PNIPAM) in water–methanol mixtures. Turbidity measurements demonstrate that SCN– and ClO4– depress the reentrant transition, whereas other anions enhance the transition. As the anion changes from chaotropic to kosmotropic, the minimum critical phase transition temperature (Tmin) decreases and the corresponding volume fraction of methanol (XM) shifts to a larger value. Our results demonstrate that anion specificity is due to the anionic structure making/breaking effect on water/methanol complexes. Cations are found to have a lesser but still significant effect on the reentrant transition, and as Tmin decreases the corresponding XM also shifts to larger values as with the anions. Our studies show that cation specificity is induced by specific interactions between cations and PNIPAM chains. Furthermore, both anion and cation specificities are amplified as XM is increased due to the formation of additional water/methanol complexes. Calorimetry measurements demonstrate that the ion specificity is dominated by changes in entropy.

Interfacial water structure at charged surfaces plays a key role in many physical, chemical, biological, environmental, and industrial processes. Understanding the release of interfacial water from the charged solid surfaces during dehydration process may provide insights into the mechanism of protein folding and the nature of weak molecular interactions. In this work, sum frequency generation vibrational spectroscopy (SFG-VS), supplemented by quartz crystal microbalance (QCM) measurements, has been applied to study the interfacial water structure at polyelectrolyte covered surfaces. Poly[2-(dimethylamino)ethyl methacrylate] (PDMAEMA) chains are grafted on solid surfaces to investigate the change of interfacial water structure with varying surface charge density induced by tuning the solution pH. At pH ≤ 7.1, SFG-VS intensity is linear to the loss of mass of interfacial water caused by the dehydration of PDMAEMA chains, and no reorientation of the strongly bonded water molecules is observed in the light of χppp/χssp ratio. χ(3) contribution to SFG signal is deduced based on the combination of SFG and QCM results. It is the first direct experimental evidence to reveal that the χ(3) has a negligible contribution to SFG signal of the interfacial water at a charged polymer surface.

We have investigated the influence of number of arms on chain interpenetration in the growth of star poly[2-(dimethylamino)ethyl methacrylate] (PDEM)/star poly(acrylic acid) (PAA) multilayers using a quartz crystal microbalance with dissipation (QCM-D). The oscillations in the changes of dissipation and frequency reflect the chain interpenetration and the variation of the mass of multilayer, respectively. The QCM-D results demonstrate that the growth of multilayers has two different mechanisms in terms of chain interpenetration. That is, the arm chains of star PDEM insert into a predeposited PAA layer to form a swollen multilayer, but the complex of star PAA with predeposited star PDEM is an “octopus-like” structure forming a dense multilayer. The transition between these two penetration modes is controlled by the number of arms in the star polyelectrolytes. As the number of arms of either PAA or PDEM increases, it becomes more difficult for star PDEM to penetrate into the PAA layer, but star PAA can more easily penetrate into the PDEM layer. According to atomic force microscopy and water contact angle measurements, all eight-bilayer multilayer surfaces have similar roughness values, and the surface wettability of the multilayers is dominated by the outermost PDEM layer.

Poly[(2-dimethylamino)ethyl methacrylate] (PDEM) is completely charged, partially charged, and uncharged at pH 4, 7, and 10, respectively. We have investigated the salt effects on the conformational change of PDEM chains grafted on a surface at different pH by using quartz crystal microbalance with dissipation (QCM-D) and surface plasmon resonance (SPR). The changes in frequency (Δf) and dissipation (ΔD) in QCM-D measurements demonstrate that the conformational behavior is governed by counterion condensation at pH 4 and 7 but by nonelectrostatic anion adsorption at pH 10. The addition of Na2SO4 induces more collapse of the grafted layer than that of NaClO3 at pH 4 and 7. However, they have a similar effect at pH 10. The shift of resonance unit (ΔRU) in SPR measurements reflects the changes of layer thickness and layer refractive index. At pH 4, ΔRU decreases with ionic strength in the presence of Na2SO4, indicating the decrease of layer thickness or the chain collapse. However, ΔRU exhibits a minimum as the ionic strength increases in the case of NaClO3. This is because the effects of the layer thickness and refractive index are dominant in the low and high ionic strength regimes, respectively. At pH 7, ΔRU slightly varies with ionic strength in the case of either Na2SO4 or NaClO3, indicating that the effects of the layer thickness and refractive index are comparable during the layer collapse. At pH 10, the shift in ΔRU suggests that the nonelectrostatic anion adsorption governs the conformational behavior of the PDEM chains.

Like natural enzymatic systems, our study has demonstrated that the activity of the polymeric organocatalysts can be modulated by ion-specific effects via the combination of anion-specific salting-in/out effects and anion-specific polarization of hydrogen bonding induced stabilization of the transition state.

A facile method to prepare a self-healing polymeric material with tunable mechanical properties is developed. The material has a remarkable self-healing efficiency via the formation of multiple dynamic hydrogen bonds. It can resist the corrosion of various organic solvents and can also be readily processed into a range of shapes.