Improving physical properties of poly(vinyl alcohol)/montmorillonite nanocomposite hydrogels via the Hofmeister effect

Hydrogel is a kind of three-dimensional crosslinked polymer material with high moisture content.However,due to the network defects of polymer gels,traditional hydrogels are usually brittle and fragile,which limits their practical applications.Herein,we present a Hofmeister effect-aided facile strategy to prepare high-performance poly(vinyl alcohol)/montmorillonite nanocomposite hydrogels.Layered montmorillonite nanosheets can not only serve as crosslinking agents to enhance the mechanical properties of the hydrogel but also promote the ion conduction.More importantly,based on the Hofmeister effect,the presence of(NH_(4))_(2)SO_(4)can endow nanocomposite hydrogels with excellent mechanical properties by affecting PVA chains'aggregation state and crystallinity.As a result,the as-prepared nanocomposite hydrogels possess unique physical properties,including robust mechanical and electrical properties.The as-prepared hydrogels can be further assembled into a high-performance flexible sensor,which can sensitively detect large-scale and small-scale human activities.The simple design concept of this work is believed to provide a new prospect for developing robust nanocomposite hydrogels and flexible devices in the future.

Highly Flexible and Broad‑Range Mechanically Tunable All‑Wood Hydrogels with Nanoscale Channels via the Hofmeister Effect for Human Motion Monitoring

Wood-based hydrogel with a unique anisotropic structure is an attractive soft material,but the presence of rigid crystalline cellulose in natural wood makes the hydrogel less flexible.In this study,an all-wood hydrogel was constructed by cross-linking cellulose fibers,polyvinyl alcohol(PVA)chains,and lignin molecules through the Hofmeister effect.The all-wood hydrogel shows a high tensile strength of 36.5 MPa and a strain up to~438%in the longitudinal direction,which is much higher than its tensile strength(~2.6 MPa)and strain(~198%)in the radial direction,respectively.The high mechanical strength of all-wood hydrogels is mainly attributed to the strong hydrogen bonding,physical entanglement,and van der Waals forces between lignin molecules,cellulose nanofibers,and PVA chains.Thanks to its excellent flexibility,good conductivity,and sensitivity,the all-wood hydrogel can accurately distinguish diverse macroscale or subtle human movements,including finger flexion,pulse,and swallowing behavior.In particular,when“An Qi”was called four times within 15 s,two variations of the pronunciation could be identified.With recyclable,biodegradable,and adjustable mechanical properties,the all-wood hydrogel is a multifunctional soft material with promising applications,such as human motion monitoring,tissue engineering,and robotics materials.

Salt Specific Interaction Between RepresentativeHofmeister Salts and Glycine

Traditionally,Hofmeister effect was understood on the basis of hydration abilities of ions.Recent studies found short-range structuring effects of ions on water which shifted the attention from ion-water interaction to ion-protein interaction.In this study,ATR-FTIR spectroscopy at different RH is used to study the effect of a representative Kosmotrope(MgSO4),Chaotrope(NH4NO3)and neutral(KCl)salt on glycine.The salting out,salting in and neutral effects of salts on glycine are found aligned with Hofmeister effect.Interestingly,direct interaction of kosmotrope anion(SO2-4)with the glycine is observed experimentally which validates the recent idea of ion-protein interaction.Further detailed studies will be needed for deeper insight.

A theoretical exploration of the influencing factors for surface potential

Although it has been widely used to probe the interracial property, dynamics, and reactivity, the surface potential remains intractable for directly being measured, especially for charged particles in aqueous solutions. This paper presents that the surface potential is strongly dependent on the Hofmeister effect, and the theory including ion polarization and ionic correlation shows significant improvement compared with the classical theory. Ion polarization causes a strong Hofmeister effect and further dramatic decrease to surface potential, especially at low concentration; in contrast, ionic correlation that is closely associated with potential decay distance overestimates surface potential and plays an increasing role at higher ionic concentrations. Contributions of ion polarization and ionic correlation are respectively assessed, and a critical point is detected where their contributions can be exactly counteracted. Ionic correlation can be almost neglected at low ionic concentrations, while ion polarization, albeit less important at high concentrations, should be considered across the entire concentration range. The results thus obtained are applicable to other interfacial processes.

Hofmeister Effect-Assisted Strong Natural Biopolymer-Based Hydrogels with Multi-Functions

Natural biopolymer-based hydrogels have been extensively studied in recent years due to their excellent biocompatibility.However,the preparation of multi-functional and tough natural biopolymer-based hydrogels is still a challenging problem.Herein,a natural biopolymer-based hydrogel is prepared using gelatin and carboxymethyl chitosan(CMCS)through a one-step soaking method.The prepared hydrogel without any synthetic polymers and crosslinking agents has a fully physical crosslinking structure.Due to the hydrophobic interaction brought by the Hofmeister effect,the mechanical properties of soaked hydrogels(tensile stress and strain can reach 3.77 MPa and 1082%)are superior to conventional protein hydrogels.In addition,the prepared gelatin/carboxymethyl chitosan(Gel/CMCS)hydrogels exhibit a variety of appealing properties,including good shape memory,fatigue resistance,electrical conductivity,water retention,drug releasing,antibacterial property,and recyclability.This strategy opens up a new horizon to fabricate hydrogels with excellent mechanical properties and multiple functions,which can extend their applications in the biomedicine area and other related fields.

Hofmeister Effect on Thermo-responsive Poly(N-isopropylacrylamide)Hydrogels Grafted on Macroporous Poly(vinyl alcohol) Formaldehyde Sponges

In this work,the Hofmeister effects of nine kinds of anions at different concentrations on the lower critical solution temperature(LCST)of the macroporous thermo-responsive poly(N-isopropylacrylamide)grafted poly(vinyl alcohol)formaldehyde(PVF-g-PNIPAM)hydrogels are investigated with differential scanning calorimetry(DSC).Four kinds of anions with strong hydration,including CO3^2–,SO4^2–,S2 O3^2–,and F^–,and four kinds of anions with weak hydration,including Br^–,NO3^–,I^–,and ClO4^–,and Cl^–as a medium anion are systematically studied and found to demonstrate the effects of the residual hydroxyl groups and network structure of PVF on the LCST values of PVF-g-PNIPAM hydrogels in comparison with that of neat PNIPAM.On the one hand,the existence of hydroxyl groups on PVF backbone promotes the solubility of grafted PNIPAM due to their hydrophilicity and hydrogen-bond interactions with water.On the other hand,the network structure of as-prepared samples restricts free movements of grafted PNIPAM chains,which results in the increase of LCST values.In addition,the difference of grafting percentage also influences the variation of LCST values of PVF-g-PNIPAM hydrogels under salt concentration.

Muscle-inspired ion-sensitive hydrogels with highly tunable mechanical performance for versatile industrial applications

Human muscles are notably toughened or softened with specific inorganic ions.Inspired by this phenomenon,herein we report a simple strategy to endow hydrogels with comparable ion-responsive mechanical properties by treating the gels with different ionic solutions.Semi-crystalline poly(vinyl alcohol)hydrogels are chosen as examples to illustrate this concept.Similar to muscles,the mechanical property of hydrogels demonstrates strong dependence on both the nature and concentration of inorganic ions.Immersed at the same salt concentration,the hydrogels treated with different ionic solutions manifest a broad-range tunability in rigidity(Young’s modulus from 0.16 to 9.6 MPa),extensibility(elongation ratio from 100% to 570%),and toughness(fracture work from 0.82 to 35 MJm^(-3)).The mechanical property well follows the Hofmeister series,where the“salting-out”salts(kosmotropes)have a more pronounced effect on the reinforcement of the hydrogels.Besides,the hydrogels’mechanical performance exhibits a positive correlation with the salt concentration.Furthermore,it is revealed both the polymer solubility from amorphous domains and polymer crystallinity from crystalline domains are significantly influenced by the ions,which synergistically contribute to the salt-responsive mechanical performance.Benefitting from this feature,the hydrogels have demonstrated promising industrial applications,including tunable tough engineering soft materials,anti-icing coatings,and soft electronic devices.

Specific ion effect of H^(+) on variably charged soil colloid aggregation

Specific ion effects(Hofmeister effects)have recently attracted the attention of soil scientists,and it has been found that ionic non-classic polarization plays an important role in the specific ion effect in soil.However,this explanation cannot be applied to H+.The aim of this work was to characterize the specific ion effect of H+on variably charged soil(yellow soil)colloid aggregation.The total average aggregation(TAA)rate,critical coagulation concentration(CCC),activation energy,and zeta potential were used to characterize and compare the specific ion effects of H+,K+,and Na+.Results showed that strong specific ion effects of H+,K+,and Na+existed in variably charged soil colloid aggregation.The TAA rate,CCC,and activation energy were sensitive to H+,and the addition of a small amount of H+changed the TAA rate,CCC,and activation energy markedly.The zeta potential results indicated that the specific ion effects of H+,K+,and Na+on soil colloid aggregation were caused by the specific ion effects of H+,K+,and Na+on the soil electric field strength.In addition,the origin of the specific ion effect for H+was its chemical adsorption onto surfaces,while those for alkali cations were non-classic polarization.This study indicated that H+,which occurs naturally in variably charged soils,will dominate variably charged soil colloid aggregation.