Inducing pH responsiveness via ultralow thiol content in polyacrylamide (micro)gels with labile crosslinks

Here we present the synthesis and characterization of pH responsive polyacrylamide microgels, synthesized via free radical polymerization of acrylamide and bis (acryloylcystamine) (BAC). The gels were made with ultralow amounts of thiol functional groups incorporated into the polymer. The resulting gel monoliths were mechanically chopped into microgel particles with size distributions ranging from 80 to 200 mum. The gels exhibit an interesting reversible pH-dependent rheological behavior which led to gelling of the colloidal suspension when the pH was increased, and a low-viscosity suspension was obtained when the pH was taken back to the original value. The viscosity of the colloidal system containing MBA crosslinked microgels remained insensitive to pH. This observation motivated further analysis; viscosity measurements of the highly viscous (gel-like) state of the BAC crosslinked microgel colloidal suspension were carried out to further understand the rheological behavior of the colloidal system. Electrophoretic mobility measurements as function of pH of the BAC and MBA crosslinked colloidal polyacrylamide microgel suspensions were performed. The swelling behavior of the microgels for both colloidal systems was also determined as function of pH using static light scattering. This swelling behavior was used to rationalize the observed rheological behavior. The work presented here demonstrates that free thiol groups present within a polymer gel matrix confer pH responsive behavior to the gel in solution. The viscosity of a BAC crosslinked microgel suspension was also measured under reducing conditions. The viscosity of the microgel suspension reduced with time, due to the breakage of the disulfide bonds in the crosslinkers.     

pH-responsive microgels containing hydrophilic crosslinking co-monomers: shell-exploding microgels through design

pH-responsive microgels are crosslinked polymer colloids that swell when the pH approaches the pK _a of the particles. They have potential application for injectable gels for tissue repair and drug delivery systems. This study focuses on the pH-triggered gelation behaviour of a series of poly (EA/MAA/X) microgels. EA and MAA are ethylacrylate and methacrylic acid. Here, we investigate the effect of crosslinking monomer type (X) on microgel properties. The crosslinking monomers used were poly (ethyleneglycol) dimethacrylate (PEGD), ethyleneglycol dimethacrylate (EGD) and butanediol diacrylate (BDD). The microgel containing PEGD (m-PEGD) is a new system. The microgel containing BDD (m-BDD) was used as a control system. The concentrated microgel dispersions formed physical gels when the pH was increased to 5.3?C6.7, and the polymer volume fractions (? _p ) were above about 0.05. Evidence from photon correlation spectroscopy (PCS) and dynamic rheology was presented for abrupt pH-triggered increases, and then decreases of the hydrodynamic diameters for m-PEGD and the microgel prepared using EGD (m-EGD). This appears to be tuneable through crosslinker structure. An unexpected gelation behaviour, which may involve a new gel state for microgels, was found for m-PEGD dispersions. Uniquely, those dispersions formed gels at pH values less than the microgel's pK _a . This behaviour was linked to an outer-shell electrostatic repulsive interaction. The data point to a phenomenon, whereby the m-PEGD shells appear to explode at pH values above 7.0. The control microgel prepared, using BDD (m-BDD), did not show any evidence of shell fragmentation at any pH. That microgel has potential as a model pH-responsive microgel system in that the properties measured by PCS and rheology agreed well. To probe that system in more detail, the rheological data for m-BDD was analysed using scaling theory. The variation of the storage modulus (G') with ? _p gave a scaling exponent of 2.0.     

Reversible Assembly of Microgels by Metallo-Supramolecular Chemistry

The combination of supramolecular chemistry and soft colloids as microgels represents an ambitious way to develop multi-versatile colloidal assemblies. Hereafter, terpyridine-functionalized poly(N-isopropylacrylamide) (PNiPAM) microgel building blocks are shown to undergo an assemble–freeze–disassemble process. The microgel assemblies, which are controlled by monitoring the attractive and repulsive potentials between the soft colloidal particles, are then frozen by forming inter-particle metal–terpyridine bis-complexes upon addition of the metallic cation (such as Fe^II, Co^II). By oxidation of the metal–terpyridine bis-complex links, the aggregates open up, which is due to the complex dissociation releasing the connected particles in the form of single microgels. We extended our work to the development of 1D filaments and 2D membranes materials made of soft particles connected via supramolecular chemistry.     

Reversible Assembly of Microgels by Metallo‐Supramolecular Chemistry

The combination of supramolecular chemistry and soft colloids as microgels represents an ambitious way to develop multi‐versatile colloidal assemblies. Hereafter, terpyridine‐functionalized poly(N‐isopropylacrylamide) (PNiPAM) microgel building blocks are shown to undergo an assemble–freeze–disassemble process. The microgel assemblies, which are controlled by monitoring the attractive and repulsive potentials between the soft colloidal particles, are then frozen by forming inter‐particle metal–terpyridine bis‐complexes upon addition of the metallic cation (such as Fe^II, Co^II). By oxidation of the metal–terpyridine bis‐complex links, the aggregates open up, which is due to the complex dissociation releasing the connected particles in the form of single microgels. We extended our work to the development of 1D filaments and 2D membranes materials made of soft particles connected via supramolecular chemistry.     

Crystallization behavior of soft, attractive microgels

The equilibrium phase behavior and the dynamics of colloidal assemblies composed of soft, spherical, colloidal particles with attractive pair potentials have been studied by digital video microscopy. The particles were synthesized by precipitation copolymerization of N-isopropylacrylamide (NIPAm), acrylic acid (AAc), and N,N'-methylene bis(acrylamide) (BIS), yielding highly water swollen hydrogel microparticles (microgels) with temperature- and pH-tunable swelling properties. It is observed that in a pH = 3.0 buffer with an ionic strength of 10 mM, assemblies of pNIPAm-AAc microgels crystallize due to a delicate balance between weak attractive and soft repulsive forces. The attractive interactions are further confirmed by measurements of the crystal melting temperatures. As the temperature of colloidal crystals is increased, the crystalline phase does not melt until the temperature is far above the lower critical solution temperature (LCST) of the microgels, in stark contrast to what is typically observed for phases formed due to purely repulsive interactions. The unusual thermal stability of pNIPAm-AAc colloidal crystals demonstrates an enthalpic origin of crystallization for these microgels.     

Monovalent salt enhances colloidal stability during the formation of chitosan/tripolyphosphate microgels

Chitosan micro- and nanoparticles are routinely prepared through ionotropic gelation, where sodium tripolyphosphate (TPP) is added as a cross-linker to dilute chitosan solutions. Despite the wide use of these gel-like particles, their preparation currently relies on trial and error. To address this, we used isothermal titration calorimetry (ITC), dynamic light scattering (DLS), transmission electron microscopy (TEM), and ζ-potential measurements to investigate how the formation, structure, and colloidal stability of chitosan microgels are linked to the molecular interactions that underlie their self-assembly. The strength of the chitosan/TPP interactions was systematically varied through the addition of monovalent salt (NaCl). Remarkably, and contrary to other colloidal systems, this revealed that moderate amounts of NaCl (e.g., 150 mM) enhance the colloidal stability of chitosan/TPP microgels during their formation. This stems from the weakened chitosan/TPP binding, which apparently inhibits the bridging of the newly formed microgels by TPP. The enhanced colloidal stability during the ionic cross-linking process yields microgels with dramatically narrower size distributions, which hitherto have typically required the deacetylation and fractionation of the parent chitosan. Conversely, at high ionic strengths (ca. 500 mM) the chitosan/TPP binding is weakened to the point that the microgels cease to form, thus suggesting the existence of an optimal ionic strength for ionotropic microgel preparation.     

Photo-, thermally, and pH-responsive microgels

Microgels with photo-, thermally, and pH-responsive properties in aqueous suspension have been synthesized and characterized using dynamic light scattering and UV-visible spectroscopy. The new route involved first preparing poly(N-isopropylacrylamide) (PNIPAM)-allylamine copolymer microgels and a spiropyran photochrome (SP) bearing a carboxylic acid group. Then the functionalized spiropyran was coupled to the microgel via an amide bond. The dark-equilibrated gel particles feature spiropyran molecules in the polar, merocyanine form. After irradiation of visible light, the particle size becomes smaller because spiropyran changes to the relatively nonpolar, closed spiro form. The PNIPAM-SP microgels undergo a volume phase transition in water from a swollen state to a collapsed state with increasing temperature under all light conditions. However, the transition temperature range of the PNIPAM-SP is much broader than that for the PNIPAM without SP. The PNIPAM-SP microgels are monodisperse and self-assemble into a crystalline lattice while in suspension. The UV-visible spectra of an aqueous suspension of PNIPAM-SP microgel in the dark-adapted, merocyanine form showed both an absorption peak around 512 nm due to the merocyanine (giving a reddish color to the suspension) and two sharp peaks from Bragg diffraction of colloidal crystallites. Upon visible irradiation, the 512-nm band bleached significantly due to spiropyran photoisomerization. The spiropyran photoisomerization and accompanying color changes of the suspension were reversible upon alternating dark, UV, and visible light irradiation. Due to the residues of amine groups, the swelling capability of PNIPAM-SP microgels reduces as the pH value is changed from 7 to 10.     

Microgels containing methacrylic acid: effects of composition on pH-triggered swelling and gelation behaviours

pH-responsive microgels are cross-linked polymer colloids that swell when the pH approaches the pK _a of the particles. In this work, we present a comprehensive investigation of pH-triggered particle swelling and gel formation for a range of microgels containing methacrylic acid (MAA). The microgels investigated have the general composition poly(A/MAA/X), where A and X are the primary co-monomer and cross-linking monomer, respectively. The primary co-monomers were methyl methacrylate (MMA), ethyl acrylate (EA) or butyl methacrylate. The cross-linking monomers were either butanediol diacrylate (BDDA) or ethyleneglycol dimethacrylate (EGDMA). The microgels were studied using scanning electron microscopy, photon correlation spectroscopy (PCS) and dynamic rheology measurements. Gel phase diagrams were also constructed. The particles swelled significantly at pH values greater than approximately 6.0. It was shown that poly(EA/MAA/X) microgels swelled more strongly than poly(MMA/MAA/X) microgels. Furthermore, greater swelling occurred for particles prepared using EGDMA than BDDA. Concentrated dispersions of all the microgels studied exhibited pH-triggered gel formation. It was found that the fluid-to-gel transitions for the majority of the six microgel dispersions investigated could be explained using PCS data. In those cases, gelation was attributed to a colloidal glass transition. Interestingly, the microgels that were considered to have the highest hydrophobic content gelation occurred under conditions where little particle swelling was evident from PCS. The data presented show that gelled poly(EA/MAA/BDDA) and poly(MMA/MAA/EGDMA) microgel dispersions have the strongest elasticities at pH = 7.     

Thermodynamics of temperature-sensitive polyether-modified poly(acrylic acid) microgels

The temperature-induced structural changes and thermodynamics of ionic microgels based on poly(acrylic acid) (PAA) networks bonded with poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) (PEO-PPO-PEO) (Pluronic) copolymers have been studied by small-angle neutron scattering (SANS), ultra-small-angle neutron scattering (USANS), differential scanning calorimetry (DSC), and equilibrium swelling techniques. Aggregation within microgels based on PAA and either the hydrophobic Pluronic L92 (average composition, EO8PO52EO8; PPO content, 80%) or the hydrophilic Pluronic F127 (average composition, EO99PO67EO99; PPO content, 30%) was studied and compared to that in the solutions of the parent Pluronic. The neutron scattering results indicate the formation of micelle-like aggregates within the F127-based microgel particles, while the L92-based microgels formed fractal structures of dense nanoparticles. The microgels exhibit thermodynamically favorable volume phase transitions within certain temperature ranges due to reversible aggregation of the PPO chains, which occurs because of hydrophobic associations. The values of the apparent standard enthalpy of aggregation in the microgel suspensions indicate aggregation of hydrophobic clusters that are more hydrophobic than the un-cross-linked PPO chains in the Pluronic. Differences in the PPO content in Pluronics L92 and F127 result in a higher hydrophobicity of the resulting L92-PAA-EGDMAmicrogels and a larger presence of hydrophobic, densely cross-linked clusters that aggregate into supramolecular structures rather than micelle-like aggregates such as those formed in the F127-PAA-EGDMA microgels.     

Poly (N-isopropylacrylamide) microgel based assemblies for organic dye removal from water: microgel diameter effects

Poly (N-isopropylacrylamide)-co-acrylic acid (pNIPAm-co-AAc) microgel based assemblies (aggregates) were synthesized from microgels of various diameters via polymerization of the crosslinker N,N′-methylenebisacrylamide (BIS) in the presence of microgels in solution. We investigated the ability of the respective aggregates to remove the organic, azo dye molecule 4-(2-hydroxy-1-napthylazo) benzenesulfonic acid sodium salt (Orange II) from water at both room and elevated temperatures. The results from the microgel aggregates made from 1.1-μm-diameter [Parasuraman and Serpe. ACS Applied Materials & Interfaces, 2011] microgels were compared to aggregates synthesized from 321-nm and 1.43-μm-diameter microgels. Aggregates made from the same size microgels showed increased uptake efficiency as the concentration of BIS in the aggregates was increased, while for a given BIS concentration, the uptake efficiency increased with increasing microgel size in the aggregate. We attribute this to the “nature” of the aggregates; aggregates have void space between the microgels that can serve as reservoirs for Orange II uptake—the void spaces are hypothesized to increase with larger diameter microgels. By exploiting the thermoresponsive nature of the microgels, and microgel based aggregates, 85.3 % removal efficiencies can be achieved. Finally, all uptake trends for the aggregates, at room temperature, were fit with a Langmuir sorption isotherm model.     

Temperature‐Modulated Water Filtration Using Microgel‐Functionalized Hollow‐Fiber Membranes

In the present work, we investigate the potential of aqueous polymer microgels in membrane technology, especially for filtration applications. The poly(N‐vinylcaprolactam)‐based microgels exhibit thermoresponsive behavior and were employed to coat hollow‐fiber membranes used for micro‐ and ultrafiltration. We discuss the preparation of microgel‐modified membranes (by “inside‐out” as well as “outside‐in” filtration in dead‐end mode). The clean‐water permeability and stability of these membranes was studied not only as a function of time, but also of temperature. The microgel‐modified membranes exhibit a reversible thermoresponsive behavior whereby both the resistance and the retention increased with decreasing temperature.     

Photothermal patterning of microgel/gold nanoparticle composite colloidal crystals

We present a new method for laser direct writing in self-assembled hydrogel microparticle colloidal crystals via photothermal excitation of co-assembled colloidal Au particles. Close-packed colloidal crystals are assembled from approximately 224 nm diameter, thermoresponsive, poly-N-isopropylacrylamide hydrogel microparticles (microgels); these crystals display sharp Bragg diffraction peaks in the mid-visible region of the spectrum due to the periodic dielectric function of the assembly. Raising the temperature of the crystal above the characteristic volume phase transition temperature of the microgel particles results in a reversible melting of the crystalline material due to the particle-based deswelling event. This transition can be used either to anneal defects from the crystalline material or to controllably and reversibly convert the assembly from the colored, crystalline state to a nondiffracting glassy material. Crystal-to-glass transitions are similarly accomplished via photothermal excitation when 16 nm diameter colloidal Au particles are co-assembled with the responsive microgels. Excitation of the colloidal Au plasmon absorption with a frequency doubled Nd:YAG laser (lambda = 532 nm) results in optically directed conversion of either glasses to crystals or crystals to glasses, depending on the initial state of the assembly and the illumination time. These results represent a fundamentally new method for the patterning of self-assembled photonic materials.     

PH-Responsive and Self-Healing Hydrogels Fabricated with Guar Gum and Reactive Microgels

Hydrogels (MR gels) with pH-responsive and self-healing properties were prepared via guar gum solutions and reactive microgel. The reactive microgel was characterized through scanning electron microscope (SEM), laser particle-size analysis measurements, and FTIR. Compared with general hydrogels cross-linked by borax (B gels), the MR gels exhibit superior properties on the aspects of viscosity, viscoelasticies, and temperature resistance. Furthermore, the viscosities of MR gels increase with the rising pH value, and it can dynamically reconstruct after being destructed by external force. In addition, the microstructure of the MR gel was characterized by SEM, which confirms that the reactive microgel indeed as cross-linker and each microgel can cross-link several chains as if the chains were grafting from the microgels. These features show that the addition of reactive microgels can enhance the strength of MR gels significantly and indicate that the MR gels have a great potential application in hydraulic fracturing, especially in high-temperature oil fields.     

Flow of microgel capsules through topographically patterned microchannels

We investigated the flow dynamics of microgel capsules in topographically patterned microfluidic devices. For microgels flowing through channel constrictions, or orifices, we observed three phenomena: (i) the effect of confinement, (ii) the role of interactions between the microgels and the channel surface, and (iii) the effect of the velocities of microgels prior to their passage through an orifice. We studied negatively charged alginate microgels and positively charged alginate microgels coated with N-(2-hydroxy)propyl-3-trimethylammonium chitosan chloride (HTCC). Aqueous dispersions of microgels were driven through poly(dimethyl siloxane) microchannels carrying a weak negative surface charge. The velocity of the continuous phase, and hence, the velocity of the microgels increased as they passed through topographically patterned orifices. Alginate microgels were observed to have a larger increase in velocity relative to HTCC-coated alginate microgels. This effect, which was attributed to electrostatic attraction or repulsion, was found to be strongest for orifices with dimensions close to the microgel diameter. For example, when 75 microm-diameter microgels flowed through a 76 microm orifice, alginate gels (negatively charged) experienced a 2x greater increase in velocity than HTCC-coated (positively charged) microgels. This effect was exaggerated at lower initial flow rates. For example, when 75 microm-diameter microgels flowed through an 80 microm orifice, a two-fold difference in the velocity changes of the two microgel types was observed when the initial flow rate was 275 microm s(-1), while a three-fold difference in velocity changes was observed when the initial flow rate was 130 microm s(-1). We speculate that these studies will be useful for modeling the flow of suspensions of cells or other biologically relevant particles for a wide range of applications.     

Aqueous laponite clay dispersions in the presence of poly(ethylene oxide) or poly(propylene oxide) oligomers and their triblock copolymers

The effect of polyethylene oxide (PEO) or polypropylene oxide (PPO) oligomers of various molecular weight (Mw) as well as of triblock copolymers, based on PEO and PPO blocks, on aqueous laponite RD suspensions was studied with small-angle neutron scattering (SANS). The radius of gyration (RG) increases for low M w whereas the opposite occurs for larger Mw. This behavior is explained on the basis that an effective R G is given by two contributions: (1) the size of the particles coated with the polymer and (2) the interactions between the laponite RD particles which are attractive for small and repulsive for large polymers. The SANS curves in the whole Q-range are well described by a model of noninteracting polydisperse core+shell disks, where the thickness of the polymer layer increases with the Mw. The adsorbed polymer is in a more compact conformation compared to a random coil distribution while the fraction of the polymer in the shell formed around the laponite RD particles is nearly independent of Mw. For increasing laponite RD amounts, at a given polymer composition, the thickness of the polymer slightly changes. In some cases, where also gelation is sped up, a structure factor with attractive interaction was employed which allowed to evaluate the attractive forces between the laponite RD particles. The gelation time was determined for mixtures at fixed copolymer and laponite RD concentrations. Surprisingly, it is observed that gels are formed despite the fact that the binding sites of the laponite RD particles are almost covered but the polymer size is too small to prevent aggregation. The gelation rate is correlated to structure and thermodynamics of these systems. Namely, when the balance between the steric forces and the depletion attractive forces undergoes an abrupt change the gelation time also undergoes a sharp variation. For lower and comparable Mw, PPO speeds up the gelation more efficiently than PEO while for higher Mw the gelation kinetics is slowed down again. Interestingly, copolymers of PEO and PPO blocks do not induce gelation in the time-window where the homopolymers do.     

Swelling Kinetics of Microgels Embedded in a Polyacrylamide Hydrogel Matrix

Composite hydrogels—macroscopic hydrogels with embedded microgel particles—are expected to respond to external stimuli quickly because microgels swell much faster than bulky gels. In this work, the kinetics of the pH‐induced swelling of a composite hydrogel are studied using turbidity measurements. The embedded microgel is a pH‐ and thermosensitive poly(N‐isopropylacrylamide‐co‐acrylic acid) microgel and the hydrogel matrix is polyacrylamide. A rapid pH‐induced swelling of the embedded microgel particles is observed, confirming that composite hydrogels respond faster than ordinary hydrogels. However, compared with the free microgels, the swelling of the embedded microgel is much slower. Diffusion of OH^? into the composite hydrogel film is identified as the main reason for the slow swelling of the embedded microgel particles, as the time of the pH‐induced swelling of this film is comparable to that of OH^? diffusion into the film. The composition of the hydrogel matrix does not significantly change the characteristic swelling time of the composite hydrogel film. However, the swelling pattern of the film changes with composition of the hydrogel matrix.     

Synthesis of polyampholyte microgels from colloidal salts of pectinic acid and their application as pH-responsive emulsifiers

A novel method for obtaining cross-linked microgels of apple pectin has been introduced. This method is based on the Ugi four-component condensation in colloidal suspensions of pectinic acid and amines. Using various processing parameters (the polysaccharide concentration, the type and density of crosslink, and the optimal pH range), particles with controlled colloidal properties have been obtained. Lightly cross-linked polysaccharide chains acquire anionic character due to deprotonation of the carboxyl groups at pH?9–10. Increasing the degree of cross-linking leads to a polyampholyte microgel, which can be protonated in acidic medium or deprotonated in basic medium. Polyampholyte microgels derived from apple pectin have proved to be an effective Pickering emulsifier at low concentrations and pH?2–3, forming stable oil-in-water emulsions. These Pickering emulsions exhibited pH-responsive behavior: raising the solution pH to 10 resulted in immediate demulsification due to the destabilization of microgel network at the oil–water interface.     

微凝胶胶体晶体研究进展

Poly(N-isopropylacrylamide)(PNIPAM)微凝胶粒子是一种软的胶体粒子.和单分散的SiO_2、PS、PMMA等硬的胶体粒子一样,单分散的PNIPAM微凝胶粒子也可以自组装成为高度有序的胶体晶体.微凝胶粒子软物质的特性及其对外部刺激的响应性赋予其不同于硬球的组装行为.微凝胶胶体晶体的高度有序结构及其刺激响应性使其在诸多领域有重要用途.本文分别介绍了三维及二维微凝胶胶体晶体组装的研究进展,并对已开发的基于微凝胶胶体晶体的应用进行了总结.     

Self-assembly of Hollow PNIPAM Microgels to Form Discontinuously Hollow Fibers

A new kind of hollow hydrogel microfiber with discontinuous hollow structure was prepared by an ice-segregation-induced self-assembly process. Monodisperse thermo-responsive hollow poly（N-isopropylacrylamide）（PNIPAM） microgels were first synthesized by seed precipitation polymerization using colloidal Si O2 nanoparticles as seeds, followed by removing the silica cores of the formed Si O2/PNIPAM core/shell composite microgels with hydrofluoric acid. Then, the discontinuously hollow hydrogel microfibers were produced by unidirectional freezing of 1 wt% hollow PNIPAM microgel aqueous dispersion in liquid nitrogen bath, followed by freeze-drying to remove the formed ice crystals. Many orderly arrayed dents were observed on the surfaces of the hydrogel microfibers by field-emission scanning electron microscopy, indicating that they are constructed by closely packed monodisperse hollow PNIPAM microgels. The effect of freezing method and the hollow microgel concentration in the aqueous dispersion on the morphological structure of the hollow hydrogel microfibers was investigated.