Stimuli‐Responsive Polypeptide‐Based Supramolecular Hydrogels Mediated by Ca2+ Ion Cross‐Linking

Hydrogels cross‐linked with metal ions (e.g., Ca²⁺) represent a promising class of bioinspired materials for a wide range of biomedical applications. Herein, we report a facile approach to obtain cross‐linked stimuli‐responsive supramolecular polypeptide hydrogels. The hydrogel is prepared by statistical/block copoly(L‐glutamate)s based copolymers cross‐linked with calcium ions. The incorporation of both oligo(ethylene glycol) (OEG) and glutamic acid residues in the polymer offers thermal‐responsive property and cooperative binding sites with Ca²⁺ ions simultaneously. We present a systematic study of the influence of calcium ions on the gelation behaviors of these copolymers. It is observed that the addition of calcium ions induces the formation of hydrogels. Increasing the concentration of Ca²⁺ ions can significantly enhance the gelation ability of the samples as indicated by increased storage modulus and decreased sol‐to‐gel transition temperature (T_sol‐gel). We further demonstrate that the influence of monomer distribution on the gelation behavior is trivial, which is possibly due to similar morphology of the self‐assemblies. The obtained hydrogels exhibit thermal‐responsive gelation behavior mediated by ion cross‐linking, which enables them to be ideal smart hydrogel system for many applications.     

Hydrophobic guar gum derivatives prepared by controlled grafting processes–Part II: rheological and degradation properties toward fracturing fluids applications

Introduction of polyalkoxyalkyleneamide grafts to guar gum produces new water soluble guar derivatives as described in an earlier publication. 10 In this paper, the rhelogical behavior of these products was explored in more detail at 25 and 65°C. In addition, the viscosity was measured at high temperatures (90 and 120°C) and pressure (150 psi) to partially simulate the down hole conditions of oil wells. Upon treatment with zirconium lactate, the cross‐linked hydrophobically‐modified CMG derivatives exhibited better high‐temperature stability and higher gel viscosities than the corresponding CMHPG derivatives. The cross‐linked gel viscosities indicate that gels will be capable of supporting a high proppant carrying capacity. To facilitate removal of the gels from the formation, the hydrophobically modified derivatives were treated with an enzyme breaker system which produced fragments capable of producing stable emulsions when extracted with toluene. Thus, the clean up process will be enhanced by emulsification of the gel fragments produced by the gel hydrolysis. The low viscosities of the linear derivatives, the rapid formation of high viscosity gels upon cross‐linking and generation of emulsifiers during the gel removal suggest that these new derivatives are good candidates for fracturing fluid applications. Copyright © 2007 John Wiley & Sons, Ltd.     

Sonication‐Triggered Instantaneous Gel‐to‐Gel Transformation

Two new peptide‐based isomers containing cholesterol and naphthalic groups have been designed and synthesized. We found that the position of L ‐alanine in the linker could tune the gelation properties and morphologies. The molecule with the L ‐alanine residue positioned in the middle of the linker ( 1 b ) shows better gelation behavior than that with L ‐alanine directly linked to the naphthalimido moiety ( 1 a ). As a result, a highly thermostable organogel of 1 b with a unique core–shell structure was obtained at high temperature and pressure in acetonitrile. Moreover, the gels of 1 a and 1 b could undergo an instantaneous gel‐to‐gel transition triggered by sonication. Ultrasound could break the core–shell microsphere of 1 b and the micelle structure of 1 a into entangled fibers. By studying the mechanism of the sonication‐triggered gel‐to‐gel transition process of these compounds, it can be concluded that ultrasound has a variety of effects on the morphology, such as cutting, knitting, unfolding, homogenizing, and even cross‐linking. Typically, ultrasound can cleave and homogenize π‐stacking and hydrophobic interactions among the gel molecules and then reshape the morphologies to form a new gel. This mechanism of morphology transformation triggered by sonication might be attractive in the field of material storage and controlled release.     

Rheological and swelling behavior of semi‐interpenetrating networks of polyacrylamide and scleroglucan

Preparation and characterization of novel semi‐interpenetrating polymer network (semi‐IPN) hydrogels based on partially hydrolyzed polyacrylamide (HPAM) and scleroglucan solution crosslinked with chromium triacetate are described. Effects of scleroglucan concentration on the gelation process and swelling behavior of synthesized hydrogels in different media were investigated using dynamic rheometery and swelling tests, respectively. Oscillatory shear rheology showed that the limiting storage modulus of the semi‐IPN gels increased with increase in scleroglucan concentration. It was also found that the viscous energy dissipating properties of the semi‐IPN gels decreased with increase in the crosslinker concentration of the gelation system. In addition, the loss factor slightly decreased by increasing the scleroglucan content, indicating that the viscous properties of this gelling system decreased more than its elastic properties. The swelling tests showed that the equilibrium swelling ratio (ESR) of the semi‐IPN networks decreased with increase in scleroglucan content, due to the decrease of ionic groups of polyelectrolyte hydrogel. However, the semi‐IPN gels showed lower salt sensitivity in synthetic oil reservoir water as compared with HPAM gels. Therefore, these semi‐IPN hydrogels may be considered potentially good candidates for enhanced oil recovery (EOR) applications. Copyright © 2009 John Wiley & Sons, Ltd.     

Study of a Double Cross-Linked HPAM Gel for in-Depth Profile Control

The concept of profile control is one of the most important strategies to enhance oil recovery in a high water production field, with polymer gels being used as a gelant matrix in various reservoirs around the globe. In an effort to reach a suitable profile control, previous attempts lead to an increase of polymer concentration, resulting in a poor injection and insufficient in-depth profile control. The work presented here introduces a novel gel system, using both key functional groups on HPAM to react with two types of cross-linking agents. Different formulations and the properties of this double cross-linked HPAM gel system have been studied. The experimental results indicate that the studied double cross-linked HPAM gel system exhibits a higher gel strength, an improved salt and shear resistance as well as an improved plugging effect compared to a single cross-linked HPAM gel system. Moreover, as a result of higher gel strength, the double cross-linked HPAM gel system also shows a longer gelation time, a parameter particularly useful for in-depth profile control. The gel microstructures have been evaluated, with the double cross-linked HPAM gel exhibiting a molecular structure that is more compact. The latter is a clear indication for the improved properties of the system as will be detailed in subsequent sections.     

The Nature of Crosslinking in N‐Vinylformamide Free‐Radical Polymerization

N‐Vinylformamide (NVF) free‐radical polymerization was found to form polymer gels at high conversions both in bulk and in solution. The polymerization was conducted at different temperatures, monomer and initiator concentrations to show the gelation conditions. Gel fractions and gel swelling ratios were also measured after separating the gel from the polymer samples. In order to confirm the crosslinking unit, a series of hydrolysis experiments were conducted on the gel samples. The hydrolysis results showed that the crosslinks in PNVF gels could be destroyed by alkaline hydrolysis. The most appropriate explanation to this fact is that crosslinking takes place via the amide group.     

Self‐ and cross‐associations in two‐component mixed polymer gels

The gel properties of two‐component mixed polymer gels are investigated using a cascade model, which assumes that the gel network is formed via the self‐association of one of the two components and the cross‐association of the two components. The effects of the model parameters, such as the equilibrium constants and the functionalities for cross‐associations and self‐associations, on the composition dependence of the modulus and gel point curves are examined to elucidate the contribution of self‐associations to the gel network. The results show that the characteristics of self‐associations become pronounced when the equilibrium constant or the functionality for self‐associations is comparable to that for cross‐associations. The model is applied to analyze the critical gelling concentration data for xanthan/locust bean gum mixed gels, which shows significant self‐associations at high xanthan compositions. The resulting model curves agree well with the experimental data at all temperatures. The analysis of the temperature dependence of the best‐fit equilibrium constant yields values of enthalpy change that are consistent with previous findings. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 80–91, 2008     

Water-soluble polymers for hostile environment enhanced oil recovery applications

This paper describes polymerization and properties of a number of water-soluble polymers suitable for enhanced oil recovery applications. The polymers described here can tolerate long-term exposure to hostile environment conditions of elevated temperatures and high salinity and hardness levels encountered in deeper petroleum reservoirs. The stable polymers reported here, in principle contain two or more of the following monomers: acrylamide, N-vinyl-2-pyrrolidone, sodium 2-acrylamido-2-methylpropanesulfonate and N,N-dimethylacrylamide in proper ratios. The polymers reported here can be used directly to increase the viscosity of the injected water and consequently reducing its mobility to recover additional oil from petroleum reservoirs. Alternatively, these polymers can be used in combination with a suitable crosslinker to produce gels in-situ to block high permeability channels or fractures under hostile environment applications.     

Microgel Capsules Tailored by Droplet‐Based Microfluidics

Microgel capsules are micrometer‐sized particles that consist of a cross‐linked, solvent‐swollen polymer network complexed with additives. These particles have various applications, such as drug delivery, catalysis, and analytics. To optimize the performance of microgel capsules, it is crucial to control their size, shape, and content of encapsulated additives with high precision. There are two classes of microgel‐capsule structures. One class comprises bulk microcapsules that consist of a polymer network spanning the entire particle and entrapping the additive within its meshes. The other class comprises core–shell structures; in this case, the microgel polymer network just forms the shell of the particles, whereas their interior is hollow and hosts the encapsulated payload. Both types of structures can be produced with exquisite control by droplet‐based microfluidic templating followed by subsequent droplet gelation. This article highlights some early and recent achievements in the use of this technique to tailor soft microgel capsules; it also discusses applications of these particles. A special focus is on the encapsulation of living cells, which are very sensitive and complex but also very useful additives for immobilization within microgel particles.     

Self‐Assembling Supramolecular Hybrid Hydrogel Beads

With the goal of imposing shape and structure on supramolecular gels, we combine a low‐molecular‐weight gelator (LMWG) with the polymer gelator (PG) calcium alginate in a hybrid hydrogel. By imposing thermal and temporal control of the orthogonal gelation methods, the system either forms an extended interpenetrating network or core–shell‐structured gel beads—a rare example of a supramolecular gel formulated inside discrete gel spheres. The self‐assembled LMWG retains its unique properties within the beads, such as remediating Pd^II and reducing it in situ to yield catalytically active Pd⁰ nanoparticles. A single PdNP‐loaded gel bead can catalyse the Suzuki–Miyaura reaction, constituting a simple and easy‐to‐use reaction‐dosing form. These uniquely shaped and structured LMWG‐filled gel beads are a versatile platform technology with great potential in a range of applications.     

Rheology and Permeability of Crosslinked Polyacrylamide Gel

Gels produced by crosslinking polyacrylamide solutions with chromium (III) have been characterized by dynamic rheology studies. To vary the gel strength, different polymer concentrations were used, while keeping the temperature, salinity, and crosslinker concentration constant. Both the loss and storage moduli increased with the polymer concentration for this gel system. The storage modulus at the end of the gelation was used to characterize the gel strength. Steady-state water flow experiments through gel-filled capillary tubes were performed, with the aim of linking the gel strength and flow behavior. The permeability was found to be a function of the water flow rate (velocity) and polymer concentration. Two parameters were used to characterize the flow behavior, intrinsic gel permeability and elasticity index, which are each functions of the polymer concentration. However, only one parameter is needed to fully identify the flow and rheological gel properties, as the elasticity index and storage modulus are linked by a power-law relationship. The loss modulus and intrinsic permeability are correlated with the storage modulus and elasticity index, respectively. A theoretical model for this behavior linking both gel properties based on the dual domain structure was used to demonstrate that the flow and rheological behavior of the gel are indeed related and that the gel strength controls the water permeability. Implications for prediction of flow of water through gels emplaced in a porous medium are discussed.     

Temperature‐induced self‐assembly of degalactosylated xyloglucan at low concentration

Xyloglucan is a natural polysaccharide having a cellulose‐like backbone and hydroxyl groups‐rich side‐chains. In its native form the polymer is water‐soluble and forms gel only in presence of selected co‐solutes. When a given fraction of galactosyl residues are removed by enzymatic reaction, the polymer acquires the ability to form a gel in aqueous solution at physiological temperatures, a property of great interest for biomedical/pharmaceutical applications. This work presents data on the effect of a temperature increase on degalactosylated xyloglucan dispersed in water at concentration low enough not to run into macroscopic gelation. Results obtained over a wide interval of length scales show that, on increasing temperature, individual polymer chains and pre‐existing clusters self‐assemble into larger structures. The process implies a structural rearrangement over a few nanometers scale and an increase of dynamics homogeneity. The relation of these findings to coil‐globule transition and phase separation is discussed. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1727–1735     

Thermoreversible gelation of helical polypeptide/single‐walled carbon nanotubes and their solid‐state structures

Single‐walled carbon nanotubes (SWCNTs) have been functionalized with poly(γ‐benzyl‐L ‐glutamate)s (PBLGs) having well‐defined polymer molecular weight (M_n = 7.5–21.1 kg·mol^?1) and molecular weight distribution (PDI = 1.05–1.20) by a graft‐to method. Toluene solutions containing 5 wt % free PBLG and variable amounts of PBLG‐functionalized SWCNTs (PBLG‐SWCNTs) form gels at room temperature. Differential scanning calorimetry (DSC) analysis reveals that the gelation occurs thermoreversibly, in accord with previous studies on the pristine PBLG/toluene gels. The heat of gel melting (ΔH_m) is slightly elevated for the composite gels compared with the pristine gel, which suggests enhanced interactions between PBLGs in the former. But the gelation temperatures of the composites are unaffected by the presence of PBLG‐SWCNTs. Small‐angle X‐ray scattering (SAXS) analysis of the composite and pristine gels at different temperatures by the Guinier method suggests that PBLG‐SWCNTs promote interactions between PBLG rods, as indicated by the larger PBLG bundle size with increasing PBLG‐SWCNT content in the gel and the melt state. W/SAXS analysis of the dry gels reveals that PBLG‐SWCNTs induce significant changes in the PBLG packing order, resulting in a nematic phase, in contrast to a weakly ordered smectic C phase containing tilted PBLG rods that is observed in the pristine gel. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

An experimental investigation of polyacrylamide and sulfonated polyacrylamides based gels crosslinked with cr(III)-acetate for water shutoff in fractured oil reservoirs

Abstract

Water injection as one of the most efficient and worldwide extensively employed approach in homogenous oil reservoirs suffers from early water breakthrough time as well as low oil sweep efficiency values in fractured oil reservoirs. This study investigates the potential application of Cr(III)-acetate based gel polymer system in a typical water injection process using one fractured micromodel. For this purpose, three sulfonated polyacrylamides, different in solfunation degree, and one hydrolyzed polyacrylamide were studied regarding gelation time, gel strength and stability to find the optimized conditions in terms of polymer type and concentration, and polymer/Cr(III)-acetate ratio, which were subsequently used for one dynamic test. Results illustrated the optimized conditions as AN 105 polymer with concentration of 5000?ppm and polymer/Cr(III) ratio of 5. Moreover, results showed that implementing such gel system yields an increased oil recovery value of 24.46% OOIP at 1.55 PV and delays the breakthrough time from 0.47 PV to 0.51 PV.     

Novel Gel with Controllable Strength for In-Depth Conformance Control: Bulk Gelation Performance and Propagation Properties in Porous Media

Polymer gel has been widely used to control excessive water production in mature oilfields. However, in view of reservoir conditions characterized by serious heterogeneous thick oil layers, high strength and in-depth propagation are required of polymer gel to achieve good treatment efficiency. Based on the concept of in-depth conformance control, a novel gel with controllable strength composed of polymer, resorcinol/hexamethylenetetramine (HMTA), acetic acid and gel strength modifier was developed. The effects of component concentrations on bulk gelation properties were investigated. The microstructures of conventional gel and novel gel at different aging time were studied by scanning electron microscopy (SEM), which can provide insight into the mechanism of controllable gel strength. Moreover, sandpack flow experiments were carried out on sandpacks (Φ2.5 × 100 cm) with multi-point pressure taps to investigate whether the novel gel can propagate in porous media. Compared with the conventional gel, SEM results showed that the three-dimensional network structure of novel gel was weakened more seriously, resulting in the decrease of gel strength. Due to decreased gel strength at different aging time, the novel gel can propagate in porous media to achieve in-depth conformance control.     

Study of the polymer concentration and polymer/crosslinker ratio effect on gelation time of a novel grafted polymer gel for water shutoff using a central composite design method

In this research article, a hydrogel was prepared by crosslinking of carboxymethyl cellulose‐g‐polyacrylamide copolymer aqueous solution with chromium(III) acetate for the purpose of a water shutoff job in the oil reservoir. The experiments were conducted to investigate the main effects of copolymer concentration and crosslinker/copolymer ratio on gelation time of the hydrogel system. Then the effects of these two factors and their interactions on the gelation time were determined by using a central composite design (CCD) of the response surface method. CCD was used to generate the quadratic mathematical model for the gelation time response as a function of copolymer concentration, crosslinker/copolymer ratio, and their interaction. Furthermore, the analysis of variance (ANOVA) was used to evaluate the quality of the quadratic model. The ANOVA result of the developed model showed that the model was highly significant. The result also showed that the crosslinker/polymer ratio had more effects on the gelation time than did the polymer concentration and their interaction. A response surface method provides an optimum gel formulation. Core flooding experiments reveal that a significant permeability reduction on the sand pack cores can be achieved at reservoir conditions, when it is treated with an optimum gel formulation. Hence, this gel system may be suitable in the water shutoff job required for enhanced oil recovery from the oil fields. Copyright © 2015 John Wiley & Sons, Ltd.     

Solid‐state NMR characterization of tri‐ethyleneglycol grafted polyisocyanopeptides

In aqueous media, ethylene glycol substituted polyisocyanopeptides (PICPs) change their state (undergo a sol‐to‐gel transition) as a response to temperature. This makes them promising materials for various biomedical applications, for instance, for controlled drug release and non‐damaging wound dressing. To utilize PICP in biomedical applications, understanding of the origin of the gelation process is needed, but this is experimentally difficult because of the notoriously low gelator concentration in combination with the slow polymer dynamics in the sample. This paper describes a detailed characterization of the dried state of PICPs by solid‐state NMR measurements. Both the ¹³C and the ¹H NMR resonances were assigned using a combination of 1D cross‐polarization magic angle spinning, 2D ¹³C–¹H heteronuclear correlation spectra and ¹H–¹H single quantum–double quantum experiments. In addition, the chemical groups involved in dipolar interaction with each other were used to discuss the dynamics and spatial conformation of the polymer. In contrast to other PICP polymers, two resonances for the backbone carbon are observed, which are present in equal amounts. The possible origin of these resonances is discussed in the last section of this work. The data obtained during the current studies will be further used in elucidating mechanisms of the bundling and gelation. A comprehensive picture will make it possible to tailor polymer properties to meet specific needs in different applications. Copyright © 2015 John Wiley & Sons, Ltd.     

Supramolecular polymer gels formed from carboxy‐terminated telechelic polybutadiene and polyamidine through amidinium‐carboxylate salt bridge

In this article, we report the preparation and properties of the bulk supramolecular polymer gels prepared from a polybutadiene based on the amidinium‐carboxylate salt bridge, highlighting the difference from a well‐established network system based on carboxylic acid and amine. We have prepared the amidinium‐carboxylate salt bridge‐based supramolecular polymer gels from a carboxy‐terminated telechelic polybutadiene and a linear polyamidine having N,N′‐di‐substituted acetamidine group in the main chain. FTIR analysis along with Small angle X‐ray scattering measurements indicated that the salt bridge was attributed to the gelation through three‐dimensional network formation. Virtually no fluidity was observed for the supramolecular gel containing equimolar amounts of the carboxyl group and the amidine group, which showed a high G′ value of about 1 MPa at room temperature and a T_gel of 37 °C. For comparison, the supramolecular polymer gels crosslinked by ammonium‐carboxylate salt were prepared using a linear polyethyleneimine instead of the polyamidine. The gel with equimolar amounts of the carboxyl group and the secondary amino group showed liquid‐like fluidity with a G′ value of about 0.01 MPa at room temperature, which was attributed to the fact that a certain amount of the carboxyl group remained as its free form without salt formation, as evidenced by FTIR analysis. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1815–1824     

Water flow in poly(N-isopropylacrylamide) gels

Friction between a polymer network of poly(N-isopropylacrylamide) gels and solvent water was investigated. The gel was mechanically constrained in a glass capillary at gelation, and hydrostatic pressure was directly applied to the cross section of the cylinder. The temperature dependence of the flow velocity was extensively measured in the vicinity of the transition temperature for gels with different lengths, l(0), at gelation. As the temperature increased, the friction slightly decreased at the transition point and increased rapidly in the collapsed phase. Although the flow velocity depended on l(0), the friction in the vicinity of the transition point was well scaled by l(0) based on the Hagen-Poiseuille equation for the flux of water flow in a capillary. The results suggested that the assumption that the gel is a bundle of microcapillaries was applicable to the water flow through the hydrogel, which was largely deformed not only by the pressure applied to the solvent but also by the shrinking force caused by the temperature increment. Macroscopic deformation did not affect the friction between the three-dimensional polymer network and water.     

Characteristics of several kinds of polyethylene gel estimated by small‐angle light scattering under cross polarization

Unusual phenomenon was confirmed in the gelation of polymer solution when branched low molecular weight polyethylene (B‐LMWPE) and ultrahigh molecular weight polyethylene (UHMWPE) solutions were quenched at their gelation temperature. That is, polarized light scattering (Hv scattering) from B‐LMWPE gels containing 95% solvent yielded a four‐leaf clover type as like the scattering from a perfect spherulite under Hv scattering but the corresponding polarized optical microscopy (POM) showed dark image showing no spherulite with Maltese cross color indicating considerable orientation fluctuation between the optical axes with respect to the radial axis of the spherulite. Hv scattering from pristine UHMWPE gels containing more than 99% solvent had an X‐type pattern, which became clearer with time. The corresponding POM images change from being dark, indicating no superstructure, to being slightly brighter, indicating the presence of indistinct superstructures. To analyze this unusual phenomenon of Hv scattering from B‐LMWPE and UHMWPE gels, new models were proposed using a statistical approach and optically anisotropic elements in three‐dimensional space. The theoretical patterns were in agreement with observation. Thus, it came to a conclusion that Hv scattering from the gels is attributed to strong distance correlation between polar and rotational angles of two optically anisotropic elements in the polymer‐rich phase. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010