Critical Association Concentration Research Articles

Rheological behavior of hydrophobic association polyacrylamides with high salt resistance and corrosion inhibition: Cross-linking modification based on trace dopamine hydrochloride derivatives

Hydrophobic association polyacrylamides (HAPAMs) have great potential for use in polymer flooding because of their unique aggregative, hygroscopic, and other compatible properties; however, their poor solubility in high-salt reservoir environments is one of the drawbacks of current polymers for enhanced oil recovery (EOR) applications. Herein, an amphipathic hydrophobic monomer (hexadecyldimethylallyl ammonium chloride, DMAAC16) and a dopamine hydrochloride-derived monomer (DAAM) were successfully introduced into HAPAM to synthesize novel dopamine hydrochloride-modified hydrophobic association polymers (HAPAMC16D). As a result, HAPAMC16D exhibited not only good comprehensive properties based on its porous network structure but also excellent viscosity due to the presence of the DAAM monomer. When the concentration of the polymer solution was greater than the critical association concentration (CAC), the apparent viscosity reached 614 mPa s at 5 g/L C16D5. Importantly, the salt resistance increased significantly in the representative sodium and calcium ion tests, which was attributed to the degree of chemical cross-linking and the intermolecular hydrophobic bonding force. The temperature and salt resistance tests simulating different environments for EOR showed that C16D4 had an apparent viscosity of 158 mPa s, a retention rate of 28.52 % at 90 °C and a total dissolved solids (TDS) greater than 30,000. Additionally, the weight loss method and electrochemical experiments indicated that the highly salt-resistant hydrophobic association polymers had favorable corrosion inhibition effects, with an inhibition efficiency of up to 99.02 % in the 1 M hydrochloric acid-Q235 carbon steel system. This hydrophobic association strategy provides a new approach for designing highly salt-resistant materials for polymer flooding in harsh reservoir environments.

Preparation and Performance Evaluation of Amphiphilic Polymers for Enhanced Heavy Oil Recovery.

The continuous growth in global energy and chemical raw material demand has drawn significant attention to the development of heavy oil resources. A primary challenge in heavy oil extraction lies in reducing crude oil viscosity. Alkali-surfactant-polymer (ASP) flooding technology has emerged as an effective method for enhancing heavy oil recovery. However, the chromatographic separation of chemical agents presents a formidable obstacle in heavy oil extraction. To address this challenge, we utilized a free radical polymerization method, employing acrylamide, 2-acrylamido-2-methylpropane sulfonic acid, lauryl acrylate, and benzyl acrylate as raw materials. This approach led to the synthesis of a multifunctional amphiphilic polymer known as PAALB, which we applied to the extraction of heavy oil. The structure of PAALB was meticulously characterized using techniques such as infrared spectroscopy and Nuclear Magnetic Resonance Spectroscopy. To assess the effectiveness of PAALB in reducing heavy oil viscosity and enhancing oil recovery, we conducted a series of tests, including contact angle measurements, interfacial tension assessments, self-emulsification experiments, critical association concentration tests, and sand-packed tube flooding experiments. The research findings indicate that PAALB can reduce oil-water displacement, reduce heavy oil viscosity, and improve swept volume upon injection into the formation. A solution of 5000 mg/L PAALB reduced the contact angle of water droplets on the core surface from 106.55° to 34.95°, shifting the core surface from oil-wet to water-wet, thereby enabling oil-water displacement. Moreover, A solution of 10,000 mg/L PAALB reduced the oil-water interfacial tension to 3.32 × 10-4 mN/m, reaching an ultra-low interfacial tension level, thereby inducing spontaneous emulsification of heavy oil within the formation. Under the condition of an oil-water ratio of 7:3, a solution of 10,000 mg/L PAALB can reduce the viscosity of heavy oil from 14,315 mPa·s to 201 mPa·s via the glass bottle inversion method, with a viscosity reduction rate of 98.60%. In sand-packed tube flooding experiments, under the injection volume of 1.5 PV, PAALB increased the recovery rate by 25.63% compared to traditional hydrolyzed polyacrylamide (HPAM) polymer. The insights derived from this research on amphiphilic polymers hold significant reference value for the development and optimization of chemical flooding strategies aimed at enhancing heavy oil recovery.

Synergistic effect of hydrophobic modified Welan gum and sodium alcohol ether sulphate in saline solution

Surfactants are often used to change the structure of natural polysaccharide polymers and improve their properties for industrial applications. However, implementing surfactants to boost the Welan gum has yet to be studied. This study prepared the compound system HWG-A by Sodium alcohol ether sulphate (AES) with hydrophobic modified Welan gum (HWG). Compared with HWG, the critical association concentration of HWG-A they have decreased from 3.8 × 103 mg L-1 to 2.8 × 103 mg L-1. The viscosity of 2 × 103 mg L-1 HWG-A remained at 244 mPa s when the salinity was 96,670 mg L-1. The rheological test showed that HWG-A still maintained the characteristics of pseudoplastic fluid under different polysaccharide concentrations, pH and salinity. The viscoelastic test showed that the elasticity of HWG-A was interdependent with the concentration of polysaccharides. When HWG-A was higher than the critical association concentration, the elasticity dominated the whole system. The temperature resistance test showed that the viscosity of HWG-A was still much higher than that of Welan gum and HWG when the salinity was 19,334 mg L-1 at 140 ℃ and lower than the critical association concentration, and the viscosity remained above 350 mPa s. SEM showed that HWG-A presented a regular large network structure when the concentration was lower than its critical association concentration. Otherwise, HWG-A presented a gel shape. Our study promotes the industrial potential of Welan gum in such as Enhanced Oil Recovery (EOR) process. It suggests that the interaction between surfactants and natural polysaccharides is essential in determining the functional properties of the fluid system.

Synthesis and molecular dynamics simulation of amphoteric hydrophobically associating polymer

To address the practical issues of poor temperature and salt tolerance of polymers, a new amphoteric monomer (E)-N-(docos-13-enoyl)-N-methylglycine named CQ was developed. The polymer CQMP was synthesized by acrylamide (AM) and CQ as an associative monomer and sodium p-styrene sulfonate (SSS) as a functional monomer in aqueous solution. The structure of the products was confirmed by FTIR, 1H NMR and TGA, while the micro-morphology of the polymer was observed by SEM. Taking HAPAM as a control, the properties of polymer in aqueous solution were studied as a function of salinity, shear rate, temperature, and polymer concentration. The oil displacement performance was also evaluated in detail. Additionally, the surface tension (SFT) and interfacial tension (IFT) of CQMP solution were measured. The critical micelle concentration (CMC) values of CQMP in aqueous solution and in NaCl solution are 2.13 g·L-1 and 1.79 g·L-1,respectively. The copolymer can reduce the interfacial tension between water and crude oil from Changqing Oilfield, with an IFT value of about 15.96 mN·m−1. The results indicate that the critical association concentration (CAC) is approximately 600 mg·L-1, and the polymer exhibits good salt tolerance and oil flooding performance. Furthermore, molecular dynamics simulation demonstrated that CQ can enhance intermolecular interactions while maintaining the same hydrophobic chain content, thereby reinforcing the polymer’s resistance temperature and salt. The laboratory flooding experiment showed that the enhance oil recovery of CQMP with 0.5 PV 3000 mg·L-1 was 12.23 % greater than that of HAPAM, which is promising for multiple applications in complex oil fields.

Zwitter-ionic amphiphilic calixresorcinarenes: Micellization in the bulk solution and non-surface activity

Here the amphiphilic calix[4]resorcinarenes, which form self-associates in an aqueous solution but do not exhibit surface activity, are described. Aqueous solutions of calix[4]resorcinarenes with different zwitter-ionic groups on the upper rim: carboxybetaine (C5-CB, C11-CB, C12OPh-CB), sulfobetaine (C5-SB, C11-SB), hydroxysulfobetaine (C5-hSB, C11-hSB), - and different hydrophobic substituents on the lower rim (pentyl, undecyl, dodecyloxyphenyl) were studied by fluorimetry, Fourier transform pulsed-gradient spin-echo (FT-PGSE) NMR spectroscopy, UV–vis spectroscopy, dynamic light scattering (DLS), and tensiometry. It was found that all macrocycles spontaneously form self-associates in an aqueous solution, but only sulfobetaine and hydroxysulfobetaine calixresorcinarenes with pentyl substituents on the lower rim are surface active. The critical association concentration (CAC) values, which were obtained by different methods, as well as values of averaged hydrodynamic diameter, averaged self-association numbers, solubilizing power, and other parameters of self-association are presented and discussed.

Influence of temperature and pH on polyacrylamide-based drilling fluid: Characterization and rheological study

Polyacrylamide (PAM) is a biodegradable polymer with good lubricity in friction reduction. However, there is insufficient guidance on the dosage of PAM and poor rheological information on the effects of temperature and pH. This study aimed to investigate the characterization of the material and rheological analysis regarding the effects of concentration, pH, and temperature of PAM. In material characterization, PAM has been shown to offer hydrophilic surfaces. In a rheological study, 1000 ppm PAM was the critical association concentration, as the rheological properties below 1000 ppm PAM were superior. This was due to the dispersion stability effect caused by the polymer concentration. Additionally, a low concentration of polymer contributes to bridging flocculation with an unstable rheological profile and low association networking. When the polymer concentration is further increased to the saturated adsorption level, the rheological profile of PAM above 1000 ppm is significantly affected as a result of the alternation from steric stabilization to depletion flocculation in a polymer system. Furthermore, the rheological performance of PAM was significantly affected by temperature and pH, showing better performance after heating to 60 °C and at pH = 10. Future studies can further develop modified PAM with specific additives at an optimized temperature and pH to investigate the rheological performance of drilling.

Synthesis of Hydrophobically Associating Polymers with Natural Product Structures by a One‐Pot Method – Comparison of Ethanol Treatment and Freeze‐Drying

AbstractPolyacrylamide‐based hydrophobically associating polymers (HAPAM) containing capsaicin derivatives and itaconic acid with acrylamide (AM) and methacrylic acid (MAA) as the main bodies, and N‐vinylpyrrolidone (NVP) as the functional monomer are prepared by a one‐pot synthesis of the soap‐free emulsion polymerization process. The structure is characterized by fourier transform infrared (FTIR) and 1H nuclear magnetic resonance (1H NMR), and thermal gravimetric analyzer (TGA) explores thermal stability. For achieving proper purification, excellent preservation and convenient transportation of the polymer and to advance its practical engineering applications, two different treatments, namely ethanol washout and freeze‐drying, are carried out and compared. The surface morphology observation manifests that the freeze‐drying products (DHPAM) better protect the three‐dimensional cross‐linked network structure formed by various supramolecular forces such as hydrophobic association, electrostatic and hydrogen bonding inside the polymer than the ethanol washout products (EHPAM), which well explains why DHPAM has lower critical association concentration (CAC), greater resistance to high temperature and high salt, and better corrosion inhibition performance than EHPAM. It is significant for strengthening the application of polymers in related fields, especially oil and gas extraction.

Synthesis of cardanol grafted hydrophilic polymers and its mechanism of coal dust inhibition

A novel hygroscopic sodium cardanol polyoxyethylene ether sulfate (SCPES) dust suppressant was synthesized via graft copolymerization, sulfonation, and alkalization reactions of cardanol and polyoxyethylene. The critical micelle concentration, chemical synthesis and wetting mechanism of SCPES were investigated using pyrene fluorescence spectroscopy, Fourier transform infrared spectroscopy, quantum chemistry and molecular dynamics software. SCPES was synthesized in three steps: first, the phenolic –OH of cardanol was de-H and grafted with polyoxyethylene to form cardanol polyoxyethylene ether (CPE); second, the H atom of CPE was replaced by the –SO3H of H2SO4 to generate cardanol polyoxyethylene ether sulfate (CPES); finally, the H+ of CPES was alkalized with the OH− of NaOH to form SCPES. It was found that the active centers of the three reactions were all at the O–H bond, the activation energies were 233.66, 85.99, and − 66.91 KJ/mol, and the final composite had distinct aromatic ether (Ar–O, R–O), S–O, and S = O infrared absorption peaks, proving that SCPES had been successfully prepared. 0.10 g/L and 0.25 g/L were the critical association concentration and critical micelle concentration of SCPES, and the surface tension and contact angle at the critical micelle concentration were 33.12 mN/m and 39.5°. Compared with the H2O-lignite system, the H2O-SCPES-lignite system exhibited an increase in the total number of hydrogen bonds from 2082 to 2136, a decrease in the interaction energies from − 13863.35 kcal/mol to − 17817.77 kcal/mol, and an increase in the diffusion coefficients of H2O molecules from 0.12 to 0.73. The results indicated that the long hydrophobic tail chain in the molecular structure of SCPES was entangled with the hydrophobic sites on the coal surface, acting as intermediate carriers between water and coal to improve the wettability of coal dust, and providing a new technical means for coal dust inhibition.

Molecular Insights into Cyclodextrin-Adamantane-Modified Copolymer Host-Guest Interactions.

Supramolecular polymer flooding has great potential in solving the problems of difficult injection and low recovery in low-permeability polymer reservoirs. However, the self-assembly mechanism of supramolecular polymers is not yet to be fully understood at the molecular level. In this work, molecular dynamics simulations were used to explore the formation of cyclodextrin and adamantane-modified supramolecular polymer hydrogels; the self-assembly mechanism was summarized; and the effect of concentration on the oil displacement index was evaluated. The assembly mechanism of supramolecular polymers can be attributed to the "node-rebar-cement" mode of action. At the same time, Na+ can form intermolecular and intramolecular salt bridges with supramolecular polymers, and together with the "node-rebar-cement" mode of action, the supramolecular polymers can form a more compact 3D network structure. When the polymer concentration was increased, especially up to its critical association concentration (CAC), the association increased significantly. Besides, the construction of a 3D network was promoted, which results in a higher viscosity. This work investigated the assembly process of supramolecular polymers from the molecular scale and explained its mechanism of action, which makes up for the deficiencies of other research methods and provides a theoretical basis for screening out functional units that can be used for the supramolecular polymer assembly.

Synthesis and Characterization of Nanoparticle-Based Dexamethasone-Polypeptide Conjugates as Potential Intravitreal Delivery Systems

The use of dexamethasone for eye disease treatment is limited by its low solubility, bioavailability, and rapid elimination when applied topically. The covalent conjugation of dexamethasone with polymeric carriers is a promising strategy to overcome existing drawbacks. In this work, amphiphilic polypeptides capable of self-assembly into nanoparticles were proposed as potential delivery systems for intravitreal delivery. The nanoparticles were prepared and characterized using poly(L-glutamic acid-co-D-phenylalanine) and poly(L-lysine-co-D/L-phenylalanine) as well as poly(L-lysine-co-D/L-phenylalanine) covered with heparin. The critical association concentration for the polypeptides obtained was in the 4.2-9.4 μg/mL range. The hydrodynamic size of the formed nanoparticles was between 90 and 210 nm, and they had an index of polydispersity between 0.08 and 0.27 and an absolute zeta-potential value between 20 and 45 mV. The ability of nanoparticles to migrate in the vitreous humor was examined using intact porcine vitreous. Conjugation of DEX with polypeptides was performed by additional succinylation of DEX and activation of carboxyl groups introduced to react with primary amines in polypeptides. The structures of all intermediate and final compounds were verified by 1H NMR spectroscopy. The amount of conjugated DEX can be varied from 6 to 220 µg/mg of polymer. The hydrodynamic diameter of the nanoparticle-based conjugates was increased to 200-370 nm, depending on the polymer sample and drug loading. The release of DEX from the conjugates due to hydrolysis of the ester bond between DEX and the succinyl moiety was studied both in a buffer medium and a vitreous/buffer mixture (50/50, v/v). As expected, the release in the vitreous medium was faster. However, the release rate could be controlled in the range of 96-192 h by varying the polymer composition. In addition, several mathematical models were used to assess the release profiles and figure out how DEX is released.

Carboxybetaine and Carboxybetaine Ester Derivatives of Tetra(dodecyloxyphenyl)-calix[4]resorcinarene: Synthesis, Self-Assembly and In Vitro Toxicity

Amphiphilic calix[4]resorcinarenes are a class of macrocyclic compounds with broad potential utility including nanomedicine. Here the synthesis of new carboxybetaine and carboxybetaine ester calix[4]resorcinarene bearing 4-(dodecyloxy)phenyl groups on the lower rim is presented. The compounds were characterized by 1H-NMR, 13C-NMR, 2D NMR, IR, ESI and elemental analysis. The critical association concentration values are 1.00 × 10−5 and 1.18 × 10−5 mol·L−1 for carboxybetain and ester, respectively. The hemolytic activity of the macrocycles and their cytotoxicity against normal (WI-38, Chang liver) and tumor cells (M-HeLa) are also estimated.

Сalixresorcine cavitands bearing lipophilic cationic fragments in the construction of mitochondrial-targeting supramolecular nanoparticles

The development of mitochondrial-targeting therapeutic nanoparticles is one of the crucial tasks of nanotechnology and nanomedicine. Here the study of supramolecular macrocycles decorated by lipophilic cationic mitochondrial-targeting fragments in the formation of supramolecular nanoparticles with the potential mitochondria-dependent apoptosis ability is described. Four cavitands based on tetrapentyl- and tetraundecylcalix[4]resorcines were functionalized with pyridinium (С5-Pyr and C11-Pyr, respectively) and triethylammonium groups (С5-NEt3 and C11-NEt3, respectively). Cavitands demonstrate amphiphilic character with critical association concentration values of 1.21, 1.20, 0.27 and 0.13 mM for С5-Pyr, С5-NEt3, C11-Pyr, and C11-NEt3, respectively (DMSO/Н2О 5/95 v/v, conductometry), and form small self-associates (D2O, DMSO-d6/D2О 5/95 v/v, FT-PGSE NMR method). The supramolecular modification of cavitands self-associates by the formation of polymer complexes with biocompatible polymer alginate sodium (AlgNa) was carried out. It was found that the size and stability of polymer complexes depends on the cavitand choice; the average hydrodynamic diameter of particles is 142 nm for С5-Pyr + AlgNa, 122 nm for С5-NEt3 + AlgNa and C11-NEt3 + AlgNa, and 615 nm for C11-Pyr + AlgNa complexes (DLS method). The formation of polymer complexes mainly is the result of electrostatic interaction and leads to the binding of cavitands by alginate in the form of self-associates (electrophoretic light scattering method, IR, fluorimetry). It was shown that pentylcavitands С5-Pyr and С5-NEt3 show higher hemotoxicity and cytotoxicity against normal (Chang liver cells) and tumor cells (M-HeLa cells) than undecylcavitands C11-Pyr and С11-NEt3. It was found that cavitand С5-NEt3 reduces the mitochondrial membrane potential and leads to the increase of ROS in M-HeLa cells (Flow cytometry analysis). However С5-NEt3 + AlgNa complex loses the ability to reduce the membrane potential of mitochondria, the possible reason of which is discussed.

Intrinsically Viscoelastic Supramolecular Conjugated Polymer toward Suppressing Coffee-Ring Effect

Intrinsically Viscoelastic Supramolecular Conjugated Polymer toward Suppressing Coffee-Ring Effect

Stable foam systems for improving oil recovery under high-temperature and high-salt reservoir conditions

Foams have high apparent viscosity when flowing in porous media, therefore foam flooding could significantly improve unfavorable mobility ratios, increase sweep efficiency, and enhance oil recovery. However, the applications of foam flooding in high-temperature and high-salt reservoirs are seriously restricted as foam systems often have inferior foamability and stability in these reservoirs. In this study, to improve foam flooding effectiveness in high-temperature and high-salt reservoirs, novel foam systems with excellent stability and plugging capacity are developed by combining surfactants, additives, and polymers. The performance of bulk foam, physical properties of the solutions, and properties of foam systems in core-flow experiments are investigated to determine the synergistic effects among the components of the foam systems and their foamability and plugging effect in cores. In foam systems with sodium alcohol ether sulfate (AES) and dodecylhydroxypropyl sulfobetaine (DHSB) as surfactants, and dodecanol as additive, the combination of the components makes surface tension decreased and surface dilatational modulus increased, therefore the foamability and stability of the systems are improved. The results of core-flow experiments under high-temperature and high-salt conditions show that these combined systems require low injection rate for foam generation in reservoirs, which is beneficial for foam regeneration in reservoirs. Moreover, to further improve the foam performance, a hydrophobically associating water-soluble polymer (HAWP) is employed. The interactions between HAWP and the surfactants reduce the critical association concentration of HAWP, and result in the increase of solution apparent viscosity and foam stability. The results of core-flow experiments under high-temperature and high-salt conditions show that polymer-enhanced foam systems could significantly increase the sealing pressure, widen the sealing permeability range, and deal with the gas-channeling problem of foam flooding. These foam systems could provide a potential technical pathway for improving the effectiveness of foam flooding in high-temperature and high-salt reservoirs.

Synthesis of a hydrophobic association polymer with an inner salt structure for fracture fluid with ultra-high-salinity water

This study used a compound initiation free radical polymerization process to synthesize a hydrophobic association polymer (PDMA1) with good salt resistance for use in ultra-high salinity reservoirs. The critical association and entanglement concentrations of PDMA1 in deionized (DI) water were 1596 and 2799 mg/L, respectively. The properties of the polymer in simulated formation (SF) water were investigated using viscosity change and conductivity tests, and the apparent viscosity of the PDMA1 solution was investigated using apparent viscosity, viscoelasticity, and thixotropy experiments. To a certain extent, the apparent viscosity of the solution was found to be influenced by metal ions. Under total dissolved solids (TDS) concentrations of up to 239,500 ppm, when the polymer concentration exceeded the critical entanglement concentration, the apparent viscosity of the polymer remained close to that of DI water. Additionally, the viscosity of the PDMA1 solution was affected by different types of metal ions, and the polymer solution thickened owing to divalent cations. PDMA1 is resistant to salt owing to hydrophobic interaction, electrostatic shielding, and double-layer compression. The results of the thixotropy and viscoelasticity tests revealed the thixotropy loop area of the PDMA1 solution in SF water to be greater than that in DI water. Under these conditions, PDMA1 is mostly viscous at low shear frequencies and mostly elastic at high shear frequencies. The PDMA1 inner-salt hydrophobic association polymer can be utilized as a chemical agent for tertiary recovery and fracturing, processes in high-salinity reservoirs, particularly for aggravating fracturing fluid.

Application of environmentally friendly amphoteric polyacrylamide hydrophobically modified with plant oil as additive in water-based drilling fluid

Hydrophobic associating polymers show great potential in formulation of high-performance drilling fluids, due to their hydrophobic associative ability in high-temperature and high-salt conditions. Herein, a novel amphoteric polyacrylamide of poly(acrylamide/2-acrylamido-2-methyl-1-propanesulfonic acid/methylacrylethyl trimethylammonium chloride) hydrophobically modified with epoxidized soybean oil denoted as PAADE was prepared and applied in water-based drilling fluid, and one without hydrophobic modification (PAAD) was also used for comparison. Compared with PAAD, PAADE displayed characteristic association behavior with a critical association concentration (CAC) of 0.3 w/v%, and a salt thickening phenomenon over 3 w/v% NaCl concentration. The impacts of PAADE and PAAD on rheological and filtration properties of bentonite-based drilling fluid (BTDF) were evaluated under different salinity. The fitted Herschel-Bulkley rheological parameters indicated that BTDF containing PAADE showed stronger yield stress, easier flowability and better salt resistance at a reasonable concentration below CAC. Meanwhile, PAADE largely reduced the fluid loss of BTDF before and after thermal aging at 150°C, showing high temperature tolerance. The addition of NaCl promoted larger reduction of filtration. The superior properties of PAADE in BTDF were revealed to be the competitive results of salt-induced hydrophobic association and inter-particles configuration transition. Moreover, the incorporation of epoxidized soybean oil improved the biodegradability of PAADE.

Poly(ε-caprolactone) grafted cashew gum nanoparticles as an epirubicin delivery system

Polysaccharide based copolymers have been the focus of several research, particularly for the development of drug delivery systems. This study reports on the preparation of nanoparticles from an amphiphilic copolymer obtained by the poly(ε-caprolactone) graft in the structure of cashew gum, via ring-opening polymerization. The synthesis of copolymers was confirmed by Fourier transform infrared spectroscopy and nuclear magnetic resonance. The copolymers exhibit self-organization capability in water, with critical association concentration of 42 and 50 μg mL−1. The nanoparticle hydrodynamic diameters (212 and 202 nm) revealed a decreasing trend with increasing poly(ε-caprolactone) graft percentage. Epirubicin was used as an anticancer drug model and incorporated into the nanoparticles. The encapsulation efficiency reached 50% and 5.0% drug load. Nanoparticles showed an epirubicin controlled release profile, with maximum release of 93.0 ± 4.0% in 72 h, as well as excellent biocompatibility, according to hemolysis and cytotoxicity assays.

Polymer viscosifier systems with potential application for enhanced oil recovery: a review

Due to the growing demand for oil and the large number of mature oil fields, Enhanced Oil Recovery (EOR) techniques are increasingly used to increase the oil recovery factor. Among the chemical methods, the use of polymers stands out to increase the viscosity of the injection fluid and harmonize the advance of this fluid in the reservoir to provide greater sweep efficiency. Synthetic polymers based on acrylamide are widely used for EOR, with Partially Hydrolyzed Polyacrylamide (PHPA) being used the most. However, this polymer has low stability under harsh reservoir conditions (High Temperature and Salinity – HTHS). In order to improve the sweep efficiency of polymeric fluids under these conditions, Hydrophobically Modified Associative Polymers (HMAPs) and Thermo-Viscosifying Polymers (TVPs) are being developed. HMAPs contain small amounts of hydrophobic groups in their water-soluble polymeric chains, and above the Critical Association Concentration (CAC), form hydrophobic microdomains that increase the viscosity of the polymer solution. TVPs contain blocks or thermosensitive grafts that self-assemble and form microdomains, substantially increasing the solution’s viscosity. The performance of these systems is strongly influenced by the chemical group inserted in their structures, polymer concentration, salinity and temperature, among other factors. Furthermore, the application of nanoparticles is being investigated to improve the performance of injection polymers applied in EOR. In general, these systems have excellent thermal stability and salinity tolerance along with high viscosity, and therefore increase the oil recovery factor. Thus, these systems can be considered promising agents for enhanced oil recovery applications under harsh conditions, such as high salinity and temperature. Moreover, stands out the use of genetic programming and artificial intelligence to estimate important parameters for reservoir engineering, process improvement, and optimize polymer flooding in enhanced oil recovery.

Redox-sensitive carrier-free nanoparticles self-assembled by disulfide-linked paclitaxel-tetramethylpyrazine conjugate for combination cancer chemotherapy.

Rationale: Combinations of two or more therapeutic agents targeting different signaling pathways involved in tumor progression can have synergistic anticancer effects. However, combination chemotherapies are greatly limited by the different pharmacokinetics, tumor targeting, and cellular uptake capacities of the combined drugs. We have previously demonstrated the potential synergistic efficacy of paclitaxel (PTX) and the natural anti-angiogenic agent tetramethylpyrazine (TMP) for suppressing ovarian carcinoma growth. An efficient, facile, and smart nanosystem to deliver PTX and TMP simultaneously in vivo is greatly desired.Methods: We constructed a redox-sensitive nanosystem based on the amphiphilic PTX-ss-TMP conjugate, in which PTX and TMP are linked by a disulfide bond. We characterized the structure of the drug conjugate by 1H NMR and LC-MS, and then prepared PTX-ss-TMP NPs by a one-step nanoprecipitation method. We investigated the redox sensitivity, tumor-targeting ability, anticancer efficacy, and anti-angiogenesis activity of PTX-ss-TMP NPs in vitro and in vivo.Results: The amphiphilic PTX-ss-TMP conjugate readily self-assembled into stable nanoparticles in aqueous solution with a low critical association concentration of 1.35 µg/mL, well-defined spherical structure, small particle size (152 nm), high drug loading, redox-responsive drug release, high biocompatibility, and high storage stability. In cancer cells pretreated with GSH-OEt, PTX-ss-TMP NPs exhibited higher cytotoxicity, apoptosis rate, and cell-cycle arrest than monotherapy or combination therapy with free drugs, which was attributed to their improved cellular uptake and rapid intracellular drug release. Additionally, PTX-ss-TMP NPs also had a stronger anti-angiogenesis effect in HUVECs than free drug, which was mediated by VEGFR2-involved downstream signals. Finally, PTX-ss-TMP NPs showed tumor-specific accumulation and excellent antitumor activity in A2780 xenograft mice compared with free drug.Conclusions: These in vitro and in vivo results provide clear evidence that this redox-responsive carrier-free nanosystem with intrinsic amphiphilicity has great potential for combination cancer chemotherapy.

Association between Nonionic Amphiphilic Polymer and Ionic Surfactant in Aqueous Solutions: Effect of Polymer Hydrophobicity and Micellization.

The interaction in aqueous solutions of surfactants with amphiphilic polymers can be more complex than the surfactant interactions with homopolymers. Interactions between the common ionic surfactant sodium dodecyl sulfate (SDS) and nonionic amphiphilic polymers of the poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) (PEO-PPO-PEO) type have been probed utilizing a variety of experimental techniques. The polymer amphiphiles studied here are Pluronic F127 (EO100PO65EO100) and Pluronic P123 (EO19PO69EO19), having the same length PPO block but different length PEO blocks and, accordingly, very different critical micellization concentrations (CMC). With increasing surfactant concentration in aqueous solutions of fixed polymer content, SDS interacts with unassociated PEO-PPO-PEO molecules to first form SDS-rich SDS/Pluronic assemblies and then free SDS micelles. SDS interacts with micellized PEO-PPO-PEO to form Pluronic-rich SDS/Pluronic assemblies, which upon further increase in surfactant concentration, break down and transition into SDS-rich SDS/Pluronic assemblies, followed by free SDS micelle formation. The SDS-rich SDS/Pluronic assemblies exhibit polyelectrolyte characteristics. The interactions and mode of association between nonionic macromolecular amphiphiles and short-chain ionic amphiphiles are affected by the polymer hydrophobicity and its concentration in the aqueous solution. For example, SDS binds to Pluronic F127 micelles at much lower concentrations (~0.01 mM) when compared to Pluronic P123 micelles (~1 mM). The critical association concentration (CAC) values of SDS in aqueous PEO-PPO-PEO solutions are much lower than CAC in aqueous PEO homopolymer solutions.