Copolymers In Aqueous Solution Research Articles

Molecular Simulation Study of the Kinetics and Mechanism of Micellization of Charged and Uncharged Block Copolymer in Aqueous Solution: Polystyrene-Block-Poly(acrylic acid) PS-b-PAA

The micellization kinetics, dynamics, and diffusional properties of poly(styrene)-block-poly(acrylic acid) copolymer chains in salt-free aqueous solution have been investigated as a function of the copolymer composition (XPS ) for the cases of un-ionized (charge density f = 0) and ionized PAA blocks (charge density f = 1), for the first time to our knowledge via atomistic molecular dynamic simulations. The micelle formation mechanism was inspected by tracking the population of unimers and clusters across the simulation trajectory; it confirmed that the asymmetric copolymer micelle formation followed a combined approach of unimer insertion and cluster fusion mechanisms, while symmetric micelle formation followed the unimer insertion method exclusively. Micelle formation took a longer time for copolymers having charged (ionized) PAA blocks (f > 0) and relatively short PS blocks (number fraction of PS repeat units in copolymer XPS < 0.5) due to the presence of a greater number of hydrophobic groups, in agreement with the micellization kinetics observed for model copolymer micelles via DPD (Dissipative Particle Dynamics) simulation studies in literature. The conformational dynamics were studied using the relaxation of backbone dihedral angles and radius of gyration, for the core and corona blocks, respectively, showed that the PS blocks relaxed slower as compared to the soluble PAA blocks in solution due to their hydrophobic nature. The conformational relaxation time increased linearly for the PS blocks and was invariant for the PAA blocks with respect to XPS. The interaction dynamics of the PS-b-PAA copolymer micelles studied via the relaxation times of the PAA-PAA inter-chain (τHB,PP) and PAA-water inter-molecular hydrogen bonds (τHB,PW) showed the increase of τHB,PP, and the decrease of τHB,PW in solution with the increase in XPS. The PAA-water H-bond relaxes slower at f = 1 than that at f = 0 due to the stronger affinity of ionized PAA units with water molecules. The diffusivity of the copolymer chains decreased exponentially with an increase in XPS value, which is in agreement with the theoretical and experimental observations described in the literature.

Effect of Ionic Strength and pH on the Sorption of Heavy Metals onto Polyaniline Copolymers in Aqueous Solutions.

Polyaniline (PANI) and two copolymers, poly(aniline-co-o-toluidine) (PoTOL-50) and poly(aniline-co-o-anisidine) (PoANI-50) were synthesized with equal input ratios (1:1) to enhance PANI as sensing material for the sensing of various heavy metal analytes in aqueous solutions. The polymers were evaluated for both their sensitivity and selectivity toward four heavy metals (Ba2+, Cd2+, Cu2+, and Ni2+) and two common matrix interferents (Ca2+ and Mg2+) at 10 and 40 ppm. The effect of pH and ionic strength of the aqueous solutions on the sensitivity and selectivity was also evaluated. All three polymers showed high sensitivity and selectivity to Ba2+. Varying the pH and ionic strength of solutions did not show significant differences in either the selectivity or the sensitivity of the polymers.

Current paradigms in employing self-assembled structures: Drug delivery implications with improved therapeutic potential

Recent efforts have focused on developing improved drug delivery systems with enhanced therapeutic efficacy and minimal side effects. Micelles, self-assembled from amphiphilic block copolymers in aqueous solutions, have gained considerable attention for drug delivery. However, there is a need to further enhance their efficiency. These micelles offer benefits like biodegradability, biocompatibility, sustained drug release, and improved patient compliance. Yet, researchers must address stability issues and reduce toxicity. Nanoscale self-assembled structures have shown promise as efficient drug carriers, offering an alternative to conventional methods. Fine-tuning at the monomeric and molecular levels, along with structural modifications, is crucial for optimal drug release profiles. Various strategies, such as entrapping hydrophobic drugs and using polyethylene oxide diblock copolymer micelles to resist protein adsorption and cellular adhesion, protect the hydrophobic core from degradation. The polyethylene oxide corona also provides stealth properties, prolonging blood circulation for extended drug administration. Amphiphilic copolymers are attractive for drug delivery due to their adjustable properties, allowing control over micelle size and morphology. Emerging tools promise complex and multifunctional platforms. This article summarizes about the challenges as far as the use of micelles is concerned, including optimizing performance, rigorous pre-clinical and clinical research, and suggests further improvement for drug delivery efficacy.

Hydrogen bonding regulation on phase change in stimuli responsive copolymer aqueous solution

Hydrogen bonding (HB) is vital for the phase transition and physical properties of stimuli responsive copolymers. However, the governing mechanism remains unclear. Herein, we investigated the HB dynamics in a representative thermo-responsive copolymer (PNIPAM-AM) aqueous solution. Three types of HB were identified: polymer-polymer chain (CO:H–N), polymer chain-water molecule (CO:H–O) and water-water molecules (H–O:H–O) by vibrational spectroscopy. Increasing polymer concentration, the H–O:H–O softened and CO:H–O stiffened, leading to the destruction of HB network in water-water clusters. Upon increasing solution temperature, CO:H–O softened while CO:H–N stiffened, resolving the dehydration and cross-linking of polymer chains. Confinement of water molecules in the “cages” (∼ tens to hundreds of micrometers) after sol-gel phase transition was visualized, disclosing the mechanism of water holding capacity of PNIPAM-AM. The correlation of molecule vibration and copolymer microscopic structure was established, contributing to the fundamental understanding of phase behavior and physical properties regulations in stimuli responsive copolymer aqueous solution.

Hybrid polyionic complexes as nanoreactors for the synthesis of iron oxide nanoparticles: From size control to modulation of magnetic and catalytic properties

Hybrid polyion complexes (HPICs) obtained from the complexation in aqueous solution of a double hydrophilic block copolymers and metal ions can act as efficient precursors for the controlled synthesis of hybrid nanoparticles. Hence, HPICs based on a mixture of ferrous and ferric ions with poly(ethylene oxide)-block-poly(acrylic acid) were used to initiate, after the addition at 70 °C of a solution of NH4OH, the formation of iron oxide nanoparticles. The careful choice of the molar ratio between polymer and metal ions within HPICs enables to tune the morphology and size of the obtained iron oxide nanoparticles while maintaining the same surface composition. This control of size and composition was further used to highlight the relationship between the size of these particles and their catalytic and magnetic properties.

Hydrodynamic and Conformational Behavior of N-Vinylformamide–Sodium 4-Styrenesulfonate Copolymers in Aqueous Solutions

Hydrodynamic and Conformational Behavior of N-Vinylformamide–Sodium 4-Styrenesulfonate Copolymers in Aqueous Solutions

Synthesis and characterization of polystyrene-b-poly(vinyldipicolinic acid) pH-responsive core-shell nanoparticles

The self-assembly of a new series of amphiphilic polystyrene-b-poly(4-vinyldipicolinic acid) PS-b-PVDPA diblock copolymers in aqueous solution is reported in order to obtain core–shell nanoparticles composed of a PS core and a PVDPA shell. Diblock copolymers were synthesized by Supplemental Activation Reducing Agent-Atom Transfer Radical Polymerization (SARA-ATRP) with a degree of polymerization (DP) of the PS block in the range 112–260 and a DP of PVDPA block of 10, 30 or 50. Anionic latex nanoparticles of PS-b-PVDPA were prepared by solvent displacement methods. All the nanoparticle suspensions had a narrow size distribution (0.014 ≤ PDI ≤ 0.144) with zeta potential in the range −27 mV to −38 mV indicating electrostatic repulsions due to carboxylate anions and therefore high colloidal stability. DLS was used to determine nanoparticle size, with SEM and TEM used to determine and confirm both size and spherical shape. All three methods found the size for these nanoparticles to be in the range 75–120 nm. Using fluorimetry and DLS methods, Critical Aggregation Concentration (CAC) for each type of nanoparticle was determined to be within the range of 33–69 mg/L. Micelles were pH-responsive with stability in aqueous conditions for pH > 3.5. Micelles were stable at pH 5.5 for up to 40 days and at temperature up to 60 °C.

Formation of Hydrophobic-Hydrophilic Associates in the N-Vinylpyrrolidone and Vinyl Propyl Ether Copolymer Aqueous Solutions.

Utilizing turbidimetry data, an examination is conducted on the behavior of solutions containing N-vinylpyrrolidone and vinyl propyl ether copolymer within a temperature range coinciding with the occurrence of a phase transition. The investigation reveals that within specific conditions prevailing in this domain, the emergence of entities denoted as hydrophobic-hydrophilic associates is conceivable. These entities are characterized by the presence of a relatively dense core, upheld by hydrophobic interplays, and they are proficient in effectively dispersing irradiation within the optical spectrum. Encircling this core is a hydrophilic periphery that impedes the formation of insoluble precipitates. The development of such associates transpires when hydrophobic interactions have attained a discernible prominence, although they remain inadequate to counteract the forces that drive the expansion of macromolecular coils. Under these circumstances, the energetically favored course of action entails the constitution of a core for the aforementioned associates, involving discrete segments from diverse macromolecules. Notably, the introduction of an additional constituent (ethanol) to the solution, which selectively mitigates hydrophobic interactions, serves to stabilize the hydrophobic-hydrophilic associations.

Synthesis and Characterization of Thermoresponsive Chitosan-graft-poly(N-isopropylacrylamide) Copolymers.

Thermoresponsive chitosan-graft-poly(N-isopropylacrylamide) (CS-g-PNIPAAm) copolymers of different composition were synthesized by free-radical polymerization of chitosan (CS) and N-isopropylacrylamide (NIPAAm) in aqueous solution using potassium persulfate (PPS) as an initiator. By changing the molar ratio of CS:NIPAAm from 1:0.25 to 1:10 graft copolymers with a CS backbone and different amounts of PNIPAM side chains were prepared. The chemical structure of the obtained CS-g-PNIPAAm copolymers was confirmed by FTIR and 1H NMR spectroscopy. 1H NMR spectra were also used to calculate the content of attached PNIPAAm side chains. Moreover, the lower critical solution temperature (LCST) behavior of synthesized copolymers was assessed by cloud point, differential scanning calorimetry and particle size measurements. The aqueous solutions of copolymers containing ≥12 molar percent of PNIPAAm side chains demonstrated LCST behavior with the phase separation at around 29.0-32.7 °C. The intensity of thermoresponsiveness depended on the composition of copolymers and increased with increasing content of poly(N-isopropylacrylamide) moieties. The synthesized thermoresponsive chitosan-graft-poly(N-isopropylacrylamide) copolymers could be potentially applied in drug delivery systems or tissue engineering.

Self-assembly behavior of fluorinated amphiphilic copolymer in aqueous solution and its properties in the solid film state

Owing to the high electronegativity of fluorine atoms, incorporation of fluorinated moieties in a polymer can confer unique properties such as low surface energy and self-assembling ability in solution. In this study, a series of amphiphilic copolymers were prepared by radical polymerization using three monomers: 2-((2,3,3,3- tetrafluoro- 2- (1,1,2,3,3,3- hexafluoro −2- (perfluoroethoxy) propoxy) propanoyl)oxy) ethyl acrylate (FHEMA), maleic anhydride (MAH), and acrylic acid (AA). The PFHEMA block provided low surface tension, and the MAH and AA blocks (containing carboxyl) increased solubility. The properties of the polymer (PFHEMA-co-PMAH-co-PAA) can be regulated by changing the PFHEMA length. Characterization by Fourier-transform infrared spectroscopy (FTIR) and gel permeation chromatography (GPC) indicated successful polymerization (FHA01 and FHA02). When the FHEMA/MAH/AA molar ratio was 3:8:9 (FAA02), the surface tension of the hydrolyzed amphiphilic copolymers FAA02 at 300 mg·mL−1 in aqueous solution was 15.76 mN·m−1, the lowest value due to a higher fluorine content than FAA01. FAA02 self-assembled in water to form pH-sensitive micelles with diameters greater than 140 nm. For the FAA02 film, both the F/C ratio and arrangement of fluorine-containing side chains decreased with increasing film depth. Thus, this type of fluorine-containing low surface free energy material can be developed into a high performance coating material.

Synthesis of copolymer nanocomposite by in situ intercalative polymerization for batch and fixed bed adsorption

AbstractPartially neutralized acrylic acid (AA)/sodium acrylate (NaAA) and N, N′‐methylenebisacrylamide (MBA) were subjected to intercalative copolymerization in aqueous solution of polyvinyl alcohol (PVA) in the presence of sodium montmorillonite (NaMMT) nano clay to prepare filled semi‐interpenetrating network (FSIPN) type composite polymer networks. Filled Full IPN (FFIPN) composites were prepared in a similar way by additional crosslinking of PVA with maleic acid (MA) crosslinker. The polymers were characterized with FTIR, NMR, XRD, TGA, SEM, EDAX, TEM, XPS, DLS, PZC, and pH reversibility test. The synthesis variables were optimized with respect to batch adsorption of 100 mg/L each of methyl violet (MV) and congo red (CR) dye as response using the central composite design (CCD) of response surface methodology (RSM). The FFIPN prepared from polyacrylic acid (PAA)/sodium polyacrylate containing PVA/Clay/MBA/MA of optimized composition of 4/1.5/0.75/4 (wt.% of AA/NaAA), respectively, showed an optimized adsorption (mg/g adsorbent) of 459.16/417.31 of MV/CR as single dye and 438.01/417.31 of MV/CR in 1:1 binary mixtures of 100 mg/L feed concentration. The FFIPN showed an adsorption (mg/g) of 41.54/37.61 and removal% of 88.5/80.12 at a feed flow rate, bed height, and feed inlet concentration of 20 mL/min, 20 mm, and 50 mg/L, respectively.

Multitunable LCST and UCST Behaviors of Y-Junction-Bearing Polyacrylamides

Rational design of thermoresponsive polymers allows facile control over LCST/UCST and nano-object shapes. Despite tremendous progress, it remains a challenge to monitor chain conformations as the solvent isotope affects types of phase transitions. This study aims at addressing the challenge by construction of thermoresponsive Y-junction-bearing polyacrylamides with nontraditional intrinsic luminescence. With an increasing carbon number of substituents connecting with ester groups (x = 1, 2, 3, 4, 6, 8, 10, and 12), copolymers transform from hydrophilic (x = 1) to LCST (x = 2) and dual LCST/UCST (x ≥ 3) in H2O, while no UCST is available in D2O due to more stable amide–solvent hydrogen bonding and strengthened intra-/intermolecular interactions. Meanwhile, copolymer aqueous solutions can exhibit substituent/pH-dependent evolution orders of single, dual, and triple phase transitions, and asymmetric V-shaped evolution of LCST/UCST values with increasing pH is usually observed. Although 1H NMR analysis can only reveal the solvation status of subunits in the LCST region, fluorescence analysis allows to elucidate intra-/intermolecular hydrogen bonding interactions in LCST/UCST regions. Thermoinduced self-assembly in water renders sphere-to-nanocapsule-to-lamella-to-nanocapsule transitions. These important findings provide us with considerable insight into hydrogen bonding-related UCST formation by rational macromolecular design. Our study may open new avenues for regulating phase transitions and exploring solvent isotope effects.

Superabsorbent polymer with enhanced gel strength and heat resistance using itaconic acid‐based oligomer

AbstractThe preparation of an itaconic acid‐based oligomer and its polymerization with acrylic acid via aqueous solution copolymerization are described herein for application as novel superabsorbent polymers (SAPs). The structure of the SAP is characterized using Fourier transform infrared (FT‐IR) spectroscopy. In addition, the absorption properties of the SAPs with various oligomer contents and degrees of monomer neutralization are evaluated by measuring the free absorbency, centrifuge retention capacity (CRC), and absorbency under load (AUL) in 0.9 wt% saline solution. Further, the gel strengths and thermal stabilities are examined via rheological thermo gravimetric analyses. The results demonstrate that the introduction of the IA‐based oligomer into the SAP network is improves the AUL, gel strength, and thermal stability of the SAP. We found the best performance of an SAP using IA‐based oligomer with a CRC of 36.7 and AUL of 22.7 g/g.

Using the SAFT-γ-Mie to Generate Coarse-Grained Force Fields Useable in Molecular Dynamics Simulations: Describing the Micellar Phases of Polyalkylglycols in Aqueous Solutions

In this work, we showcase the potential of the SAFT-γ-Mie equation of state to obtain, in a top-down approach, coarse-grained molecular models capable of describing micellization phenomena. For this purpose, we selected polyethylene oxide (PEO)/polypropylene oxide (PPO) triblock copolymers in aqueous solutions as a case study. The model was fitted to reproduce the thermophysical properties─liquid densities and vapor pressures─of small PEO/PPO oligomers as well as the activity coefficients or liquid–liquid phase diagrams of their binary mixtures with water. At low concentrations, the MD simulations show the formation of spherical micelles of morphology comparable to experiments, with the characteristic star-shaped or flower-shaped morphology depending on the polymer block sequence. The local structure and molecular conformations were analyzed, showing distinctions between the two types of aggregates. At higher concentrations, depending on the co-polymer sequence, the molecules form larger micelles or coalesce into larger aggregates when signs of phase separation are observed, as expected.

Unexpected influence of acrylamide on clouding behavior of PEO-PPO-PEO triblock copolymers in aqueous solution

Unexpected influence of acrylamide on clouding behavior of PEO-PPO-PEO triblock copolymers in aqueous solution

Double Stimuli-Responsive di- and Triblock Copolymers of Poly(N-isopropylacrylamide) and Poly(1-vinylimidazole): Synthesis and Self-Assembly.

For the first time, double stimuli-responsive properties of poly(N-isopropylacrylamide) (PNIPA) and poly(1-vinylimidazole) (PVIM) block copolymers in aqueous solutions were studied. The synthesis of PNIPA60-b-PVIM90 and PNIPA28-b-PVIM62-b-PNIPA29 was performed using reversible addition-fragmentation chain transfer (RAFT) polymerization. The polymers were characterized by size exclusion chromatography and 1H NMR spectroscopy. The conformational behavior of the polymers was studied using dynamic light scattering (DLS) and fluorescence spectroscopy (FS). It was found that PNIPA and block copolymers conformation and ability for self-assembly in aqueous medium below and above cloud point temperature depend on the locus of hydrophobic groups derived from the RAFT agent within the chain. Additionally, the length of PVIM block, its locus in the chain and charge perform an important role in the stabilization of macromolecular micelles and aggregates below and above cloud point temperature. At 25 °C the average hydrodynamic radius (Rh) of the block copolymer particles at pH 3 is lower than at pH 9 implying the self-assembling of macromolecules in the latter case. Cloud points of PNIPA60-b-PVIM90 are ~43 °C and ~37 °C at a pH of 3 and 9 and of PNIPA28-b-PVIM62-b-PNIPA29 they are ~35 °C and 31 °C at a pH of 3 and 9. Around cloud point independently of pH, the Rh value for triblock copolymer rises sharply, achieves the maximum value, then falls and reaches the constant value, while for diblock copolymer, it steadily grows after reaching cloud point. The information about polarity of microenvironment around polymer obtained by FS accords with DLS data.

A Generalized Mechano-statistical Transient Network Model for Unravelling the Network Topology and Elasticity of Hydrophobically Associating Multiblock Copolymers in Aqueous Solutions

In this contribution, we unravel the transient network topology and elasticity of micellar networks formed by hydrophobically associating multiblock copolymers in aqueous solutions. Unlike studies on conventional triblock copolymers bearing hydrophobic blocks as end groups, our research focuses on alternating poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO) multiblock copolymers having multiple hydrophobic PPO blocks along the chain. We adopt a combinatorics approach to extend and generalize the mechano-statistical transient network model developed by Annable et al. for telechelic triblock copolymers [ Journal of Rheology, 1993, 37, 695] to multiblock copolymers. The model allows one to predict the concentration dependent elasticity of networks formed by multiblock copolymers with known molecular characteristics by using knowledge of the micellar network microstructure. The spatial distribution of the hydrophobic nodes is inferred from Small-Angle X-ray Scattering (SAXS) by converting the structure factor to the radial distribution function. The number of closely neighboring micellar cores between which an elastic bridge can be formed (nm) is calculated by spherical integration of the radial distribution function up to a distance of the radius of gyration of an intermediate soluble PEO block. Using the evolution of nm with concentration as an input for the model, the predictions show good agreement with experimental elasticity data, as inferred from the plateau modulus in linear shear rheology. The network evolves from loop-dominated, poorly elastic with cross-linking nodes with low functionality at low concentrations to bridge-dominated, highly elastic with higher node functionalities at more elevated concentrations. It is anticipated that our generalized mechano-statistical transient network model can also be used for equally spaced, multisticker associating polymers forming networks by multifunctional interactions other than micellar aggregation.

PH-Responsive, Thermo-Resistant Poly(Acrylic Acid)-g-Poly(boc-L-Lysine) Hydrogel with Shear-Induced Injectability.

In this study we report the rheological behavior of aqueous solutions of an amphiphilic graft copolymer constituting a polyacrylic acid (PAA) grafted by poly(boc-L-lysine), P(b-LL). Due to the highly hydrophobic nature of the grafted chains, the copolymer self-assembles spontaneously in aqueous media forming three-dimensional (3D) finite size networks (microgels). The rheological analysis demonstrated that the copolymer behaves as a strong elastic hydrogel, showing characteristics of a "frozen" network. Moreover, it is noteworthy that the formulation shows the above-described characteristics in very small concentrations (0.25-1.20 wt%) compared to other naturally cross-linked hydrogels that have been studied so far. Concentration significantly affects the rheological properties of the hydrogel, showing considerable increase in elastic modulus, following the scaling law G'~C1.93. At the same time, the hydrogels can be described as intelligent stimuli-responsive systems, showing pH and shear responsiveness as well as stability with temperature changes. Thanks to the pH dependance of the degree of ionization of the weak polyelectrolyte PAA backbone, stiffness and swelling of the hydrogels can be tuned effectively by adjusting the pH conditions. Simulating conditions such as those of injection through a 28-gauge syringe needle, the gel demonstrates excellent response to shear, due to its remarkable shear thinning behavior. The combination of pH-sensitivity and shear responsiveness leads to excellent injectability and self-healing properties, given that it flows easily upon applying a low stress and recovers instantly in the site of injection. Therefore, the physically cross-linked PAA-g-P(b-LL) hydrogel exhibits remarkable features, namely biocompatibility, biodegradability of cross-links, pH responsiveness, shear-induced injectability and instantaneous self-healing, making it a potential candidate for various biomedical applications.

Loose Semirigid Aromatic Polyester Bottle Brushes at Poly(2-isopropyl-2-oxazoline) Side Chains of Various Lengths: Behavior in Solutions and Thermoresponsiveness.

A polycondensation aromatic polyester with an oxygen spacer was synthesized and used as a macroinitiator for the grafting of linear poly(2-isopropyl-2-oxazoline) (PiPrOx) by the cationic polymerization method. The length of the thermosensitive side chains was varied by the initiator:monomer ratio. Using methods of molecular hydrodynamics, light scattering and turbidimetry, the copolymers were studied in organic solvents and in water. The molecular characteristics of the main chain and graft copolymers, the polymerization degree of side chains and their grafting density have been determined. The equilibrium rigidity of the macroinitiator and the conformations of grafted macromolecules were evaluated. In selective solvents, they take on a star-like conformation or aggregate depending on the degree of shielding of the main chain by side chains. The thermoresponsiveness of graft copolymers in aqueous solutions was studied, and their LCST were estimated. The results are compared with data for graft copolymers composed of PiPrOx side chains and flexible or rigid chain backbones of aromatic polyester type.

Structure and Dynamics of Inhomogeneities in Aqueous Solutions of Graft Copolymers of N-Isopropylacrylamide with Lactide (P(NIPAM-graft-PLA)) by Spin Probe EPR Spectroscopy.

Coil-to-globule transition and dynamics of inhomogeneities in aqueous solutions of graft copolymers of NIPAM with different content of oligolactide groups were studied using spin probe continuous wave EPR spectroscopy. The technique of the suppressing of TEMPO as spin probe by spin exchange with Cu2+ ions was applied. This approach allowed us to detect individual EPR spectra of the probe in collapsed globules and estimate its magnetic and dynamic parameters reliably. The formation of inhomogeneities at temperatures lower than the volume phase transition temperature measured via transmission, and differential scanning calorimetry was fixed. An increase in oligolactide content in copolymers leads to the formation of looser globules, allowing for the exchange of the probe molecules between the globules and the external solution.