Flory-Huggins Interaction Parameter Research Articles

Integrating thermodynamic and kinetic approaches for the design of effective and sustainable PET chemical upcycling systems

Understanding and optimizing the individual contributions of recycling process components are critical in the development of effective and sustainable upcycling systems. Herein, each process component, i.e., alcohol, co-solvent, Lewis acid, and reaction conditions, is newly and holistically assessed for the alcohol-based conversion of postconsumer polyethylene terephthalate (PET) to terephthalic acid (TPA) and its precursors by integrating thermodynamic and kinetic considerations. First, an analysis based on the Flory-Huggins interaction parameter (χ1,2) establishes the importance of co-solvents in the depolymerization process due to reduction of thermodynamic potential. Second, a kinetic analysis of the catalyst component proves the vitality of the solubility of the Lewis acid source for efficient PET deconstruction. In addition, further validation experiments determine methanol as the most effective option in tandem alcoholysis given its reduced steric hindrance and relatively higher nucleophilicity, whereas process optimization tests suggest the existence of an optimum methanol molar ratio (XMetOH) of 0.16 and operation at 50 °C to realize TPA yields that exceed 90 % within 15 min across various pure and mixed PET feedstocks. Selection and implementation of greener solvents in the process is also found to reduce co-solvent based emissions by 96.3 % whilst retaining comparable monomer production efficiency. Overall, the implementation of thermodynamic considerations and kinetics-based understanding of roles played by each component is found to boost the overall depolymerization process, and the integration of these thermodynamic and kinetic approaches provides a unified avenue for optimizing and developing sustainable recycling processes for post-consumer plastic waste.

Systematic Investigation on the Swelling Response and Oil Resistance of NBR Using the Prediction Models Determined by the Modified Flory-Huggins Interaction Parameter.

The equilibrium swelling test was employed to determine the swelling response of Nitrile Butadiene Rubber (NBR) with various acrylonitrile (ACN) contents, and the three-dimensional solubility parameter (HSP) and modified Flory-Huggins interaction parameter (χHSP) were used to establish the prediction model of the oil-resistant property. The results indicate that the energy difference (Ra) between NBR and solvents calculated by HSP values can be correlated with the swelling response qualitatively with an inversed "S-shape", and high swelling response occurs at Ra < 8 MPa1/2 for NBR. For the purpose of establishing the prediction model, the new modified χHSP value has been calculated and fitted with the swelling response using exponential and logarithmic fittings, respectively. Two prediction models considering all the possible influencing factors have been obtained to determine the swelling response and oil resistance of NBR-based rubber products in bio-fuels, represented by the bio-diesel and IRM 903 test oil in this work. The swelling response of NBR can be evaluated precisely, and high swelling regions can be predicted and avoided in the new emerging fuels through the prediction models. Thus, the oil resistance of NBR-based rubber products, such as seals, holes and gaskets can be well predicted now.

A unifying approach to drug-in-polymer solubility prediction: Streamlining experimental workflow and analysis

This method paper describes currently used experimental methods to predict the drug-in-polymer solubility of amorphous solid dispersions and offers a combined approach for applying the Melting-point-depression method, the Recrystallization method, and the Melting-and-mixing method. It aims to describe and expand on the theoretical basis as well as the analytical methodology of the recently published Melting-and-mixing method. This solubility method relies on determining the relationship between drug loads and the enthalpy of melting and mixing of a crystalline drug in the presence of an amorphous polymer. This relationship is used to determine the soluble drug load of an amorphous solid dispersion from the recorded enthalpy of melting and mixing of the crystalline drug portion in a drug-polymer sample at equilibrium solubility. Due to the complex analytical methodology of the Melting-and-mixing method, a software solution called the Glass Solution Companion app was developed. Using this new tool, it is possible to calculate the predicted drug-in-polymer solubility and Flory-Huggins interaction parameter from experimental samples, as well as to generate the resulting solubility-temperature curve. This software can be used for calculations for all three experimental methods, which would be useful for comparing the applicability of the methods on a given drug-polymer system. Since it is difficult to predict the suitability of these drug-in-polymer solubility methods for a specific drug-polymer system in silico, some experimental investigation is necessary. By optimizing the experimental protocol, it is possible to collect data for the three experimental methods simultaneously for a specific drug-polymer system. These results can then be readily analyzed using the Glass Solution Companion app to find the most appropriate method for the drug-polymer system, and therefore, the most reliable drug-in-polymer solubility prediction.

Topology Effect on Order-Disorder Transition of High-χ Block Copolymers.

This work aims to systematically examine the topology effect on the self-assembly of block copolymers. Compositionally, symmetric polystyrene-block-polydimethylsiloxane block copolymers (BCPs) with different chain topologies (diblock, three-arm star-block, and four-arm star-block) and various molecular weights are synthesized. These purposely designed block copolymers are used as a model system to investigate the topology effect on order-to-disorder transition temperature (T ODT) by temperature-resolved small-angle X-ray scattering experiments. An increase of the T ODT is observed when the arm number of BCPs with equivalent arm length (i.e., molecular weight) is increased from one to four. Based on the random-phase approximation (RPA), Flory-Huggins interaction parameter (χ) is determined from the regression of the measured T ODT. The observation by differential scanning calorimetry also demonstrates the shifting of the endothermic peak from the order-to-disorder transition of star-blocks to the higher temperature region, consistent with the scattering experiments and the RPA prediction.

Miscibility, crystallization and morphology in the novel polylactide/poly(4-hydroxybutyrate) blends

The novel marine degradable poly (4-hydroxybutyrate) (P4HB) synthesized by chemical technique could obviously improve the brittleness of polylactide (PLLA) via physical blending. However, the miscibility, crystallization and morphology in PLLA/P4HB blends are still unexplored. In this article, the PLLA/P4HB blends with different weight ratios were prepared by the solution casting method, followed by the melting crystallization treatment. The PLLA and P4HB were demonstrated to be miscible near the melting temperature of PLLA as revealed by the Flory-Huggins interaction parameter calculating by melting point depression method. Anyway, PLLA and P4HB are supposed to be immiscible at room temperature according to the interfacial tension, fourier transform infrared spectroscopy (FTIR) analysis and scanning electron microscopy (SEM) observation. Both of PLLA and P4HB could form the highly crystalline crystals as casting from solution. The existence of P4HB could significantly induce the cold crystallization of PLLA on the second heating curves characterized by differential scanning calorimetry (DSC), showing of a sharp reduction in peak temperature of about 40 °C lower than that of pristine PLLA. The polarized optical microscopy (POM) and atomic force microscopy (AFM) observation revealed that the P4HB phase could penetrate into the region between fibrous crystals of PLLA spherulites during the isothermal crystallization at 130 °C, and the P4HB fragmented crystals will form after cooling to room temperature, leading to the formation of vertical phase separation in PLLA/P4HB blends associating with the surface tension data. The findings will provide theoretical guidance to understand the miscibility in PLLA based fully biodegradable blends, modulating the morphology and properties of the blends.

Morphological Transitions of Block Copolymer Micelles: Implications for Mesoporous Materials Ordering

AbstractThe design of block‐copolymer‐based functional materials, including mesoporous membranes and nanoparticles, requires a comprehensive understanding of the hierarchical assembly of block copolymers in selective solvents into micelles and subsequent ordered phases. It is hypothesized that micellar ordering and characteristic assembly can be described using a set of phase parameters that account for entropic and enthalpic interactions. Dissipative particle dynamics (DPD) simulations are used to systematically investigate the self‐assembly of semidiluted block copolymers, resembling isoporous membrane preparation conditions. The effect of Flory–Huggins interaction parameters, block lengths, and concentration on the morphology and polydispersity of the micelles is evaluated. The interaction parameters are mapped into Flory–Huggins theory by considering the block's conformation. These results reveal the effect of polymer concentration and solvent affinity on the morphological transition of the aggregates, in agreement with existing experimental evidence. It is identified that monodisperse‐spherical micelles in solution are fundamental to stabilize ordered states. Weak solvent segregation of the largest block, curvature of the core‐corona interface, and stretching of the corona‐forming one are found to be key to stabilize monodisperse assemblies. These conditions can be predicted using spherical‐micelles packing considerations and a global phase parameter from the Flory–Huggins theory. This study provides valuable insights into the self‐assembly of diblock copolymers and offers a potential way to optimize the preparation of mesoporous ordered structures and micelle ordering in semidiluted systems.

Chemically tailored block copolymers for highly reliable sub-10-nm patterns by directed self-assembly

While block copolymer (BCP) lithography is theoretically capable of printing features smaller than 10 nm, developing practical BCPs for this purpose remains challenging. Herein, we report the creation of a chemically tailored, highly reliable, and practically applicable block copolymer and sub-10-nm line patterns by directed self-assembly. Polystyrene-block-[poly(glycidyl methacrylate)-random-poly(methyl methacrylate)] (PS-b-(PGMA-r-PMMA) or PS-b-PGM), which is based on PS-b-PMMA with an appropriate amount of introduced PGMA (10–33 mol%) is quantitatively post-functionalized with thiols. The use of 2,2,2-trifluoroethanethiol leads to polymers (PS-b-PGFMs) with Flory–Huggins interaction parameters (χ) that are 3.5–4.6-times higher than that of PS-b-PMMA and well-defined higher-order structures with domain spacings of less than 20 nm. This study leads to the smallest perpendicular lamellar domain size of 12.3 nm. Furthermore, thin-film lamellar domain alignment and vertical orientation are highly reliably and reproducibly obtained by directed self-assembly to yield line patterns that correspond to a 7.6 nm half-pitch size.

Electrical properties of MAH-g-PP modified PP/SEBS matrix semi-conductive composite materials

Polypropylene (PP) becomes a superior candidate material for new environmental-friendly cable insulation layer with its excellent heat resistance, electrical properties and degradability. At present, most of studies focus on the insulation layer of PP cable. However, there are few studies on semi-conductive shielding layer of PP cable which match its insulation layer. In this paper, polypropylene (PP)/styrene ethylene butylene styrene (SEBS) is adopted as matrix of PP cable semi-conductive layer to matching its insulation layer. Meanwhile, Maleic anhydride grafted polypropylene (MAH-g-PP) is used to cooperatively improve the compatibility between PP and SEBS. The physicochemical properties, space charge injection properties and compatibility of semi-conductive composites with different CB and MAH-g-PP contents is studied by combining experiment and simulation methods. The experimental results show that the surface roughness of the semi-conductive layer and the space charge inside the insulation layer decrease first and then increase with the increase of CB addition. Among them, the two parameters of 25 phr CB semi-conductive layer is the lowest, respectively 13.98 nm and 2.25 × 10−8C. These two parameters are significantly reduced after the addition of compatibilizer MAH-g-PP, which decreased by 29.47 % and 62.22 %, respectively. The simulation results show that the Flory-Huggins interaction parameters (χ) of MAH-g-PP with PP and SEBS are −73.3 and −45.2, respectively, which are 236.24 % and 107.34 % lower than those of PP/SEBS. The χ value of MAH-g-PP/CB is 8.20, which is 33.27 % and 9.59 % lower than CB/PP and CB/SEBS, respectively. It shows that MAH-g-PP can effectively improve the compatibility of matrix and filler. This work has important guiding significance for the research of semi-conductive layer formulation of PP cable.

Investigation of Polymer-Asphalt Compatibility Using Molecular Dynamics Simulation.

Polymer modification is a promising approach to enhancing the performance of asphalt binders. However, a major issue plaguing polymer mixing with asphalt is the phase separation of these two components post-mixing. In the field of polymer science, the Flory-Huggins theory has been long established as the way to describe the conditions under which a mixture is stable or unstable. This Flory-Huggins interaction parameter χ and the molecular weights of the components are required under this theory. This work uses molecular dynamics simulations to calculate χ between various polymers found in waste plastics and asphalt. The compatibility of these polymers with the asphalt binder is discussed as a function of binder composition, molecular weight, and temperature. Four common polymers (polyethylene, polystyrene, polypropylene, and polybutadiene) were tested. While none of the polymers showed good compatibility with asphalt, PE was the most compatible. Stable compatibilization of plastics with asphalt will require additives or chemical modification of the plastic.

High Modulus, Strut-like poly(ether ether ketone) Aerogels Produced from a Benign Solvent.

Poly(ether ether ketone) (PEEK) was found to form gels in the benign solvent 1,3-diphenylacetone (DPA). Gelation of PEEK in DPA was found to form an interconnected, strut-like morphology composed of polymer axialites. To our knowledge, this is the first report of a strut-like morphology for PEEK aerogels. PEEK/DPA gels were prepared by first dissolving PEEK in DPA at 320 °C. Upon cooling to 50 °C, PEEK crystallizes and forms a gel in DPA. The PEEK/DPA phase diagram indicated that phase separation occurs by solid-liquid phase separation, implying that DPA is a good solvent for PEEK. The Flory-Huggins interaction parameter, calculated as χ12 = 0.093 for the PEEK/DPA system, confirmed that DPA is a good solvent for PEEK. PEEK aerogels were prepared by solvent exchanging DPA to water then freeze-drying. PEEK aerogels were found to have densities between 0.09 and 0.25 g/cm3, porosities between 80 and 93%, and surface areas between 200 and 225 m2/g, depending on the initial gel concentration. Using nitrogen adsorption analyses, PEEK aerogels were found to be mesoporous adsorbents, with mesopore sizes of about 8 nm, which formed between stacks of platelike crystalline lamellae. Scanning electron microscopy and X-ray scattering were utilized to elucidate the hierarchical structure of the PEEK aerogels. Morphological analysis found that the PEEK/DPA gels were composed of a highly nucleated network of PEEK axialites (i.e., aggregates of stacked crystalline lamellae). The highly connected axialite network imparted robust mechanical properties on PEEK aerogels, which were found to densify less upon freeze-drying than globular PEEK aerogel counterparts gelled from dichloroacetic acid (DCA) or 4-chlorphenol (4CP). PEEK aerogels formed from DPA were also found to have a modulus-density scaling that was far more efficient in supporting loads than the poorly connected aerogels formed from PEEK/DCA or PEEK/4CP solutions. The strut-like morphology in these new PEEK aerogels also significantly improved the modulus to a degree that is comparable to high-performance crosslinked aerogels based on polyimide and polyurea of comparable densities.

Molecular dynamics study of the thermodynamic properties of triglyceride/methanol mixtures in the presence of cosolvent

Biodiesel is a renewable source of energy that has the potential to replace fossil fuel-based resources. It is produced via the transesterification reaction in which a triglyceride reacts with methanol in the presence of a catalyst. Cosolvents are usually added to the reactants in transesterification to improve the mutual solubility of methanol and triglycerides and to create a single phase. The commonly used cosolvents in transesterification include tetrahydrofuran (THF) and diethyl ether (DEE). Understanding the thermodynamic properties of this system is important in the selection of cosolvent. In this study, molecular dynamics simulations were used to study the mixing behavior between the components of ternary mixtures of triolein/methanol/THF and triolein/methanol/DEE via the application of Flory-Huggins theory of solutions. A simple approach to calculation of the Flory-Huggins interaction parameters is used in which the mixing energy is derived from averaged non-bonded pair interaction energies. Apart from pure triolein, these ternary systems resemble the experimentally studied ternary systems employing various plant-based oils. The binary interaction parameters, Gibbs Free energy and chemical potentials of the components were calculated to study the mixing behavior. Our results show that along the experimental phase boundary the binary interaction parameters remain relatively unchanged with a deviation observed at the highest volume fractions of triolein where the highest binary interactions were observed indicating the possibility of phase separation. The Gibbs energy of mixing for the systems changed from positive to negative as one moves from two phase to single phase part of the ternary system as expected and in agreement with experimental data. The chemical potentials of the ternary mixture components were calculated from the partial derivatives of the Gibbs free energy of mixing. The activities calculated from Flory-Huggins chemical potentials were compared to those calculated using the UNIFAC model. There is good agreement between the two, with both able to predict a single and biphasic mixture. However, disagreements are noted at low and high concentrations of triolein.

Mixing temperature optimization and modification mechanism of medical masks modified asphalt: Insights from computational chemistry

Masks modified asphalt (MMA) offers a solution to pollution caused by discarded medical masks. Mixing temperature plays a crucial role in storage stability and even rheological performance of MMA. Traditional selection method overly relies on trial-and-error experiment, neglecting the convenience offered by computational chemistry. Furthermore, previous literature lacks precise elucidation of MMA’s physical modification mechanism, especially concerning the binding mode and energy composition. To address these issues, the optimal mixing temperature for MMA was recommended based on molecular dynamics. The rationality of recommended temperature was validated through laboratory tests, simultaneously investigating the impact of heating time. Fluorescence microscopy and multi-band spectroscopy were employed to acquire the microstructure. Binding modes in MMA were determined using binding sites exploration, evaluating the energy composition of each binding mode through quantum chemistry. The interaction mechanism was explained based on surface properties of isolated molecules. Results indicated that 170℃ was the recommended optimal mixing temperature derived from mixing free energy and Flory-Huggins interaction parameter. The fluctuations in softening point difference (ΔTR&B) and separation ratio (RS) concurrently tended towards stability, thereby validating the reliability of recommended temperature. Moreover, even after 72 h heating, MMA prepared at recommended temperature remained within a reasonable range concerning ΔTR&B, RS, and microscopic structure. Perpendicular, parallel, toroidal, and spherical modes emerged in MMA. Perpendicular and parallel modes exhibited the highest binding energies, while circular mode demonstrated the lowest. Binding energy is primarily governed by van der Waals interaction, attributed to the dominance of dispersion term on MMA’s molecular surface. Besides, due to the presence of polycyclic aromatic hydrocarbons in asphalt molecules, electrostatic interaction contributed to specific molecular bindings.

Theory and quantitative assessment of pH-responsive polyzwitterion-polyelectrolyte complexation.

We introduce a theoretical framework to describe the pH-sensitive phase behavior of polyzwitterion-polyelectrolyte complex coacervates that reasonably captures the phenomenon from recent experimental observations. The polyzwitterion is described by a combinatorial sequence of the four states in which each zwitterionic monomer can occupy: dipolar, quasi-cationic, quasi-anionic, and fully neutralized. We explore the effects of various modifiable chemical and physical properties of the polymers-such as, pKa of the pH-active charged group on the zwitterion, equilibrium constant of salt condensation on the permanently charged group on the zwitterion, degrees of polymerization, hydrophobicity (via the Flory-Huggins interaction parameter), and dipole lengths-on the window of complexation across many stoichiometric mixing ratios of polyzwitterion and polyelectrolyte. The properties that determine the net charge of the polyzwitterion have the strongest effect on the pH range in which polyzwitterion-polyelectrolyte complexation occurs. We finish with general guidance for those interested in molecular design of polyzwitterion-polyelectrolyte complex coacervates and opportunities for future investigation.

Effect of cosolvents on the phase separation of polyelectrolyte complexes.

Evidence is shown that cosolvent mixtures control the coacervation of mixtures of oppositely charged polyelectrolytes. Binary and ternary solvent mixtures lead to non-monotonic solubility as a function of the average dielectric constants of the solvent mixtures. These data are rationalized by considering both electrostatic-driven phase separation and solvophobic-driven phase separation using group contribution effects on solubility parameters. These estimates are introduced into an effective Flory-Huggins interaction parameter within the framework of Voorn-Overbeek theory with variable dielectric constants and temperature dependences. Despite its simplicity, the model recovers salient experimental observations not only on their coacervate stabilities, but also on their lower critical solution temperature behaviors. These observations highlight the importance of weak van der Waals interactions in determining the phase behaviors of polyelectrolyte complexes relative to electrostatic correlations.

Thermoresponsive Polymers under Pressure with a Focus on Poly(N-isopropylacrylamide) (PNIPAM).

Pressure is a key variable in the phase behavior of responsive polymers, both for applications and from a fundamental point of view. In this feature article, we review recent developments, particularly applications of neutron techniques such as small-angle neutron scattering (SANS) and quasi-elastic neutron scattering (QENS), across the temperature-pressure phase diagram. These are complemented by kinetic SANS experiments following pressure jumps. In the prototype system poly(N-isopropylacrylamide) (PNIPAM), QENS revealed the pressure-dependent characteristics of hydration water around the lower critical solution temperature transition. The size, water content, and inner structure of the mesoglobules formed in the two-phase region depend strongly on pressure, as shown by SANS. Beside these changes at the phase transition, the mesoglobule formation at low pressure is determined by kinetic factors, namely the formation of a polymer-rich, rigid shell, which hampers further growth by coalescence. At high pressure, in contrast, the growth proceeds by diffusion-limited coalescence without any kinetic hindrance. The disintegration of the mesoglobules evolves either via chain release from their surface or via swelling, depending on the osmotic pressure of the water. Moreover, we report on the profound influence of pressure on the cononsolvency effect. In the temperature-pressure frame, the one-phase region is hugely expanded upon the addition of the cosolvent methanol. SANS experiments unveil the enthalpic and entropic contributions to the effective Flory-Huggins interaction parameter between the segments and the solvent mixture. QENS experiments demonstrate an increase in polymer associated water with pressure, whereas methanol is released. Correspondingly, the solvent phase becomes enriched in methanol, providing a mechanism for the breakdown of cononsolvency at a high pressure. Finally, we outline future opportunities for high-pressure studies of thermoresponsive polymers, with a focus on neutron methods.

Reductive amination of oxidized hydroxypropyl cellulose with ω-aminoalkanoic acids as an efficient route to zwitterionic derivatives

Zwitterionic polymers, with their equal amounts of cationic and anionic functional groups, have found widespread utility including as non-fouling coatings, hydrogel materials, stabilizers, antifreeze materials, and drug carriers. Polysaccharide-derived zwitterionic polymers are attractive because of their sustainable origin, potential for lower toxicity, and possible biodegradability, but previous methods for synthesis of zwitterionic polysaccharide derivatives have been limited in terms of flexibility and attainable degree of substitution (DS) of charged entities. We report herein successful design and synthesis of zwitterionic polysaccharide derivatives, in this case based on cellulose, by reductive amination of oxidized 2-hydroxypropyl cellulose (Ox-HPC) with ω-aminoalkanoic acids. Reductive amination products could be readily obtained with DS(cation) (= DS(anion)) up to 1.6. Adduct hydrophilic/hydrophobic balance (amphiphilicity) can be influenced by selecting the appropriate chain length of the ω-aminoalkanoic acid. This strategy is shown to produce a range of amphiphilic, water-soluble, moderately high glass transition temperature (Tg) polysaccharide derivatives in just a couple of efficient steps from commercially available building blocks. The adducts were evaluated as crystallization inhibitors. They are strong inhibitors of crystallization even for the challenging, poorly soluble, fast-crystallizing prostate cancer drug enzalutamide, as supported by surface tension and Flory–Huggins interaction parameter results.

Connecting Structural Characteristics and Material Properties in Phase-Separating Polymer Solutions: Phase-Field Modeling and Physics-Informed Neural Networks.

The formed morphology during phase separation is crucial for determining the properties of the resulting product, e.g., a functional membrane. However, an accurate morphology prediction is challenging due to the inherent complexity of molecular interactions. In this study, the phase separation of a two-dimensional model polymer solution is investigated. The spinodal decomposition during the formation of polymer-rich domains is described by the Cahn-Hilliard equation incorporating the Flory-Huggins free energy description between the polymer and solvent. We circumvent the heavy burden of precise morphology prediction through two aspects. First, we systematically analyze the degree of impact of the parameters (initial polymer volume fraction, polymer mobility, degree of polymerization, surface tension parameter, and Flory-Huggins interaction parameter) in a phase-separating system on morphological evolution characterized by geometrical fingerprints to determine the most influential factor. The sensitivity analysis provides an estimate for the error tolerance of each parameter in determining the transition time, the spinodal decomposition length, and the domain growth rate. Secondly, we devise a set of physics-informed neural networks (PINN) comprising two coupled feedforward neural networks to represent the phase-field equations and inversely discover the value of the embedded parameter for a given morphological evolution. Among the five parameters considered, the polymer-solvent affinity is key in determining the phase transition time and the growth law of the polymer-rich domains. We demonstrate that the unknown parameter can be accurately determined by renormalizing the PINN-predicted parameter by the change of characteristic domain size in time. Our results suggest that certain degrees of error are tolerable and do not significantly affect the morphology properties during the domain growth. Moreover, reliable inverse prediction of the unknown parameter can be pursued by merely two separate snapshots during morphological evolution. The latter largely reduces the computational load in the standard data-driven predictive methods, and the approach may prove beneficial to the inverse design for specific needs.

Composition Dependency of the Flory-Huggins Interaction Parameter in Drug-Polymer Phase Behavior.

An innovative strategy to address recent challenges in the oral administration of poorly soluble drugs is the formulation of amorphous solid dispersions (ASDs), where the drug is dissolved in a highly soluble carrier polymer. Therefore, special knowledge of the drug-polymer phase behavior is essential for an effective product and process design, accelerating the introduction of novel efficacious ASD products. Flory-Huggins theory can be applied to model solubility temperatures of crystalline drugs in carrier polymers over the drug fraction. However, predicted solubility temperatures lack accuracy in cases of strong drug/polymer interactions that are not represented in the Flory-Huggins lattice model. Within this study, a modeling strategy is proposed to improve the predictive power through an extension of the Flory-Huggins interaction parameter by a correlation with the drug fraction. Therefore, the composition dependency of the Flory-Huggins interaction parameter was evaluated experimentally for various drug-polymer formulations that cover a wide variety of drug and polymer characteristics regarding molecular weights, glass transition temperatures and melting temperatures, as well as drug-polymer interactions of different strengths and effects. The extended model was successfully approved for nine exemplary ASD formulations containing the drugs acetaminophen, itraconazole, and griseofulvine, as well as the following polymers: basic butylated methacrylate copolymer, Soluplus®, and vinylpyrrolidone/vinyl acetate copolymer. A high correlation between the predicted solubility temperatures and experimental and literature data was found, particularly at low drug fractions, since the model accounts for composition dependent drug-polymer interactions.

Simple Mathematical Approach for Determining the Compositions of the Different Phases Resulting From the Phase Separation Behavior of Polymer Blends

In this article, the Flory–Huggins theory is utilized to formulate two essential equations for determining the compositions of the different phases resulting from the phase separation behavior of polymer blends. The equations use a graphical approach to determine the numerical outcomes of the compositions of the different phases, serving as a universally applicable illustration. The results show that when the Flory–Huggins interaction parameter is less than the critical value, the graphs of the equations have no intersection point, indicating the absence of phase separation. Conversely, when the Flory–Huggins interaction parameter equals the critical value, the graphs of the equations display a single intersection point. Furthermore, if the parameter value exceeds the critical value, the graphs of the equations show two symmetrical intersection points, indicating that phase separation can occur. The present study also includes a discussion on the correlations between the compositions of the different phases and the Flory–Huggins interaction parameter.

Structure of Single-Chain Nanoparticles under Crowding Conditions: A Random Phase Approximation Approach.

The conformation of poly(methyl methacrylate) (PMMA)-based single-chain nanoparticles (SCNPs) and their corresponding linear precursors in the presence of deuterated linear PMMA in deuterated dimethylformamide (DMF) solutions has been studied by small-angle neutron scattering (SANS). The SANS profiles were analyzed in terms of a three-component random phase approximation (RPA) model. The RPA approach described well the scattering profiles in dilute and crowded solutions. Considering all the contributions of the RPA leads to an accurate estimation of the single chain form factor parameters and the Flory-Huggins interaction parameter between PMMA and DMF. The value of the latter in the dilute regime indicates that the precursors and the SCNPs are in good solvent conditions, while in crowding conditions, the polymer becomes less soluble.