Impact of nanopore confinement on phase behavior and enriched gas minimum miscibility pressure in asphaltenic tight oil reservoirs.

Miscible gas injection in tight/shale oil reservoirs presents a complex problem due to various factors, including the presence of a large number of nanopores in the rock structure and asphaltene and heavy components in crude oil. This method performs best when the gas injection pressure exceeds the minimum miscibility pressure (MMP). Accordingly, accurate calculation of the MMP is of special importance. A critical issue that needs to be considered is that the phase behavior of the fluid in confined nanopores is substantially different from that of conventional reservoirs. The confinement effect may significantly affect fluid properties, flow, and transport phenomena characteristics in pore space, e.g., considerably changing the critical properties and enhancing fluid adsorption on the pore wall. In this study, we have investigated the MMP between an asphaltenic crude oil and enriched natural gas using Peng-Robinson (PR) and cubic-plus-association (CPA) equations of state (EoSs) by considering the effect of confinement, adsorption, the shift of critical properties, and the presence of asphaltene. According to the best of our knowledge, this is the first time a model has been developed considering all these factors for use in porous media. We used the vanishing interfacial tension (VIT) method and slim tube test data to calculate the MMP and examined the effects of pore radius, type/composition of injected gas, and asphaltene type on the computed MMP. The results showed that the MMP increased with an increasing radius of up to 100 nm and then remained almost constant. This is while the gas enrichment reduced the MMP. Asphaltene presence changed the trend of IFT reduction and delayed the miscibility achievement so that it was about 61% different from the model without the asphaltene precipitation effect. However, the type of asphaltene had little impact on the MMP, and the controlling factor was the amount of asphaltene in the oil. Moreover, although cubic EoSs are particularly popular for their simplicity and accuracy in predicting the behavior of hydrocarbon fluids, the CPA EoS is more accurate for asphaltenic oils, especially when the operating pressure is within the asphaltene precipitation range.

Predicting the Stability of Formulations Containing Lyophilized Human Serum Albumin and Sucrose/Trehalose Using Solid-State NMR Spectroscopy.

Stabilization of proteins by disaccharides in lyophilized formulations depends on the interactions between the protein and the disaccharide (system homogeneity) and the sufficiently low mobility of the system. Human serum albumin (HSA) was lyophilized with disaccharides (sucrose and/or trehalose) in different relative concentrations. Solid-state nuclear magnetic resonance (ssNMR) spectroscopy 1H T1 and 1H T1ρ relaxation times were measured to determine the homogeneity of the lyophilized systems on 20-50 and 1-3 nm domains, respectively, with 1H T1 relaxation times also being used to determine the ß-relaxation rate. HSA/sucrose systems had longer 1H T1 relaxation times and were slightly more stable than HSA/trehalose systems in almost all cases shown. HSA/sucrose/trehalose systems have 1H T1 relaxation times between the HSA/sucrose and HSA/trehalose systems and did not result in a more stable system compared with binary systems. Inhomogeneity was evident in a sample containing relative concentrations of 10% HSA and 90% trehalose, suggesting trehalose crystallization during lyophilization. Under these stability conditions and with these ssNMR acquisition parameters, a 1H T1 relaxation time below 1.5 s correlated with an unstable sample, regardless of the disaccharide(s) used.

Biomembranes balance many types of leaflet asymmetries.

Many biological membranes host different lipid species in their two leaflets. Since their spontaneous curvatures are typically not the same, this compositional asymmetry generally entails bending torques, which can be counteracted by differential stress-the difference between the two leaflet tensions. This stress, in turn, can affect elastic parameters or phase behavior of the membrane or each individual leaflet, or push easily flippable species, especially cholesterol, from the compressed leaflet into the tense leaflet. In short, breaking the symmetry of a single observable (to wit: composition), essentially breaks all other symmetries as well, with many potentially interesting consequences. This brief report examines the elastic aspects of this interplay, focusing on some elementary conditions of mechanical and thermodynamic equilibrium, but also shows how this poses novel questions that we are only beginning to appreciate.

Rational Design of 2D Supramolecular Networks Switchable by External Electric Fields.

The reversible formation of hydrogen bonds is a ubiquitous mechanism for controlling molecular assembly in biological systems. However, achieving predictable reversibility in artificial two-dimensional (2D) materials remains a significant challenge. Here, we use an external electric field (EEF) at the solid/liquid interface to trigger the switching of H-bond-linked 2D networks using a scanning tunneling microscope. Assisted by density functional theory and molecular dynamics simulations, we systematically vary the molecule-to-molecule interactions, i.e., the hydrogen-bonding strength, as well as the molecule-to-substrate interactions to analyze the EEF switching effect. By tuning the building block's hydrogen-bonding ability (carboxylic acids vs aldehydes) and substrate nature and charge (graphite, graphene/Cu, graphene/SiO2), we induce or freeze the switching properties and control the final polymorphic output in the 2D network. Our results indicate that the switching ability is not inherent to any particular building block but instead relies on a synergistic combination of the relative adsorbate/adsorbate and absorbate/substrate energetic contributions under surface polarization. Furthermore, we describe the dynamics of the switching mechanism based on the rotation of carboxylic groups and proton exchange, which generate the polarizable species that are influenced by the EEF. This work provides insights into the design and control of reversible molecular assembly in 2D materials, with potential applications in a wide range of fields, including sensors and electronics.

Phase Behavior of Charged Star Block Copolymers at Fluids Interface.

The phase behavior of block copolymers (BCPs) at the water-oil interface is influenced by the segmental interaction parameter ( χ ${\chi }$ ) and chain architecture. We synthesized a series of star block copolymers (s-BCPs) having polystyrene (PS) as core and poly(2-vinylpyridine) (P2VP) as corona. The interaction parameters of block-block ( χ ${\chi }$ PS-P2VP ) and block-solvent ( χ ${\chi }$ P2VP-solvent ) were varied by adjusting the pH of the aqueous solution. Lowering pH increased the fraction of quaternized-P2VP (Q-P2VP) with enhanced hydrophilicity. By transferring the equilibrated interfacial assemblies, morphologies ranging from bicontinuous films at pH of 7 and 3.1 to nanoporous and nanotubular structure at pH of 0.65 were observed. The nanoporous films formed hexagonally packed pores in s-BCP matrix, while nanotubes comprised Q-P2VP as corona and PS as core. Control over pore size, d-spacing between pores, and nanotube diameters was achieved by varying polymer concentration, molecular weight, volume fraction and arm number of s-BCPs. Large-scale nanoporous films were obtained by freeze-drying emulsions. Remarkably, the morphologies of linear BCPs were inverted, forming hexagonal-packed rigid spherical micelles with Q-P2VP as core and PS as corona in multilayer. This work provides insights of phase behaviors of BCP at fluids interface and offer a facile approach to prepare nanoporous film with well-controlled pore structure.

Ternary Mixtures of Hard Spheres and Their Multiple Separated Phases.

We study the liquid phase behavior of ternary mixtures of monodisperse hard spheres in solution. The interactions are modeled in terms of the second virial coefficient and can be additive hard sphere (HS) or non-additive hard sphere (NAHS) interactions. We give the set of equations that defines the phase diagram for mixtures of three components. We calculate the theoretical liquid-liquid phase separation boundary for two-phase separation (the binodal) and, if applicable, the three-phase boundary, as well as the plait points and the spinodal. The sizes of the three components are fixed. The first component (A) is the smallest one, the second component (B) is four times the size of the smallest component, and the third (C) component is three times the size of the smallest one. The interaction between the first two components is fixed, and this AB sub-mixture shows phase separation. The interactions of component C with the other two components are varied. Component C can be compatible or incompatible with components A and B. Depending on the compatibility of the components, the phase diagram is altered. The addition of the third component has an influence on the phase boundary, plait points, stability region, fractionation, and volume ratio between the different phases. When all sub-mixtures (AB, AC, and BC) show phase separation, a three-phase system becomes possible when the incompatibility among all components is high enough. The position and size of the three-phase region is dependent on the interactions between the different sub-mixtures. We study the fractionation off all components depending on specific parent concentrations.

Dissipative Particle Dynamic Simulation on Self-Assembly of Symmetric CBABC Pentablock Terpolymers in Solution.

Pentablock terpolymers are potential candidates for the self-assembly of multicompartment nanostructures. In this work, Dissipative Particle Dynamic simulation is employed to investigate how the equilibrium aggregate structures of C3B3A6B3C3 pentablock terpolymers are affected by polymer-solvent interactions in a solution. Multicompartment structures, such as layered micelles, onion-like micelles, onion-like vesicles, unilamellar vesicles, and vesicle-in-vesicle structures, are observed. Vesicles are obtained when the two end C-blocks or the central A-block are hydrophilic. The solvent encapsulation ability and vesicle membrane permeability are assessed. The unilamellar vesicle shows higher encapsulation efficiency and lower membrane permeability compared with the onion-like vesicles. Additionally, the two vesicles show different responses to shear. While the cargo release rate of the onion-like vesicle is not affected by shear, shear results in a slowdown of the release rate for the unilamellar vesicle. The membrane thickness of the unilamellar vesicle can be adjusted using the length of the central A-blocks. Vesicles with thicker membranes hold cargo more effectively.

Effect of Film Thickness on the Self-Assembly of CBABC Symmetric Pentablock Terpolymer Melts under 1D Confinement: A Dissipative Particle Dynamic Study.

The study investigates the impact of film thickness on the phase behavior of pentablock terpolymers, denoted as C3B3A6B3C3, when subjected to wall confinement by utilizing the dissipative particle dynamics method. Phase diagrams were constructed to elucidate how factors such as block-block interaction strength, film thickness, and wall properties affect the self-assembly structures. In cases where the wall exhibits no preference for any of the blocks, lamellae phases with orientations perpendicular to the wall are observed. The order-disorder transition (ODT) temperature is found to be influenced by the interaction between the polymer and the wall in thin confinement scenarios. When the wall displays a preference for specific blocks, the orientation of lamellae structures undergoes variations. Lamellae tend to align parallel to the wall when the wall favors A or C blocks, and they orient perpendicularly when B blocks are favored. Furthermore, the mechanical properties of the lamellae structures are related to the conformations of the polymer chains. Structures where chains predominantly adopt a loop conformation exhibit enhanced elastic properties. The ratio of looping to bridging conformations can be adjusted by altering the film thickness and wall selectivity.

Phase Behavior and Structure of Poloxamer Block Copolymers in Protic and Aprotic Ionic Liquids.

Ionic liquids are promising media for self-assembling block copolymers in applications such as energy storage. A robust design of block copolymer formulations in ionic liquids requires fundamental knowledge of their self-organization at the nanoscale. To this end, here, we focus on modeling two-component systems comprising a Poly(ethylene oxide)-poly (propylene oxide)-Poly(ethylene oxide) (PEO-PPO-PEO) block copolymer (Pluronic P105: EO37PO58EO37) and room temperature ionic liquids (RTILs): protic ethylammonium nitrate (EAN), aprotic ionic liquids (1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF6), or 1-butyl-3-methylimidazolium tetrafluoroborate (BMIMBF4). Rich structural polymorphism was exhibited, including phases of micellar (sphere) cubic, hexagonal (cylinder), bicontinuous cubic, and lamellar (bilayer) lyotropic liquid crystalline (LLC) ordered structures in addition to solution regions. The characteristic scales of the structural lengths were obtained using small-angle X-ray scattering (SAXS) data analysis. On the basis of phase behavior and structure, the effects of the ionic liquid solvent on block copolymer organization were assessed and contrasted to those of molecular solvents, such as water and formamide.

Dissipative Particle Dynamics Simulation for the Self-Assembly of Symmetric Pentablock Terpolymers Melts under 1D Confinements.

The phase behavior of CBABC pentablock terpolymers confined in thin films is investigated using the Dissipative Particle Dynamic method. Phase diagrams are constructed and used to reveal how chain length (i-block length), block composition and wall selectivity influence the self-assembly structures. Under neutral walls, four categories of morphologies, i.e., perpendicular lamellae, core-shell types of microstructures, complex networks, and half-domain morphologies, are identified with the change in i-block length. Ordered structures are more common at weak polymer-polymer interaction strengths. For polymers of a consistent chain length, when one of the three components has a relatively smaller length, the morphologies transition is sensitive to block composition. With selective walls, parallel lamellae structures are prevalent. Wall selectivity also impacts chain conformations. While a large portion of chains form loop conformations under A-selective walls, more chains adopt bridge conformation when the wall prefers C-blocks. These findings offer insights for designing nanopatterns using symmetric pentablock terpolymers.

Phase Behavior and Viscosity in Biomass Burning Organic Aerosol and Climatic Impacts.

Smoke particles generated by burning biomass consist mainly of organic aerosol termed biomass burning organic aerosol (BBOA). BBOA influences the climate by scattering and absorbing solar radiation or acting as nuclei for cloud formation. The viscosity and the phase behavior (i.e., the number and type of phases present in a particle) are properties of BBOA that are expected to impact several climate-relevant processes but remain highly uncertain. We studied the phase behavior of BBOA using fluorescence microscopy and showed that BBOA particles comprise two organic phases (a hydrophobic and a hydrophilic phase) across a wide range of atmospheric relative humidity (RH). We determined the viscosity of the two phases at room temperature using a photobleaching method and showed that the two phases possess different RH-dependent viscosities. The viscosity of the hydrophobic phase is largely independent of the RH from 0 to 95%. We use the Vogel-Fulcher-Tamman equation to extrapolate our results to colder and warmer temperatures, and based on the extrapolation, the hydrophobic phase is predicted to be glassy (viscosity >1012 Pa s) for temperatures less than 230 K and RHs below 95%, with possible implications for heterogeneous reaction kinetics and cloud formation in the atmosphere. Using a kinetic multilayer model (KM-GAP), we investigated the effect of two phases on the atmospheric lifetime of brown carbon within BBOA, which is a climate-warming agent. We showed that the presence of two phases can increase the lifetime of brown carbon in the planetary boundary layer and polar regions compared to previous modeling studies. Hence, the presence of two phases can lead to an increase in the predicted warming effect of BBOA on the climate.

Phase Behavior and Role of Organic Additives for Self-Doped CsPbI3 Perovskite Semiconductor Thin Films.

The phase change of all-inorganic cesium lead halide (CsPbI3) thin film from yellow δ-phase to black γ-/α-phase has been a topic of interest in the perovskite optoelectronics field. Here, the main focus is how to secure a black perovskite phase by avoiding a yellow one. In this work, we fabricated a self-doped CsPbI3 thin film by incorporating an excess cesium iodide (CsI) into the perovskite precursor solution. Then, we studied the effect of organic additive such as 1,8-diiodooctane (DIO), 1-chloronaphthalene (CN), and 1,8-octanedithiol (ODT) on the optical, structural, and morphological properties. Specifically, for elucidating the binary additive-solvent solution thermodynamics, we employed the Flory-Huggins theory based on the oligomer level of additives' molar mass. Resultantly, we found that the miscibility of additive-solvent displaying an upper critical solution temperature (UCST) behavior is in the sequence CN:DMF > ODT:DMF > DIO:DMF, the trends of which could be similarly applied to DMSO. Finally, the self-doping strategy with additive engineering should help fabricate a black γ-phase perovskite although the mixed phases of δ-CsPbI3, γ-CsPbI3, and Cs4PbI6 were observed under ambient conditions. However, the results may provide insight for the stability of metastable γ-phase CsPbI3 at room temperature.

An experimental workflow to assess the applicability of microemulsions for conformance improvement in oil-bearing reservoir.

A comprehensive workflow approach is necessary to link multiple experimental tasks and identify microemulsion (ME) formulations with 'optimal' stability, displacement behavior and technical feasibility in the petroleum industry. In this paper, a systematic approach is described with the aid of a case study which involves the formulation of an anionic sodium dodecyl sulfate-based microemulsion. The design of such ME systems requires a proper methodology, substantial laboratory work, and functional assessment from research/industrial viewpoints. The surfactant has been screened in terms of its micellization potential, followed by phase behavior analysis and Winsor classification of prepared microemulsions. The desired composition(s) are characterized via several tools to determine droplet size, morphology, oil/water solubilization potentials and salinity scan results. The suitability of the microemulsion system for conformance improvement technology (CIT) is proposed to be assessed via physicochemical evaluation studies encompassing two attributes: rheology and stability. For a favorable 'conforming' drive, the microemulsion must exhibit phase stability, sufficient injectivity, and moderate-to-high viscosity under shear. Technical assessment by the industry and research team must also include factors related to cost, availability of chemicals, environmental degradation, and reservoir considerations. The article demonstrates a comprehensive all-inclusive workflow methodology to design and formulate surfactant-stabilized microemulsions via case study analysis for application in CIT. This represents a sound approach to identifying efficient, cost-effective injection fluid systems and provides a framework to identify useful parameters for ME formulation design and employ the proposed (effective) strategy for conformance control.

Recent Experimental Advances in Characterizing the Self-Assembly and Phase Behavior of Polypeptoids.

Polypeptoids are a family of synthetic peptidomimetic polymers featuring N-substituted polyglycine backbones with large chemical and structural diversity. Their synthetic accessibility, tunable property/functionality, and biological relevance make polypeptoids a promising platform for molecular biomimicry and various biotechnological applications. To gain insight into the relationship between the chemical structure, self-assembly behavior, and physicochemical properties of polypeptoids, many efforts have been made using thermal analysis, microscopy, scattering, and spectroscopic techniques. In this review, we summarize recent experimental investigations that have focused on the hierarchical self-assembly and phase behavior of polypeptoids in bulk, thin film, and solution states, highlighting the use of advanced characterization tools such as in situ microscopy and scattering techniques. These methods enable researchers to unravel multiscale structural features and assembly processes of polypeptoids over a wide range of length and time scales, thereby providing new insights into the structure-property relationship of these protein-mimetic materials.

Kinetics of Water-Induced Amorphous Phase Separation in Amorphous Solid Dispersions via Raman Mapping.

The poor bioavailability of an active pharmaceutical ingredient (API) can be enhanced by dissolving it in a polymeric matrix. This formulation strategy is commonly known as amorphous solid dispersion (ASD). API crystallization and/or amorphous phase separation can be detrimental to the bioavailability. Our previous work (Pharmaceutics 2022, 14(9), 1904) provided analysis of the thermodynamics underpinning the collapse of ritonavir (RIT) release from RIT/poly(vinylpyrrolidone-co-vinyl acetate) (PVPVA) ASDs due to water-induced amorphous phase separation. This work aimed for the first time to quantify the kinetics of water-induced amorphous phase separation in ASDs and the compositions of the two evolving amorphous phases. Investigations were performed via confocal Raman spectroscopy, and spectra were evaluated using so-called Indirect Hard Modeling. The kinetics of amorphous phase separation were quantified for 20 wt% and 25 wt% drug load (DL) RIT/PVPVA ASDs at 25 °C and 94% relative humidity (RH). The in situ measured compositions of the evolving phases showed excellent agreement with the ternary phase diagram of the RIT/PVPVA/water system predicted by PC-SAFT in our previous study (Pharmaceutics 2022, 14(9), 1904).

Thermodynamic Modeling of the Amorphous Solid Dispersion-Water Interfacial Layer and Its Impact on the Release Mechanism.

During the dissolution of amorphous solid dispersion (ASD) formulations, the gel layer that forms at the ASD/water interface strongly dictates the release of the active pharmaceutical ingredient (API) and, hence, the dissolution performance. Several studies have demonstrated that the switch of the gel layer from eroding to non-eroding behavior is API-specific and drug-load (DL)-dependent. This study systematically classifies the ASD release mechanisms and relates them to the phenomenon of the loss of release (LoR). The latter is thermodynamically explained and predicted via a modeled ternary phase diagram of API, polymer, and water, and is then used to describe the ASD/water interfacial layers (below and above the glass transition). To this end, the ternary phase behavior of the APIs, naproxen, and venetoclax with the polymer poly(vinylpyrrolidone-co-vinyl acetate) (PVPVA64) and water was modeled using the perturbed-chain statistical associating fluid theory (PC-SAFT). The glass transition was modeled using the Gordon-Taylor equation. The DL-dependent LoR was found to be caused by API crystallization or liquid-liquid phase separation (LLPS) at the ASD/water interface. If crystallization occurs, it was found that API and polymer release was impeded above a threshold DL at which the APIs crystallized directly at the ASD interface. If LLPS occurs, an API-rich phase and a polymer-rich phase are formed. Above a threshold DL, the less mobile and hydrophobic API-rich phase accumulates at the interface which prevents API release. LLPS is further influenced by the composition and glass transition temperature of the evolving phases and was investigated at 37 °C and 50 °C regarding impact of temperature of. The modeling results and LoR predictions were experimentally validated by means of dissolution experiments, microscopy, Raman spectroscopy, and size exclusion chromatography. The experimental results were found to be in very good agreement with the predicted release mechanisms deduced from the phase diagrams. Thus, this thermodynamic modeling approach represents a powerful mechanistic tool that can be applied to classify and quantitatively predict the DL-dependent LoR release mechanism of PVPVA64-based ASDs in water.

Coupling effect of critical properties shift and capillary pressure on confined fluids: A simulation study in tight reservoirs.

Critical properties shift and large capillary pressure are important contributors for the phase behavior altering of nanopore fluid. However, the effects of critical properties shift and large capillary pressure on the phase behavior are ignored in traditional compositional simulators, leading to inaccurate evaluation results of tight reservoirs. In this study, phase behavior and production of confined fluid in nanopores are studied. First, we developed a method for coupling the effect of critical properties shift and capillary pressure into the vapor-liquid equilibrium calculation base on Peng-Robinson equation of state. Second, a novel fully compositional numerical simulation algorithm considering effect of critical properties shift and capillary pressure on phase behavior is accomplished. Third, we have discussed the alterations of critical properties shift effect, capillary pressure effect and coupling effect on the composition of oil and gas production in detail. The critical properties shift and capillary pressure effects on oil and gas production in tight reservoirs are analyzed quantitatively through four cases, and the influences of the two effects in oil/gas production are compared. Based on the fully compositional numerical simulation, the simulator can rigorously simulate the impacts of component changes during production. The simulation results show that both the critical properties shift effect and the capillary pressure effect reduce the bubble point pressure of Changqing shale oil, and the influence are more prevalent in pores of smaller radius. In pores is larger than 50 nm, the phase behavior altering of the fluid can be ignored. In addition, we devised four cases to comprehensively investigate the effects of critical properties shift and large capillary pressure on production performance of tight reservoirs. The comparisons between the four cases show that the capillary pressure effect impacts the reservoir production performances greater than the critical properties shift effect, such as higher oil production, higher GOR, and lower content of lighter component and higher content of heavier component in the residual oil/gas. The results of coupling effects indicate that the critical properties shift effect would suppress the effect of the capillary pressure effect. In particular, the difference between the simulation results of the coupling effects and the base case is smaller than that between the simulation results of the capillary pressure effect and the base case.

Recent Trends in Continuum Modeling of Liquid Crystal Networks: A Mini-Review.

This work aims to provide a comprehensive review of the continuum models of the phase behaviors of liquid crystal networks (LCNs), novel materials with various engineering applications thanks to their unique composition of polymer and liquid crystal. Two distinct behaviors are primarily considered: soft elasticity and spontaneous deformation found in the material. First, we revisit these characteristic phase behaviors, followed by an introduction of various constitutive models with diverse techniques and fidelities in describing the phase behaviors. We also present finite element models that predict these behaviors, emphasizing the importance of such models in predicting the material's behavior. By disseminating various models essential to understanding the underlying physics of the behavior, we hope to help researchers and engineers harness the material's full potential. Finally, we discuss future research directions necessary to advance our understanding of LCNs further and enable more sophisticated and precise control of their properties. Overall, this review provides a comprehensive understanding of the state-of-the-art techniques and models used to analyze the behavior of LCNs and their potential for various engineering applications.

Drug Release from Surfactant-Containing Amorphous Solid Dispersions: Mechanism and Role of Surfactant in Release Enhancement.

PURPOSE: To understand how surfactants affect drug release from ternary amorphous solid dispersions (ASDs), and to investigate different mechanisms of release enhancement. METHODS: Ternary ASDs containing ritonavir (RTV), polyvinylpyrrolidone/vinyl acetate (PVPVA) and a surfactant (sodium dodecyl sulfate (SDS), Tween 80, Span 20 or Span 85) were prepared with rotary evaporation. Release profiles of ternary ASDs were measured with surface normalized dissolution. Phase separation morphologies of ASD compacts during hydration/dissolution were examined in real-time with a newly developed confocal fluorescence microscopy method. The water ingress rate of different formulations was measured with dynamic vapor sorption. Microscopy was employed to check for matrix crystallization during release studies. RESULTS: All surfactants improved drug release at 30% DL, while only SDS and Tween 80 improved drug release at higher DLs, although SDS promoted matrix crystallization. The dissolution rate of neat polymer increased when SDS and Tween 80 were present. The water ingress rate also increased in the presence of all surfactants. Surfactant-incorporation affected both the kinetic and thermodynamics factors governing phase separation of RTV-PVPVA-water system, modifying the phase morphology during ASD dissolution. Importantly, SDS increased the miscibility of RTV-PVPVA-water system, whereas other surfactants mainly affected the phase separation kinetics/drug-rich barrier persistence. CONCLUSION: Incorporation of surfactants enhanced drug release from RTV-PVPVA ASDs compared to the binary system. Increased drug-polymer-water miscibility and disruption of the drug-rich barrier at the gel-solvent interface via plasticization are highlighted as two key mechanisms underlying surfactant impacts based on direct visualization of the phase separation process upon hydration and release.

pH-induced complex coacervation of fish gelatin and carboxylated chitosan: Phase behavior and structural properties.

The aim of this study was to investigate the phase behavior and structural properties of fish gelatin complex coacervation with carboxylated chitosan as a function of pH by varying the amount of carboxylated chitosan added (0-0.25%, w/v) while keeping the fish gelatin concentration constant at 0.667% (w/v). Zeta potential indicated that electrostatic interaction drove the complex coalescence of fish gelatin and carboxylated chitosan to form soluble or insoluble complexes. The turbidity of the fish gelatin-carboxylated chitosan complex system was greatest at a carboxylated chitosan concentration of 0.2%. UV and fluorescence spectroscopy indicated that the carboxylated chitosan changed the tertiary conformation of fish gelatin. Circular dichroism showed that complexation of fish gelatin with carboxylated chitosan resulted in a shift from the α-helix to the ß-sheet structure of fish gelatin. In particular, at pH 5, the fish gelatin complexed with carboxylated chitosan had a disordered structure. X-ray diffraction and scanning electron microscopy of the composite coacervates both investigated that electrostatic interaction between the two replaced molecular interaction within the carboxylated chitosan to form a new lamellar porous structure. These findings may in future enable the use of fish gelatin-carboxylated chitosan complex systems in the design of new food matrices.