The effect of twelve cyclic molecules on the rheological response of a 10 wt% mixture of sodium lauryl ether sulfate and cocoamidopropyl betaine (BS) was evaluated. The results demonstrate that all studied additives effectively reduced the salt concentration required to reach peak viscosity and narrowed the width of the salt curve. The specific effect on the magnitude of the peak viscosity depends on the molecular structure of the additive. Hydrocarbons, along with hydrophobic phenols, increase the peak viscosity, while alcohols and simple phenol, decrease it. SAXS and NMR measurements revealed that hydrocarbons are primarily incorporated into the micellar core, and the observed viscosity enhancement is attributed to the suppression of micellar branching. In contrast, molecules possessing an OH-group intercalate between the surfactant headgroups or reside at the micellar surface. For hydrophobic phenols, the ability to form stable hydrogen bonds results in a significant increase in the maximum viscosity. This interaction substantially reduces the salt concentration required to reach peak viscosity; in this case, the micellar charge density remains relatively high, and electrostatic repulsion hinders micellar branching. On the other hand, simple phenols and alcohols decrease viscosity because their higher water solubility allows them to easily redistribute across different regions of the micelle surface, thereby facilitating micellar branching. The dimensionless parameters accounting for the effect of the studied additives on the salt curve characteristics were determined. These parameters were shown to depend on a composite molecular parameter, defined as the ratio of the surfactant volume to the additive volume multiplied by the octanol–water partition coefficient, vBS/vALogP.

Developability assessment facilitates the selection of antibody drug candidates with desirable pharmaceutical properties. However, it remains uncertain whether agitation-induced aggregation can be predicted from standard developability parameters. Here, we investigated whether key biophysical parameters predict agitation-induced aggregation of monoclonal antibodies (mAbs). To this end, we generated a benchmark data set by characterizing the aggregation upon agitation in the presence of an air–liquid interface of ten approved mAbs reformulated in a common surfactant-free buffer. The extent of aggregation varied substantially among mAbs and was primarily dependent on antibody identity. Flow imaging microscopy combined with machine learning revealed micrometre-sized aggregates with distinct morphologies, consistent with aggregation at air–liquid interfaces. Examination of thin liquid films and foams confirmed the presence of aggregates directly at the air–liquid interface and, therefore, the critical role of this interface for antibody aggregation during agitation. We then applied fluorescence-based, light scattering, and chromatographic techniques to determine standard developability parameters for each mAb, including apparent melting temperature (Tm), nonreversibility onset temperature (Tnr), aggregation onset temperature (Tagg), diffusion self-interaction parameter (kD), hydrophobic interaction chromatography retention time, and relative monomer yield after isothermal refolding from chemical denaturants. Notably, none of these parameters correlated with agitation-induced aggregation. Finally, we assessed the surface properties of the mAbs via drop shape analysis and found that the combination of surface pressure and elastic modulus yields a good correlation with the concentration of micrometre-sized aggregates formed due to agitation. Overall, these findings highlight limitations in predicting mAb interfacial stability using standard developability assays and underscore the importance of studying antibody behavior at interfaces.

Sugar esters, a class of surfactants derived from renewable resources, have attracted significant attention due to their biodegradability, low toxicity, and broad applications in food, cosmetic, and pharmaceutical formulations. Despite their widespread use, the phase behavior of these compounds in aqueous systems remains incompletely understood. In this study, we investigate the self-assembly of a nonionic sucrose ester of lauric acid in 1–40 wt% concentration range using rheological measurements, dynamic light scattering, X-ray scattering, DOSY NMR, and molecular dynamics simulations. Formation of spherical micelles with a diameter of 5.4 nm is observed at low surfactant concentrations, driven by hydrophobic interactions between the alkyl tails. These solutions exhibit Newtonian flow behavior with viscosities close to that of pure water. However, the viscosity increases from 5 mPa.s at 16 wt% to 640 mPa.s at 40 wt%, while the Newtonian character persists even at 40 wt%. This behavior is explained with the formation of interconnected, thread-like micellar structures of (almost) spherical micelles that largely preserve their distinctiveness, resembling the “pearl necklace” arrangement known for polymer systems. The main driving force for this supramolecular organization was found to be the hydrogen bonding between sucrose headgroups. The addition of 6 M urea, a known hydrogen bond disruptor, significantly reduces micelle clustering and the viscosity decreases to 150 mPa.s at 40 wt% concentration, supporting the proposed aggregation mechanism. These findings contribute to a deeper understanding of the self-assembly behavior of sucrose esters in aqueous environment and highlight their potential for controlled aggregation in practical formulations.

Polysorbates are hydrophilic, nonionic surfactants widely used in food, cosmetic, and pharmaceutical products. Often, these emulsifiers are used in combination with different preservatives, and it is essential to conduct an in-depth study of the influence of such additives on the properties of Polysorbate 60 solutions. In the current study, we investigated the effect of various food additives: citric acid, sodium benzoate, potassium sorbate, a mixture of citric acid and sodium citrate, and propylene glycol on the stability and micellar properties of Polysorbate 60 by using different experimental methods such as GC, DSC, SAXS, DLS, optical observations in polarised light, and NMR. When stored at room temperature without additives, solutions of Polysorbate 60 slowly undergo phase separation over time. Our results show that citric acid, a mixture of citric acid and sodium citrate, and propylene glycol increase the rate of this phase separation. In contrast, sodium benzoate and potassium sorbate are incorporated into the mixed micelles. They localize within the palisade layer, a region of the micelle where the surfactant tails begin, effectively preventing the phase separation. As a result, Polysorbate 60 solutions with these specific additives remain transparent and stable for over a year

Alkyl sarcosinates are amino acid-based anionic surfactants commonly used as primary surfactants in sulfate-free personal care products. The major aim of this study is to identify the key factors influencing the rheological behaviour of sodium sarcosinate solutions and their mixtures with nonionic, zwitterionic, and cationic co-surfactants. To achieve this, we examined the effects of salt type and concentration for alkyl sarosinates with different chain lengths (dodecyl, tetradecyl, and cocoyl) across concentration range of 2–20 wt%. Experimental results reveal two distinct regions in the salt curve for the three studied sarcosinates. At low electrolyte concentrations, viscosity remains constant until reaching the critical electrolyte concentration, C1, beyond which viscosity increases logarithmically with salt concentration. Further electrolyte addition leads to phase separated solutions at the critical precipitation concentration, CTR. Both C1 and CTR decrease as the hydrocarbon chain length increases from dodecyl to tetradecyl. However, the presence of shorter chain molecules in cocoyl sarocisinate significantly increases both C1 and CTR due to the formation of spherical micelles. A theoretical expression for predicting viscosity dependence on salt concentration is derived and successfully applied to describe the experimental data. The adsorption energy of sodium and potassium to alkyl sacrosinate micelle surfaces is found to be much smaller than that to sodium lauroyl ether sulfate surfactants (1 vs. 3 kBT for Na+ and 0.8 vs. 3.8 kBT for K+). No significant effect of amphoteric co-surfactants, including cocoamidopropyl betaine, sulfobetaine, or decylamine oxide, is observed. NMR analysis confirms that cocoamidopropyl betaine and sodium dodecyl sarcosinate form mixed micelles that are structurally similar to sarcosinate micelles, as carboxyl groups remain exposed on the micelle surfaces in both cases. When using amine oxide and sulfobetaine, the increase in viscosity is attributed to the elongation of mixed micelles, though steric hindrance from side methyl groups limits their growth. The practical significance of this study lies in the finding that longer-chain alkyl sarcosinates (such as tetradecyl, as investigated here) can attain significantly higher viscosities at lower salt concentrations compared to shorter-chain analogs or surfactant mixtures. The scientific significance stems from the development of a theoretical model capable of predicting the viscosity of alkyl sarcosinate solutions across various surfactant and salt concentrations.