Understanding Ecotoxicological Responses of Fish Embryos and Gill Cells to Cationic Polymers.

Cationic polymers are considered by the scientific and regulatory communities as a group of greater interest amongst the polymers in commerce. As a category, relatively little hazard information is available in the public literature. Very few examples exist of published, high-quality polymer characterization and quantification of exposure. In the present study we describe a series of fish embryo toxicity (FET) and fish gill cytotoxicity assays used to establish a baseline understanding of several representative polyquaternium categories (PQ-6, PQ-10, PQ-16) in animal alternative models, accompanied by high-quality analytical characterization. Materials were chosen to encompass a range of molecular weights and charge densities to determine the influence of test material characteristics on toxicity. Both chorionated and dechorionated FET assays were generally similar to published acute fish toxicity data. Toxicity was correlated with cationic polymer charge density, and not with molecular weight, and was a combination of physical effects and likely toxicity at the site of action. Toxicity could be ameliorated by humic acid in a dose-dependent manner. Fish gill cytotoxicity results were orders of magnitude less sensitive than FET test responses. Environ Toxicol Chem 2022;41:2259-2272. © 2022 SETAC.

Salt- and pH-Dependent Viscosity of SDS/LAPB Solutions: Experiments and a Semiempirical Thermodynamic Model.

We present novel data on the composition-, pH-, and salt-dependent zero shear viscosity of the commercially important mixture of anionic sodium dodecyl sulfate (SDS) and zwitterionic lauramidopropyl betaine (LAPB). We show via proton NMR experiments that the notionally zwitterionic LAPB exhibits a large pKa shift in the presence of SDS and can become partially cationic at formulation-relevant pH ranges of 4.5-6.0-that is, the binary system is effectively a ternary system. This has a pronounced effect on the viscosity of the system at low pH, especially if the fraction of LAPB is high. We use theoretical arguments to motivate a semiempirical but practical approach to model the viscosity of the mixtures using thermodynamic parameters such as the excess chemical potentials or activity coefficients of the surfactants. We demonstrate this using an augmented regular solution theory-based mixed micelle thermodynamic model and develop robust regression models using Bayesian approaches. We also show how the pKa shift from NMR experiments can be used to parameterize the thermodynamic model. This framework should be extensible to other arbitrary surfactant mixtures in the future and hence will be of broad interest for the development of surfactant formulations for household, personal care, and other applications.

Enthalpy and Entropy of Scission in Wormlike Micelles.

The free scission energy is the thermodynamic parameter that governs the contour length of wormlike micelles (WLMs). It is the contour length and the propensity to coil and entangle that determine the viscoelastic properties of this commercially important substance class. The free scission energy Δ Fsc and the associated change in enthalpy Δ Hsc and entropy Δ Ssc on scission have been determined for a mixed anionic/zwitterionic surfactant system (sodium laureth sulfate and cocamidopropyl betaine) at various salt concentrations (3-5 wt % NaCl). Both enthalpy Δ Hsc and entropy Δ Ssc changes decrease linearly with increasing NaCl concentration. At NaCl concentrations above 4 wt %, Δ Ssc even adopts negative values. The term TΔ Ssc decreases more rapidly than Δ Hsc around room temperature and causes the observed elongation of WLMs upon addition of NaCl. It is suggested that Δ Ssc is initially positive due to fewer bound counterions per surfactant molecule at end caps compared to the intact, cylindrical parts before scission, leading to a net release of ions upon scission. Negative values of Δ Ssc are attributed to hydrophobic hydration occurring at the end caps at high salt concentrations. 23Na NMR measurements indicate the presence of immobilized ions, supporting a previously proposed ion-cloud model based on neutron scattering results.

Control elements in dynamically determined selectivity on a bifurcating surface.

The mechanism and the nature of the dynamically determined product selectivity in Diels-Alder cycloadditions of 3-methoxycarbonylcyclopentadienone (2) with 1,3-dienes was studied by a combination of product studies, experimental kinetic isotope effects, standard theoretical calculations, and quasiclassical trajectory calculations. The low-energy transition structures in these reactions are structurally balanced between [4pi(diene) + 2pi(dienone)] and the [2pi(diene) + 4pi(dienone)] modes of cycloaddition. The accuracy of these structures and their bispericyclic nature is supported by the experimental isotope effects. Trajectories passing through these transition structures can lead to both [4pi(diene) + 2pi(dienone)] and [2pi(diene) + 4pi(dienone)] cycloadducts, and the mixture of products obtained varies with the structure of the diene. The factors affecting this selectivity are analyzed. The geometry of the transition structure is a useful predictor of the major product, but the selectivity is also guided by the shape of the energy surface as trajectories approach the products and by how trajectories cross the transition state ridge.