Tuning the water intrinsic permeability of PEGDA hydrogel membranes by adding free PEG chains of varying molar masses.

We explore the effect of poly(ethylene glycol) (PEG) molar mass on the intrinsic permeability and structural characteristics of poly(ethylene glycol) diacrylate PEGDA/PEG composite hydrogel membranes. We observe that by varying the PEG content and molar mass, we can finely adjust the water intrinsic permeability by several orders of magnitude. Notably, we show the existence of maximum water intrinsic permeability, already identified in a previous study to be located at the critical overlap concentration C* of PEG chains, for the highest PEG molar mass studied. Furthermore, we note that the maximum intrinsic permeability follows a non-monotonic evolution with respect to the PEG molar mass and reaches its peak at 35 000 g mol-1. Besides, our results show that a significant fraction of PEG chains is irreversibly trapped within the PEGDA matrix even for the lowest molar masses down to 600 g mol-1. This observation suggests the possibility of covalent grafting of the PEG chains onto the PEGDA matrix. CryoSEM and AFM measurements demonstrate the presence of large micron-sized cavities separated by PEGDA-rich walls whose nanometric structures strongly depend on the PEG content. By combining our permeability and structural measurements, we suggest that the PEG chains trapped inside the PEGDA-rich walls induce nanoscale defects in the crosslinking density, resulting in increased permeability below C*. Conversely, above C*, we speculate that partially trapped PEG chains may form a brush-like arrangement on the surface of the PEGDA-rich walls, leading to a reduction in permeability. These two opposing effects are anticipated to exhibit molar-mass-dependent trends, contributing to the non-monotonic variation of the maximum intrinsic permeability at C*. Overall, our results demonstrate the potential to fine-tune the properties of hydrogel membranes, offering new opportunities for separation applications.

The mechanical properties of lipid nanoparticles depend on the type of biomacromolecule they are loaded with.

For drug delivery systems, the mechanical properties of drug carriers are suspected to play a crucial role in the delivery process. However, there is a lack of reliable methods available to measure the mechanical properties of drug carriers, which hampers the establishment of a link between delivery efficiency and the mechanical properties of carriers. Lipid nanoparticles (LNPs) are advanced systems for delivering nucleic acids to target cell populations for vaccination purposes (mRNA) or the development of new drugs. Hence, it is crucial to develop reliable techniques to measure the mechanical properties of LNPs. In this article, we used AFM to image and probe the mechanical properties of LNPs which are loaded with two different biopolymers either pDNA or mRNA. Imaging the LNPs before and after indentation, as well as recording the retraction curve, enables us to obtain more insight into how the AFM tip penetrates into the particle and to determine whether the deformation of the LNPs is reversible. For pDNA, the indentation by the tip leads to irreversible rupture of the LNPs, while the deformation is reversible for the mRNA-loaded LNPs. Moreover, the forces reached for pDNA are higher than for mRNA. These results pave the way toward the establishment of the link between the LNP formulation and the delivery efficiency.

Sieving and Clogging in PEG-PEGDA Hydrogel Membranes.

Hydrogels are promising systems for separation applications due to their structural characteristics (i.e., hydrophilicity and porosity). In our study, we investigate the permeation of suspensions of rigid latex particles of different sizes through free-standing hydrogel membranes prepared by photopolymerization of a mixture of poly(ethylene glycol) diacrylate (PEGDA) and large poly(ethylene glycol) (PEG) chains of 300,000 g·mol-1 in the presence of a photoinitiator. Atomic force microscopy and cryoscanning electron microscopy (cryoSEM) were employed to characterize the structures of the hydrogel membranes. We find that the 20 nm particle permeation depends on both the PEGDA/PEG composition and the pressure applied during filtration. In contrast, we do not measure a significant permeation of the 100 nm and 1 µm particles, despite the presence of large cavities of 1 µm evidenced by the cryoSEM images. We suggest that the PEG chains induce local nanoscale defects in the cross-linking of PEGDA-rich walls separating the micrometer-sized cavities, which control the permeation of particles and water. Moreover, we discuss the decline of the permeation flux observed in the presence of latex particles compared to that of pure water. We suggest that a thin layer of particles forms on the surface of the hydrogels.