Fully Degradable Polyphosphoester Cubosomes for Sustainable Agrochemical Delivery.

Microplastic pollution and the urgent need for sustainable agriculture have raised interest in developing degradable carriers for controlled agrochemical release. Porous polymeric particles are particularly promising due to their unique release profiles compared to solid or core-shell carriers. However, creating degradable, mesoporous (2-50 nm) microparticles is challenging, and their potential for agrochemical delivery is largely unexplored. A straightforward self-assembly method is demonstrated for fully degradable porous polymer cubosomes (PCs), showcasing their ability to load and release agrochemicals. Using fully degradable block copolymers (BCPs), poly(ethyl ethylene phosphate)-b-polylactide (PEEP-b-PLA), PCs are synthesized in water with high inner order and open pores averaging 19 ± 3 nm in diameter. During the self-assembly process in the presence of the hydrophobic fungicide tebuconazole, polymersomes transform into PCs by enriching the hydrophobic polymer domain and altering the BCP packing parameter. After self-assemby, highly porous and fungicide-loaded PCs are obtained. Fungicide-loaded PCs show high antimycotic activity against Botrytis cinerea (grey mold), adhere to Vitis vinifera Riesling leaves even after simulated rain, and release the fungicide continuously over several days with different release-kinetics compared to solid particles. PCs hydrolyze completely into lactic acid and phosphate derivatives, highlighting their potential as microplastic-free agrochemical delivery systems for sustainable agriculture.

Characterization of size-tuneable aescin-lipid nanoparticles as platform for stabilization of membrane proteins.

Disc-like lipid nanoparticles stabilized by saponin biosurfactants display fascinating properties, including their temperature-driven re-organization. ß-Aescin, a saponin from seed extract of the horse chestnut tree, shows strong interactions with lipid membranes and has gained interest due to its beneficial therapeutic implications as well as its ability to decompose continuous lipid membranes into size-tuneable discoidal nanoparticles. Here, we characterize lipid nanoparticles formed by aescin and the phospholipid 1,2-dimyristoyl-sn-glycero-3-phosphocholine. We present site-resolved insights into central molecular interactions and their modulations by temperature and aescin content. Using the membrane protein bacteriorhodopsin, we additionally demonstrate that, under defined conditions, aescin-lipid discs can accommodate medium-sized transmembrane proteins. Our data reveal the general capability of this fascinating system to generate size-tuneable aescin-lipid-protein particles, opening the road for further applications in biochemical, biophysical and structural studies.

Confined microemulsions: pore diameter induced change of the phase behavior.

In the present work, the temperature-dependent phase behavior of a C10E4 based microemulsion is studied in different meso-macroporous glasses, as a function of their pore diameter. The phase behavior in these pores is investigated by small-angle X-ray scattering (SAXS). The crucial parameter we discuss based on the SAXS results is the domain size of the bicontinuous phase. Using a simplified model to fit the scattering data, we can observe the microemulsion inside the pores. These experiments reveal a temperature-dependent change in domain sizes of the bicontinuous microemulsion only for large pores.

Photocleavable Polymer Cubosomes: Synthesis, Self-Assembly, and Photorelease.

Polymer cubosomes (PCs) are a recent class of self-assembled block copolymer (BCP) microparticles with an accessible periodic channel system. Most reported PCs consist of a polystyrene scaffold, which provides mechanical stability for templating but has a limited intrinsic functionality. Here, we report the synthesis of photocleavable BCPs with compositions suitable for PC formation. We analyze the self-assembly mechanism and study the model release of dyes during irradiation, where the transition of the BCPs from amphiphilic to bishydrophilic causes the rapid disassembly of the PCs. A combination of modeling and experiment shows that the evolution of PCs proceeds first via liquid-liquid phase separation into polymer-rich droplets, followed by microphase separation within this droplet confinement, and finally, membrane reorganization into high internal order. This insight may encourage exploration of alternative preparation strategies to better control the size and homogeneity of PCs.

Interactions between DMPC Model Membranes, the Drug Naproxen, and the Saponin ß-Aescin.

In this study, the interplay among the phospholipid 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) as a model membrane, the nonsteroidal anti-inflammatory drug naproxen, and the saponin ß-aescin are investigated. The naproxen amount was fixed to 10 mol%, and the saponin amount varies from 0.0 to 1.0 mol%. Both substances are common ingredients in pharmaceutics; therefore, it is important to obtain deeper knowledge of their impact on lipid membranes. The size and properties of the DMPC model membrane upon naproxen and aescin addition were characterized with differential scanning calorimetry (DSC), small- and wide-angle X-ray scattering (SAXS, WAXS), and photon correlation spectroscopy (PCS) in a temperature-dependent study. The interaction of all substances was dependent on the lipid phase state, which itself depends on the lipid's main phase transition temperature Tm. The incorporation of naproxen and aescin distorted the lipid membrane structure and lowers Tm. Below Tm, the DMPC-naproxen-aescin mixtures showed a vesicle structure, and the insertion of naproxen and aescin influenced neither the lipid chain-chain correlation distance nor the membrane thickness. Above Tm, the insertion of both molecules instead induced the formation of correlated bilayers and a decrease in the chain-chain correlation distance. The presented data clearly confirm the interaction of naproxen and aescin with DMPC model membranes. Moreover, the incorporation of both additives into the model membranes is evidenced.