In this work, we compare our experimental results with the latest computational findings for the synthesis of nanoparticles via Laser Ablation in Liquids (LAL). In addition, we demonstrate the usefulness of shadowgraphy imaging of the cavitation bubble in determination of ablation thresholds and irradiation efficiency.
Blended biocomposites created from the electrostatic and hydrophobic interactions between polysaccharides and structural proteins exhibit useful and unique properties. However, engineering these biopolymers into applicable forms is challenging due to the coupling of the material’s physicochemical properties to its morphology, and the undertaking that comes with controlling this. In this particular study, numerous properties of the Bombyx mori silk and microcrystalline cellulose biocomposites blended using ionic liquid and regenerated with various coagulation agents were investigated. Specifically, the relationship between the composition of polysaccharide-protein bio-electrolyte membranes and the resulting morphology and ionic conductivity is explored using numerous characterization techniques, including scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), X-ray scattering, atomic force microscopy (AFM) based nanoindentation, and dielectric relaxation spectroscopy (DRS). The results revealed that when silk is the dominating component in the biocomposite, the ionic conductivity is higher, which also correlates with higher β-sheet content. However, when cellulose becomes the dominating component in the biocomposite, this relationship is not observed; instead, cellulose semicrystallinity and mechanical properties dominate the ionic conduction.
The self-assembly of amphiphilic diblock copolymers into polymeric vesicles, commonly known as polymersomes, results in a versatile system for a variety of applications including drug delivery and microreactors. In this study, we show that the incorporation of hydrophobic plasmonic nanoparticles within the polymersome membrane facilitates light-stimulated release of vesicle encapsulants. This work seeks to achieve tunable, triggered release with non-invasive, spatiotemporal control using single-pulse irradiation. Gold nanoparticles (AuNPs) are incorporated as photosensitizers into the hydrophobic membrane of micron-scale polymersomes and the cargo release profile is controlled by varying the pulse energy and nanoparticle concentration. We have demonstrated the ability to achieve immediate vesicle rupture as well as vesicle poration resulting in temporal cargo diffusion. Additionally, changing the pulse duration, from femtosecond to nanosecond, provides mechanistic insight into the photothermal and photomechanical contributors that govern membrane disruption in this polymer–nanoparticle hybrid system.
The ability to suspend plasmonic metal nanoparticles in apolar environments is an important feat towards harnessing their optical properties for use in amphiphilic biological environments. Pulsed laser Ablation in Liquids (PLAL) is a well-established method for the production of gold nanoparticles (AuNPs) in aqueous environments; however, ablation in organic liquids for the synthesis of hydrophobic AuNPs still has many unknowns, such as the relationship between colloidal stability and the ligand shell. In this study, hydrophobic AuNPs were produced by PLAL of gold in a 1-alkanethiol/n-decane solution and treated with laser fragmentation. Results demonstrate that longer chain length ATs produced particles with a smaller average size; however, there was no strong correlation between alkanethiol (AT) concentration and particle size. Stability was investigated by monitoring the temporal evolution of the extinction spectra which revealed that lower concentrations of AT stabilize the colloids while higher concentrations tend to result in quicker particle aggregation. Furthermore, longer chain length ATs demonstrated improved stability. Additionally, vibrational spectroscopy was employed to examine the AuNP surface chemistry, which pointed to the presence of oxidized carbon species and graphitic carbon.