Micro-patterns of gold nanoparticles assembled by photovoltaic optoelectronic tweezers: application to plasmonic fluorescence enhancement.

Noble metal nanostructures are well-known for their ability to increase the efficiency of different optical or physical phenomena due to their plasmonic behavior. This work presents a simple strategy to obtain Au plasmonic patterns by optically induced nanoparticle assembly and its application as fluorescence enhancement platforms. This strategy is based on the so-called photovoltaic optoelectronic tweezers (PVOT) being the first time they are used for fabricating Au periodic micro-patterns. Fringe patterns with a sub-structure of aggregates, assembled from individual spherical nanoparticles of 3.5 or 170 nm diameters, are successfully obtained. The spatial distribution of the aggregates is controlled with micrometric accuracy and the patterns can be arranged over large-scale active areas (tens of mm2). The outcome for the ultra-small (3.5 nm) particles is particularly relevant because this diameter is the smallest one manipulated by PVOT so far. Testing experiments of plasmonic fluorescence enhancement show that the 170-nm patterns present a much better plasmonic behavior. For the 170-nm platform they reveal a 10-fold enhancement factor in the fluorescence of Rhodamine-B dye molecules and a 3-fold one for tagged DNA biomolecules. Hence, the results suggest that these latter plasmonic platforms are good candidates for efficient bio-imaging and biosensing techniques, among other applications.

In Situ Visualization of the Structural Evolution and Alignment of Lyotropic Liquid Crystals in Confined Flow.

Self-assembled materials such as lyotropic liquid crystals offer a wide variety of structures and applications by tuning the composition. Understanding materials behavior under flow and the induced alignment is wanted in order to tailor structure related properties. A method to visualize the structure and anisotropy of ordered systems in situ under dynamic conditions is presented where flow-induced nanostructural alignment in microfluidic channels is observed by scanning small angle X-ray scattering in hexagonal and lamellar self-assembled phases. In the hexagonal phase, the material in regions with high extensional flow exhibits orientation perpendicular to the flow and is oriented in the flow direction only in regions with a high enough shear rate. For the lamellar phase, a flow-induced morphological transition occurs from aligned lamellae toward multilamellar vesicles. However, the vesicles do not withstand the mechanical forces and break in extended lamellae in regions with high shear rates. This evolution of nanostructure with different shear rates can be correlated with a shear thinning viscosity curve with different slopes. The results demonstrate new fundamental knowledge about the structuring of liquid crystals under flow. The methodology widens the quantitative investigation of complex structures and identifies important mechanisms of reorientation and structural changes.

Lyotropic liquid crystal elastomers for drug delivery.

Silicone elastomers like polydimethylsiloxane (PDMS) possess a combination of attractive material and biological properties motivating their widespread use in biomedical applications. Development of elastomers with capacity to deliver active therapeutic substances in the form of drugs is of particular interest to produce medical devices with added functionality. In this work, silicone-based lyotropic liquid crystal elastomers with drug-eluting functionality were developed using PDMS and triblock copolymer (diacrylated Pluronic F127, DA-F127). Various ternary PDMS-DA-F127-H2O compositions were explored and evaluated. Three compositions were found to have specific properties of interest and were further investigated for their nanostructure, mechanical properties, water retention capacity, and morphology. The ability of the elastomers to encapsulate and release polar and nonpolar substances was demonstrated using vancomycin and ibuprofen as model drugs. It was shown that the materials could deliver both types of drugs with a sustained release profile for up to 6 and 5 days for vancomycin and ibuprofen, respectively. This works demonstrates a lyotropic liquid crystal, silicone-based elastomer with tailorable mechanical properties, water retention capacity and ability to host and release polar and nonpolar active substances.

SAXS imaging reveals optimized osseointegration properties of bioengineered oriented 3D-PLGA/aCaP scaffolds in a critical size bone defect model.

Healing large bone defects remains challenging in orthopedic surgery and is often associated with poor outcomes and complications. A major issue with bioengineered constructs is achieving a continuous interface between host bone and graft to enhance biological processes and mechanical stability. In this study, we have developed a new bioengineering strategy to produce oriented biocompatible 3D PLGA/aCaP nanocomposites with enhanced osseointegration. Decellularized scaffolds -containing only extracellular matrix- or scaffolds seeded with adipose-derived mesenchymal stromal cells were tested in a mouse model for critical size bone defects. In parallel to micro-CT analysis, SAXS tensor tomography and 2D scanning SAXS were employed to determine the 3D arrangement and nanostructure within the critical-sized bone. Both newly developed scaffold types, seeded with cells or decellularized, showed high osseointegration, higher bone quality, increased alignment of collagen fibers and optimal alignment and size of hydroxyapatite minerals.