Luca Ceseracciu

Hierarchical self-assembly of suspended branched colloidal nanocrystals into superlattice structures

Self-assembly of molecular units into complex and functional superstructures is ubiquitous in biology. The number of superstructures realized by self-assembly of man-made nanoscale units is also growing. However, assemblies of colloidal inorganic nanocrystals are still at an elementary level, not only because of the simplicity of the shape of the nanocrystal building blocks and their interactions, but also because of the poor control over these parameters in the fabrication of more elaborate nanocrystals. Here, we show how monodisperse colloidal octapod-shaped nanocrystals self-assemble, in a suitable solution environment, on two sequential levels. First, linear chains of interlocked octapods are formed, and subsequently the chains spontaneously self-assemble into three-dimensional superstructures. Remarkably, all the instructions for the hierarchical self-assembly are encoded in the octapod shape. The mechanical strength of these superstructures is improved by welding the constituent nanocrystals together.

Surface morphology and mechanical properties of new-generation flowable resin composites for dental restoration

OBJECTIVES The purpose of this study was to characterize the surface morphology and the elastic properties of four dental restorative flowable composites currently on the market (Venus Diamond Flow, Vertise Flow, Filtex Supreme XT Flow, Surefil SDR Flow). Additionally, one adhesive system (Adhese One F) and one non-flowable composite (Venus Diamond) have also been characterized as the control materials. METHODS Surface morphology was studied by both scanning electron and atomic force microscopy, and the elastic modulus and the hardness measured by instrumented indentation. Grain analysis was performed on the microscopic images, and statistical analysis was carried out on the results of the nanoindentation measurements. RESULTS It was observed that Vertise, Filtek XT and Surefil SDR exhibit stiffness similar to the non-flowable Venus Diamond, whereas Venus Diamond Flow presents itself as the more compliant flowable composite, with Adhese showing intermediate stiffness. Grain analysis of the images confirmed the general rule that the mechanical properties improve with increasing filler loading, with the notable exception of Vertise Flow that shows modulus and hardness as high as 9.1±0.6 and 0.43±0.03GPa, respectively, for an estimated loading of only ∼40% by volume. SIGNIFICANCE Whereas generally flowable composites are confirmed not to possess sufficiently strong mechanical properties for bulk restorations, exceptions can eventually be found upon appropriate laboratory screening, as presently seems to be the case for Vertise Flow. However, real practice in actual restorations and respective clinical evaluation are required for final assessment of the suggested results.

Robust and Biodegradable Elastomers Based on Corn Starch and Polydimethylsiloxane (PDMS)

Designing starch-based biopolymers and biodegradable composites with durable mechanical properties and good resistance to water is still a challenging task. Although thermoplastic (destructured) starch has emerged as an alternative to petroleum-based polymers, its poor dimensional stability under humid and dry conditions extensively hinders its use as the biopolymer of choice in many applications. Unmodified starch granules, on the other hand, suffer from incompatibility, poor dispersion, and phase separation issues when compounded into other thermoplastics above a concentration level of 5%. Herein, we present a facile biodegradable elastomer preparation method by incorporating large amounts of unmodified corn starch, exceeding 80% by volume, in acetoxy-polyorganosiloxane thermosets to produce mechanically robust, hydrophobic bioelastomers. The naturally adsorbed moisture on the surface of starch enables autocatalytic rapid hydrolysis of polyorganosiloxane to form Si-O-Si networks. Depending on the amount of starch granules, the mechanical properties of the bioelastomers can be easily tuned with high elastic recovery rates. Moreover, starch granules considerably lowered the surface friction coefficient of the polyorganosiloxane network. Stress relaxation measurements indicated that the bioelastomers have strain energy dissipation factors that are lower than those of conventional rubbers, rendering them as promising green substitutes for plastic mechanical energy dampeners. Corn starch granules also have excellent compatibility with addition-cured polysiloxane chemistry that is used extensively in microfabrication. Regardless of the starch concentration, all of the developed bioelastomers have hydrophobic surfaces with lower friction coefficients and much less water uptake capacity than those of thermoplastic starch. The bioelastomers are biocompatible and are estimated to biodegrade in Mediterranean seawater within three to six years.

Towards excimer-laser-based stereolithography: a rapid process to fabricate rigid biodegradable photopolymer scaffolds

We demonstrate high-resolution photocross-linking of biodegradable poly(propylene fumarate) (PPF) and diethyl fumarate (DEF) using UV excimer laser photocuring at 308 nm. The curing depth can be tuned in a micrometre range by adjusting the total energy dose (total fluence). Youngs moduli of the scaffolds are found to be a few gigapascal, high enough to support bone formation. The results presented here demonstrate that the proposed technique is an excellent tool for the fabrication of stiff and biocompatible structures on a micrometre scale with defined patterns of high resolution in all three spatial dimensions. Using UV laser photocuring at 308 nm will significantly improve the speed of rapid prototyping of biocompatible and biodegradable polymer scaffolds and enables its production in a few seconds, providing high lateral and horizontal resolution. This short timescale is indeed a tremendous asset that will enable a more efficient translation of technology to clinical applications. Preliminary cell tests proved that PPF : DEF scaffolds produced by excimer laser photocuring are biocompatible and, therefore, are promising candidates to be applied in tissue engineering and regenerative medicine.

Rigid biodegradable photopolymer structures of high resolution using deep-UV laser photocuring

Recently there has been increasing effort in using microstereolithography to produce scaffolds of crosslinkable and biodegradable polymers, with desired configurations of high spatial resolution, able to regulate the growth and distribution of cells and consequently the tissue development and engineering on them. The use of deep-UV radiation allows high resolution both in the transversal plane (optical resolution) and in the vertical direction (curing depth) due to the intrinsic large absorption of polymers in this region of the electromagnetic spectrum. Herein we present high-resolution photocrosslinking of the biodegradable poly(propylene fumarate) (PPF) and diethyl fumarate (DEF), using pulsed laser light at 248 nm. The curing depth can be modulated between a few hundreds of nanometers (nm) and a few micrometers (µm) by adjusting the energy dose, the number of incident pulses and the weight ratios of PPF, DEF and photoinitiator in the photocrosslinkable mixtures. The lateral resolution is evaluated by projecting a pattern of a grid with a specified line width and line spacing, and is found to be a few µm. Youngs modulus of the cured parts is measured and found to be several GPa, high enough to support bone formation. The results presented here demonstrate that the proposed technique is suitable for the fabrication of stiff and biocompatible structures with defined patterns of micrometer resolution in all three spatial dimensions, setting the first step toward deep-UV laser microstereolithography.

Modulating DNA Translocation by a Controlled Deformation of a PDMS Nanochannel Device

Several strategies have been developed for the control of DNA translocation in nanopores and nanochannels. However, the possibility to reduce the molecule speed is still challenging for applications in the field of single molecule analysis, such as ultra-rapid sequencing. This paper demonstrates the possibility to alter the DNA translocation process through an elastomeric nanochannel device by dynamically changing its cross section. More in detail, nanochannel deformation is induced by a macroscopic mechanical compression of the polymeric device. This nanochannel squeezing allows slowing down the DNA molecule passage inside it. This simple and low cost method is based on the exploitation of the elastomeric nature of the device, can be coupled with different sensing techniques, is applicable in many research fields, such as DNA detection and manipulation, and is promising for further development in sequencing technology.

P(VDF-TrFE)/BaTiO3 Nanoparticle Composite Films Mediate Piezoelectric Stimulation and Promote Differentiation of SH-SY5Y Neuroblastoma Cells.

Poly(vinylidene fluoride-trifluoroethylene, P(VDF-TrFE)) and P(VDF-TrFE)/barium titanate nanoparticle (BTNP) films are prepared and tested as substrates for neuronal stimulation through direct piezoelectric effect. Films are characterized in terms of surface, mechanical, and piezoelectric features before in vitro testing on SH-SY5Y cells. In particular, BTNPs significantly improve piezoelectric properties of the films (4.5-fold increased d31 ). Both kinds of films support good SH-SY5Y viability and differentiation. Ultrasound (US) stimulation is proven to elicit Ca(2+) transients and to enhance differentiation in cells grown on the piezoelectric substrates. For the first time in the literature, this study demonstrates the suitability of polymer/ceramic composite films and US for neuronal stimulation through direct piezoelectric effect.

Rapid fabrication of rigid biodegradable scaffolds by excimer laser mask projection technique: a comparison between 248 and 308 nm

High-resolution photocrosslinking of the biodegradable poly(propylene fumarate) (PPF) and diethyl fumarate (DEF), using pulsed laser light at 248 and 308 nm is presented. The curing depth can be modulated between a few hundreds of nm and a few μm when using 248 nm and ten to a hundred μm when using 308 nm. By adjusting the total fluence (pulse numbers×laser fluence) dose and the weight ratios of PPF, DEF, and the photoinitiator in the photocrosslinkable mixtures, the height of polymerized structures can be precisely tuned. The lateral resolution is evaluated by projecting a pattern of a grid with a specified line width and line spacing. Youngs modulus of the cured parts is measured and found to be several GPa for both wavelengths, high enough to support bone formation. Several 2D and 2.5D microstructures, as well as porous 3D scaffolds fabricated by a layer-by-layer method, are presented. The results demonstrate that excimer laser-based photocuring is suitable for the fabrication of stiff and biocompatible structures with defined patterns of micrometer resolution in all three spatial dimensions.

Healable Cotton–Graphene Nanocomposite Conductor for Wearable Electronics

Electrically conductive materials based on cotton have important implications for wearable electronics. We have developed flexible and conductive cotton fabrics (∼10 Ω/sq) by impregnation with graphene and thermoplastic polyurethane-based dispersions. Nanocomposite fabrics display remarkable resilience against weight-pressed severe folding as well as laundry cycles. Folding induced microcracks can be healed easily by hot-pressing, restoring initial electrical conductivity. Impregnated cotton fabric conductors demonstrate better mechanical properties compared to pure cotton and thermoplastic polyurethane maintaining breathability. They also resist environmental aging such as solar irradiation and high humidity.

Bio/non-bio interfaces: a straightforward method for obtaining long term PDMS/muscle cell biohybrid constructs

Stable surface modifications of polydimethylsiloxane (PDMS) are of crucial importance for the exploitation of the versatile physical properties of silicone in many biological applications. Surface hydrophobic recovery in fact poses severe time limitations to the observation of biological events and, in particular, to cell culturing. A novel method of stable modification of PDMS surface chemistry was therefore elaborated, relying on the use of genipin as a natural low-toxicity cross-linker, and involving free amine moieties. Its effectiveness to long-term cultures was studied by preparation of thin PDMS films with different stiffness. After assessment of surface chemistry and substrate stiffness, H9c2 muscle cells were cultured on the modified films, and differentiating myoblasts were observed for a period of four weeks since differentiation induction. A lower PDMS stiffness increased myotube width and supported a higher actin and myosin colocalization within myotubes, suggesting the achievement of myotube functional maturity. These results provide evidence of the effectiveness of the proposed procedures to PDMS surface chemistry modification. Furthermore, modified PDMS membranes prove to be suitable to several long-term studies of cell behaviour in vitro, including muscle cell contractility investigations.