A new silanizing agent tailored to surface bio-functionalization.

Amino-terminated surfaces can be effectively obtained by means of silanizing agents, realizing surfaces suitable for the purification of biomarkers of several pathologies. Since the level of biomarkers, such as microRNAs and cell-free DNA, into circulation may be extremely low, new and ameliorated capturing molecules and protocols are highly required. In this work, a new silane, acetone-imine propyl trimethoxysilane (AIPTMS), is synthesized with a simple and elegant reaction, via the nucleophilic addition of the primary amino group to the carbonyl group of acetone. AIPTMS and APTMS were used to silanize silicon oxide surfaces, which were characterized chemically (XPS) and morphologically (AFM). The two types of surfaces were chemically similar, but behaved very differently both for surface morphology and functional properties. The AIPTMS-modified surface was indeed very smooth and homogeneous with respect to the APTMS-modified surface. Moreover, the AIPTMS surface captured larger amounts of nucleic acids almost immediately after preparation, while APTMS-based functional surfaces needed longer time to reach comparable efficiency. AIPTMS shows several advantages over standard aminosilanes, as it realizes a more homogeneous surface coverage that, in turn, produces an improved response towards the capture of nucleic acids. AIPTMS is a very promising reagent for the reliable and reproducible preparation of active biofunctional surfaces for the purification and analysis of circulating biomarkers.

First synthesis of silicon nanocrystals in amorphous silicon nitride from a preceramic polymer.

We report the first synthesis of silicon nanocrystals embedded in a silicon nitride matrix through a direct pyrolysis of a preceramic polymer (perhydropolysilazane). Structural analysis carried out by XRD, XPS, Raman and TEM reveals the formation of silicon quantum dots and correlates the microstructures with the annealing temperature. The photoluminescence of the nanocomposites was investigated by both linear and nonlinear measurements. Furthermore we demonstrate an enhanced chemical resistance of the nitride matrix, compared to the typical oxide one, in both strongly acidic and basic environments. The proposed synthesis via polymer pyrolysis is a striking innovation potentially allowing a mass-scale production nitride embedded Si nanocrystals.

Role of sonication pre-treatment and cation valence in the sol-gel transition of nano-cellulose suspensions.

Sol-gel transition of carboxylated cellulose nanocrystals has been investigated using rheology, SAXS, NMR and optical spectroscopies to unveil the distinctive roles of ultrasound treatments and addition of various cations. Besides cellulose fiber fragmentation, sonication treatment induces fast gelling of the solution. The gelation is independent of the addition of cations, while the final rheological properties are highly influenced by the type, concentration and sequence of the operations since the cations must be added prior to sonication to produce stiff gels. The gel elastic modulus was found to increase proportionally to the ionic charge rather than the cationic size. In cases where ions were added after sonication, SAXS analysis of the Na+ hydrogel and Ca2+ hydrogel indicated the presence of structurally ordered domains in which water is confined, and 1H-NMR investigation showed the dynamics of water exchange within the hydrogels. Conversely, separated phases containing essentially free water were characteristic of the hydrogels obtained by sonication after Ca2+ addition, confirming that this ion induces irreversible fiber aggregation. The rheological properties of the hydrogels depend on the duration of the ultrasound treatments, enabling the design of programmed materials with tailored energy dissipation response.

Fabrication of complex-shaped hydrogels by diffusion controlled gelation of nanocellulose crystallites.

In this study we investigated the fabrication of small hydrogel objects by the coordination-driven assembly of supramolecular rod-like crystallites of nanocellulose, using ionotropic gelation as a methodological approach and Ca2+ as a gelling agent. We proved that the gelation process is diffusion-mediated and fitting the equations modelling this process to the profile of the Ca2+ front, a Ca2+ diffusion coefficient in the incipient hydrogel of (4.5 ± 1.1) × 10-6 cm2 s-1 was calculated. At the steady-state a spatially homogeneous distribution of Ca2+-crosslinked sites in the hydrogel network was observed. External ionotropic gelation produced beads, wires or disks, while core-shell capsules were obtained by inverse ionotropic gelation. We demonstrated that equilibrium and dynamics of the distribution of Ca2+ offer the opportunity to design precisely the size and shape of these small hydrogel objects. In particular, the core size and the shell thickness of the capsules can be tailored under kinetic controlled conditions. The proposed approach, with supramolecular structures of the natural source as assembling components and the water-in-water fabrication process, is fast, simple, and requires only sustainable chemistry and is easily implementable in automatic microfluidic platforms.

Orange and blue luminescence emission to track functionalized porous silicon microparticles inside the cells of the human immune system.

Porous silicon micro-particles (micro-pSi) with size in the range of 1-10 µm are obtained by etching of silicon wafers followed by sonication. The derivatization of the micro-pSi surface by wet chemistry (silylation and coupling with a diamine) yields an interface, which exposes negative (carboxylic) or positive (amine) groups at pH 7.4. The surface modification, beyond the introduction of groups for the drug loading by covalent or electrostatic interactions, stabilizes the intense orange luminescence characteristic of the silicon nano-crystallites. Derivatization by amines introduces also a second emission in the blue region, which follows a different excitation pathway and can be attributed to the interface defects. The micro-pSi are efficiently internalized by human dendritic cells and do not show any toxic effect even at a concentration of 1 mg mL-1. The intrinsic luminescence of the differently functionalized micro-pSi is preserved inside the cells and permits the selective and efficient tracking of the microparticles without using molecular tags and thus leaving the organic coating available for the interaction with the drug. The results obtained suggest that the functionalized micro-pSi are an efficient platform for simultaneous imaging and delivery of therapeutic agents to the disease site.

Reconfigurable optical routers based on Coupled Resonator Induced Transparency resonances.

The interferometric coupling of pairs of resonators in a resonator sequence generates coupled ring induced transparency (CRIT) resonances. These have quality factors an order of magnitude greater than those of single resonators. We show that it is possible to engineer CRIT resonances in tapered SCISSOR (Side Coupled Integrated Space Sequence of Resonator) to realize fast and efficient reconfigurable optical switches and routers handling several channels while keeping single channel addressing capabilities. Tapered SCISSORs are fabricated in silicon-on-insulator technology. Furthermore, tapered SCISSORs show multiple-channel switching behavior that can be exploited in DWDM applications.

Coupled-resonator-induced-transparency concept for wavelength routing applications.

The presence of coupled resonators induced transparency (CRIT) effects in side-coupled integrated spaced sequence of resonators (SCISSOR) of different radii has been studied. By controlling the rings radii and their center to center distance, it is possible to form transmission channels within the SCISSOR stop-band. Two different methods to exploit the CRIT effect in add/drop filters are proposed. Their performances, e. g. linewidth, crosstalk and losses, are examined also for random variations in the structural parameters. Finally, few examples of high performances mux/demux structures and 2 × 2 routers based on these modified SCISSOR are presented. CRIT based SCISSOR optical devices are particularly promising for ultra-dense wavelength division multiplexing applications.

Robust design of an optical router based on a tapered side-coupled integrated spaced sequence of optical resonators.

A novel (to our knowledge) scheme of an optical router/switch element, composed of a tapered side-coupled integrated spaced sequence of optical resonators, is proposed. It is based on a modified design of the ring sequence in which the resonance conditions are set by the single ring resonance and by the coherent feedback of the sequence of rings. This double condition yields robustness against fabrication defects, dense routing capability, and high switching efficiency.

Purcell factor and superradiance in Si-patterned waveguides.

Numerical modeling of slotted photonic crystal Si waveguides is reported. Employing multiple slots in a single waveguide, we obtained large Purcell enhancements for a large ensemble of emitters coupled with the same optical mode. This allows observation of peculiar physical phenomena, such as anisotropic bandgap superradiance.

Band gap characterization and slow light effects in one dimensional photonic crystals based on silicon slot-waveguides.

We investigate the photonic properties of one dimensional photonic crystals realized on Silicon On Insulator channel slot-waveguide to engineer slow light effects. Various geometries of the photonic pattern have been characterized and their photonic band-gap structure analyzed. The optimal geometry has been further used to realize a coupled resonator optical waveguide (CROW). A first optimization of these CROW devices shows a group velocity of more than c/10 at 1.55 mum. Full three dimensional calculations based on the planar wave expansion method have been used to compute the band diagram while full three dimensional calculations based on finite difference time domain methods have been used to study light propagation.