Directive giant upconversion by supercritical bound states in the continuum.

Photonic bound states in the continuum (BICs), embedded in the spectrum of free-space waves1,2 with diverging radiative quality factor, are topologically non-trivial dark modes in open-cavity resonators that have enabled important advances in photonics3,4. However, it is particularly challenging to achieve maximum near-field enhancement, as this requires matching radiative and non-radiative losses. Here we propose the concept of supercritical coupling, drawing inspiration from electromagnetically induced transparency in near-field coupled resonances close to the Friedrich-Wintgen condition2. Supercritical coupling occurs when the near-field coupling between dark and bright modes compensates for the negligible direct far-field coupling with the dark mode. This enables a quasi-BIC field to reach maximum enhancement imposed by non-radiative loss, even when the radiative quality factor is divergent. Our experimental design consists of a photonic-crystal nanoslab covered with upconversion nanoparticles. Near-field coupling is finely tuned at the nanostructure edge, in which a coherent upconversion luminescence enhanced by eight orders of magnitude is observed. The emission shows negligible divergence, narrow width at the microscale and controllable directivity through input focusing and polarization. This approach is relevant to various physical processes, with potential applications for light-source development, energy harvesting and photochemical catalysis.

Probing Denaturation of Protein A via Surface-Enhanced Infrared Absorption Spectroscopy.

We apply surface-enhanced infrared absorption (SEIRA) spectroscopy to monitor the denaturation process of a surface-bound protein A monolayer. Our proposed platform relies on a plasmonic metasurface comprising different spatial subregions ("pixels") that are engineered to exhibit different resonances covering the infrared region of the electromagnetic spectrum that is matched to the vibrational modes of the Amide groups. Specifically, we are able to determine changes in the Amide I and Amide II vibration coupled modes, by comparing the SEIRA reflectance spectra pertaining to the native state and a denatured state induced by a pH variation. In particular, we observe some evident red-shifts in the principal Amide I mode and the Amide II vibration coupled modes (attributable to the breaking of hydrogen bonds), which result in insurmountable barriers for refolding. Thanks to the strong field localization, and consequent enhancement of the light-matter interactions, our proposed sensing platform can operate with extremely small amounts of an analyte, with an estimated detection limit of about 3 femtomoles of molecules.

Reduced graphene oxide on silicon-based structure as novel broadband photodetector.

Heterojunction photodetector based on reduced graphene oxide (rGO) has been realized using a spin coating technique. The electrical and optical characterization of bare GO and thermally reduced GO thin films deposited on glass substrate has been carried out. Ultraviolet-visible-infrared transmittance measurements of the GO and rGO thin films revealed broad absorption range, while the absorbance analysis evaluates rGO band gap of about 2.8 eV. The effect of GO reduction process on the photoresponse capability is reported. The current-voltage characteristics and the responsivity of rGO/n-Si based device have been investigated using laser diode wavelengths from UV up to IR spectral range. An energy band diagram of the heterojunction has been proposed to explain the current versus voltage characteristics. The device demonstrates a photoresponse at a broad spectral range with a maximum responsivity and detectivity of 0.20 A/W and 7 × 1010 cmHz/W, respectively. Notably, the obtained results indicate that the rGO based device can be useful for broadband radiation detection compatible with silicon device technology.

Advanced DNA Detection via Multispectral Plasmonic Metasurfaces.

We propose and demonstrate a sensing platform based on plasmonic metasurfaces for the detection of very low concentrations of deoxyribo-nucleic acid (DNA) fragments. The platform relies on surface-enhanced infrared absorption spectroscopy, implemented via a multispectral metasurface. Specifically, different regions ("pixels") are engineered so as to separately cover the medium-infrared range of the electromagnetic spectrum extending from the functional-groups to the fingerprint region of a single analyte. In conjunction with a suitable bio-functionalization, this enables univocal and label-free recognition of specific molecules. For experimental validation, we fabricate a large-area gold metasurface on a silicon chip, and functionalize it with a recognition layer of peptide nucleic acid (PNA). Our experimental results indicate the possibility to detect complementary DNA fragments in concentrations as low as 50 fM, i.e., well below the value attained by standard methods, with additional advantages in terms of processing time, versatility and ease of implementation/operation.

Ultrasensitive Surface Refractive Index Imaging Based on Quasi-Bound States in the Continuum.

Herein, we demonstrate a cavity-enhanced hyperspectral refractometric imaging using an all-dielectric photonic crystal slab (PhCS). Our approach takes advantage of the synergy between two mechanisms, surface-enhanced fluorescence (SEF) and refractometric sensing, both based on high-Q resonances in proximity of bound states in the continuum (BICs). The enhanced local optical field of the first resonance amplifies of 2 orders of magnitude the SEF emission of a probe dye. Simultaneously, hyperspectral refractometric sensing, based on Fano interference between second mode and fluorescence emission, is used for mapping the spatially variant refractive index produced by the specimen on the PhCS. The spectral matching between first resonance and input laser is modulated by the specimen local refractive index, and thanks to the calibrated dependence with the spectral shift of the Fano resonance, the cavity tuning is used to achieve an enhanced correlative refractometric map with a resolution of 10-5 RIU within femtoliter-scale sampling volumes. This is experimentally applied also on live prostate cancer cells grown on the PhCS, reconstructing enhanced surface refractive index images at the single-cell level. This dual mechanism of quasi-BIC spatially variant gain tracked by quasi-BIC refractometric sensing provides a correlative imaging platform that can find application in many fields for monitoring physical and biochemical processes, such as molecular interactions, chemical reactions, or surface cell analysis.

Tuning the exponential sensitivity of a bound-state-in-continuum optical sensor.

In this work, we investigate the evanescent field sensing mechanism provided by an all-dielectric metasurface supporting bound states in the continuum (BICs). The metasurface is based on a transparent photonic crystal with subwavelength thickness. The BIC electromagnetic field is localized along the direction normal to the photonic crystal nanoscale-thin slab (PhCS) because of a topology-induced confinement, exponentially decaying in the material to detect. On the other hand, it is totally delocalized in the PhCS plane, which favors versatile and multiplexing sensing schemes. Liquids with different refractive indices, ranging from 1.33 to 1.45, are infiltrated in a microfluidic chamber bonded to the sensing dielectric metasurface. We observe an experimental exponential sensitivity leading to differential values as large as 226 nm/RIU with excellent FOM. This behavior is explained in terms of the physical superposition of the field with the material under investigation and supported by a thorough numerical analysis. The mechanism is then translated to the case of molecular adsorption where a suitable theoretical engineering of the optical structure points out potential sensitivities as large as 4000 nm/RIU.

Optical Biosensors Based on Photonic Crystals Supporting Bound States in the Continuum.

A novel optical label-free bio-sensing platform based on a new class of resonances supported in a photonic crystal metasurface is reported herein. Molecular binding is detected as a shift in the resonant wavelength of the bound states in the continuum of radiation modes. The new configuration is applied to the recognition of the interaction between protein p53 and its protein regulatory partner murine double minute 2 (MDM2). A detection limit of 66 nM for the protein p53 is found. The device provides an excellent interrogation stability and loss-free operation, requires minimal optical interrogation equipment and can be easily optimized to work in a wide wavelength range.

Internalization kinetics and cytoplasmic localization of functionalized diatomite nanoparticles in cancer cells by Raman imaging.

Porous biosilica nanoparticles obtained from diatomites (DNPs) have been recently demonstrated to be non-toxic nanovectors of therapeutic agents in cancer cells. In this work, the internalization kinetics and intracellular spatial distribution of functionalized DNPs incubated with human lung epidermoid carcinoma cell line (H1355) up to 72 hours are investigated by Raman imaging. The label-free Raman results are compared with confocal fluorescence microscopy and photoluminescence (PL) data. Raman bands specifically assigned to DNPs and cellular components provide evidence that the nanovectors are internalized and co-localize with lipid environments. A considerable DNPs uptake in cells is observed within 6 hours, with equilibrium being achieved after 18 hours. The obtained data show the presence of DNPs up to 72 hours, without damage to cell viability or morphology. The PL measurements performed on DNPs not penetrating the cells at different incubation times are strongly correlated with the results obtained by Raman imaging and confocal microscopy analyses.

A Microfluidic Approach for Inducing Cell Rotation by Means of Hydrodynamic Forces.

Microfluidic technology allows to realize devices in which cells can be imaged in their three-dimensional shape. However, there are still some limitations in the method, due to the fact that cells follow a straight path while they are flowing in a channel. This can result in a loss in information, since only one side of the cell will be visible. Our work has started from the consideration that if a cell rotates, it is possible to overcome this problem. Several approaches have been proposed for cell manipulation in microfluidics. In our approach, cells are controlled by only taking advantages of hydrodynamic forces. Two different devices have been designed, realized, and tested. The first device induces cell rotation in a plane that is parallel (in-plane) to the observation plane, while the second one induce rotation in a plane perpendicular (out-of-plane) to the observation plane.

Optically monitored drug delivery patch based on porous silicon and polymer microneedles.

Fabrication and characterization of an optically monitored hybrid patch for local administration of drugs, based on polymeric micro-needles and a porous silicon free-standing membrane, are reported. The micro-needles are realized by an innovative photolithographic approach that allows fine tuning of geometrical parameters, using polyethylene glycol and a commercial photo-catalyzer. The porous silicon multilayer not only increases the storage of a relevant amount of the drug, but also offers a continuous, naked-eye monitoring of the drug delivery process. As a proof-of-concept experiment, we report our results on the release of a dye molecule (fluorescein, 332 Da) in a phosphate saline buffer.

A new strategy for label-free detection of lymphoma cancer cells.

In this paper, a new strategy for highly selective and sensitive direct detection of lymphoma cells by exploiting the interaction between a peptide and its B-cell receptor, has been evaluated. In particular, an idiotype peptide, able to specifically bind the B-cell receptor of A20 cells in mice engrafted with A20 lymphoma, has been used as molecular probe. The new detection technique has been demonstrated on a planar crystalline silicon chip. Coverage of 85% of silicon surface and detection efficiency of 8.5 × 10(-3) cells/µm(2) were obtained. The recognition strategy promises to extend its application in studying the interaction between ligands and their cell-surface receptors.

Diatomite biosilica nanocarriers for siRNA transport inside cancer cells.

BACKGROUND: Diatomite is a natural porous biomaterial of sedimentary origin, formed by fragments of diatom siliceous skeletons, called "frustules". Due to large availability in many areas of the world, chemical stability, and non-toxicity, these fossil structures have been widespread used in lot of industrial applications, such as food production, water extracting agent, production of cosmetics and pharmaceutics. However, diatomite is surprisingly still rarely used in biomedical applications. In this work, we exploit diatomite nanoparticles for small interfering ribonucleic acid (siRNA) transport inside human epidermoid cancer cells (H1355). METHODS: Morphology and composition of diatomite microfrustules (average size lower than 40µm) are investigated by scanning electron microscopy equipped by energy dispersive X-ray spectroscopy, Fourier transform infrared analysis, and photoluminescence measurements. Nanometric porous particles (average size lower than 450nm) are obtained by mechanical crushing, sonication, and filtering of micrometric frustules. siRNA bioconjugation is performed on both micrometric and nanometric fragments by silanization. RESULTS: In-vitro experiments show very low toxicity on exposure of the cells to diatomite nanoparticle concentration up to 300µg/ml for 72h. Confocal microscopy imaging performed on cancer cells incubated with siRNA conjugated nanoparticles demonstrates a cytoplasmatic localization of vectors. Gene silencing by delivered siRNA is also demonstrated. CONCLUSION: Our studies endorse diatomite nanoparticles as non-toxic nanocarriers for siRNA transport in cancer cells. GENERAL SIGNIFICANCE: siRNA is a powerful molecular tool for cancer treatment but its delivery is inefficient due to the difficulty to penetrate the cell membrane. siRNA-diatomite nanoconjugate may be well suited for delivery of therapeutic to cancer cells.

Synthesis of mixed-sequence oligonucleotides on mesoporous silicon: chemical strategies and material stability.

Rapid screening tests in medical diagnostic and environmental analysis are often based on oligonucleotide biochips. In this paper, we studied the stability of functionalized mesoporous silicon supports in the solid-phase synthesis of oligonucleotides, exploiting several chemical procedures. A 19-mer mixed sequence has been successfully synthesized on aminosilane-modified porous silicon photonic structures. The process and the materials have been characterized by optical reflectivity, atomic force microscopy and high-performance liquid chromatography.

Diatomite silica nanoparticles for drug delivery.

Diatomite is a natural fossil material of sedimentary origin, constituted by fragments of diatom siliceous skeletons. In this preliminary work, the properties of diatomite nanoparticles as potential system for the delivery of drugs in cancer cells were exploited. A purification procedure, based on thermal treatments in strong acid solutions, was used to remove inorganic and organic impurities from diatomite and to make them a safe material for medical applications. The micrometric diatomite powder was reduced in nanoparticles by mechanical crushing, sonication, and filtering. Morphological analysis performed by dynamic light scattering and transmission electron microscopy reveals a particles size included between 100 and 300 nm. Diatomite nanoparticles were functionalized by 3-aminopropyltriethoxysilane and labeled by tetramethylrhodamine isothiocyanate. Different concentrations of chemically modified nanoparticles were incubated with cancer cells and confocal microscopy was performed. Imaging analysis showed an efficient cellular uptake and homogeneous distribution of nanoparticles in cytoplasm and nucleus, thus suggesting their potentiality as nanocarriers for drug delivery. PACS: 87.85.J81.05.Rm; 61.46. + w.

Optical properties of diatom nanostructured biosilica in Arachnoidiscus sp: micro-optics from mother nature.

Some natural structures show three-dimensional morphologies on the micro- and nano-scale, characterized by levels of symmetry and complexity well far beyond those fabricated by best technologies available. This is the case of diatoms, unicellular microalgae, whose protoplasm is enclosed in a nanoporous microshell, made of hydrogenated amorphous silica, called frustule. We have studied the optical properties of Arachnoidiscus sp. single valves both in visible and ultraviolet range. We found photonic effects due to diffraction by ordered pattern of pores and slits, accordingly to an elaborated theoretical model. For the first time, we experimentally revealed spatial separation of focused light in different spots, which could be the basis of a micro-bio-spectrometer. Characterization of such intricate structures can be of great inspiration for photonic devices of next generation.

Aminosilane functionalizations of mesoporous oxidized silicon for oligonucleotide synthesis and detection.

Direct solid phase synthesis of peptides and oligonucleotides (ONs) requires high chemical stability of the support material. In this work, we have investigated the passivation ability of porous oxidized silicon multilayered structures by two aminosilane compounds, 3-aminopropyltriethoxysilane and 3-aminopropyldimethylethoxysilane (APDMES), for optical label-free ON biosensor fabrication. We have also studied by spectroscopic reflectometry the hybridization between a 13 bases ON, directly grown on the aminosilane modified porous oxidized silicon by in situ synthesis, and its complementary sequence. Even if the results show that both devices are stable to the chemicals (carbonate/methanol) used, the porous silica structure passivated by APDMES reveals higher functionalization degree due to less steric hindrance of pores.

Critically coupled silicon Fabry-Perot photodetectors based on the internal photoemission effect at 1550 nm.

In this paper, design, fabrication and characterization of an all-silicon photodetector (PD) at 1550 nm, have been reported. Our device is a surface-illuminated PD constituted by a Fabry-Perot microcavity incorporating a Cu/p-Si Schottky diode. Its absorption mechanism, based on the internal photoemission effect (IPE), has been enhanced by critical coupling condition. Our experimental findings prove a peak responsivity of 0.063 mA/W, which is the highest value obtained in a surface-illuminated IPE-based Si PD around 1550 nm. Finally, device capacitance measurements have been carried out demonstrating a capacitance < 5 pF which has the potential for GHz operation subject to a reduction of the series resistance of the ohmic contact.

Hydrophobin Vmh2-glucose complexes self-assemble in nanometric biofilms.

Hydrophobins are small proteins secreted by fungi, which self-assemble into amphipathic membranes at air-liquid or liquid-solid interfaces. The physical and chemical properties of some hydrophobins, both in solution and as a biofilm, are affected by poly or oligosaccharides. We have studied the interaction between glucose and the hydrophobin Vmh2 from Pleurotus ostreatus by spectroscopic ellipsometry (SE), atomic force microscopy (AFM) and water contact angle (WCA). We have found that Vmh2-glucose complexes forms a chemically stable biofilm, obtained by drop deposition on silicon, 1.6 nm thick and containing 35 per cent of glucose, quantified by SE. AFM highlighted the presence of nanometric rodlet-like aggregates (average height, width and length being equal to 3.6, 23.8 and 40 nm, respectively) on the biofilm surface, slightly different from those obtained in the absence of glucose (4.11, 23.9 and 64 nm). The wettability of a silicon surface, covered by the organic layer of Vmh2-glucose, strongly changed: WCA decreased from 90° down to 17°.

Numerical optimization of a microfluidic assisted microarray for the detection of biochemical interactions.

Finite element method analysis was applied to the characterization of the biomolecular interactions taking place in a microfluidic assisted microarray. Numerical simulations have been used for the optimization of geometrical and physical parameters of the sensing device. Different configurations have been analyzed and general considerations have been derived. We have shown that a parallel disposition of the sensing area allows the homogeneous formation of the target molecular complex in all the active zones of the microarray. Stationary and time dependent results have also been obtained.

A microfluidics assisted porous silicon array for optical label-free biochemical sensing.

A porous silicon (PSi) based microarray has been integrated with a microfluidic system, as a proof of concept device for the optical monitoring of selective label-free DNA-DNA interaction. A 4 × 4 square matrix of PSi one dimensional photonic crystals, each one of 200 µm diameter and spaced by 600 µm, has been sealed by a polydimethylsiloxane (PDMS) channels circuit. The PSi optical microarray elements have been functionalized by DNA single strands after sealing: the microfluidic circuit allows to reduce significantly the biologicals and chemicals consumption, and also the incubation time with respect to a not integrated device. Theoretical calculations, based on finite element method, taking into account molecular interactions, are in good agreement with the experimental results, and the developed numerical model can be used for device optimization. The functionalization process and the interaction between DNA probe and target has been monitored by spectroscopic reflectometry for each PSi element in the microchannels.