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.

Design and Optimization of All-Dielectric Fluorescence Enhancing Metasurfaces: Towards Advanced Metasurface-Assisted Optrodes.

The need for miniaturized biological sensors which can be easily integrated into medical needles and catheters for in vivo liquid biopsies with ever-increasing performances has stimulated the interest of researchers in lab-on-fiber (LOF) technology. LOF devices arise from the integration of functional materials at the nanoscale on the tip of optical fibers, thus endowing a simple optical fiber with advanced functionalities and enabling the realization of high-performance LOF biological sensors. Consequently, in 2017, we demonstrated the first optical fiber meta-tip (OFMT), consisting of the integration of plasmonic metasurfaces (MSs) on the optical fiber end-face which represented a major breakthrough along the LOF technology roadmap. Successively, we demonstrated that label-free biological sensors based on the plasmonic OFMT are able to largely overwhelm the performance of a standard plasmonic LOF sensor, in view of the extraordinary light manipulation capabilities of plasmonic array exploiting phase gradients. To further improve the overall sensitivity, a labelled sensing strategy is here suggested. To this end, we envision the possibility to realize a novel class of labelled LOF optrodes based on OFMT, where an all-dielectric MS, designed to enhance the fluorescence emission by a labelled target molecule, is integrated on the end-face of a multimode fiber (MMF). We present a numerical environment to compute the fluorescence enhancement factor collected by the MMF, when on its tip a Silicon MS is laid, consisting of an array of cylindrical nanoantennas, or of dimers or trimers of cylindrical nanoantennas. According to the numerical results, a suitable design of the dielectric MS allows for a fluorescence enhancement up to three orders of magnitudes. Moreover, a feasibility study is carried out to verify the possibility to fabricate the designed MSs on the termination of multimode optical fibers using electron beam lithography followed by reactive ion etching. Finally, we analyze a real application scenario in the field of biosensing and evaluate the degradation in the fluorescence enhancement performances, taking into account the experimental conditions. The present work, thus, provides the main guidelines for the design and development of advanced LOF devices based on the fluorescence enhancement for labelled biosensing applications.

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.

Impact of dealcoholization on quality properties in white wine at various alcohol content levels.

The reduction of alcohol content in wines has two main objectives, the former is decreasing the wines' strength and the latter is producing new low alcohol beverages. To accomplish the latter, in this study, we focused on the dealcoholization of a white wine (cv Falanghina, 12.5 vol%) obtained from an ancient Italian grape variety that has recently aroused a renewed interest. It was dealcoholized at various alcohol content levels ranging from 9.8 to 0.3 vol% through the osmotic distillation process, and the main quality parameters of the obtained dealcoholized samples were evaluated. No significant differences (p < 0.05) in total phenols, flavonoids, organic acids and total acidity were observed among the wine samples at different alcohol content levels. On the contrary, the volatile compounds content decreased with increasing alcohol removal. Specifically, almost 50% of higher alcohols with acids and lactones were preserved in dealcoholized wine at 9.8 vol% alcohol content, but this percentage reduced to 30% in the sample at 6.8 vol%, and was even lower in the dealcoholized wine with lower alcohol content. It was argued that the transport of volatile compounds through the membrane, beside the membrane selectivity, is highly correlated with the Henry constant (R2 > 0.8021 for 9.8 vol% of dealcoholized wine). Moreover, results of the sensory evaluation indicated a significant change in terms of acidity, odour, sweetness and body taste in dealcoholized wine (0.3 vol%), giving an overall perceived imbalance and unacceptable taste with respect to the original wine. Therefore, in order to balance acid sensation and enhance body and aftertaste, an attempt was made to formulate an alcohol-free wine-based beverage with enhanced odour and sweetness, by adding some floral wine flavours, up to the amount present in the original wine.

A novel Lab-on-Fiber Radiation Dosimeter for Ultra-high Dose Monitoring.

In this work, we report on the first demonstration of Lab on Fiber (LOF) dosimeter for ionizing radiation monitoring at ultra-high doses. The new dosimeter consists in a metallo-dielectric resonator at sub-wavelength scale supporting localized surface plasmon resonances realized on the optical fiber (OF) tip. The resonating structure involves two gold gratings separated by a templated dielectric layer of poly(methyl methacrylate) (PMMA). Two LOF prototypes have been manufactured and exposed at the IRRAD Proton Facility at CERN in Geneva to 23 GeV protons for a total fluence of 0.67 × 1016 protons/cm2, corresponding to an absorbed dose of 1.8 MGy. Experimental data demonstrated the "radiation resistance" feature of the LOF devices and a clear dependence of the reflected spectrum versus the total dose, expressed by a cumulative blue-shift of ~1.4 nm of the resonance combined with a slight increase of 0.16 dBm in the reflected spectrum. The numerical analysis carried out to correlate the experimental results with the dimensional and physical properties of the resonator, expected to be tightly connected to the absorbed dose, suggests that the main phenomenon induced by exposure to proton beam and able to explain the measured spectral behavior is the reduction of the PMMA thickness, which is also consistent with past literature in the field. Preliminary results demonstrated the potentiality of the proposed platform as dosimeter at MGy dose levels for high energy physics experiments.

Optical fiber meta-tips.

We report on the first demonstration of a proof-of-principle optical fiber 'meta-tip', which integrates a phase-gradient plasmonic metasurface on the fiber tip. For illustration and validation purposes, we present numerical and experimental results pertaining to various prototypes implementing generalized forms of the Snell's transmission/reflection laws at near-infrared wavelengths. In particular, we demonstrate several examples of beam steering and coupling with surface waves, in fairly good agreement with theory. Our results constitute a first step toward the integration of unprecedented (metasurface-enabled) light-manipulation capabilities in optical-fiber technology. By further enriching the emergent 'lab-on-fiber' framework, this may pave the way for the widespread diffusion of optical metasurfaces in real-world applications to communications, signal processing, imaging and sensing.

Impedimetric Label-Free Immunosensor on Disposable Modified Screen-Printed Electrodes for Ochratoxin A.

An impedimetric label-free immunosensor on disposable screen-printed carbon electrodes (SPCE) for quantitative determination of Ochratoxin A (OTA) has been developed. After modification of the SPCE surface with gold nanoparticles (AuNPs), the anti-OTA was immobilized on the working electrode through a cysteamine layer. After each coating step, the modified surfaces were characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The capacitance was chosen as the best parameter that describes the reproducible change in electrical properties of the electrode surface at different OTA concentrations and it was used to investigate the analytical parameters of the developed immunosensor. Under optimized conditions, the immunosensor showed a linear relationship between 0.3 and 20 ng/mL with a low detection limit of 0.25 ng/mL, making it suitable to control OTA content in many common food products. Lastly, the immunosensor was used to measure OTA in red wine samples and the results were compared with those registered with a competitive ELISA kit. The immunosensor was sensitive to OTA lower than 2 µg/kg, which represents the lower acceptable limit of OTA established by European legislation for common food products.

Lab-on-fiber technology: a new vision for chemical and biological sensing.

The integration of microfluidics and photonic biosensors has allowed achievement of several laboratory functions in a single chip, leading to the development of photonic lab-on-a-chip technology. Although a lot of progress has been made to implement such sensors in small and easy-to-use systems, many applications such as point-of-care diagnostics and in vivo biosensing still require a sensor probe able to perform measurements at precise locations that are often hard to reach. The intrinsic property of optical fibers to conduct light to a remote location makes them an ideal platform to meet this demand. The motivation to combine the good performance of photonic biosensors on chips with the unique advantages of optical fibers has thus led to the development of the so-called lab-on-fiber technology. This emerging technology envisages the integration of functionalized materials on micro- and nano-scales (i.e. the labs) with optical fibers to realize miniaturized and advanced all-in-fiber probes, especially useful for (but not limited to) label-free chemical and biological applications. This review presents a broad overview of lab-on-fiber biosensors, with particular reference to lab-on-tip platforms, where the labs are integrated on the optical fiber facet. Light-matter interaction on the fiber tip is achieved through the integration of thin layers of nanoparticles or nanostructures supporting resonant modes, both plasmonic and photonic, highly sensitive to local modifications of the surrounding environment. According to the physical principle that is exploited, different configurations - such as localized plasmon resonance probes, surface enhanced Raman scattering probes and photonic probes - are classified, while various applications are presented in context throughout. For each device, the surface chemistry and the related functionalization protocols are reviewed. Moreover, the implementation strategies and fabrication processes, either based on bottom-up or top-down approaches, are discussed. In conclusion we highlight some of the further development opportunities, including lab-in-a-needle technology, which could have a direct and disruptive impact in localized cancer treatment applications.

Surface sensitivity of Rayleigh anomalies in metallic nanogratings.

Sensing schemes based on Rayleigh anomalies (RAs) in metal nanogratings exhibit an impressive bulk refractive-index sensitivity determined solely by the grating period. However, the surface sensitivity (which is a key figure of merit for label-free chemical and biological sensing) needs to be carefully investigated to assess the actual applicability of this technological platform. In this paper, we explore the sensitivity of RAs in metal nanogratings when local refractive-index changes are considered. Our studies reveal that the surface sensitivity deteriorates up to two orders of magnitude by comparison with the corresponding bulk value; interestingly, this residual sensitivity is not attributable to the wavelength shift of the RAs, which are completely insensitive to local refractive-index changes, but rather to a strictly connected plasmonic effect. Our analysis for increasing overlay thickness reveals an ultimate surface sensitivity that approaches the RA bulk value, which turns out to be the upper-limit of grating-assisted surface-plasmon-polariton sensitivities.

Lab-on-fiber technology: toward multifunctional optical nanoprobes.

We propose a reliable fabrication process enabling the integration of dielectric and metallic nanostructures on the tip of optical fibers, thus representing a further step in the "lab-on-fiber" technology roadmap. The proposed fabrication procedure involves conventional deposition and nanopatterning techniques, typically used for planar devices, but here adapted to directly operate on optical fiber tip. Following this approach, we demonstrate a first technological platform based on the integration onto the optical fiber tip of two-dimensional hybrid metallo-dielectric nanostructures supporting localized surface plasmon resonances. By means of experimental measurements and full-wave numerical simulations, we characterize these resonant phenomena and investigate the underlying physics. We show that resonances can be easily tuned by acting on the physical and geometrical parameters of the structure. Moreover, with a view toward possible applications, we present some preliminary results demonstrating how the proposed device can work effectively as an optical probe for label-free chemical and biological sensing as well as a microphone for acoustic wave detection.