An Infrared Nanospectroscopy Technique for the Study of Electric-Field-Induced Molecular Dynamics.

Static electric fields play a considerable role in a variety of molecular nanosystems as diverse as single-molecule junctions, molecules supporting electrostatic catalysis, and biological cell membranes incorporating proteins. External electric fields can be applied to nanoscale samples with a conductive atomic force microscopy (AFM) probe in contact mode, but typically, no structural information is retrieved. Here we combine photothermal expansion infrared (IR) nanospectroscopy with electrostatic AFM probes to measure nanometric volumes where the IR field enhancement and the static electric field overlap spatially. We leverage the vibrational Stark effect in the polymer poly(methyl methacrylate) for calibrating the local electric field strength. In the relevant case of membrane protein bacteriorhodopsin, we observe electric-field-induced changes of the protein backbone conformation and residue protonation state. The proposed technique also has the potential to measure DC currents and IR spectra simultaneously, insofar enabling the monitoring of the possible interplay between charge transport and other effects.

Infrared Spectroscopy of SARS-CoV-2 Viral Protein: from Receptor Binding Domain to Spike Protein.

Spike (S) glycoprotein is the largest structural protein of SARS-CoV-2 virus and the main one involved in anchoring of the host receptor ACE2 through the receptor binding domain (RBD). S protein secondary structure is of great interest for shedding light on various aspects, from functionality to pathogenesis, finally to spectral fingerprint for the design of optical biosensors. In this paper, the secondary structure of SARS-CoV-2 S protein and its constituting components, namely RBD, S1 and S2 regions, are investigated at serological pH by measuring their amide I infrared absorption bands through Attenuated Total Reflection Infrared (ATR-IR) spectroscopy. Experimental data in combination with MultiFOLD predictions, Define Secondary Structure of Proteins (DSSP) web server and Gravy value calculations, provide a comprehensive understanding of RBD, S1, S2, and S proteins in terms of their secondary structure content, conformational order, and interaction with the solvent.

Characterization of CuAg Alloys with Low Ag Concentrations.

Copper-based alloys designed to combine high electronic and thermal conductivities with high mechanical strength find a wide range of applications in different fields. Among the principal representatives, strongly diluted CuAg alloys are of particular interest as innovative materials for the realization of accelerating structures when the use of high-gradient fields requires increasingly high mechanical and thermal performances to overcome the limitations induced by breakdown phenomena. This work reports the production and optical characterization of CuAg crystals at low Ag concentrations, from 0.028% wt to 0.1% wt, which guarantee solid solution hardening while preserving the exceptional conductivity of Cu. By means of Fourier Transform Infrared (FTIR) micro-spectroscopy experiments, the low-energy electrodynamics of the alloys are compared with that of pure Cu, highlighting the complete indistinguishability in terms of electronic transport for such low concentrations. The optical data are further supported by Raman micro-spectroscopy and SEM microscopy analyses, allowing the demonstration of the full homogeneity and complete solubility of solid Ag in copper at those concentrations. Together with the solid solution hardening deriving from the alloying process, these results support the advantage of strongly diluted CuAg alloys over conventional materials for their application in particle accelerators.

Biocompatibility and Connectivity of Semiconductor Nanostructures for Cardiac Tissue Engineering Applications.

Nano- or microdevices, enabling simultaneous, long-term, multisite, cellular recording and stimulation from many excitable cells, are expected to make a strategic turn in basic and applied cardiology (particularly tissue engineering) and neuroscience. We propose an innovative approach aiming to elicit bioelectrical information from the cell membrane using an integrated circuit (IC) bearing a coating of nanowires on the chip surface. Nanowires grow directly on the backend of the ICs, thus allowing on-site amplification of bioelectric signals with uniform and controlled morphology and growth of the NWs on templates. To implement this technology, we evaluated the biocompatibility of silicon and zinc oxide nanowires (NWs), used as a seeding substrate for cells in culture, on two different primary cell lines. Human cardiac stromal cells were used to evaluate the effects of ZnO NWs of different lengths on cell behavior, morphology and growth, while BV-2 microglial-like cells and GH4-C1 neuroendocrine-like cell lines were used to evaluate cell membrane-NW interaction and contact when cultured on Si NWs. As the optimization of the contact between integrated microelectronics circuits and cellular membranes represents a long-standing issue, our technological approach may lay the basis for a new era of devices exploiting the microelectronics' sensitivity and "smartness" to both improve investigation of biological systems and to develop suitable NW-based systems available for tissue engineering and regenerative medicine.

Low-Temperature Stability and Sensing Performance of Mid-Infrared Bloch Surface Waves on a One-Dimensional Photonic Crystal.

The growing need for new and reliable surface sensing methods is arousing interest in the electromagnetic excitations of ultrathin films, i.e., to generate electromagnetic field distributions that resonantly interact with the most significant quasi-particles of condensed matter. In such a context, Bloch surface waves turned out to be a valid alternative to surface plasmon polaritons to implement high-sensitivity sensors in the visible spectral range. Only in the last few years, however, has their use been extended to infrared wavelengths, which represent a powerful tool for detecting and recognizing molecular species and crystalline structures. In this work, we demonstrate, by means of high-resolution reflectivity measurements, that a one-dimensional photonic crystal can sustain Bloch surface waves in the infrared spectral range from room temperature down to 10 K. To the best of our knowledge, this is the first demonstration of infrared Bloch surface waves at cryogenic temperatures. Furthermore, by exploiting the enhancement of the surface state and the high brilliance of infrared synchrotron radiation, we demonstrate that the proposed BSW-based sensor has a sensitivity on the order of 2.9 cm-1 for each nanometer-thick ice layer grown on its surface below 150 K. In conclusion, we believe that Bloch surface wave-based sensors are a valid new class of surface mode-based sensors for applications in materials science.

A Simple Ball Milling and Thermal Oxidation Method for Synthesis of ZnO Nanowires Decorated with Cubic ZnO2 Nanoparticles.

In this work, we propose the synthesis of ZnO nanostructures through the thermal oxidation of ball-milled powders with the introduction of Mg and Sn doping species at the preliminary step of milling. We investigate the advantages and challenges of this two steps process for the production and fabrication of highly crystalline ZnO nanowires. This simple method allows us to fabricate ZnO nanowires with a higher quality core crystal at a much lower temperature and for a shorter processing time than the state-of-the-art, and decorated with by ZnO2 nanoparticles as determined via TEM analysis. The main findings will show that the crystalline core of the nanowires is of hexagonal ZnO while the nanoparticles on the surface are ZnO2 cubic type. Generally, the method proves to be suitable for applications that require a high surface-to-volume ratio, for example, catalysis phenomena, in which the presence of zinc oxides species can play an important role.

Spectral Characterization of Mid-Infrared Bloch Surface Waves Excited on a Truncated 1D Photonic Crystal.

The many fundamental roto-vibrational resonances of chemical compounds result in strong absorption lines in the mid-infrared region (λ ∼ 2-20 µm). For this reason, mid-infrared spectroscopy plays a key role in label-free sensing, in particular, for chemical recognition, but often lacks the required sensitivity to probe small numbers of molecules. In this work, we propose a vibrational sensing scheme based on Bloch surface waves (BSWs) on 1D photonic crystals to increase the sensitivity of mid-infrared sensors. We report on the design and deposition of CaF2/ZnS 1D photonic crystals. Moreover, we theoretically and experimentally demonstrate the possibility to sustain narrow σ-polarized BSW modes together with broader π-polarized modes in the range of 3-8 µm by means of a customized Fourier transform infrared spectroscopy setup. The multilayer stacks are deposited directly on CaF2 prisms, reducing the number of unnecessary interfaces when exciting in the Kretschmann-Raether configuration. Finally, we compare the performance of mid-IR sensors based on surface plasmon polaritons with the BSW-based sensor. The figures of merit found for BSWs in terms of confinement of the electromagnetic field and propagation length puts them as forefrontrunners for label-free and polarization-dependent sensing devices.

The Molecular Weight Dependence of Thermoelectric Properties of Poly (3-Hexylthiophene).

Organic materials have been found to be promising candidates for low-temperature thermoelectric applications. In particular, poly (3-hexylthiophene) (P3HT) has been attracting great interest due to its desirable intrinsic properties, such as excellent solution processability, chemical and thermal stability, and high field-effect mobility. However, its poor electrical conductivity has limited its application as a thermoelectric material. It is therefore important to improve the electrical conductivity of P3HT layers. In this work, we studied how molecular weight (MW) influences the thermoelectric properties of P3HT films. The films were doped with lithium bis(trifluoromethane sulfonyl) imide salt (LiTFSI) and 4-tert butylpyridine (TBP). Various P3HT layers with different MWs ranging from 21 to 94 kDa were investigated. UV-Vis spectroscopy and atomic force microscopy (AFM) analysis were performed to investigate the morphology and structure features of thin films with different MWs. The electrical conductivity initially increased when the MW increased and then decreased at the highest MW, whereas the Seebeck coefficient had a trend of reducing as the MW grew. The maximum thermoelectric power factor (1.87 µW/mK2) was obtained for MW of 77 kDa at 333 K. At this temperature, the electrical conductivity and Seebeck coefficient of this MW were 65.5 S/m and 169 µV/K, respectively.

ZnO Nanostructures and Electrospun ZnO-Polymeric Hybrid Nanomaterials in Biomedical, Health, and Sustainability Applications.

ZnO-based nanomaterials are a subject of increasing interest within current research, because of their multifunctional properties, such as piezoelectricity, semi-conductivity, ultraviolet absorption, optical transparency, and photoluminescence, as well as their low toxicity, biodegradability, low cost, and versatility in achieving diverse shapes. Among the numerous fields of application, the use of nanostructured ZnO is increasingly widespread also in the biomedical and healthcare sectors, thanks to its antiseptic and antibacterial properties, role as a promoter in tissue regeneration, selectivity for specific cell lines, and drug delivery function, as well as its electrochemical and optical properties, which make it a good candidate for biomedical applications. Because of its growing use, understanding the toxicity of ZnO nanomaterials and their interaction with biological systems is crucial for manufacturing relevant engineering materials. In the last few years, ZnO nanostructures were also used to functionalize polymer matrices to produce hybrid composite materials with new properties. Among the numerous manufacturing methods, electrospinning is becoming a mainstream technique for the production of scaffolds and mats made of polymeric and metal-oxide nanofibers. In this review, we focus on toxicological aspects and recent developments in the use of ZnO-based nanomaterials for biomedical, healthcare, and sustainability applications, either alone or loaded inside polymeric matrices to make electrospun composite nanomaterials. Bibliographic data were compared and analyzed with the aim of giving homogeneity to the results and highlighting reference trends useful for obtaining a fresh perspective about the toxicity of ZnO nanostructures and their underlying mechanisms for the materials and engineering community.

Submicron Size Schottky Junctions on As-Grown Monolayer Epitaxial Graphene on Ge(100): A Low-Invasive Scanned-Probe-Based Study.

We report on the investigation of the Schottky barrier (SB) formed at the junction between a metal-free graphene monolayer and Ge semiconductor substrate in the as-grown epitaxial graphene/Ge(100) system. In order to preserve the heterojunction properties, we defined submicron size graphene/Ge junctions using the scanning probe microscopy lithography in the local oxidation configuration, a low-invasive processing approach capable of inducing spatially controlled electrical separations among tiny graphene regions. Characteristic junction parameters were estimated from I-V curves obtained using conductive-atomic force microscopy. The current-voltage characteristics showed a p-type Schottky contact behavior, ascribed to the n-type to p-type conversion of the entire Ge substrate due to the formation of a large density of acceptor defects during the graphene growth process. We estimated, for the first time, the energy barrier height in the as-grown graphene/Ge Schottky junction (φB ≈ 0.45 eV) indicating an n-type doping of the graphene layer with a Fermi level ≈ 0.15 eV above the Dirac point. The SB devices showed ideality factor values around 1.5 pointing to the high quality of the heterojunctions.

Thermal-electric model for piezoelectric ZnO nanowires.

The behavior of ZnO nanowires under uniaxial loading is characterized by means of a numerical model that accounts for all coupled mechanical, electrical, and thermal effects. The paper shows that thermal effects in the nanowires may greatly impact the predicted performance of piezoelectric and piezotronic nanodevices. The pyroelectric effect introduces new equivalent volumic charge in the body of the nanowire and surface charges at the boundaries, where Kapitza resistances are located, that act together with the piezoelectric charges to improve the predicted performance. It is shown that the proposed model is able to reproduce several effects experimentally observed by other research groups, and is a promising tool for the design of ultra-high efficient nanodevices.

Design Concepts, Fabrication and Advanced Characterization Methods of Innovative Piezoelectric Sensors Based on ZnO Nanowires.

Micro- and nano-scale materials and systems based on zinc oxide are expected to explode in their applications in the electronics and photonics, including nano-arrays of addressable optoelectronic devices and sensors, due to their outstanding properties, including semiconductivity and the presence of a direct bandgap, piezoelectricity, pyroelectricity and biocompatibility. Most applications are based on the cooperative and average response of a large number of ZnO micro/nanostructures. However, in order to assess the quality of the materials and their performance, it is fundamental to characterize and then accurately model the specific electrical and piezoelectric properties of single ZnO structures. In this paper, we report on focused ion beam machined high aspect ratio nanowires and their mechanical and electrical (by means of conductive atomic force microscopy) characterization. Then, we investigate the suitability of new power-law design concepts to accurately model the relevant electrical and mechanical size-effects, whose existence has been emphasized in recent reviews.

The clash of mechanical and electrical size-effects in ZnO nanowires and a double power law approach to elastic strain engineering of piezoelectric and piezotronic devices.

The piezoelectric performance of ultra-strength ZnO nanowires (NWs) depends on the subtle interplay between electrical and mechanical size-effects. "Size-dependent" modeling of compressed NWs illustrates why experimentally observed mechanical stiffening can indeed collide with electrical size-effects when the size shrinks, thereby lowering the actual piezoelectric function from bulk estimates. "Smaller" is not necessarily "better" in nanotechnology.

Growth of InAs/InAsSb heterostructured nanowires.

We report the growth of InAs/InAs(1-x)Sb(x) single and double heterostructured nanowires by Au-assisted chemical beam epitaxy. The InAs(1-x)Sb(x) nanowire segments have been characterized in a wide range of antimony compositions. Significant lateral growth is observed at intermediate compositions (x ~ 0.5), and the nucleation and step-flow mechanism leading to this lateral growth has been identified and described. Additionally, CuPt ordering of the alloy has been observed with high resolution transmission electron microscopy, and it is correlated to the lateral growth process. We also show that it is possible to regrow InAs above the InAsSb alloy segment, at least up to an intermediate antimony composition. Such double heterostructures might find applications both as mid-infrared detectors and as building blocks of electronic devices taking advantage of the outstanding electronic and thermal properties of antimonide compound semiconductors.