Specific buffer effects on the formation of BSA protein corona around amino-functionalized mesoporous silica nanoparticles.

The effect of buffer species on biomolecules and biomolecule-nanoparticle interactions is a phenomenon that has been either neglected, or not understood. Here, we study the formation of a BSA protein corona (PC) around amino-functionalized mesoporous silica nanoparticles (MSN-NH2) in the presence of different buffers (Tris, BES, cacodylate, phosphate, and citrate) at the same pH (7.15) and different concentrations (10, 50, and 100 mM). We find that BSA adsorption is buffer specific, with the adsorbed amount of BSA being 4.4 times higher in the presence of 100 mM Tris (184 ± 3 mg/g) than for 100 mM citrate (42 ± 2 mg/g). That is a considerable difference that cannot be explained by conventional theories. The results become clearer if the interaction energies between BSA and MSN-NH2, considering the electric double layer (EEDL) and the van der Waals (EvdW) terms, are evaluated. The buffer specific PC derives from buffer specific zeta potentials that, for MSN-NH2, are positive with Tris and negative with citrate buffers. A reversed sign of zeta potentials can be obtained by considering polarizability-dependent dispersion forces acting together with electrostatics to give the buffer specific outcome. These results are relevant not only to our understanding of the formation of the PC but may also apply to other bio- and nanosystems in biological media.

Complex Biophysical and Computational Analyses of G-Quadruplex Ligands: The Porphyrin Stacks Back.

G-quadruplexes (G4s), as non-canonical DNA structures, attract a great deal of research interest in the molecular biology as well as in the material science fields. The use of small molecules as ligands for G-quadruplexes has emerged as a tool to regulate gene expression and telomeres maintenance. Meso-tetrakis-(N-methyl-4-pyridyl)porphyrin (TMPyP4) was shown as one of the first ligands for G-quadruplexes and it is still widely used. We report an investigation comprising molecular docking and dynamics, synthesis and multiple spectroscopic and spectrometric determinations on simple cationic porphyrins and their interaction with different DNA sequences. The study allowed to synthesize a few compounds that have shown to interact with DNA; the detailed characterization has shown that the presence of amide groups at the periphery improves selectivity for parallel G4s binding over other structures. Taking into account the ease of synthesis, 5,10,15,20-tetrakis-(1-acetamido-4-pyridyl)porphyrin bromide could be considered a better alternative to TMPyP4 in studies involving G4 binding.

PMUT-Based System for Continuous Monitoring of Bolted Joints Preload.

In this paper, we present a bolt preload monitoring system, including the system architecture and algorithms. We show how Finite Element Method (FEM) simulations aided the design and how we processed signals to achieve experimental validation. The preload is measured using a Piezoelectric Micromachined Ultrasonic Transducer (PMUT) in pulse-echo mode, by detecting the Change in Time-of-Flight (CTOF) of the acoustic wave generated by the PMUT, between no-load and load conditions. We performed FEM simulations to analyze the wave propagation inside the bolt and understand the effect of different configurations and parameters, such as transducer bandwidth, transducer position (head/tip), presence or absence of threads, as well as the frequency of the acoustic waves. In order to couple the PMUT to the bolt, a novel assembly process involving the deposition of an elastomeric acoustic impedance matching layer was developed. We achieved, for the first time with PMUTs, an experimental measure of bolt preload from the CTOF, with a good signal-to-noise ratio. Due to its low cost and small size, this system has great potential for use in the field for continuous monitoring throughout the operative life of the bolt.

IoT System for Real-Time Posture Asymmetry Detection.

The rise of the Internet of Things (IoT) has enabled the development of measurement systems dedicated to preventing health issues and monitoring conditions in smart homes and workplaces. IoT systems can support monitoring people doing computer-based work and avoid the insurgence of common musculoskeletal disorders related to the persistence of incorrect sitting postures during work hours. This work proposes a low-cost IoT measurement system for monitoring the sitting posture symmetry and generating a visual alert to warn the worker when an asymmetric position is detected. The system employs four force sensing resistors (FSR) embedded in a cushion and a microcontroller-based read-out circuit for monitoring the pressure exerted on the chair seat. Java-based software performs the real-time monitoring of the sensors' measurements and implements an uncertainty-driven asymmetry detection algorithm. The shifts from a symmetric to an asymmetric posture and vice versa generate and close a pop-up warning message, respectively. In this way, the user is promptly notified when an asymmetric posture is detected and invited to adjust the sitting position. Every position shift is recorded in a web database for further analysis of the sitting behavior.

Cation and buffer specific effects on the DNA-lipid interaction.

Knowledge of DNA - lipid layer interactions is key for the development of biosensors, synthetic nanopores, scaffolds, and gene-delivery systems. These interactions are strongly affected by the ionic composition of the solvent. We have combined quartz crystal microbalance (QCM) and ellipsometry measurements to reveal how pH, buffers and alkali metal chloride salts affect the interaction of DNA with lipid bilayers (DOTAP/DOPC 30:70 in moles). We found that the thickness of the DNA layer adsorbed onto the lipid bilayer decreased in the order citrate > phosphate > Tris > HEPES. The effect of cations on the thickness of the DNA layer decreased in the order (K+ > Na+ > Cs+ ∼ Li+). Rationalization of the experimental results requires that adsorption, due to cation specific charge screening, is driven by the simultaneous action of two mechanisms namely, the law of matching water affinities for kosmotropes (Li+) and ion dispersion forces for chaotropes (Cs+). The outcome of these two opposing mechanisms is a "bell-shaped" specific cations sequence. Moreover, a superimposed buffer specificity, which goes beyond the simple effect of pH regulation, further modulated cation specificity. In summary, DNA-lipid bilayer interactions are maximized if citrate buffer (50 mM, pH 7.4) and KCl (100 mM) are used.

The melting curves of calf thymus-DNA are buffer specific.

The specific effects of salts (strong electrolytes) on biomolecular properties have been investigated for more than a century. By contrast, the specific role of pH buffers (weak electrolytes and their salts) has usually been ignored. Here, specific buffer effects on DNA thermal stability were evaluated by measuring the melting curve of calf thymus DNA through UV-vis spectroscopy. The study was carried out using phosphate, Tris, citrate and cacodylate buffers at fixed pH 7.4 at concentrations varying systematically in the range 1-600 mM. DNA stability increases with buffer concentration and is influenced specifically by buffer type. To interpret empirical data, a theoretical model was applied with parameters quantifying the impact of buffer on the DNA backbone charge. Comparing the buffer effects via buffer ionic strength rather than buffer concentration, we find that the buffers stabilize DNA in the order Tris > cacodylate > phosphate > citrate.

The Performance of Graphene-Enhanced THz Grating: Impact of the Gold Layer Imperfectness.

We report the performance of a graphene-enhanced THz grating fabricated by depositing a gold layer on the femtosecond micromachined SiO2 substrate. The morphology of the gold plated patterned substrate was studied by scanning electron microscopy (SEM) and atomic force microscopy (AFM), while the quality of the chemical vapor deposition (CVD) graphene was evaluated by Raman spectroscopy. The electromagnetic (EM) response of the metasurface comprising the graphene sheet and the gold plated substrate was studied by THz time domain spectroscopy in the 100 GHz-1 THz frequency range. We employed the finite elements method (FEM) to model the metasurface EM response by adjusting the ac conductivity of the gold layer covering the patterned SiO2 substrate to reproduce the measured transmission/reflection spectra. The results of the numerical simulation reveal the impact of the imperfectness of the gold layer on the performance of the THz metasurface. The experimental results are well described in terms of the Drude-Smith model of metal conductivity that takes into account the anisotropic scattering of the carriers in thin metal films.

Numerical Evaluation of the Effect of Geometric Tolerances on the High-Frequency Performance of Graphene Field-Effect Transistors.

The interest in graphene-based electronics is due to graphene's great carrier mobility, atomic thickness, resistance to radiation, and tolerance to extreme temperatures. These characteristics enable the development of extremely miniaturized high-performing electronic devices for next-generation radiofrequency (RF) communication systems. The main building block of graphene-based electronics is the graphene-field effect transistor (GFET). An important issue hindering the diffusion of GFET-based circuits on a commercial level is the repeatability of the fabrication process, which affects the uncertainty of both the device geometry and the graphene quality. Concerning the GFET geometrical parameters, it is well known that the channel length is the main factor that determines the high-frequency limitations of a field-effect transistor, and is therefore the parameter that should be better controlled during the fabrication. Nevertheless, other parameters are affected by a fabrication-related tolerance; to understand to which extent an increase of the accuracy of the GFET layout patterning process steps can improve the performance uniformity, their impact on the GFET performance variability should be considered and compared to that of the channel length. In this work, we assess the impact of the fabrication-related tolerances of GFET-base amplifier geometrical parameters on the RF performance, in terms of the amplifier transit frequency and maximum oscillation frequency, by using a design-of-experiments approach.

Acoustic reflectivity minimization in Capacitive Micromachined Ultrasonic Transducers (CMUTs).

When Capacitive Micromachined Ultrasonic Transducers (CMUTs) are coupled with water, they show high front-face acoustic reflectivity, due to the impedance mismatch between the transducer substrate material, typically based on silicon, and the propagation medium. During pulse-echo operation, surface reflectivity is responsible for multiple reflections of the received acoustic signals, which result in a set of unwanted echoes. In ultrasound imaging applications, this signal reverberation creates artifacts and reduces the image contrast. In this paper, a method to reduce front-face reflectivity is proposed, and a Reverberation Level (RL) index is introduced in order to quantify the unwanted reverberation of the signal returned to the transducer surface. The proposed method combines the increase of the bias voltage, the application of an optimized resistive load and the addition of a low-impedance acoustic backing to CMUTs realized by Reverse Fabrication Process (RFP). In this way, the mechanical energy conversion and transmission to the backing, as well as the electrical energy dissipation, are improved, thus reducing the energy reflection into the medium. The proposed method is analyzed by means of Finite Element simulations and is experimentally validated by characterizing single-element RFP-CMUTs, provided with different backing materials and electrical loads. In the analyzed prototypes, a RL reduction of 8.6dB is obtained.