Performance characterization of an insulator-based dielectrophoretic microdevice

Dielectrophoresis (DEP), the motion of particles in nonuniform electric fields, is a nondestructive electrokinetic (EK) transport mechanism can be used to concentrate and separate bioparticles. Traditionally, DEP has been performed employing microelectrodes, an approach that is expensive due to the cost of microelectrode fabrication. An alternative is insulator-based DEP (iDEP), an inexpensive method where nonuniform electric fields are created with arrays of insulating structures. This study presents the effects of operating conditions on the dielectrophoretic behavior of polystyrene microparticles under iDEP. Experiments were performed employing microchannels containing insulating structures that worked as insulators. The parameters varied were pH (8-9) and conductivity (25-100 microS/cm) of the bulk medium, and the magnitude of the applied field (200-850 V/cm). Optimal operating conditions in terms of pH and conductivity were obtained, and the microdevice performance was characterized in terms of concentration factor and minimum electric field required (minimum energy consumption). This is the first report on improving iDEP processes when EOF is present. DEP and EOF have been studied extensively, however, this study integrates the effect of suspending medium characteristics on both EK phenomena. These findings will allow improving the performance of iDEP microdevices achieving the highest concentration fold with the lowest energy consumption.     

Stability and interface quality of GeO2 films grown on Ge by atomic oxygen assisted deposition

The composition of GeO(2) films grown on Ge has been studied for different molecular deposition processes and after exposure to ambient air. The stoichiometry, the interaction with moisture, and the interfacial details of the films are shown to be dramatically process dependent.     

Computational DFT investigation of vicinal amide group anchimeric assistance in ether cleavage

Density functional theory (DFT) computations in solvent have been used to investigate the mechanism of anchimeric assistance (by a vicinal amide group) in the acid-induced ether cleavage. The calculations were carried out at the B3LYP/6-31G* level of theory via full geometry optimizations within the IEF-PCM continuum solvent model. Two different mechanisms have been investigated here that were previously hypothesized for the rate-determining step of this process: the first (mechanism A1) involves a protonated amide and an ethereal oxygen as the nucleophile, while the second (mechanism A2) involves protonation of the ethereal oxygen followed by a nucleophilic attack of the amide. Computations clearly show that the second (involving protonation of the less basic site) is the most favorite route and leads to the formation of an oxazolidinic intermediate that triggers ether hydrolysis. Results are produced that are in excellent agreement with the experiments, and a rationale for them is provided, which represents a general interpretative basis for similar anchimerically assisted processes, such as the ones characterizing the glycosidic activity of two very important classes of enzymes: beta-hexosaminidases and O-GlcNAcases.     

Complexes of Al(III) with d-gluconic acid

The complexation of Al(III) with d-gluconic acid was studied in solution by means of pH-potentiometry, ESI mass spectrometry and one- and two-dimensional NMR spectroscopy. Six complexes were found to form in solution from pH 2 to 10: [AlL]²⁺, [AlLH₋₁]⁺, [AlLH₋₂], [AlLH₋₃]⁻, [AlL₂H₋₁] and [AlL₂H₋₂]⁻. NMR spectroscopy indicated very complicated chemical exchange processes between the free ligand and gluconic acid molecules bound in the metal complexes, with different coordination modes resulting in changes both of the chemical shift and of the line shape of the signals. A solid complex [AlL₂H₋₁] · 2H₂O was isolated as a microcrystalline powder and characterized. The structures of the complexes are discussed on the basis of the spectroscopic results and MM force field calculations.     

Hair analysis as a new tool to monitor adherence to long-term therapy to statins

Statins are cholesterol-lowering medications which are widely prescribed as first-line treatment for hyperlipidemia, against high blood cholesterol aimed at reducing the risk of atherosclerotic diseases. Notwithstanding their undoubted efficacy, the needed long-term treatment with these drugs is characterized by a high percentage of dropout. Consequently, an effective tool to verify the patients’ compliance to statin therapy is needed. In this context, the analysis for drugs and drug metabolites in the hair may represent an almost ideal tool because, according to a sound body of forensic toxicological literature, concentrations in the hair matrix reflect the chronic intake of drugs and pharmaceuticals. In this light, in the present study, a novel, specific and sensitive ultra-performance liquid chromatography–tandem mass spectrometry method has been developed to determine six statins and their metabolites (namely atorvastatin, (p)α-OH-atorvastatin-lactone, (o)α-OH-atorvastatin-lactone, rosuvastatin, N-desmethyl rosuvastatin and pravastatin) in human hair. After optimization, the method was successfully validated in terms of selectivity, linearity, sensitivity, precision, accuracy, stability and matrix effect. Moreover, the practical applicability of this method for verifying adherence to statin therapy was assessed by testing samples of hair collected from subjects under long-term therapy with statins.     

Evidence for Multiple Binding Modes in the Initial Contact Between SARS-CoV-2 Spike S1 Protein and Cell Surface Glycans**

Infection of host cells by SARS-CoV-2 begins with recognition by the virus S (spike) protein of cell surface heparan sulfate (HS), tethering the virus to the extracellular matrix environment, and causing the subunit S1-RBD to undergo a conformational change into the ‘open’ conformation. These two events promote the binding of S1-RBD to the angiotensin converting enzyme 2 (ACE2) receptor, a preliminary step toward viral-cell membrane fusion. Combining ligand-based NMR spectroscopy with molecular dynamics, oligosaccharide analogues were used to explore the interactions between S1-RBD of SARS CoV-2 and HS, revealing several low-specificity binding modes and previously unidentified potential sites for the binding of extended HS polysaccharide chains. The evidence for multiple binding modes also suggest that highly specific inhibitors will not be optimal against protein S but, rather, diverse HS-based structures, characterized by high affinity and including multi-valent compounds, may be required.     

Host-guest Assembly Based on γ-Cyclodextrin-functionalized Multiwalled Carbon Nanotubes for Rutin Electrochemical Sensing

Here, we report multiwalled carbon nanotubes (MWCNTs) functionalized with γ-cyclodextrins (γCD) as a novel electrochemical strategy for Rutin determination, showing superior performance than β-cyclodextrins (βCD) modified MWCNTs, suggesting an adequate environment for host-guest interactions. Under optimized conditions, the sensor showed a linear range of 39–975 nmol L⁻¹ and a limit of detection of 7 nmol L⁻¹. When tested with quercetin, catechin, and caffeine, the platform presented high selectivity with an interference response <10 %. The method was employed to quantify Rutin in spiked pharmaceutical and herbal extracts, providing recovery of 93–98.4 %. Also, HPLC-PDA confirmed the method‘s accuracy.     

Heptagon-Containing Nanographene Embedded into [10]Cycloparaphenylene

We report the synthesis and characterization of a novel type of nanohoop, consisting of a cycloparaphenylene derivative incorporating a curved heptagon-containing π-extended polycyclic aromatic hydrocarbon (PAH) unit. We demonstrate that this new macrocycle behaves as a supramolecular receptor of curved π-systems such as fullerenes C₆₀ and C₇₀, with remarkably large binding constants (ca. 10⁷ M⁻¹), as estimated by fluorescence measurements. Nanosecond and femtosecond spectroscopic analysis show that these host-guest complexes are capable of quasi-instantaneous charge separation upon photoexcitation, due to the ultrafast charge transfer from the macrocycle to the complexed fullerene. These results demonstrate saddle-shaped PAHs with dibenzocycloheptatrienone motifs as structural components for new macrocycles displaying molecular receptor abilities and versatile photochemical responses with promising electron-donor properties in host-guest complexes.     

First-order transverse phonon deformation potentials of tetragonal perovskites

A theoretical formalism is put forward with the aim of describing the softening of first-order transverse optical phonons in a strained tetragonal perovskitic lattice. On the basis of the dynamical equation for nondegenerate polar modes, the influence of oblique phonons could be first described by assuming a prevalence of short-range interatomic forces; then, the softening effect arising from external stress could be explicitly expressed as a function of orientation of the crystallographic texture. As a further step in the adopted formalism, the microstructure of a perovskitic polycrystal has been ideally modeled as an ensemble of mesocrystals, whose individual crystallographic directions corresponded to an average orientation over the unit volume of the probe. An experimental confirmation of the theoretical formalism is concurrently carried out, and phonon deformation potentials (PDP) have been directly measured for the first-order transverse phonon of a tetragonal PbZrTiO3 perovskite lattice.