Morphology and Mechanics of Star Copolymer Ultrathin Films Probed by Atomic Force Microscopy in the Air and in Liquid.

Star copolymer films were produced by using spin-coating, drop-casting, and casting deposition techniques, thus obtaining ultrathin and thick films, respectively. The morphology is generally flat, but it becomes substrate-dependent for ultrathin films where the planarization effect of films is not efficient. The indentation hardness of films was investigated by Force Volume Maps in both the air and liquid. In the air, ultrathin films are in the substrate-dominated zone and, thus, the elastic modulus E is overestimated, while E reaches its bulk value for drop-casted ultrathin and thick films. In liquid (water), E follows an exponential decay for all films with a minimum soaked time t0 of 0.37 and 2.65 h for ultrathin and drop-casted ultrathin and thick films, respectively. After this time, E saturates to a value on average 92% smaller than that measured in the air due to film swelling. Such results support the role of film morphology in the antimicrobial activity envisaged in the literature, suggesting also an additional role of film hardness.

Imaging the Quantum Capacitance of Strained MoS2 Monolayers by Electrostatic Force Microscopy.

We implemented radio frequency-assisted electrostatic force microscopy (RF-EFM) to investigate the electric field response of biaxially strained molybdenum disulfide (MoS2) monolayers (MLs) in the form of mesoscopic bubbles, produced via hydrogen (H)-ion irradiation of the bulk crystal. MoS2 ML, a semiconducting transition metal dichalcogenide, has recently attracted significant attention due to its promising optoelectronic properties, further tunable by strain. Here, we take advantage of the RF excitation to distinguish the intrinsic quantum capacitance of the strained ML from that due to atomic scale defects, presumably sulfur vacancies or H-passivated sulfur vacancies. In fact, at frequencies fRF larger than the inverse defect trapping time, the defect contribution to the total capacitance and to transport is negligible. Using RF-EFM at fRF = 300 MHz, we visualize simultaneously the bubble topography and its quantum capacitance. Our finite-frequency capacitance imaging technique is noninvasive and nanoscale and can contribute to the investigation of time- and spatial-dependent phenomena, such as the electron compressibility in quantum materials, which are difficult to measure by other methods.

New Aß(1-42) ligands from anti-amyloid antibodies: Design, synthesis, and structural interaction.

Alzheimer's disease (AD), is the most common neurodegenerative disorder of the aging population resulting in progressive cognitive and functional decline. Accumulation of amyloid plaques around neuronal cells is considered a critical pathogenetic event and, in most cases, a hallmark of the pathology. In the attempt to identify anti-AD drug candidates, hundreds of molecules targeting Aß peptides have been screened. Peptide molecules have been widely explored, appreciating chemical stability, biocompatibility, and low production cost. More recently, many anti-Aß(1-42) monoclonal antibodies have been developed, given the excellent potential of immunotherapy for treating or preventing AD. Antibodies are versatile ligands that bind a large variety of molecules with high affinity and specificity; however, their extensive therapeutic application is complex and requires huge economic investments. Novel approaches to identify alternative antibody formats are considered with great interest. In this context, taking advantage of the favorable peptide properties and the availability of Aß-antibodies structural data, we followed an innovative research approach to identify short peptide sequences on the model of the binding sites of Aß(1-42)/antibodies. WAibH and SYSTPGK were designed as mimics of solanezumab and aducanumab, respectively. Circular dichroism and nuclear magnetic resonance analysis reveal that the antibody-derived peptides interact with Aß(1-42) in the soluble monomeric form. Moreover, AFM microscopy imaging shows that WAibH and SYSTPGK are capable of controlling the Aß(1-42) aggregation. The strategy to identify WAibH and SYSTPGK is innovative and can be widely applied for new anti-Aß antibody mimicking peptides.

A New Approach to Supramolecular Structure Determination in Pharmaceutical Preparation of Self-Assembling Peptides: A Case Study of Lanreotide Autogel.

The supramolecular structure in peptides' prolonged-released gel formulations is the most critical parameter for the determination of the pharmaceutical profile of the drug. Here, we report our investigation on lanreotide Autogel as a case study. For the first time, we describe the use of the pulsed field gradient (PFG) diffusion-ordered spectroscopy (DOSY) magic-angle spinning NMR to characterize the supramolecular self-assembly and molecular mobility of different samples of lanreotide Autogel formulations prepared according to different formulation protocols. The diffusion coefficient was used to calculate the hydrodynamic radii of supramolecular assemblies and build relative molecular models. DOSY data were integrated with NMR imaging (MRI) measurements and atomic force microscopy (AFM) imaging.

Exceptional Elasticity of Microscale Constrained MoS2 Domes.

The outstanding mechanical performances of two-dimensional (2D) materials make them appealing for the emerging fields of flextronics and straintronics. However, their manufacturing and integration in 2D crystal-based devices rely on a thorough knowledge of their hardness, elasticity, and interface mechanics. Here, we investigate the elasticity of highly strained monolayer-thick MoS2 membranes, in the shape of micrometer-sized domes, by atomic force microscopy (AFM)-based nanoindentation experiments. A dome's crushing procedure is performed to induce a local re-adhesion of the dome's membrane to the bulk substrate under the AFM tip's load. It is worth noting that no breakage, damage, or variation in size and shape are recorded in 95% of the crushed domes upon unloading. Furthermore, such a procedure paves the way to address quantitatively the extent of the van der Waals interlayer interaction and adhesion of MoS2 by studying pull-in instabilities and hysteresis of the loading-unloading cycles. The fundamental role and advantage of using a superimposed dome's constraint are also discussed.

Emergence and Evolution of Crystallization in TiO2 Thin Films: A Structural and Morphological Study.

Among all transition metal oxides, titanium dioxide (TiO2) is one of the most intensively investigated materials due to its large range of applications, both in the amorphous and crystalline forms. We have produced amorphous TiO2 thin films by means of room temperature ion-plasma assisted e-beam deposition, and we have heat-treated the samples to study the onset of crystallization. Herein, we have detailed the earliest stage and the evolution of crystallization, as a function of both the annealing temperature, in the range 250-1000 °C, and the TiO2 thickness, varying between 5 and 200 nm. We have explored the structural and morphological properties of the as grown and heat-treated samples with Atomic Force Microscopy, Scanning Electron Microscopy, X-ray Diffractometry, and Raman spectroscopy. We have observed an increasing crystallization onset temperature as the film thickness is reduced, as well as remarkable differences in the crystallization evolution, depending on the film thickness. Moreover, we have shown a strong cross-talking among the complementary techniques used displaying that also surface imaging can provide distinctive information on material crystallization. Finally, we have also explored the phonon lifetime as a function of the TiO2 thickness and annealing temperature, both ultimately affecting the degree of crystallinity.

Proximity-Induced Superconductivity in Monolayer MoS2.

Proximity effects in superconducting normal (SN) material heterostructures with metals and semiconductors have long been observed and theoretically described in terms of Cooper pair wave functions and Andreev reflections. Whereas the semiconducting N-layer materials in the proximity experiments to date have been doped and tens of nanometers thick, we present here a proximity tunneling study involving a pristine single-layer transition-metal dichalcogenide film of MoS2 placed on top of a Pb thin film. Scanning tunneling microscopy and spectroscopy experiments together with parallel theoretical analysis based on electronic structure calculations and Green's function modeling allow us to unveil a two-step process in which MoS2 first becomes metallic and then is induced into becoming a conventional s-wave Bardeen-Cooper-Schrieffer-type superconductor. The lattice mismatch between the MoS2 overlayer and the Pb substrate is found to give rise to a topographic moiré pattern. Even though the induced gap appears uniform in location, the coherence peak height of the tunneling spectra is modulated spatially into a moiré pattern that is similar to but shifted with respect to the moiré pattern observed in topography. The aforementioned modulation is shown to originate from the atomic-scale structure of the SN interface and the nature of local atomic orbitals that are involved in generating the local pairing potential. Our study indicates that the local modulation of induced superconductivity in MoS2 could be controlled via geometrical tuning, and it thus shows promise toward the integration of monolayer superconductors into next-generation functional electronic devices by exploiting proximity-effect control of quantum phases.

The Effects of Atomic-Scale Strain Relaxation on the Electronic Properties of Monolayer MoS2.

The ability to control nanoscale electronic properties by introducing macroscopic strain is of critical importance for the implementation of two-dimensional (2D) materials into flexible electronics and next-generation strain engineering devices. In this work, we correlate the atomic-scale lattice deformation with a systematic macroscopic bending of monolayer molybdenum disulfide films by using scanning tunneling microscopy and spectroscopy implemented with a custom-built sample holder to control the strain. Using this technique, we are able to induce strains of up to 3% before slipping effects take place and relaxation mechanisms prevail. We find a reduction of the quasiparticle bandgap of about 400 meV per percent local strain measured with a minimum gap of 1.2 eV. Furthermore, unintentional nanoscale strain relaxation of van der Waals monolayer sheets can negatively impact strain engineered device performance. Here we investigate such strain relaxation mechanisms that include one-dimensional ripples and 2D wrinkles which alter the spatial electronic density of states and strain distribution on the atomic scale.

Quantitative magnetic force microscopy using calibration on superconducting flux quanta.

We present a new procedure that takes advantage of the magnetic flux quantization of superconducting vortices to calibrate the magnetic properties of tips for magnetic force microscopy (MFM). Indeed, a superconducting vortex, whose quantized flux is dependent upon Plank constant, speed of light and electron charge, behaves as a very well defined magnetic reference object. The proposed calibration procedure has been tested on new and worn tips and shows that the monopole point-like approximation of the probe is a reliable model. This procedure has been then applied to perform quantitative MFM experiments on a soft ferromagnetic thin film of permalloy, leading to the determination of the local out-of-plane component of the canted magnetization, together with its spatial variations across a few µm2 scan area.

Aggregation of Aß(25-35) on DOPC and DOPC/DHA bilayers: an atomic force microscopy study.

ß amyloid peptide plays an important role in both the manifestation and progression of Alzheimer disease. It has a tendency to aggregate, forming low-molecular weight soluble oligomers, higher-molecular weight protofibrillar oligomers and insoluble fibrils. The relative importance of these single oligomeric-polymeric species, in relation to the morbidity of the disease, is currently being debated. Here we present an Atomic Force Microscopy (AFM) study of Aß(25-35) aggregation on hydrophobic dioleoylphosphatidylcholine (DOPC) and DOPC/docosahexaenoic 22∶6 acid (DHA) lipid bilayers. Aß(25-35) is the smallest fragment retaining the biological activity of the full-length peptide, whereas DOPC and DOPC/DHA lipid bilayers were selected as models of cell-membrane environments characterized by different fluidity. Our results provide evidence that in hydrophobic DOPC and DOPC/DHA lipid bilayers, Aß(25-35) forms layered aggregates composed of mainly annular structures. The mutual interaction between annular structures and lipid surfaces end-results into a membrane solubilization. The presence of DHA as a membrane-fluidizing agent is essential to protect the membrane from damage caused by interactions with peptide aggregates; to reduces the bilayer defects where the delipidation process starts.

Morphological and structural aspects of the extremely halophilic archaeon Haloquadratum walsbyi.

Ultrathin square cell Haloquadratum walsbyi from the Archaea domain are the most abundant microorganisms in the hypersaline water of coastal salterns and continental salt lakes. In this work, we explore the cell surface of these microorganisms using amplitude-modulation atomic-force microscopy in nearly physiological conditions. We demonstrate the presence of a regular corrugation with a periodicity of 16-20 nm attributed to the surface layer (S-layer) protein lattice, striped domains asymmetrically distributed on the cell faces and peculiar bulges correlated with the presence of intracellular granules. Besides, subsequent images of cell evolution during the drying process indicate the presence of an external capsule that might correspond to the giant protein halomucin, predicted by the genome but never before observed by other microscopy studies.