A methodology based on molecular dynamics simulations is presented to determine the chemical potential of thiol self-assembled monolayers on a gold surface. The thiol de-solvation and then the ...monolayer formation are described by thermodynamic integration with a gradual decoupling of one molecule from the environment, with the necessary corrections to account for standard state changes. The procedure is applied both to physisorbed undissociated thiol molecules and to chemisorbed dissociated thiyl radicals, considering in the latter case the possible chemical potential of the produced hydrogen. We considered monolayers formed by either 7-mercapto-4-methylcoumarin (MMC) or 3-mercapto-propanoic acid (MPA) on a flat gold surface: the free energy profiles with respect to the monolayer density are consistent with a transition from a very stable lying-down phase at low densities to a standing-up phase at higher densities, as expected. The maximum densities of thermodynamically stable monolayers are compared to experimental measures performed with reference-free grazing-incidence X-ray fluorescence (RF-GIXRF) on the same systems, finding a better agreement in the case of chemisorbed thiyl radicals.
Investigation of the formation process of self-assembled monolayers by computationally estimating the chemical potential of thiyl and thiol monolayers on gold.
Bipolar resistive switching memories based on metal oxides offer a great potential in terms of simple process integration, memory performance, and scalability. In view of ultrahigh density memory ...applications, a reduced device size is not the only requirement, as the distance between different devices is a key parameter. By exploiting a bottom-up fabrication approach based on block copolymer self-assembling, we obtained the parallel production of bilayer Pt/Ti top electrodes arranged in periodic arrays over the HfO2/TiN surface, building memory devices with a diameter of 28 nm and a density of 5 × 1010 devices/cm2. For an electrical characterization, the sharp conducting tip of an atomic force microscope was adopted for a selective addressing of the nanodevices. The presence of devices showing high conductance in the initial state was directly connected with scattered leakage current paths in the bare oxide film, while with bipolar voltage operations we obtained reversible set/reset transitions irrespective of the conductance variability in the initial state. Finally, we disclosed a scalability limit for ultrahigh density memory arrays based on continuous HfO2 thin films, in which a cross-talk between distinct nanodevices can occur during both set and reset transitions.
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The azobenzene chromophore is used as a functional dye for the development of smart microfluidic devices. A single layer microfluidic channel is produced, exploiting the potential of a dye doped PDMS ...formulation. The key advantage of this approach is the possibility to control the fluid flow by means of a simple light stimulus. Furthermore, the deformation can be controlled in time, space and intensity, giving rise to several degrees of freedom in the actuation of the channel squeezing. A future perspective will be the implementation of the microfluidic platform with structured light, to have the possibility to control the flow in a parallel and reversible manner at several points, modifying the pattern in real time.
Reversible and real time light-triggered control of flows in a microfluidic azo doped device.
Hydroxyl-terminated P(S-r-MMA) random copolymers (RCPs) with molecular weights (M n) from 1700 to 69000 and a styrene unit fraction of approximately 61% were grafted onto a silicon oxide surface and ...subsequently used to study the orientation of nanodomains with respect to the substrate, in cylinder-forming PS-b-PMMA block copolymer (BCP) thin films. When the thickness (H) of the grafted layer is greater than 5–6 nm, a perpendicular orientation is always observed because of the efficient decoupling of the BCP film from the polar SiO2 surface. Conversely, if H is less than 5 nm, the critical thickness of the grafted layer, which allows the neutralization of the substrate and promotion of the perpendicular orientation of the nanodomains in the BCP film, is found to depend on the M n of the RCP. In particular, when M n = 1700, a 2.0 nm thick grafted layer is sufficient to promote the perpendicular orientation of the PMMA cylinders in the PS-b-PMMA BCP film. A proximity shielding mechanism of the BCP molecules from the polar substrate surface, driven by chain stretching of the grafted RCP molecules, is proposed.
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Controlling the location and the distribution of hot spots is a crucial aspect in the fabrication of surface-enhanced Raman spectroscopy (SERS) substrates for bio-analytical applications. The choice ...of a suitable method to tailor the dimensions and the position of plasmonic nanostructures becomes fundamental to provide SERS substrates with significant signal enhancement, homogeneity and reproducibility. In the present work, we studied the influence of the long-range ordering of different flexible gold-coated Si nanowires arrays on the SERS activity. The substrates are made by nanosphere lithography and metal-assisted chemical etching. The degree of order is quantitatively evaluated through the correlation length (ξ) as a function of the nanosphere spin-coating speed. Our findings showed a linear increase of the SERS signal for increasing values of ξ, coherently with a more ordered and dense distribution of hot spots on the surface. The substrate with the largest ξ of 1100 nm showed an enhancement factor of 2.6 · 10
and remarkable homogeneity over square-millimetres area. The variability of the signal across the substrate was also investigated by means of a 2D chemical imaging approach and a standard methodology for its practical calculation is proposed for a coherent comparison among the data reported in literature.
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Cardiomyocytes from human induced pluripotent stem cells (hiPSC-CMs) are the most promising human source with preserved genetic background of healthy individuals or patients. This study aimed to ...establish a systematic procedure for exploring development of hiPSC-CM functional output to predict genetic cardiomyopathy outcomes and identify molecular targets for therapy. Biomimetic substrates with microtopography and physiological stiffness can overcome the immaturity of hiPSC-CM function. We have developed a custom-made apparatus for simultaneous optical measurements of hiPSC-CM action potential and calcium transients to correlate these parameters at specific time points (day 60, 75 and 90 post differentiation) and under inotropic interventions. In later-stages, single hiPSC-CMs revealed prolonged action potential duration, increased calcium transient amplitude and shorter duration that closely resembled those of human adult cardiomyocytes from fresh ventricular tissue of patients. Thus, the major contribution of sarcoplasmic reticulum and positive inotropic response to β-adrenergic stimulation are time-dependent events underlying excitation contraction coupling (ECC) maturation of hiPSC-CM; biomimetic substrates can promote calcium-handling regulation towards adult-like kinetics. Simultaneous optical recordings of long-term cultured hiPSC-CMs on biomimetic substrates favor high-throughput electrophysiological analysis aimed at testing (mechanistic hypothesis on) disease progression and pharmacological interventions in patient-derived hiPSC-CMs.
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We investigated the dewetting process on flat and chemically patterned surfaces of ultrathin films (thickness between 2 and 15 nm) of a cylinder forming polystyrene-block-poly(methyl methacrylate) ...(PS-b-PMMA) spin coated on poly(styrene-r-methyl methacrylate) random copolymers (RCPs). When the PS-b-PMMA film dewets on a 2 nm-thick RCP layer, the ordering of the hexagonally packed PMMA cylinders in the dewetted structures extends over distances far exceeding the correlation length obtained in continuous block copolymer (BCP) films. As a result, micrometer-sized circular droplets featuring defectless single grains of self-assembled PS-b-PMMA with PMMA cylinders perpendicularly oriented with respect to the substrate are generated and randomly distributed on the substrate. Additionally, alignment of the droplets along micrometric lines was achieved by performing the dewetting process on large-scale chemically patterned stripes of 2 nm thick RCP films by laser lithography. By properly adjusting the periodicity of the chemical pattern, it was possible to tune and select the geometrical characteristics of the dewetted droplets in terms of maximum thickness, contact angle and diameter while maintaining the defectless single grain perpendicular cylinder morphology of the circular droplets.
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The enhancement factor (EF) is an essential parameter in the field of surface-enhanced Raman spectroscopy (SERS), indicating the magnification of the Raman signal of molecules interacting with the ...surface of plasmonic nanostructures. The calculation of EF requires a careful evaluation of both the signal intensities and the number of molecules in SERS and normal Raman conditions. The determination of the surface density of molecules adsorbed on the plasmonic substrate is a challenging task, but essential for the estimation of the number of SERS-active molecules. This paper describes the determination of EF using 7-mercapto-4-methylcoumarin (MMC) as the probe molecule on gold-coated silicon nanowires, integrating SERS and normal Raman spectroscopy with X-ray fluorescence (RF-XRF) data that provide a reference-free quantitative measurement of the molecular surface density. In addition, the surface coverage of MMC on the substrate is modelled by molecular mechanics (MM) and molecular dynamics (MD) simulations.
Determination of the SERS enhancement factor through the challenging measurement of the molecular surface density by reference-free X-ray fluorescence.
Novel materials with defined composition and structures at the nanoscale are increasingly desired in several research fields spanning a wide range of applications. The development of new approaches ...of synthesis that provide such control is therefore required in order to relate the material properties to its functionalities. Self-assembling materials such as block copolymers (BCPs), in combination with liquid phase infiltration (LPI) processes, represent an ideal strategy for the synthesis of inorganic materials into even more complex and functional features. This review provides an overview of the mechanism involved in the LPI, outlining the role of the different polymer infiltration parameters on the resulting material properties. We report newly developed methodologies that extend the LPI to the realisation of multicomponent and 3D inorganic nanostructures. Finally, the recently reported implementation of LPI into different applications such as photonics, plasmonics and electronics are highlighted.
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New low molar mass (Mn ~ 20 kg mol−1) polystyrene-b-poly(methyl methacrylate-co-perfluorohexylethyl acrylate) (PS-b-P(MMA-co-FA)) block copolymers were synthesized all consisting of ~70 mol% PS block ...and ~30 mol% P(MMA-co-FA) block. The amount of FA counits in the latter block was increased (0.5, 1, 3 and 4 mol%) in order to enhance the incompatibility between the two blocks and to form different self-assembled nanostructures. The block copolymers were thermally annealed by Rapid Thermal Processing (RTP) over wide ranges of temperatures and times. Complementary SEM and AFM analyses evidenced that the introduction of FA counits above a critical content (~2 mol%) drove a self-assembly process through mixed morphologies. These were formed at a distance from the polymer–air interface and consisted of perpendicular cylinders of P(MMA-co-FA) in a PS matrix laying at the substrate– polymer interface, and surmounted PS stripes and PS dots. Modification by low amounts of FA produced block copolymer samples that self-assembled in new, mixed nanostructures, even though they possessed much lower molar masses than those of analogous well established PS-b-PMMA block copolymers.
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•New fluorinated BCPs are synthesized that form an unexpected mixed morphology.•The preferential enrichment of FA-units at the polymer-air interface influences SA.•Higher contents of FA-units produce periodic arrangements irrespective of ta and Ta.•The mixed morphology evolves moving into the inner part of the film.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
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