Structural organization and dynamics of FCHo2 docking on membranes.

Clathrin-mediated endocytosis (CME) is a central trafficking pathway in eukaryotic cells regulated by phosphoinositides. The plasma membrane phosphatidylinositol-4,5-bisphosphate (PI(4,5)P2) plays an instrumental role in driving CME initiation. The F-BAR domain-only protein 1 and 2 complex (FCHo1/2) is among the early proteins that reach the plasma membrane, but the exact mechanisms triggering its recruitment remain elusive. Here, we show the molecular dynamics of FCHo2 self-assembly on membranes by combining minimal reconstituted in vitro and cellular systems. Our results indicate that PI(4,5)P2 domains assist FCHo2 docking at specific membrane regions, where it self-assembles into ring-like-shaped protein patches. We show that the binding of FCHo2 on cellular membranes promotes PI(4,5)P2 clustering at the boundary of cargo receptors and that this accumulation enhances clathrin assembly. Thus, our results provide a mechanistic framework that could explain the recruitment of early PI(4,5)P2-interacting proteins at endocytic sites.

Metal-Induced Crystallization in Metal Oxides.

ConspectusThe properties of a material depend upon its physical characteristics, one of these being its crystalline state. Next generation solid-state technologies will integrate crystalline oxides into thermal sensitive processes and composite materials. Crystallization of amorphous phases of metal oxides in the solid state typically requires substantial energy input to induce the amorphous to crystalline phase transformation. In the case of silica, the transformation to α-quartz in a furnace occurs above 1300 °C and that of titania, above 400 °C. These calcination processes are costly in energy but also often degrade complex material architectures or compositions.Thus, low temperature crystallization techniques are required that preserve macro- and mesostructures and complex elemental composition (e.g., organic-, metal-, and semiconductor-metal oxide hybrids/composites). Some solution-based techniques exist to directly fabricate crystalline metal oxides. However, these are not always compatible with the specificities of the system or industrial constraints. A postsynthetic, solid-state approach that reduces crystallization temperature in metal oxides is metal-induced crystallization (MIC).MIC is the introduction of catalytic amounts of a cation, which can be an s-block, p-block, or d-block cation, that migrates through the solid metal oxide lattice. The cation is thought to temporarily break metal oxide bonds, allowing [MOx] polyhedra to rotate and reform bonds with neighboring [MOx] groups in a lower energy crystalline phase. Depending on the system, the cation can favor or defavor the formation of a particular crystalline phase, providing a means to tune the purity and crystalline phase ratios. An advantage of MIC is that, although the crystallization occurs in the solid state, the crystallization process can be accomplished for particle suspensions in liquid media. In this case, the energy required to induce the crystallization can come from, for example, a microwave or an ultrasound bath. The crystallization of particles in suspension avoids aggregation from particle-particle sintering. In the case of thin films, the energy for crystallization typically comes from a laser or calcination.MIC is only recently being used as a low temperature metal oxide crystallization technique, despite being widely used in the semiconductor industry. Here, the mechanism and previous studies in MIC are presented for titania, silica, and other oxides. The beauty of this technique is that it is extremely easy to employ: cations can be incorporated into the system postsynthetically and then are often expelled from the lattice upon phase conversion. We expect MIC to enrich materials for photochromic, optoelectronic, catalyst, biological, and other applications.

Crystal engineering and ferroelectricity at the nanoscale in epitaxial 1D manganese oxide on silicon.

Ferroelectric oxides have attracted much attention due to their wide range of applications, particularly in electronic devices such as nonvolatile memories and tunnel junctions. As a result, the monolithic integration of these materials into silicon technology and their nanostructuration to develop alternative cost-effective processes are among the central points in the current technology. In this work, we used a chemical route to obtain nanowire thin films of a novel Sr1+δMn8O16 (SMO) hollandite-type manganese oxide on silicon. Scanning transmission electron microscopy combined with crystallographic computing reveals a crystal structure comprising hollandite and pyrolusite units sharing the edges of their MnO6 octahedra, resulting in three types of tunnels arranged along the c axis, where the ordering of the Sr atoms produces natural symmetry breaking. The novel structure gives rise to ferroelectricity and piezoelectricity, as revealed by local direct piezoelectric force microscopy measurements, which confirmed the ferroelectric nature of the SMO nanowire thin films at room temperature and showed a piezoelectric coefficient d33 value of 22 ± 6 pC N-1. Moreover, we proved that flexible vertical SMO nanowires can be harvested providing an electrical output energy through the piezoelectric effect, showing excellent deformability and high interface recombination. This work indicates the possibility of engineering the integration of 1D manganese oxides on silicon, a step which precedes the production of microelectronic devices.

Epitaxial Nanostructured α-Quartz Films on Silicon: From the Material to New Devices.

In this work, we show a detailed engineering route of the first piezoelectric nanostructured epitaxial quartz-based microcantilever. We will explain all the steps in the process starting from the material to the device fabrication. The epitaxial growth of α-quartz film on SOI (100) substrate starts with the preparation of a strontium doped silica sol-gel and continues with the deposition of this gel into the SOI substrate in a thin film form using the dip-coating technique under atmospheric conditions at room temperature. Before crystallization of the gel film, nanostructuration is performed onto the film surface by nanoimprint lithography (NIL). Epitaxial film growth is reached at 1000 °C, inducing a perfect crystallization of the patterned gel film. Fabrication of quartz crystal cantilever devices is a four-step process based on microfabrication techniques. The process starts with shaping the quartz surface, and then metal deposition for electrodes follows it. After removing the silicone, the cantilever is released from SOI substrate eliminating SiO2 between silicon and quartz. The device performance is analyzed by non-contact laser vibrometer (LDV) and atomic force microscopy (AFM). Among the different cantilever's dimensions included in the fabricated chip, the nanostructured cantilever analyzed in this work exhibited a dimension of 40 µm large and 100 µm long and was fabricated with a 600 nm thick patterned quartz layer (nanopillar diameter and separation distance of 400 nm and 1 µm, respectively) epitaxially grown on a 2 µm thick Si device layer. The measured resonance frequency was 267 kHz and the estimated quality factor, Q, of the whole mechanical structure was Q ~ 398 under low vacuum conditions. We observed the voltage-dependent linear displacement of cantilever with both techniques (i.e., AFM contact measurement and LDV). Therefore, proving that these devices can be activated through the indirect piezoelectric effect.

Micro/Nanostructure Engineering of Epitaxial Piezoelectric α-Quartz Thin Films on Silicon.

The monolithic integration of sub-micron quartz structures on silicon substrates is a key issue for the future development of piezoelectric devices as prospective sensors with applications based on the operation in the high-frequency range. However, to date, it has not been possible to make existing quartz manufacturing methods compatible with integration on silicon and structuration by top-down lithographic techniques. Here, we report an unprecedented large-scale fabrication of ordered arrays of piezoelectric epitaxial quartz nanostructures on silicon substrates by the combination of soft-chemistry and three lithographic techniques: (i) laser interference lithography, (ii) soft nanoimprint lithography on Sr-doped SiO2 sol-gel thin films, and (iii) self-assembled SrCO3 nanoparticle reactive nanomasks. Epitaxial α-quartz nanopillars with different diameters (from 1 µm down to 50 nm) and heights (up to 2 µm) were obtained. This work demonstrates the complementarity of soft-chemistry and top-down lithographic techniques for the patterning of epitaxial quartz thin films on silicon while preserving its epitaxial crystallinity and piezoelectric properties. These results open up the opportunity to develop a cost-effective on-chip integration of nanostructured piezoelectric α-quartz MEMS with enhanced sensing properties of relevance in different fields of application.

Tailoring the crystal growth of quartz on silicon for patterning epitaxial piezoelectric films.

Epitaxial films of piezoelectric α-quartz could enable the fabrication of sensors with unprecedented sensitivity for prospective applications in electronics, biology and medicine. However, the prerequisites are harnessing the crystallization of epitaxial α-quartz and tailoring suitable film microstructures for nanostructuration. Here, we bring new insights into the crystallization of epitaxial α-quartz films on silicon (100) from the devitrification of porous silica and the control of the film microstructures: we show that by increasing the quantity of devitrifying agent (Sr) it is possible to switch from an α-quartz microstructure consisting of a porous flat film to one dominated by larger, fully dense α-quartz crystals. We also found that the film thickness, relative humidity and the nature of the surfactant play an important role in the control of the microstructure and homogeneity of the films. Via a multi-layer deposition method, we have extended the maximum thickness of the α-quartz films from a few hundreds of nm to the µm range. Moreover, we found a convenient method to combine this multilayer approach with soft lithography to pattern silica films while preserving epitaxial crystallization. This improved control over crystallization and the possibility of preparing patterned films of epitaxial α-quartz on Si substrates pave the path to future developments in applications based on electromechanics, optics and optomechanics.

Direct and converse piezoelectric responses at the nanoscale from epitaxial BiFeO3 thin films grown by polymer assisted deposition.

We use an original water-based chemical method to grow pure epitaxial BiFeO3 (BFO) ultra-thin films with excellent piezoelectric properties. Particularly, we show that this novel chemical route produces higher natural ferroelectric domain size distribution and coercive field compared to similar BFO films grown by physical methods. Moreover, we measured the d33 piezoelectric coefficient of 60 nm thick BFO films by a direct approach, using Direct Piezoelectric Force Microscopy (DPFM). As a result, first piezo-generated charge maps of a very thin BFO layer were obtained applying this novel technology. We also performed a comparative study of the d33 coefficients between standard PFM analysis and DPFM microscopy showing similar values i.e. 17 pm V-1 and 22 pC N-1, respectively. Finally, we proved that the directionality of the piezoelectric effect in BFO ferroelectric thin films is preserved at low thickness dimensions demonstrating the potential of chemical processes for the development of low cost functional ferroelectric and piezoelectric devices.

Electric and Mechanical Switching of Ferroelectric and Resistive States in Semiconducting BaTiO3-δ Films on Silicon.

Materials that can couple electrical and mechanical properties constitute a key element of smart actuators, energy harvesters, or many sensing devices. Within this class, functional oxides display specific mesoscale responses which often result in great sensitivity to small external stimuli. Here, a novel combination of molecular beam epitaxy and a water-based chemical-solution method is used for the design of mechanically controlled multilevel device integrated on silicon. In particular, the possibility of adding extra functionalities to a ferroelectric oxide heterostructure by n-doping and nanostructuring a BaTiO3 thin film on Si(001) is explored. It is found that the ferroelectric polarization can be reversed, and resistive switching can be measured, upon a mechanical load in epitaxial BaTiO3-δ /La0.7 Sr0.3 MnO3 /SrTiO3 /Si columnar nanostructures. A flexoelectric effect is found, stemming from substantial strain gradients that can be created with moderate loads. Simultaneously, mechanical effects on the local conductivity can be used to modulate a nonvolatile resistive state of the BaTiO3-δ heterostructure. As a result, three different configurations of the system become accessible on top of the usual voltage reversal of polarization and resistive states.

Thermoelectric La-doped SrTiO3 epitaxial layers with single-crystal quality: from nano to micrometers.

High-quality thermoelectric La0.2Sr0.8TiO3 (LSTO) films, with thicknesses ranging from 20 nm to 0.7 µm, have been epitaxially grown on SrTiO3(001) substrates by enhanced solid-source oxide molecular-beam epitaxy. All films are atomically flat (with rms roughness < 0.2 nm), with low mosaicity (<0.1°), and present very low electrical resistivity (<5 × 10-4 Ω cm at room temperature), one order of magnitude lower than standard commercial Nb-doped SrTiO3 single-crystalline substrate. The conservation of transport properties within this thickness range has been confirmed by thermoelectric measurements where Seebeck coefficients of approximately -60 µV/K have been recorded for all films. These LSTO films can be integrated on Si for non-volatile memory structures or opto-microelectronic devices, functioning as transparent conductors or thermoelectric elements.

Preparation of Macroporous Epitaxial Quartz Films on Silicon by Chemical Solution Deposition.

This work describes the detailed protocol for preparing piezoelectric macroporous epitaxial quartz films on silicon(100) substrates. This is a three-step process based on the preparation of a sol in a one-pot synthesis which is followed by the deposition of a gel film on Si(100) substrates by evaporation induced self-assembly using the dip-coating technique and ends with a thermal treatment of the material to induce the gel crystallization and the growth of the quartz film. The formation of a silica gel is based on the reaction of a tetraethyl orthosilicate and water, catalyzed by HCl, in ethanol. However, the solution contains two additional components that are essential for preparing mesoporous epitaxial quartz films from these silica gels dip-coated on Si. Alkaline earth ions, like Sr(2+) act as glass melting agents that facilitate the crystallization of silica and in combination with cetyl trimethylammonium bromide (CTAB) amphiphilic template form a phase separation responsible of the macroporosity of the films. The good matching between the quartz and silicon cell parameters is also essential in the stabilization of quartz over other SiO2 polymorphs and is at the origin of the epitaxial growth.

Chiral habit selection on nanostructured epitaxial quartz films.

Understanding the crystallization of enantiomorphically pure systems can be relevant to diverse fields such as the study of the origins of life or the purification of racemates. Here we report on polycrystalline epitaxial thin films of quartz on Si substrates displaying two distinct types of chiral habits that never coexist in the same film. We combine Atomic Force Microscopy (AFM) analysis and computer-assisted crystallographic calculations to make a detailed study of these habits of quartz. By estimating the surface energies of the observed crystallites we argue that the films are enantiomorphically pure and we briefly outline a possible mechanism to explain the habit and chiral selection in this system.

Crystallization of hollow mesoporous silica nanoparticles.

Complex 3D macrostructured nanoparticles are transformed from amorphous silica into pure polycrystalline α-quartz using catalytic quantities of alkaline earth metals as devitrifying agent. Walls as thin as 10 nm could be crystallized without losing the architecture of the particles. The roles of cation size and the mol% of the incorporated devitrifying agent in crystallization behavior are studied, with Mg(2+), Ca(2+), Sr(2+) and Ba(2+) all producing pure α-quartz under certain conditions.

Mesoscopically structured nanocrystalline metal oxide thin films.

This review describes the main successful strategies that are used to grow mesostructured nanocrystalline metal oxide and SiO2 films via deposition of sol-gel derived solutions. In addition to the typical physicochemical forces to be considered during crystallization, mesoporous thin films are also affected by the substrate-film relationship and the mesostructure. The substrate can influence the crystallization temperature and the obtained crystallographic orientation due to the interfacial energies and the lattice mismatch. The mesostructure can influence the crystallite orientation, and affects nucleation and growth behavior due to the wall thickness and pore curvature. Three main methods are presented and discussed: templated mesoporosity followed by thermally induced crystallization, mesostructuration of already crystallized metal oxide nanobuilding units and substrate-directed crystallization with an emphasis on very recent results concerning epitaxially grown piezoelectric structured α-quartz films via crystallization of amorphous structured SiO2 thin films.

Electronic and magnetic structure of LaSr-2×4 manganese oxide molecular sieve nanowires.

In this study we combine scanning transmission electron microscopy, electron energy loss spectroscopy and electron magnetic circular dichroism to get new insights into the electronic and magnetic structure of LaSr-2×4 manganese oxide molecular sieve nanowires integrated on a silicon substrate. These nanowires exhibit ferromagnetism with strongly enhanced Curie temperature (T c >500 K), and we show that the new crystallographic structure of these LaSr-2×4 nanowires involves spin orbital coupling and a mixed-valence Mn3+/Mn4+, which is a must for ferromagnetic ordering to appear, in line with the standard double exchange explanation.

Distance dependence of the photocatalytic efficiency of TiO2 revealed by in situ ellipsometry.

Spectroscopic ellipsometry was utilized to follow in situ photodegradation of organic species in the vicinity of TiO(2) nanoparticles during UV irradiation. Stacked layers composed of TiO(2), mesoporous SiO(2), and mixed mesoporous SiO(2)/TiO(2) nanocomposites with controlled thickness and porosity were used as model materials. Lauric acid molecules and poly(vinyl chloride) (PVC) layers were used as model mobile and immobile pollutants, respectively. The local photocatalytic activity was deduced by monitoring the variation of the thickness and refractive index of each independent layer. We show that the photocatalyzed degradation of an organic pollutant takes place only when the latter is located in close vicinity to the TiO(2) nanoparticle surface or can naturally diffuse toward it. As a result, the reaction efficiency is directly related to the organic pollutant diffusion. We also show that the distance of photocatalysis efficiency (d(s)) at which radical intermediates are still present and active is <10 nm from the TiO(2) surface under the conditions of the experiments. This was confirmed by the fact that an immobile condensed organic phase such as PVC was protected from the photocatalytic degradation when separated from the TiO(2) by a 20 nm layer of mesoporous silica.

Chemical synthesis of oriented ferromagnetic LaSr-2 × 4 manganese oxide molecular sieve nanowires.

We report a chemical solution based method using nanoporous track-etched polymer templates for producing long and oriented LaSr-2 × 4 manganese oxide molecular sieve nanowires. Scanning transmission electron microscopy and electron energy loss spectroscopy analyses show that the nanowires are ferromagnetic at room temperature, single crystalline, epitaxially grown and self-aligned.

Single crystalline La0.7Sr0.3MnO3 molecular sieve nanowires with high temperature ferromagnetism.

Porous mixed-valent manganese oxides are a group of multifunctional materials that can be used as molecular sieves, catalysts, battery materials, and gas sensors. However, material properties and thus activity can vary significantly with different synthesis methods or process conditions, such as temperature and time. Here, we report on a new synthesis route for MnO(2) and LaSr-doped molecular sieve single crystalline nanowires based on a solution chemistry methodology combined with the use of nanoporous polymer templates supported on top of single crystalline substrates. Because of the confined nucleation in high aspect ratio nanopores and of the high temperatures attained, new structures with novel physical properties have been produced. During the calcination process, the nucleation and crystallization of ε-MnO(2) nanoparticles with a new hexagonal structure is promoted. These nanoparticles generated up to 30 µm long and flexible hexagonal nanowires at mild growth temperatures (T(g) = 700 °C) as a consequence of the large crystallographic anisotropy of ε-MnO(2). The nanocrystallites of MnO(2) formed at low temperatures serve as seeds for the growth of La(0.7)Sr(0.3)MnO(3) nanowires at growth temperatures above 800 °C, through the diffusion of La and Sr into the empty 1D-channels of ε-MnO(2). Our particular growth method has allowed the synthesis of single crystalline molecular sieve (LaSr-2 × 4) monoclinic nanowires with composition La(0.7)Sr(0.3)MnO(3) and with ordered arrangement of La(3+) and Sr(2+) cations inside the 1D-channels. These nanowires exhibit ferromagnetic ordering with strongly enhanced Curie temperature (T(c) > 500 K) that probably results from the new crystallographic order and from the mixed valence of manganese.

Preferential insertion of lactose permease in phospholipid domains: AFM observations.

We report the insertion of a transmembrane protein, lactose permease (LacY) from Escherichia coli (E. coli), in supported lipid bilayers (SLBs) of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoethanolamine (POPE) and 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoglycerol (POPG), in biomimetic molar proportions. We provide evidence of the preferential insertion of LacY in the fluid domains. Analysis of the self-assembled protein arrangements showed that LacY: (i) is inserted as a monomer within fluid domains of SLBs of POPE:POPG (3:1, mol/mol), (ii) has a diameter of approx. 7.8nm; and (iii) keeps an area of phospholipids surrounding the protein that is compatible with shells of phospholipids.

Synchrotron and neutron diffraction study of 4-methylpyridine-N-oxide at low temperature.

The structure of 4-methylpyridine-N-oxide has been determined at 250, 100 and 10 K by combined synchrotron (C(6)H(7)NO) and neutron (C(6)D(7)NO) powder diffraction experiments. At 250 K the space group is I4(1)/amd and the tetragonal unit cell [a = b = 7.941 (2), c = 19.600 (5) A] contains eight equivalent molecules. At 100 K the structure is orthorhombic, with space group Fddd, a = 12.138 (2), b = 10.237 (2) and c = 19.568 (3) A. The 16 equivalent molecules are rotated by about 8 degrees around the c axis with respect to positions at high temperature. At 10 K the best structural model corresponds to a tetragonal unit cell with the space group P4(1), a = b = 15.410 (2) A and c = 19.680 (3) A. The 32 molecules (eight molecules in the asymmetric unit) show complex reorientations around the three cell axes. Whereas at 250 and 100 K the deuterated methyl groups are largely disordered, at 10 K they are ordered in-phase along infinite chains parallel to a and b. Face-to-face methyl groups along c are in an eclipsed configuration. The structure at 10 K suggests that the manifold of rotational tunnelling transitions could be due to inequivalent lattice sites for crystallographically independent methyl groups.