Tuning Au/SiO2 nanostructures from 1D to 3D interconnected nanotube networks using polycarbonate porous templates.

We report a simple process, based on the combination of sol-gel deposition and nano-templating with polycarbonate membranes, for the synthesis of 1D to 3D free-standing silica (SiO2) interconnected nanotube (NT) networks. The thickness and porosity of the SiO2 nanotube walls can be, respectively, controlled by adjusting the ethanol amount in the sol-gel reaction mixture and by the addition or not of a porogen agent during the synthesis. Internal functionalization of 1D and 3D porous and non-porous SiO2 NTs by Au nanoparticles (NPs) was then performed using electroless deposition leading to particle sizes ranging from 15 to 20 nm. Characterization of all these systems by SEM-EDX, TEM, ICP and XPS clearly demonstrated the impact of the porosity of SiO2 on the amount and localization of Au NPs. Selective functionalization of the inner or the inner + outer surfaces of SiO2 NTs was achieved by keeping or freeing the SiO2 NTs from the template prior to electroless deposition, respectively. Moreover, UV-visible analysis confirmed plasmon resonance associated with Au NPs in all functionalized systems, paving the way to applications in many fields such as nano-medicine or (photo-)catalysis. In particular, the free-standing interconnected silica-based nanotube systems provide unique features of great interest for use in nanoscale fluidic bioseparation, sensing, and flow (photo)-catalytic chemistry, as demonstrated herein for the photodegradation of methylene blue.

Polycrystalline bismuth nanowire networks for flexible longitudinal and transverse thermoelectrics.

This paper reports on the preparation and the characterization of structural, electrical and thermoelectric properties of nanocomposite films formed from three-dimensional networks of polycrystalline bismuth (Bi) nanowires (NWs). The samples were fabricated by electrodeposition within polycarbonate (PC) templates with crossed cylindrical nanopores, yielding self-supported networks of Bi crossed nanowires (CNWs) with mean diameter values ranging from 23 nm to 230 nm. Temperature changes in electrical resistance and thermopower were studied by considering electric and thermal currents flowing in the plane of the films. While the values of the Seebeck coefficient are close to those of polycrystalline Bi for diameters greater than 100 nm, a progressive decrease in thermopower appears at smaller diameters, due to an increasing contribution of surface charge carriers as the diameter decreases. Transverse thermoelectricity based on the Nernst effect was also demonstrated on a network of Bi CNWs 230 nm in diameter. Such hierarchical architectures based on Bi CNWs are extremely robust, offering a reliable solution for the next generation of flexible thermoelectric devices.

Novel Platform for Regulation of Extracellular Vesicles and Metabolites Secretion from Cells Using a Multi-Linkable Horizontal Co-Culture Plate.

Microfluidics is applied in biotechnology research via the creation of microfluidic channels and reaction vessels. Filters are considered to be able to simulate microfluidics. A typical example is the cell culture insert, which comprises two vessels connected by a filter. Cell culture inserts have been used for years to study cell-to-cell communication. These systems generally have a bucket-in-bucket structure and are hereafter referred to as a vertical-type co-culture plate (VTCP). However, VTCPs have several disadvantages, such as the inability to simultaneously observe samples in both containers and the inability of cell-to-cell communication through the filters at high cell densities. In this study, we developed a novel horizontal-type co-culture plate (HTCP) to overcome these disadvantages and confirm its performance. In addition, we clarified the migration characteristics of substances secreted from cells in horizontal co-culture vessels. It is generally assumed that less material is exchanged between the horizontal vessels. However, the extracellular vesicle (EV) transfer was found to be twice as high when using HTCP. Other merits include control of the degree of co-culture via the placement of cells. We believe that this novel HTCP container will facilitate research on cell-to-cell communication in various fields.

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.

Spatioselective functionalization of gold nanopillar arrays.

A process combining electrochemical nanofabrication by hard templating with the use of a masking strategy and surface functionalization methods, is developed to produce arrays of gold nanopillars of spatially-controlled surface chemistry. Therefore, a gold nanopillar array is first fabricated by performing metal electrochemical deposition into a track-etched membrane supported on a gold substrate. After dissolution of the membrane, a protective polymer layer is deposited on the array and partially etched to specifically reveal the top of the nanopillars. Then, a polythiolactone-based copolymer is grafted on the upper part of the nanopillars. Afterwards, the sacrificial polymer layer is dissolved to reveal the non-functionalized surface corresponding to the lower part of the gold nanopillars and the background surface. This surface is subsequently modified by a self-assembled monolayer (SAM) of alkylthiol molecules which leads to nanostructured surfaces with spatio-selective surface chemistry. The grafting of gold nanoparticles and of a bioadhesive peptide on the top and on the background of the nanopillar array, respectively, is performed to prove the versatility of the approach to produce bifunctionalized nanopillar arrays for biological, biosensing or (bio)catalysis applications.

Biofunctionalized and self-supported polypyrrole frameworks as nanostructured ECM-like biointerfaces.

Hybrid nanobiointerfaces were designed as an original contribution to the challenge of synthesizing nanostructured biomaterials integrating a set of cell fate-determining cues, originally provided to cells by the extracellular matrix (ECM). The produced biointerfaces consist of a stiff framework of intersected polypyrrole (PPy) nanotubes supporting a soft multilayer composed of ECM-derived biomacromolecules: collagen (Col) and hyaluronic acid (HA). PPy frameworks with highly tunable characteristics were synthesized through chemical oxidative polymerization of pyrrole monomers, templated within track-etched polycarbonate (PC) membranes featuring a network of intersected nanopores. PPy interfaces with a porosity of 80%, composed of nanotubes with an average diameter ranging from 40 to 300 nm, intersecting at an angle of 90°, were shown to be self-supported. These rigid PPy nanostructured interfaces were functionalized with a self-assembling (HA/Col) multilayer deposited via a layer-by-layer process. Biofunctionalized and unmodified PPy frameworks were both shown to promote sustained cell adhesion, therefore demonstrating the cytocompatibility of the engineered matrices. Such nanobiointerfaces, combining a mechanically-stable framework of tunable dimensions with a soft biopolymeric multilayer of highly versatile nature, pave the way towards cell-instructive biomaterials able to gather a wide range of cues guiding cell behavior. The developed self-supported structures could be used as a coating or as membranes bridging different tissues.

Artificially modified magnetic anisotropy in interconnected nanowire networks.

Interconnected or crossed magnetic nanowire networks have been fabricated by electrodeposition into a polycarbonate template with crossed cylindrical nanopores oriented ±30° with respect to the surface normal. Tailor-made nanoporous polymer membranes have been designed by performing a double energetic heavy ion irradiation with fixed incidence angles. The Ni and Ni/NiFe nanowire networks have been characterized by magnetometry as well as ferromagnetic resonance and compared with parallel nanowire arrays of the same diameter and density. The most interesting feature of these nanostructured materials is a significant reduction of the magnetic anisotropy when the external field is applied perpendicular and parallel to the plane of the sample. This effect is attributed to the relative orientation of the nanowire axes with the applied field. Moreover, the microwave transmission spectra of these nanowire networks display an asymmetric linewidth broadening, which may be interesting for the development of low-pass filters. Nanoporous templates made of well-defined nanochannel network constitute an interesting approach to fabricate materials with controlled anisotropy and microwave absorption properties that can be easily modified by adjusting the relative orientation of the nanochannels, pore sizes and material composition along the length of the nanowire.

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.

Stable field emission from arrays of vertically aligned free-standing metallic nanowires.

We present a fully elaborated process to grow arrays of metallic nanowires with controlled geometry and density, based on electrochemical filling of nanopores in track-etched templates. Nanowire growth is performed at room temperature, atmospheric pressure and is compatible with low cost fabrication and large surfaces. This technique offers an excellent control of the orientation, shape and nanowires density. It is applied to fabricate field emission arrays with a good control of the emission site density. We have prepared Co, Ni, Cu and Rh nanowires with a height of 3 µm, a diameter of 80 nm and a density of ∼10(7) cm(-2). The electron field emission measurements and total energy distributions show that the as-grown nanowires exhibit a complex behaviour, first with emission activation under high field, followed by unstable emission. A model taking into account the effect of an oxide layer covering the nanowire surface is developed to explain this particular field emission behaviour. Finally, we present an in situ cleaning procedure by ion bombardment that collectively removes this oxide layer, leading to a stable and reproducible emission behaviour. After treatment, the emission current density is ∼1 mA cm(-2) for a 30 V µm(-1) applied electric field.