Strain-graded quantum dots with spectrally pure, stable and polarized emission.

Structural deformation modifies the bandgap, exciton fine structure and phonon energy of semiconductors, providing an additional knob to control their optical properties. The impact can be exploited in colloidal semiconductor quantum dots (QDs), wherein structural stresses can be imposed in three dimensions while defect formation is suppressed by controlling surface growth kinetics. Yet, the control over the structural deformation of QDs free from optically active defects has not been reached. Here, we demonstrate strain-graded CdSe-ZnSe core-shell QDs with compositionally abrupt interface by the coherent pseudomorphic heteroepitaxy. Resulting QDs tolerate mutual elastic deformation of varying magnitudes at the interface with high structural fidelity, allowing for spectrally stable and pure emission of photons at accelerated rates with near unity luminescence efficiency. We capitalize on the asymmetric strain effect together with the quantum confinement effect to expand emission envelope of QDs spanning the entire visible region and exemplify their use in photonic applications.

A Kinetic Approach to Synergize Bactericidal Efficacy and Biocompatibility in Silver-Based Sol-Gel Coatings.

Silver ions are antimicrobial agents with powerful action against bacteria. Applications in surface treatments, as Ag+-functionalized sol-gel coatings, are expected in the biomedical field to prevent contaminations and infections. The potential cytotoxicity of Ag+ cations toward human cells is well known though. However, few studies consider both the bactericidal activity and the biocompatibility of the Ag+-functionalized sol-gels. Here, we demonstrate that the cytotoxicity of Ag+ cations is circumvented, thanks to the ability of Ag+ cations to kill Escherichia coli (E. coli) much faster than normal human dermal fibroblasts (NHDFs). This phenomenon was investigated in the case of two silver nitrate-loaded sol-gel coatings: one with 0.5 w/w% Ag+ cations and the second with 2.5 w/w%. The maximal amount of released Ag+ ions over time (0.25 mg/L) was ten times lower than the minimal inhibition (MIC) and minimal bactericidal (MBC) concentrations (respectively, 2.5 and 16 mg/L) for E. coli and twice lower to the minimal cytotoxic concentration (0.5 mg/L) observed in NHDFs. E. coli were killed 8-18 times, respectively, faster than NHDFs by silver-loaded sol-gel coatings. This original approach, based on the kinetic control of the biological activity of Ag+ cations instead of a concentration effect, ensures the bactericidal protection while maintaining the biocompatibility of the Ag+ cation-functionalized sol-gels. This opens promising applications of silver-loaded sol-gel coatings for biomedical tools in short-term or indirect contacts with the skin.

Inactivation of SARS-CoV-2 on salt-coated surfaces: an in vitro study.

In the COVID-19 pandemic, caused by the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2), face masks have become a very important safety measure against the main route of transmission of the virus: droplets and aerosols. Concerns that masks contaminated with SARS-CoV-2 infectious particles could be a risk for self-contamination have emerged early in the pandemic as well as solutions to mitigate this risk. The coating of masks with sodium chloride, an antiviral and non-hazardous to health chemical, could be an option for reusable masks. To assess the antiviral properties of salt coatings deposited onto common fabrics by spraying and dipping, the present study established an in vitro bioassay using three-dimensional airway epithelial cell cultures and SARS-CoV-2 virus. Virus particles were given directly on salt-coated material, collected, and added to the cell cultures. Infectious virus particles were measured by plaque forming unit assay and in parallel viral genome copies were quantified over time. Relative to noncoated material, the sodium chloride coating significantly reduced virus replication, confirming the effectiveness of the method to prevent fomite contamination with SARS-CoV-2. In addition, the lung epithelia bioassay proved to be suitable for future evaluation of novel antiviral coatings.

In vitro testing of salt coating of fabrics as a potential antiviral agent in reusable face masks.

During the coronavirus disease (COVID-19) pandemic, wearing face masks in public spaces became mandatory in most countries. The risk of self-contamination when handling face masks, which was one of the earliest concerns, can be mitigated by adding antiviral coatings to the masks. In the present study, we evaluated the antiviral effectiveness of sodium chloride deposited on a fabric suitable for the manufacturing of reusable cloth masks using techniques adapted to the home environment. We tested eight coating conditions, involving both spraying and dipping methods and three salt dilutions. Influenza A H3N2 virus particles were incubated directly on the salt-coated materials, collected, and added to human 3D airway epithelial cultures. Live virus replication in the epithelia was quantified over time in collected apical washes. Relative to the non-coated material, salt deposits at or above 4.3 mg/cm2 markedly reduced viral replication. However, even for larger quantities of salt, the effectiveness of the coating remained dependent on the crystal size and distribution, which in turn depended on the coating technique. These findings confirm the suitability of salt coating as antiviral protection on cloth masks, but also emphasize that particular attention should be paid to the coating protocol when developing consumer solutions.

Ultrasensitive 3D Aerosol-Jet-Printed Perovskite X-ray Photodetector.

X-ray photon detection is important for a wide range of applications. The highest demand, however, comes from medical imaging, which requires cost-effective, high-resolution detectors operating at low-photon flux, therefore stimulating the search for novel materials and new approaches. Recently, hybrid halide perovskite CH3NH3PbI3 (MAPbI3) has attracted considerable attention due to its advantageous optoelectronic properties and low fabrication costs. The presence of heavy atoms, providing a high scattering cross-section for photons, makes this material a perfect candidate for X-ray detection. Despite the already-successful demonstrations of efficiency in detection, its integration into standard microelectronics fabrication processes is still pending. Here, we demonstrate a promising method for building X-ray detector units by 3D aerosol jet printing with a record sensitivity of 2.2 × 108 µC Gyair-1 cm-2 when detecting 8 keV photons at dose rates below 1 µGy/s (detection limit 0.12 µGy/s), a 4-fold improvement on the best-in-class devices. An introduction of MAPbI3-based detection into medical imaging would significantly reduce health hazards related to the strongly ionizing X-rays' photons.

Controlling mesopore size and processability of transparent enzyme-loaded silica films for biosensing applications.

Silica-based nanoporous thin films including large mesopores are relevant as enzyme supports for applications in biosensing. The diffusion and immobilization of large biomolecules such as enzymes in such porous films require the presence of large mesopores. Creating such morphologies based on a bottom-up synthesis using colloidal templates is a challenge in view of the combination of desired material properties and the robustness of the casting process for the fabrication of thin films. Here a strategy to reproducibly synthesize transparent porous silica thin films with submicrometer thickness and homogeneously distributed porosity is presented. For this purpose, polystyrene-poly-2-vinylpyridine (PS-P2VP) amphiphilic block copolymers are used as porogenic templates. Low-chain alcohols are employed as both selective solvents for the P2VP blocks and reaction media for silica synthesis. Rheology measurements reveal a strong influence of the block copolymer length on the behavior of PS-P2VP micelles in suspension. The pore distribution and accessibility into the film are controlled by adjusting the silica to block copolymer weight ratio. The solvent choice is shown to control not only the micelle size and the generated pore morphology but also the structural homogeneity of the films. Finally, the suitability of the synthesized films as supports for enzymes is tested using a model enzyme, horseradish peroxidase EC 1.11.1.7. Our approach is innovative, robust, and reproducible and provides a convenient alternative to synthesize large mesopores up to small macropores (20-100 nm) in nanostructured thin films with applications in biosensing and functional coatings.

Self-patterned nanoparticle layers for vertical interconnects: application in tandem solar cells.

We demonstrate self-patterned insulating nanoparticle layers to define local electrical interconnects in thin-film electronic devices. We show this with thin-film silicon tandem solar cells, where we introduce between the two component cells a solution-processed SiO2 nanoparticle layer with local openings to allow for charge transport. Because of its low refractive index, high transparency, and smooth surface, the SiO2 nanoparticle layer acts as an excellent intermediate reflector allowing for efficient light management.

Molecular transport through nanoporous silicon nitride membranes produced from self-assembling block copolymers.

To achieve fast and selective molecular filtration, membrane materials must ideally exhibit a thin porous skin and a high density of pores with a narrow size distribution. Here, we report the fabrication of nanoporous silicon nitride membranes (NSiMs) at the full wafer scale using a versatile process combining block copolymer (BCP) self-assembly and conventional photolithography/etching techniques. In our method, self-assembled BCP micelles are used as templates for creating sub-100 nm nanopores in a thin low-stress silicon nitride layer, which is then released from the underlying silicon wafer by etching. The process yields 100 nm thick free-standing NSiMs of various lateral dimensions (up to a few mm(2)). We show that the membranes exhibit a high pore density, while still retaining excellent mechanical strength. Permeation experiments reveal that the molecular transport rate across NSiMs is up to 16-fold faster than that of commercial polymeric membranes. Moreover, using dextran molecules of various molecular weights, we also demonstrate that size-based separation can be achieved with a very good selectivity. These new silicon nanosieves offer a relevant technological alternative to commercially available ultra- and microfiltration membranes for conducting high resolution biomolecular separations at small scales.

Optimizing the osteogenicity of nanotopography using block co-polymer phase separation fabrication techniques.

Both temporary and permanent orthopedic implants have, by default or design, surface chemistry, and topography. There is increasing evidence that controlling nanodisorder can result in increased osteogenesis. Block co-polymer phase separation can be used to fabricate a nanotopography exhibiting a controlled level of disorder, both reproducibly and cost-effectively. Two different topographies, produced through the use of block co-polymer phase separation, were embossed onto the biodegradable thermoplastic, polycaprolactone (PCL). Analysis of the topography itself was undertaken with atomic force microscopy, and the topography's effect on human osteoblasts studied through the use of immunocytochemistry and fluorescence microscopy. Planar controls had a surface roughness 0.93 nm, and the substrates a high fidelity transfer of a disordered pattern of 14 and 18 nm. Cytoskeletal organization and adhesion, and increased expression of Runx2 were significantly greater on the smallest nanotopography. Expression of osteopontin and osteocalcin protein, and alizarin red staining of bone nodules were greatest on the smallest feature nanopatterns. Highly osteogenic, disordered nanotopographies can be manufactured into thermoplastics in a rapid and cost-effective way through the use of block co-polymer phase separation. Osteogenic topographies reproducibly and cost-effectively produced have a potentially useful application to the fields of implant technology and regenerative orthopedics.

Hierarchical positioning of gold nanoparticles into periodic arrays using block copolymer nanoring templates.

We report a simple and versatile self-assembly method for controlling the placement of functional gold nanoparticles on silicon substrates using micellar templates. The hierarchical positioning of gold nanoparticles is achieved in one-step during the spontaneous phase inversion of spherical poly(styrene)-block-poly(2-vinylpyridine) copolymer micelles into nanoring structures. The placement is mainly driven by the establishment of electrostatic interactions between the nanoparticle ligands and the pyridine groups exposed at the interface. In particular, we show the formation of ordered arrangements of single gold nanoparticles or nanoparticle clusters and demonstrate that their morphologies, densities and periodicities can be tuned by simply varying the initial block copolymer molecular weight or the deposition conditions. Besides gold nanoparticles, the method can be used for controlling the assembly of a large variety of nanoscale building blocks, thus opening an attractive pathway for generating functional hybrid surfaces with periodic nanopatterns.

Dynamic perspective on the function of thermoresponsive nanopores from in situ AFM and ATR-IR investigations.

This article describes the morphological and chemical characterization of stimuli-responsive functionalized silicon surfaces provided in parallel by atomic force spectroscopy (AFM) and Fourier transform infrared spectroscopy (FT-IR) enhanced by the single-beam sample reference attenuated total reflection method (SBSR-ATR). The stimuli-responsive behavior of the surfaces was obtained by grafting-to in melt carboxyl-terminated poly-N-isopropylacryl amides (PNIPAAM) with different degree of polymerization (DP) on epoxide-functionalized silicon substrates. The unprecedented real time and in situ physicochemical insight into the temperature-triggered response of the densely packed superficial brushes allowed for the selection of a PNIPAAM with a specific DP as a suitable polymer for the fabrication of silicon membranes exhibiting switchable nanopores. The fabrication process combines the manufacture of nanoporous silicon surfaces and their subsequent chemical functionalization by the grafting-to in melt of the selected polymer. Then, relevant information was obtained in what concerns the chemical modifications behind the topographical changes that drive the functioning of PNIPAAM-based hybrid nanovalves as well as the timescale on which the opening and closing of the nanopores occur.

Inexpensive and fast wafer-scale fabrication of nanohole arrays in thin gold films for plasmonics.

In this paper, a fast and inexpensive wafer-scale process for the fabrication of arrays of nanoscale holes in thin gold films for plasmonics is shown. The process combines nanosphere lithography using spin-coated polystyrene beads with a sputter-etching process. This allows the batch fabrication of several 1000 microm(2) large hole arrays in 200 nm thick gold films without the use of an adhesion layer for the gold film. The hole size and lattice period can be tuned independently with this method. This allows tuning of the optical properties of the hole arrays for the desired application. An example application, refractive index sensing, is demonstrated.

Use of force spectroscopy to investigate the adhesion of living adherent cells.

The use of force spectroscopy to study the adhesion of living fibroblasts to their culture substrate was investigated. Both primary fibroblasts (PEMF) and a continuous cell line (3T3) were studied on quartz surfaces. Using a fibronectin-coated AFM cantilever, it was possible to detach a large proportion of the 3T3 cells from the quartz surfaces. Their adhesion to the quartz surface and the effects of topography on this adhesion could be quantified. Three parameters characteristic of the adhesion were measured: the maximum force of detachment, the work of adhesion, and the distance of detachment. Few PEMF cells were detached under the same experimental conditions. The potential and limitations of this method in measuring cell/surface interactions for adherent cells are discussed.

Fabrication of nanopore arrays and ultrathin silicon nitride membranes by block-copolymer-assisted lithography.

Here we show a method for patterning a thin metal film using self-assembled block-copolymer micelles monolayers as a template. The obtained metallic mask is transferred by reactive ion etching in silicon oxide, silicon and silicon nitride substrates, thus fabricating arrays of hexagonally packed nanopores with tunable diameters, interspacing and aspect ratios. This technology is compatible with integration into a standard microtechnology sequence for wafer-scale fabrication of ultrathin silicon nitride nanoporous membranes with 80 nm mean pore diameter.

J-aggregation of cyanine dyes by self-assembly.

The importance of highly ordered surfaces, containing adsorptive surface states, is discussed for J-aggregation by self-assembly. Such nucleating surfaces are nanometer-sized edges and corners of cubic AgBr microcrystals, or surface iodide-clusters located along edges and corners of AgBr:I microcrystals. Of particular interest are dendrimers, monoatomic steps on terraced silver halide microcrystals and fullerene derivatives as nucleating surfaces. Molecular organisation into J-aggregates by self-assembly was realized using aprotic, apolar solvents for fullerenes, and polar solvents for dendrimers and monoatomic surface steps. By using dendrimers as nucleating agents in mesopores of metal oxide nanoparticle coatings, size-controlled and stable J-aggregates with high optical densities and strong fluorescence were obtained reproducibly. Such films may be useful for sensors, opto-electronics, lighting and photovoltaics.

Gold nanoring arrays from responsive block copolymer templates.

We report a pH-mediated synthetic route for the production of ordered and size-tuneable arrays of gold nanorings using responsive block copolymer micelles as templates.

Poly(N-isopropylacrylamide) thin films densely grafted onto gold surface: preparation, characterization, and dynamic AFM study of temperature-induced chain conformational changes.

Thermally responsive poly(N-isopropylacrylamide) (PNIPAM) films are attracting considerable attention since they offer the possibility to achieve reversible control over surface wettability and biocompatibility. In this paper, we first report a new and simple method for the grafting under melt of amine-terminated PNIPAM chains onto gold surfaces modified with a self-assembled monolayer (SAM) of reactive thiols. The formation of homogeneous tethered PNIPAM films, whose thickness can be tuned by adjusting polymer molecular weight or SAM reactivity, is evidenced by using the combination of ellipsometry, X-ray photon spectroscopy, infrared spectroscopy (PM-IRRAS), and atomic force microscopy. The calculation of grafting parameters from experimental measurements indicated the synthesis of densely grafted PNIPAM films and allowed us to predict a "brushlike" regime for the chains in good solvent. In a second part, the temperature-induced responsive properties are studied in situ by conducting dynamic AFM measurements using the amplitude modulation technique. Imaging in water environment first revealed the reversible modification of surface morphology below and above the theoretical lower critical solution temperature (LCST) of PNIPAM. Then, the determination of amplitude and phase approach curves at various temperatures provided direct measurement of the evolution of the damping factor, or similarly the dissipated energy, as a function of the probe indentation into the PNIPAM film. Most interestingly, we clearly showed the subtle and progressive thermally induced chain conformational change occurring at the scale of several nanometers around the expected LCST.

Scattering of light by a single layer of randomly packed dielectric microspheres giving color effects in transmission.

Strong scattering properties are obtained for a monolayer of randomly packed polystyrene microspheres. This gives rise to structural colors in transmission. For a sphere diameter between 0.5 and 1 micron, light is mainly scattered in the forward direction. Consequently, in-plane multiple scattering can be neglected when spheres are not too close to each others. This allows one to use a single scattering approximation to reproduce transmission spectra of the system. The film color is dependent on the sphere size, but also on the observation angle. This angular dependant color is reproduced taking into account multiple scattering between spheres. These films can be useful when low reflection is needed.

Self-assembly, DNA complexation, and pH response of amphiphilic dendrimers for gene transfection.

Cationic lipids and polymers are routinely used for cell transfection, and a variety of structure-activity relation data have been collected. Few studies, however, focus on the structural aspects of self-assembly as a crucial control parameter for gene delivery. We present here the observations collected for a set of cationic dendritic amphiphiles based on a stiff tolane core (1-4) that are built from identical subunits but differ in the number and balance of their hydrophobic and cationic hydrophilic moieties. We established elsewhere that vectors 3 and 4 have promising transfection properties. Scanning probe microscopy (AFM, STM), cryo-transmission electron microscopy (cryo-TEM), and Langmuir techniques provide insight into the self-assembly properties of the molecules under physiological conditions. Furthermore, we present DNA and pH "jump" experiments where we study the response of Langmuir films to a sudden increase in DNA concentration or a drop in pH. We find that the primary self-assembly of the amphiphile is of paramount importance and influences DNA binding, serum sensitivity, and pH response of the vector system.

Organization of nanoparticles on hard substrates using block copolymer films as templates.

We present a technique for the organization of pre-synthesized nanoparticles on hard substrates, using block copolymer films as sacrificial templates. A thin block copolymer film is dip-coated on the substrate of interest and the sample is exposed to a solution containing nanoparticles. Spontaneous preferential adsorption of the nanoparticles on one phase of the block copolymer film results in their lateral organization. An oxygen plasma etch is used to remove the polymer film; the nanoparticles end up organized on the substrate. We demonstrate that this is a general approach for the patterning of inorganic nanoparticles on hard substrates, showing the organization of metal and semiconductor nanoparticles having different chemistries at the particle/solvent and solvent/polymer interfaces. The nanoparticle patterns that we present have typical periodicities in the nanometer scale. In some cases, microcontact printing is used to create a double length scale of organization, on the micrometer and on the nanometer level. The characteristic periodicity of the template is studied with respect to the nanoparticle size in order to optimize the organization. Finally, we describe how to extend this technique for the production of continuous gold nanowires on hard substrates. We expect that the flexibility of this approach and the degree of control that can be obtained over nanoparticle organization should make it a powerful tool for nanoscale fabrication.