Surface Engineering Approach Research Articles

Construction of Silica-Based Micro/Nanoplatforms for Ultrasound Theranostic Biomedicine.

Ultrasound (US)-based biomedicine has been extensively explored for its applications in both diagnostic imaging and disease therapy. The fast development of theranostic nanomedicine significantly promotes the development of US-based biomedicine. This progress report summarizes and discusses the recent developments of rational design and fabrication of silica-based micro/nanoparticles for versatile US-based biomedical applications. The synthetic strategies and surface-engineering approaches of silica-based micro/nanoparticles are initially discussed, followed by detailed introduction on their US-based theranostic applications. They have been extensively explored in contrast-enhanced US imaging, US-based multi-modality imaging, synergistic high-intensity focused US (HIFU) ablation, sonosensitizer-enhanced sonodynamic therapy (SDT), as well as US-triggered chemotherapy. Their biological effects and biosafety have been briefly discussed to guarantee further clinical translation. Based on the high biocompatibility, versatile composition/structure and high performance in US-based theranostic biomedicine, these silica-based theranostic agents are expected to pave a new way for achieving efficient US-based theranostics of disease by taking the specific advantages of material science, nanotechnology and US-based biomedicine.

Pancreatic islet surface bioengineering with a heparin-incorporated starPEG nanofilm

Cell surface engineering could protect implanted cells from host immune rejections while modify the cellular landscape for better post-transplantation graft function and survival. Islet transplantation is considered the most promising therapeutic option with the potential to cure diabetes. Current approach to improve clinical efficacy of pancreatic islet transplantation is alginate encapsulation. However, disappointing outcomes have been reported in clinical trials due to larger islet size resulted by encapsulation and alginate-elicited host immune responses. We have developed an ultrathin nanofilm of starPEG with incorporated heparin (Hep-PEG) that binds covalently to the amine groups of islet surface membrane via its N-hydroxysuccinimide groups. The Hep-PEG nanocoating elicited minimal alteration on islet volume in culture. Hep-PEG-coated islets exhibited robust islet viability accompanied by uncompromised islet insulin secretory function. Instant blood-mediated inflammatory reaction was also reduced by Hep-PEG islet coating, accompanied by enhanced intra-islet revascularization. In addition, despite its semi-permeability, Hep-PEG islet coating promoted the survival of islets exposed to pro-inflammatory cytokines. Considering that inflammation and hypoxia are primary causes of immediate cell loss for cell therapy, the Hep-PEG nanofilm represents a viable approach for cell surface engineering which would improve the clinical outcome of cell therapies.

Surface engineering of semiconducting polymer nanoparticles for amplified photoacoustic imaging.

Despite the deeper tissue penetration of photoacoustic (PA) imaging, its sensitivity is generally lower than optical imaging. This fact partially restricts the applications of PA imaging and greatly stimulates the development of sensitive PA imaging agents. We herein report that the surface coating of semiconducting polymer nanoparticles (SPNs) with the silica layer can simultaneously amplify fluorescence and PA brightness while maintaining their photothermal conversion efficiency nearly unchanged. As compared with the bare SPNs, the silica-coated SPNs (SPNs-SiO2) have higher photothermal heating rate in the initial stage of laser irradiation due to the higher interfacial thermal conductance between the silica layer and water relative to that between the SP and water. Such an interfacial effect consequently results in sharp temperature increase and in turn amplified PA brightness for SPNs-SiO2. By conjugating poly(ethylene glycol) (PEG) and cyclic-RGD onto SPNs-SiO2, targeted PA imaging of tumor in living mice is demonstrated after systemic administration, showing a high signal to background ratio. Our study provides a surface engineering approach to amplify the PA signals of organic nanoparticles for molecular imaging.

Polysulfide Anchoring Mechanism Revealed by Atomic Layer Deposition of V2O5 and Sulfur-Filled Carbon Nanotubes for Lithium-Sulfur Batteries.

Despite the promise of surface engineering to address the challenge of polysulfide shuttling in sulfur-carbon composite cathodes, melt infiltration techniques limit mechanistic studies correlating engineered surfaces and polysulfide anchoring. Here, we present a controlled experimental demonstration of polysulfide anchoring using vapor phase isothermal processing to fill the interior of carbon nanotubes (CNTs) after assembly into binder-free electrodes and atomic layer deposition (ALD) coating of polar V2O5 anchoring layers on the CNT surfaces. The ultrathin submonolayer V2O5 coating on the CNT exterior surface balances the adverse effect of polysulfide shuttling with the necessity for high sulfur utilization due to binding sites near the conductive CNT surface. The sulfur loaded into the CNT interior provides a spatially separated control volume enabling high sulfur loading with direct sulfur-CNT electrical contact for efficient sulfur conversion. By controlling ALD coating thickness, high initial discharge capacity of 1209 mAh/gS at 0.1 C and exceptional cycling at 0.2 C with 87% capacity retention after 100 cycles and 73% at 450 cycles is achieved and correlated to an optimal V2O5 anchoring layer thickness. This provides experimental evidence that surface engineering approaches can be effective to overcome polysulfide shuttling by controlled design of molecular-scale building blocks for efficient binder free lithium sulfur battery cathodes.

Geometry-dependent compressive responses in nanoimprinted submicron-structured shape memory polyurethane.

High resolution surface textures, when rationally designed, provide an attractive surface engineering approach to enhance surface functionalities. Designing smart surfaces by coupling surface texture with shape memory polymers has garnered attention in achieving tunable mechanical properties. We investigate the structure-mechanical property relationships for programmable, shape-memorizing submicron-scale pillar arrays subjected to flat-punch compression. The geometrically-dependent deformation of structured surfaces with two different aspect ratios (250 nm-pillars 1 : 1 and 550 nm-pillars 2.4 : 1) were investigated, and their moduli were found to be lower than that of non-patterned surface. From finite element analysis, the pillar deformation is correlated to a mechanistic transition from a discrete, unidirectional compression of 250 nm-pillars to lateral constraints caused by interpillar contact in 550 nm-pillars. This lateral pillar-pillar contact in the 550 nm-pillars resulted in an increased and maximum strain-dependent modulus but lower elastic recovery and energy dissipation as compared with the 250 nm-pillars. Furthermore, the compressive responses of temporarily shaped pillars (programmed by stretching) were compared with the permanently shaped pillars. The extent of lateral constraints controlled by pillar shape and spacing in 550 nm-pillars was responsible for the modulus differences between the original and stretched patterns, whereas the modulus of 250 nm-pillars remained as a constant value with different levels of stretching. This study provides mechanistic insights into how the mechanical behavior can be modulated by designing the aspect ratio of shape memory pillar arrays and by programming the surface geometry, thus revealing the potential of developing ingenious designs of responsive surfaces sensitive to mechanical deformation.

(Invited) Silicon Nano-Tip Pattern Approach for Surface and Interface Engineering of Fully Coherent, High Ge Content Nanostructure Arrays for High Performance Photodetection

Defects in form of dislocations at the interface and threading arms in the film as well as SiGe intermixing are the main mechanisms to release the crystallographic misfit strain in Germanium (Ge) heterostructures grown on the mature Silicon (Si) wafer platform, severely deteriorating thereby the superior optoelectronic properties of Ge for device applications. We demonstrate here a novel technique, enabling fully coherent, high Ge content islands on nano-tip patterned Si (001) substrates by the suppression of plastic relaxation as well as SiGe intermixing. The Si-tip patterned substrate, fabricated by complementary metal-oxide-semiconductor (CMOS) compatible nanotechnology, features ~50 nm wide Si tips emerging from a SiO2 matrix and arranged in an ordered lattice. Molecular beam epitaxy (MBE) growths result in Ge nano-islands with high selectivity and having homogeneous shape and size. The ~850°C growth temperature required for ensuring selective growth has been shown to lead to the formation of Ge islands of high crystalline quality without extensive Si intermixing (with 91 at.% Ge). Nano-tip patterned wafers result in geometric, kinetic diffusion barrier intermixing hindrance (in particular surface diffusion suppression) confining the major intermixing to the pedestal region of Ge islands where kinetic diffusion barriers are however high. Theoretical calculations suggest that the self-assembled thin SiGe layer at the interface plays nevertheless a significant role in realizing fully coherent Ge nano-islands free from extended defects especially dislocations. Finally, single layer graphene (SLG)/Ge/Si-tip Schottky junctions were fabricated and thanks to the absence of extended defects and SiGe intermixing in the Ge islands, high performance photodetection characteristics with responsivity and Ion/Ioff ratio of ~45 mA/W and ~103, respectively, are demonstrated.

Bio-inspired sensitive and reversible mechanochromisms via strain-dependent cracks and folds.

A number of marine organisms use muscle-controlled surface structures to achieve rapid changes in colour and transparency with outstanding reversibility. Inspired by these display tactics, we develop analogous deformation-controlled surface-engineering approaches via strain-dependent cracks and folds to realize the following four mechanochromic devices: (1) transparency change mechanochromism (TCM), (2) luminescent mechanochromism (LM), (3) colour alteration mechanochromism (CAM) and (4) encryption mechanochromism (EM). These devices are based on a simple bilayer system that exhibits a broad range of mechanochromic behaviours with high sensitivity and reversibility. The TCM device can reversibly switch between transparent and opaque states. The LM can emit intensive fluorescence as stretched with very high strain sensitivity. The CAM can turn fluorescence from green to yellow to orange as stretched within 20% strain. The EM device can reversibly reveal and conceal any desirable patterns.

Creating cellular patterns using genetically engineered, gold- and cell-binding polypeptides.

Patterning cells on material surfaces is an important tool for the study of fundamental cell biology, tissue engineering, and cell-based bioassays. Here, the authors report a simple approach to pattern cells on gold patterned silicon substrates with high precision, fidelity, and stability. Cell patterning is achieved by exploiting adsorbed biopolymer orientation to either enhance (gold regions) or impede (silicon oxide regions) cell adhesion at particular locations on the patterned surface. Genetic incorporation of gold binding domains enables C-terminal chemisorption of polypeptides onto gold regions with enhanced accessibility of N-terminal cell binding domains. In contrast, the orientation of polypeptides adsorbed on the silicon oxide regions limit the accessibility of the cell binding domains. The dissimilar accessibility of cell binding domains on the gold and silicon oxide regions directs the cell adhesion in a spatially controlled manner in serum-free medium, leading to the formation of well-defined cellular patterns. The cells are confined within the polypeptide-modified gold regions and are viable for eight weeks, suggesting that bioactive polypeptide modified surfaces are suitable for long-term maintenance of patterned cells. This study demonstrates an innovative surface-engineering approach for cell patterning by exploiting distinct ligand accessibility on heterogeneous surfaces.

Modified surface loading process for achieving improved performance of the quantum dot-sensitized solar cells

Achieving high surface coverage of the colloidal quantum dots (QDs) on TiO2 films has been challenging for quantum dot-sensitized solar cells (QDSCs). Herein, a general surface engineering approach was proposed to increase the loading of these QDs. It was found that S2− treatment/QD re-uptake process can significantly improve the attachment of the QDs on TiO2 films. Surface concentration of the QDs was improved by ∼60%, which in turn greatly enhances light absorption and decreases carrier recombination in QDSCs. Ensuing QDSCs with optimized QD loading exhibit a power conversion efficiency of 3.66%, 83% higher than those fabricated with standard procedures.

Fatigue resistant carbon coatings for rolling/sliding contacts

The growing demands for renewable energy production have recently resulted in a significant increase in wind plant installation. Field data from these plants show that wind turbines suffer from costly repair, maintenance and high failure rates. Often times the reliability issues are linked with tribological components used in wind turbine drivetrains. The primary failure modes in bearings and gears are associated with micropitting, wear, brinelling, scuffing, smearing and macropitting all of which occur at or near the surface. Accordingly, a variety of surface engineering approaches are currently being considered to alter the near surface properties of such bearings and gears to prevent these tribological failures. In the present work, we have evaluated the tribological performance of compliant highly hydrogenated diamond like carbon coating developed at Argonne National Laboratory, under mixed rolling/sliding contact conditions for wind turbine drivetrain components. The coating was deposited on AISI 52100 steel specimens using a magnetron sputter deposition system. The experiments were performed on a PCS Micro-Pitting-Rig (MPR) with four material pairs at 1.79GPa contact stress, 40% slide to roll ratio and in polyalphaolefin (PAO4) basestock oil (to ensure extreme boundary conditions). The post-test analysis was performed using optical microscopy, surface profilometry, and Raman spectroscopy. The results obtained show a potential for these coatings in sliding/rolling contact applications as no failures were observed with coated specimens even after 100 million cycles compared to uncoated pair in which they failed after 32 million cycles, under the given test conditions.

A Review to the Laser Cladding of Self-Lubricating Composite Coatings

Liquid lubricants are extremely viable in reducing wear damage and friction of mating components. However, due to the relentless pressure and the recent trend towards higher operating environments in advanced automotive and aerospace turbo-machineries, these lubricants cease to perform and hence, an alternate system is required for maintaining the self-lubricating environment. From the viewpoint of tribologist, wear is related to near-surface regions and hence, surface coatings are considered suitable for improving the functioning of tribo-pairs. Wear resistant coatings can be fabricated with the addition of various solid lubricants so as to reduce friction drag. In order to protect bulk substrates, self-lubricating wear resistant composite coatings have been fabricated by employing various surface coating techniques such as electrochemical process, physical and chemical vapor depositions, thermal and plasma spraying, laser cladding etc. Studies related to laser-based surface engineering approaches have remained vibrant and are recognized in altering the near surface regions. In this work, the latest developments in laser based self-lubricating composite coatings are highlighted. Furthermore, the effect of additives, laser processing parameters and their corresponding influence on mechanical and tribological performance is briefly reviewed.

Rapid preparation of mutated influenza hemagglutinins for influenza virus pandemic prevention.

Influenza viruses have periodically caused pandemic due to frequent mutation of viral proteins. Influenza viruses have two major membrane glycoproteins: hemagglutinin (HA) and neuraminidase (NA). Hemagglutinin plays a crucial role in viral entry, while NA is involved in the process of a viral escape. In terms of developing antiviral drugs, HA is a more important target than NA in the prevention of pandemic, since HA is likely to change the host specificity of a virus by acquiring mutations, thereby to increase the risk of pandemic. To characterize mutated HA functions, current approaches require immobilization of purified HA on plastic wells and carriers. These troublesome methods make it difficult to respond to emerging mutations. In order to address this problem, a yeast cell surface engineering approach was investigated. Using this technology, human HAs derived from various H1N1 subtypes were successfully and rapidly displayed on the yeast cell surface. The yeast-displayed HAs exhibited similar abilities to native influenza virus HAs. Using this system, human HAs with 190E and 225G mutations were shown to exhibit altered recognition specificities from human to avian erythrocytes. This system furthermore allowed direct measurement of HA binding abilities without protein purification and immobilization. Coupled with the ease of genetic manipulation, this system allows the simple and comprehensive construction of mutant protein libraries on yeast cell surface, thereby contributing to influenza virus pandemic prevention.Electronic supplementary materialThe online version of this article (doi:10.1186/s13568-016-0179-y) contains supplementary material, which is available to authorized users.

A Facile Approach to Functionalize Cell Membrane-Coated Nanoparticles.

Convenient strategies to provide cell membrane-coated nanoparticles (CM-NPs) with multi-functionalities beyond the natural function of cell membranes would dramatically expand the application of this emerging class of nanomaterials. We have developed a facile approach to functionalize CM-NPs by chemically modifying live cell membranes prior to CM-NP fabrication using a bifunctional linker, succinimidyl-[(N-maleimidopropionamido)-polyethyleneglycol] ester (NHS-PEG-Maleimide). This method is particularly suitable to conjugate large bioactive molecules such as proteins on cell membranes as it establishes a strong anchorage and enable the control of linker length, a critical parameter for maximizing the function of anchored proteins. As a proof of concept, we show the conjugation of human recombinant hyaluronidase, PH20 (rHuPH20) on red blood cell (RBC) membranes and demonstrate that long linker (MW: 3400) is superior to short linker (MW: 425) for maintaining enzyme activity, while minimizing the changes to cell membranes. When the modified membranes were fabricated into RBC membrane-coated nanoparticles (RBCM-NPs), the conjugated rHuPH20 can assist NP diffusion more efficiently than free rHuPH20 in matrix-mimicking gels and the pericellular hyaluronic acid matrix of PC3 prostate cancer cells. After quenching the unreacted chemical groups with polyethylene glycol, we demonstrated that the rHuPH20 modification does not reduce the ultra-long blood circulation time of RBCM-NPs. Therefore, this surface engineering approach provides a platform to functionlize CM-NPs without sacrificing the natural function of cell membranes.

Engineered porous scaffold for periprosthetic infection prevention

Event Abstract Back to Event Engineered porous scaffold for periprosthetic infection prevention Giorgio Iviglia1, 2, Clara Cassinelli1, Elisa Torre1, Francresco Baino2*, Marco Morra1* and Chiara Vitale Brovarone2* 1 Nobil Bio Ricerche srl, R&D, Italy 2 Politecnico di Torino, Department of Applied Science and Technology, Italy Introduction: Periprosthetic infection (PPI) is a devastating consequence of implant insertion involving 1% - 5% of procedures[1],[2]. Strategies to PPI prevention involve either increasing the rate of new bone formation or the release of antibiotics such as vancomycin. Modern surface-engineering approaches allow to combine these strategies: an innovative three-dimensional porous scaffold using HA and β-TCP, coupled with pectin(PEC)-chitosan(CHIT) polyelectrolite (PEI), loaded with vancomycin (VCA) was developed. By this approach, it is possible to achieve a controlled vancomycin release, inhibiting the bacterial growth until 1 week, and promoting bone formation in vitro. Materials and Methods: All materials used were purchased from Sigma-Aldrich. A slurry was prepared by mixing the HA/ β-TCP (25:75 % wt.) powder, binding agent, dispersing agent and water. Polyurethane sponge impregnation method was used[3]. Sintered scaffold was filled with a solution of Pectin-Vancomycin (1% wt - 5% wt), freeze-dried and then a Chitosan functionalization was made in order to generate a polyelectrolite structure on ceramic surface.Physiochemical and biological properties were analyzed by SEM, micro-CT, XPS,HPLC drug release, mechanical and degradation test, RT-PCR and in vitro osteoblast cell culture. Results and Discussion: Usually periprosthetic zone exhibits an acidic environment, engineered PEC-CHIT-VCA functionalization provides an excellent protection at pH 3, only 9% of mass was lost after 4 days and the efficacy was mantained. Drug release test, combined with serial bacterial dilution test demonstrated that the system HA/ β-TCP – PEC-VCA-CHIT yields a controlled release during 1 week, unlike HA/ β-TCP - VCA and HA/ β-TCP - PEC-VCA that shown a “burst” release in less than 24h. The Agar germ test confirmed that the entrapped antibiotic is able to inhibit the growth and proliferation of Staphylococcus epidermidis. RT-PCR on Engineered scaffold of macrophages cell culture after 4 h, shown a decrease of fold expression for Interleukin1β and MCP-1 genes, and a conseguent increase of Interleukin 10, proving that PEC-CHIT-VCA treatement elicits anti-inflammatory responses. Since fibroblast from gingiva proliferate faster than osteoblast, the PEC-CHIT-VCA coating was studied in order to avoid early infiltration, but the linear degradation rate of PEI guide bone regeneration, exposing porous ceramic phase to osteoblast, pro-osteogenics response was further demonstrated by SAOS-2 osteoblast, after 24h, 72h and 5 days of cell culture, SEM analysis shows a good cell infiltration, and RT-PCR shown a increasing in pro-osteogenic genes, as ALP and OCN. Conclusion: By coupling a bio-ceramic scaffold and a polyelectrolyte polysaccharide, a complex biomimetic bone substitute which reduce inflamation, and promotes cell infiltration and proliferation was obtained. The PEC-VCA-CHIT formulation allows to obtain high concentration of antibiotic in situ with a controlled and prolonged release. HA/βTCP-PEC/VCA /CHIT could then represent an ideal system to struggle against PPI in dental applications, by stimulating new bone formation and inhibiting bacterial growth.

Surface engineering of titanium with simvastatin-releasing polymer nanoparticles for enhanced osteogenic differentiation

We describe a novel approach for surface engineering of titanium (Ti) with polymer nanoparticles that can sustainably release an osteogenic compound, simvastatin (SV). The SV-loaded nanoparticles (SV-GC-CA) were prepared by self-assembly of 5β-cholanic acid-conjugated glycol chitosan (GC-CA) in the presence of SV. Dynamic light scattering (DLS) and transmission electron microscopy (TEM) analyses showed that the SV-GC-CA nanoparticles had a hydrodynamic diameter of 371.4 nm with a spherical shape. The surface engineering of Ti was performed by pre-treatment of Ti surface with polydopamine (PD) coatings, followed by immobilization of the SV-GC-CA nanoparticles. The immobilization of the SV-GC-CA nanoparticles onto PD-treated Ti surfaces could be achieved by a simple dipping method in an aqueous solution. The successful immobilization of the SV-GC-CA nanoparticles onto Ti surfaces was confirmed by field-emission scanning electron microscopy (FE-SEM), and the density of immobilized nanoparticles could be controlled. SV was sustainably released for up to 20 days, and the release rate was dependent on the loading amount of SV. The Ti substrate functionalized with SV-releasing nanoparticles significantly promoted alkaline phosphatase (ALP) activity of osteoblast-like cells (MC3T3-E1). The surface engineering approach described in this work has an applicability for various medical devices to generate surfaces with improved osteogenic potentials.

Cell surface engineering with polyelectrolyte-stabilized magnetic nanoparticles: A facile approach for fabrication of artificial multicellular tissue-mimicking clusters

Abstract Regenerative medicine requires new ways to assemble and manipulate cells for fabrication of tissue-like constructs. Here we report a novel approach for cell surface engineering of human cells using polymer-stabilized magnetic nanoparticles (MNPs). Cationic polyelectrolyte-coated MNPs are directly deposited onto cellular membranes, producing a mesoporous semi-permeable layer and rendering cells magnetically responsive. Deposition of MNPs can be completed within minutes, under cell-friendly conditions (room temperature and physiologic media). Microscopy (TEM, SEM, AFM, and enhanced dark-field imaging) revealed the intercalation of nanoparticles into the cellular microvilli network. A detailed viability investigation was performed and suggested that MNPs do not inhibit membrane integrity, enzymatic activity, adhesion, proliferation, or cytoskeleton formation, and do not induce apoptosis in either cancer or primary cells. Finally, magnetically functionalized cells were employed to fabricate viable layered planar (two-cell layers) cell sheets and 3D multicellular spheroids.

Effect of micro/nano-scale textures on anti-adhesive wear properties of WC/Co-based TiAlN coated tools in AISI 316 austenitic stainless steel cutting

In cutting of stainless steel with coated tool, the steel chip adhering to tool surface is usually severe and consequently causes serious adhesive and frictional problems, which is the major reason for the failure of coated tool. To solve the problem, a surface engineering approach, namely, a highly functionalization of tool surfaces by textures may be of great importance. Thus, the effect of micro/nano-scale textures on anti-adhesive wear properties of TiAlN coated tools in AISI 316 austenitic stainless steel cutting was investigated. For this purpose, two types of surface textures were fabricated on the rake faces of WC/Co carbide tools: (i) micro-scale textures fabricated by Nd:YAG laser, (ii) micro/nano-scales textures fabricated by Nd:YAG laser and femtosecond laser. Then, these textured tools were deposited with TiAlN coatings using cathode arc-evaporation technique. Wet cutting experiments were carried out with the micro-scale textured coated tool (MCT), micro/nano-scale textured coated tool (MNCT), and the conventional coated tool (CCT). Results obtained in this work demonstrated the feasibility of fabricating micro- or micro/nano-scale textures on tools substrate surfaces to improve the anti-adhesive wear properties of TiAlN coated tool. The rake face micro/nano-scale textured tool was the most effective. Moreover, mechanisms for the anti-adhesive properties enhancement were proposed.

Surface engineering and palladium dispersion in MCM-41 for methane oxidation

Highly dispersed palladium oxide nanoparticles (Ø∼2nm) were obtained in mesostructured silica of MCM-41 type from divalent palladium complexes tethered from grafted propylamine ligands themselves highly dispersed using a surface engineering approach based on a molecular stencil patterning technique (MSP). A partial surface coverage obtained by incomplete extraction of the surfactant produces a self-assembled and patterned molecular mask that is fixed by silanol capping. After removal of the masking surfactant, the unreacted silanol groups are reacted with 3-(aminopropyl) trimethoxysilane ligands, which are further metallated using an acetonitrile solution of palladium trifluoroacetate Pd(O2CCF3)2. Then, calcination yields PdO nanoparticles of ca. 2 or 6nm depending of the masking percentage of the surface. In some case, calcination was accompagnied by a partial collapse that is undergone by the structure. The structural and textural characteristics of these materials were studied by means of different physico-chemical techniques such as XRD, N2 sorption isotherms, TGA, elemental analysis (EA) by ICP, 29Si-NMR, UV–visible, FT-IR, and Raman spectroscopies. Light-off reactivity curves of methane combustion reveals that these catalysts possess no external PdO phase and follow the gold rule of higher activity for higher active phase dispersion. Eventually, intermediate structural collapse that decreases the molecular diffusion limitation may invert this tendency.

Evolution of the SrTiO3-MoO3 Interface Electronic Structure: An in Situ Photoelectron Spectroscopy Study.

Modifying the surface energetics, particularly the work function of advanced materials, is of critical importance for a wide range of surface- and interface-based devices. In this work, using in situ photoelectron spectroscopy, we investigated the evolution of electronic structure at the SrTiO3 surface during the growth of ultra-thin MoO3 layers. Because of the large work function difference between SrTiO3 and MoO3, the energy band alignment on the SrTiO3 surface is significantly modified. The charge transfer and dipole formation at the SrTiO3-MoO3 interface leads to a large modulation of work function and to apparent doping in SrTiO3. The measured evolutions of electronic structure and upward band bending suggest that the growth of ultra-thin MoO3 layers is a powerful tool with which to modulate the surface energetics of SrTiO3, and this surface engineering approach could be generalized to other functional oxides.

Colossal positive magnetoresistance in surface-passivated oxygen-deficient strontium titanite.

Modulation of resistance by an external magnetic field, i.e. magnetoresistance effect, has been a long-lived theme of research due to both fundamental science and device applications. Here we report colossal positive magnetoresistance (CPMR) (>30,000% at a temperature of 2 K and a magnetic field of 9 T) discovered in degenerate semiconducting strontium titanite (SrTiO3) single crystals capped with ultrathin SrTiO3/LaAlO3 bilayers. The low-pressure high-temperature homoepitaxial growth of several unit cells of SrTiO3 introduces oxygen vacancies and high-mobility carriers in the bulk SrTiO3, and the three-unit-cell LaAlO3 capping layer passivates the surface and improves carrier mobility by suppressing surface-defect-related scattering. The coexistence of multiple types of carriers and inhomogeneous transport lead to the emergence of CPMR. This unit-cell-level surface engineering approach is promising to be generalized to others oxides, and to realize devices with high-mobility carriers and interesting magnetoelectronic properties.