ALBERT

Beschreibung: Bacterial contamination is a severe issue that affects medical devices, hospital tools and surfaces. When microorganisms adhere to a surface (e.g., medical devices or implants) they can develop into a biofilm, thereby becoming more resistant to conventional biocides and disinfectants. Nanoparticles can be used as an antibacterial agent in medical instruments or as a protective coating in implantable devices. In particular, attention is being drawn to photothermally active nanoparticles that are capable of converting absorbed light into heat. These nanoparticles can efficiently eradicate bacteria and biofilms upon light activation (predominantly near the infrared to near-infrared spectral region) due a rapid and pronounced local temperature increase. By using this approach new, protective, antibacterial surfaces and materials can be developed that can be remotely activated on demand. In this review, we summarize the state-of-the art regarding the application of various photothermally active nanoparticles and their corresponding nanocomposites for the light-triggered eradication of bacteria and biofilms.

Beschreibung: The adsorption behavior of tin phthalocyanine (SnPc) molecules on rutile TiO2(110) was studied by scanning tunneling microscopy (STM). Low-temperature STM measurements of single molecules reveal the coexistence of two conformations of molecules on the TiO2 surface. Density functional theory-based simulations (DFT) indicate that the difference originates from the position of the tin atom protruding from the molecule plane. The irreversible switching of Sn-up molecules into the Sn-down conformation was observed either after sample annealing at 200 °C or as a result of tip-induced manipulation. Room-temperature measurements conducted for a coverage of close to a monolayer showed no tendency for molecular arrangement.

Beschreibung: Tip-enhanced Raman spectroscopy is combined with polarization angle-resolved spectroscopy to investigate the nanometer-scale structural properties of core–shell silicon nanowires (crystalline Si core and amorphous Si shell), which were synthesized by platinum-catalyzed vapor–liquid–solid growth and silicon overcoating by thermal chemical vapor deposition. Local changes in the fraction of crystallinity in these silicon nanowires are characterized at an optical resolution of about 300 nm. Furthermore, we are able to resolve the variations in the intensity ratios of the Raman peaks of crystalline Si and amorphous Si by applying tip-enhanced Raman spectroscopy, at sample positions being 8 nm apart. The local crystallinity revealed using confocal Raman spectroscopy and tip-enhanced Raman spectroscopy agrees well with the high-resolution transmission electron microscopy images. Additionally, the polarizations of Raman scattering and the photoluminescence signal from the tip–sample nanogap are explored by combining polarization angle-resolved emission spectroscopy with tip-enhanced optical spectroscopy. Our work demonstrates the significant potential of resolving local structural properties of Si nanomaterials at the sub-10 nanometer scale using tip-enhanced Raman techniques.

Beschreibung: A nanometer-scaled resonant tunneling diode based on lateral heterojunctions of armchair graphene and boron nitride nanoribbons, exhibiting negative differential resistance is proposed. Low-bandgap armchair graphene nanoribbons and high-bandgap armchair boron nitride nanoribbons are used to design the well and the barrier region, respectively. The effect of all possible substitutional defects (including BC, NC, CB, and CN) at the interface of graphene and boron nitride nanoribbons on the negative differential resistance behavior of the proposed resonant tunneling diode is investigated. Transport simulations are carried out in the framework of tight-binding Hamiltonians and non-equilibrium Green’s functions. The results show that a single substitutional defect at the interface of armchair graphene and boron nitride nanoribbons can dramatically affect the negative differential resistance behavior depending on its type and location in the structure.

Beschreibung: The mechanical properties of cells could serve as an indicator for disease progression and early cancer diagnosis. This study utilized atomic force microscopy (AFM) to measure the viscoelastic properties of ovarian cancer cells and then examined the association with the invasion of ovarian cancer at the level of living single cells. Elasticity and viscosity of the ovarian cancer cells OVCAR-3 and HO-8910 are significantly lower than those of the human ovarian surface epithelial cell (HOSEpiC) control. Further examination found a dramatic increase of migration/invasion and an obvious decease of microfilament density in OVCAR-3 and HO-8910 cells. Also, there was a significant relationship between viscoelastic and biological properties among these cells. In addition, the elasticity was significantly increased in OVCAR-3 and HO-8910 cells after the treatment with the anticancer compound echinomycin (Ech), while no obvious change was found in HOSEpiC cells after Ech treatment. Interestingly, Ech seemed to have no effect on the viscosity of the cells. Ech significantly inhibited the migration/invasion and significantly increased the microfilament density in OVCAR-3 and HO-8910 cells, which was significantly related with the elasticity of the cells. An increase of elasticity and a decrease of invasion were found in OVCAR-3 and HO-8910 cells after Ech treatment. Together, this study clearly demonstrated the association of viscoelastic properties with the invasion of ovarian cancer cells and shed a light on the biomechanical changes for early diagnosis of tumor transformation and progression at single-cell level.

Beschreibung: The multimodal magnetic resonance imaging (MRI) technique has been extensively studied over the past few years since it offers complementary information that can increase diagnostic accuracy. Simple methods to synthesize contrast agents are necessary for the development of multimodal MRI. Herein, uniformly distributed Fe3O4/Gd2O3 nanocubes for T 1–T 2 dual-mode MRI contrast agents were successfully designed and synthesized. In order to increase hydrophilicity and biocompatibility, the nanocubes were coated with nontoxic 3,4-dihydroxyhydrocinnamic acid (DHCA). The results show that iron (Fe) and gadolinium (Gd) were homogeneously distributed throughout the Fe3O4/Gd2O3-DHCA (FGDA) nanocubes. Relaxation time analysis was performed on the images obtained from the 3.0 T scanner. The results demonstrated that r 1 and r 2 maximum values were 67.57 ± 6.2 and 24.2 ± 1.46 mM−1·s−1, respectively. In vivo T 1- and T 2-weighted images showed that FGDA nanocubes act as a dual-mode contrast agent enhancing MRI quality. Overall, these experimental results suggest that the FGDA nanocubes are interesting tools that can be used to increase MRI quality, enabling accurate clinical diagnostics.

Beschreibung: We report on the synthesis of composite nanobeads with antibacterial properties. The particles consist of polystyrene cores that are surrounded by sulfonic gel shells with embedded silver nanoparticles. The nanocomposite beads are prepared by sulfonation of polystyrene particles followed by accumulation of silver ions in the shell layer and subsequent reduction with sodium borohydride. The resulting material has been characterized by electron microscopy, vibrational and X-ray photoelectron spectroscopy and several other experimental techniques. It was shown that sodium borohydride reduces silver ions embedded in the gel layer producing silver nanoparticles but also transforms a fraction of sulfonic groups in the polymer to moieties with sulfur in a lower oxidation state, likely thiols. It is hypothesized that the generated thiol groups are anchoring the nanoparticles in the gel shell of the nanobeads stabilizing the whole structure. The silver-decorated nanobeads appear to be a promising material with considerable antimicrobial activity and were tested against Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus and Staphylococcus epidermidis. The determined minimum inhibitory (MIC) and minimum biofilm inhibitory (MBIC) concentrations are comparable to those of non-incorporated silver nanoparticles.

Beschreibung: We propose the use of gold nanoparticles grown on the surface of nanoporous TiO2 films as surface-enhanced Raman scattering (SERS) sensors for the detection of 17β-estradiol. Gold deposition on top of a TiO2 surface leads to the formation of nanoparticles the plasmonic properties of which fulfil the requirements of a SERS sensor. The morphological and optical properties of the surface were investigated. Specifically, we demonstrate that the TiO2 background pressure during pulsed laser deposition and the annealing conditions offer control over the formation of Au nanoparticles with different sizes, shapes and distributions, yielding a versatile sensor. We have exploited the surface for the detection of 17β-estradiol, an emerging contaminant in environmental waters. We have found a limit of detection of 1 nM with a sensitivity allowing for a dynamic range of five orders of magnitude (up to 100 µM).

Beschreibung: Hard carbons are promising candidates for high-capacity anode materials in alkali metal-ion batteries, such as lithium- and sodium-ion batteries. High reversible capacities are often coming along with high irreversible capacity losses during the first cycles, limiting commercial viability. The trade-off to maximize the reversible capacities and simultaneously minimizing irreversible losses can be achieved by tuning the exact architecture of the subnanometric pore system inside the carbon particles. Since the characterization of small pores is nontrivial, we herein employ Kr, N2 and CO2 gas sorption porosimetry, as well as H2O vapor sorption porosimetry, to investigate eight hard carbons. Electrochemical lithium as well as sodium storage tests are compared to the obtained apparent surface areas and pore volumes. H2O, and more importantly CO2, sorption porosimetry turned out to be the preferred methods to evaluate the likelihood for excessive irreversible capacities. The methods are also useful to select the relatively most promising active materials within chemically similar materials. A quantitative relation of porosity descriptors to the obtained capacities remains a scientific challenge.

Beschreibung: The study of magnetohydrodynamic flow of a nanoparticle suspension under the influence of varied dimensionless parameters has been the focus of research in contemporary times. This work models the effect of magnetic field, heat generation and absorption parameter in a steady, laminar, two-dimensional boundary layer flow of a nanofluid over a permeable stretching sheet at a given surface temperature and partial slip. The highly nonlinear governing equations are solved numerically using similarity transformations with suitable boundary conditions and converted to ordinary differential equations. A computational model is setup using FORTRAN, where a relevant Adam’s predictor–corrector method is employed to solve the equations. The impact of the dimensionless parameters, including the Brownian motion, thermophoresis, magnetic field, heat generation and absorption parameters, on the velocity, temperature and nanoparticle concentration of fluid flow are analysed systematically.

Beschreibung: A comparative study of the anodization processes occurring at the GaAs(111)A and GaAs(111)B surfaces exposed to electrochemical etching in neutral NaCl and acidic HNO3 aqueous electrolytes is performed in galvanostatic and potentiostatic anodization modes. Anodization in NaCl electrolytes was found to result in the formation of porous structures with porosity controlled either by current under the galvanostatic anodization, or by the potential under the potentiostatic anodization. Possibilities to produce multilayer porous structures are demonstrated. At the same time, one-step anodization in a HNO3 electrolyte is shown to lead to the formation of GaAs triangular shape nanowires with high aspect ratio (400 nm in diameter and 100 µm in length). The new data are compared to those previously obtained through anodizing GaAs(100) wafers in alkaline KOH electrolyte. An IR photodetector based on the GaAs nanowires is demonstrated.

Beschreibung: Luminescent nanomaterials have emerged as attractive candidates for sensing, catalysis and bioimaging applications in recent years. For practical use in bioimaging, nanomaterials with high photoluminescence, quantum yield, photostability and large Stokes shifts are needed. While offering high photoluminescence and quantum yield, semiconductor quantum dots suffer from toxicity and are susceptible to oxidation. In this context, atomically precise gold nanoclusters protected by thiol monolayers have emerged as a new class of luminescent nanomaterials. Low toxicity, bioavailability, photostability as well as tunable size, composition, and optoelectronic properties make them suitable for bioimaging and biosensing applications. In this review, an overview of the sensing of pathogens, and of in vitro and in vivo bioimaging using luminescent gold nanoclusters along with the limitations with selected examples are discussed.

Beschreibung: Inorganic materials are receiving significant interest in medicine given their usefulness for therapeutic applications such as targeted drug delivery, active pharmaceutical carriers and medical imaging. However, poor knowledge of the side effects related to their use is an obstacle to clinical translation. For the development of molecular drugs, the concept of safe-by-design has become an efficient pharmaceutical strategy with the aim of reducing costs, which can also accelerate the translation into the market. In the case of materials, the application these approaches is hampered by poor knowledge of how the physical and chemical properties of the material trigger the biological response. Hemocompatibility is a crucial aspect to take into consideration for those materials that are intended for medical applications. The formation of nanoparticle agglomerates can cause severe side effects that may induce occlusion of blood vessels and thrombotic events. Additionally, nanoparticles can interfere with the coagulation cascade causing both pro- and anti-coagulant properties. There is contrasting evidence on how the physicochemical properties of the material modulate these effects. In this work, we developed two sets of tailored carbon and silica nanoparticles with three different diameters in the 100–500 nm range with the purpose of investigating the role of surface curvature and chemistry on platelet aggregation, activation and adhesion. Substantial differences were found in the composition of the protein corona depending on the chemical nature of the nanoparticles, while the surface curvature was found to play a minor role. On the other hand, large carbon nanoparticles (but not small carbon nanoparticles or silica nanoparticles) have a clear tendency to form aggregates both in plasma and blood. This effect was observed both in the presence or absence of platelets and was independent of platelet activation. Overall, the results presented herein suggest the existence of independent modes of action that are differently affected by the physicochemical properties of the materials, potentially leading to vessel occlusion and/or formation of thrombi in vivo.

Beschreibung: In the vast majority of studies on semiconductor particles ligands or capping agents are used that bind to the surface of the particles covering them with an electrically insulating shell. Since the transport of charge carriers and/or energy across interfaces is desirable for a variety of applications, the use of π-conjugated ligands becomes increasingly interesting. Among them are compounds that react to external stimuli. Molecular switches in particular are fascinating because the properties of the interfaces can be potentially adjusted as required. However, there is debate about how the properties of such special ligands are influenced by the presence of a semiconductor and vice versa. Here ammonium-modified azobenzene compounds were selected as prototypes for molecular switches and organic–inorganic hybrid perovskites as semiconductor materials. The class of ammonium–lead–halide phases as prototypes is peculiar because, in addition to the surface functionalization of 3D crystals, organic compounds can actually be incorporated into the crystal as 2D phases. Thus, for example, layered Ruddlesden–Popper phases are obtained. We present photoswitchable azobenzene ligands with different head-group lengths for the synthesis of 2D and 3D hybrid perovskite phases. The energy transfer mechanisms are influenced by the length of the molecular spacer moiety, which determines the distance between the π system and the semiconductor surfaces. We find huge differences in the photoswitching behaviour between the free, surface-coordinated and integrated ligands between the perovskite layers. Photoswitching of azobenzene ligands incorporated in 2D phases is nearly quenched, while the same mechanism for surface-coordinating ligands is greatly improved, compared to the free ligands. The improvement originates from an energy transfer from perovskite to azobenzene, which is strongly distance-dependent. This study provides evidence for the photoswitching of azobenzenes as ligands of hybrid perovskites, which depends on the spacing between the chromophore and the perovskite phase.

Beschreibung: A chain of superconductor–insulator–superconductor junctions based on Al–AlO x –Al nanostructures and fabricated using conventional lift-off lithography techniques was measured at ultra-low temperatures. At zero magnetic field, the low current bias dynamic resistance can reach values of ≈1011 Ω. It was demonstrated that the system can provide a decent quality current biasing circuit, enabling the observation of Coulomb blockade and Bloch oscillations in ultra-narrow Ti nanowires associated with the quantum phase-slip effect.

Beschreibung: A number of bacterial glycans are specific markers for the detection and the serological identification of microorganisms and are also widely used as antigenic components of vaccines. The use of gold nanoparticles as carriers for glyco-epitopes is becoming an important alternative to the traditional conjugation with proteins and synthetic polymers. In this study, we aimed to prepare and evaluate in vivo glyco-gold nanoparticles (glyco-GNPs) bearing the terminal-branched hexaarabinofuranoside fragment (Ara6) of arabinan domains of lipoarabinomannan and arabinogalactan, which are principal polysaccharides of the cell wall of Mycobacterium tuberculosis, the causative agent of tuberculosis. In particular, we were interested whether the antibodies generated against Ara6-GNPs would recognize the natural saccharides on the cell surface of different mycobacterial strains. Two synthetic Ara6 glycosides with amino-functionalized spacer aglycons differing in length and hydrophilicity were directly conjugated with spherical gold nanoparticles (d = 15 nm) to give two sets of glyco-GNPs, which were used for the immunization of rabbits. Dot assays revealed cross-reactions between the two obtained antisera with the hexaarabinofuranoside and the 2-aminoethyl aglycon used for the preparation of glyco-GNPs. Both antisera contained high titers of antibodies specific for Mycobacteria as shown by enzyme-linked immunosorbent assay using M. bovis and M. smegmatis cells as antigens while there was only a weak response to M. phlei cells and no interaction with E. coli cells. The results obtained suggest that glyco-GNPs are promising agents for the generation of anti-mycobacterial antibodies.

Beschreibung: Atomic force microscopy (AFM) is an important tool for measuring a variety of nanoscale surface properties, such as topography, viscoelasticity, electrical potential and conductivity. Some of these properties are measured using contact methods (static contact or intermittent contact), while others are measured using noncontact methods. Some properties can be measured using different approaches. Conductivity, in particular, is mapped using the contact-mode method. However, this modality can be destructive to delicate samples, since it involves continuously dragging the cantilever tip on the surface during the raster scan, while a constant tip–sample force is applied. In this paper we discuss a possible approach to develop an intermittent-contact conductive AFM mode based on Fourier analysis, whereby the measured current response consists of higher harmonics of the cantilever oscillation frequency. Such an approach may enable the characterization of soft samples with less damage than contact-mode imaging. To explore its feasibility, we derive the analytical form of the tip–sample current that would be obtained for attractive (noncontact) and repulsive (intermittent-contact) dynamic AFM characterization, and compare it with results obtained from numerical simulations. Although significant instrumentation challenges are anticipated, the modelling results are promising and suggest that Fourier-based higher-harmonics current measurement may enable the development of a reliable intermittent-contact conductive AFM method.

Beschreibung: In the present study Ar+ cluster ions accelerated by voltages in the range of 5–10 kV are used to irradiate single crystal ZnO substrates and nanorods to fabricate self-assembled surface nanoripple arrays. The ripple formation is observed when the incidence angle of the cluster beam is in the range of 30–70°. The influence of incidence angle, accelerating voltage, and fluence on the ripple formation is studied. Wavelength and height of the nanoripples increase with increasing accelerating voltage and fluence for both targets. The nanoripples formed on the flat substrates remind of aeolian sand ripples. The ripples formed at high ion fluences on the nanorod facets resemble well-ordered parallel steps or ribs. The more ordered ripple formation on nanorods can be associated with the confinement of the nanorod facets in comparison with the quasi-infinite surface of the flat substrates.

Beschreibung: The present work explores the ability of poly(1-vinylimidazole) (PVI) to complex small interfering RNA (siRNA) silencing vascular endothelial growth factor (VEGF) and the in vitro efficiency of the formed complexes in A549 lung cancer cells. The polyplex formed was found to exhibit 66% complexation efficiency. The complexation was confirmed by gel retardation assays, FTIR and thermal analysis. The blank PVI polymer was not toxic to cells. The polyplex was found to exhibit excellent internalization and escaped the endosome effectively. The polyplex was more effective than free siRNA in silencing VEGF in lung cancer cells. The silencing of VEGF was quantified using Western blot and was also reflected in the depletion of HIF-1α levels in the cells treated with the polyplex. VEGF silencing by the polyplex was found to augment the cytotoxic effects of the chemotherapeutic agent 5-fluorouracil. Microarray analysis of the mRNA isolated from cells treated with free siRNA and the polyplex reveal that the VEGF silencing by the polyplex also altered the expression levels of several other genes that have been connected to the proliferation and invasion of lung cancer cells. These results indicate that the PVI complexes can be an effective agent to counter lung cancer.

Beschreibung: This study is dedicated to link the nanoscale pore space of carbon materials, prepared by hard-templating of meso-macroporous SiO2 monoliths, to the corresponding nanoscale polyaromatic microstructure using two different carbon precursors wthat generally exhibit markedly different carbonization properties, i.e., a graphitizable pitch and a non-graphitizable resin. The micro- and mesoporosity of these monolithic carbon materials was studied by the sorption behavior of a relatively large organic molecule (p-xylene) in comparison to typical gas adsorbates (Ar). In addition, to obtain a detailed view on the nanopore space small-angle neutron scattering (SANS) combined with in situ physisorption was applied, using deuterated p-xylene (DPX) as a contrast-matching agent in the neutron scattering process. The impact of the carbon precursor on the structural order on an atomic scale in terms of size and disorder of the carbon microstructure, on the nanopore structure, and on the template process is analyzed by special evaluation approaches for SANS and wide-angle X-ray scattering (WAXS). The WAXS analysis shows that the pitch-based monolithic material exhibits a more ordered microstructure consisting of larger graphene stacks and similar graphene layer sizes compared to the monolithic resin. Another major finding is the discrepancy in the accessible micro/mesoporosity between Ar and deuterated p-xylene that found for the two different carbon precursors, pitch and resin, which can be regarded as representative carbon precursors in general. These differences essentially indicate that physisorption using probe gases such as Ar or N2 can provide misleading parameters if to be used to appraise the accessibility of the nanoscale pore space.

Beschreibung: We present a quantitative study of the current–voltage characteristics (CVC) of SFIFS Josephson junctions (S = bulk superconductor, F = metallic ferromagnet, I = insulating barrier) with weak ferromagnetic interlayers in the diffusive limit. The problem is solved in the framework of the nonlinear Usadel equations. We consider the case of a strong tunnel barrier such that the left SF and the right FS bilayers are decoupled. We calculate the density of states (DOS) in SF bilayers using a self-consistent numerical method. Then we obtain the CVC of corresponding SFIFS junctions, and discuss their properties for different set of parameters including the thicknesses of ferromagnetic layers, the exchange field, and the magnetic scattering time. We observe an anomalous nonmonotonic CVC in case of weak ferromagnetic interlayers, which we attribute to DOS energy dependencies in the case of small exchange fields in the F layers.

Beschreibung: Lipid nanoemulsions are attractive drug delivery systems for lipophilic drugs. To produce nanoemulsions with droplets of very small diameter (

Beschreibung: The structure of the rutile TiO2(110)-(1 × 2) reconstructed surface is a phase induced by oxygen reduction. There is ongoing debate about the (1 × 2) reconstruction, because it cannot be clarified whether the (1 × 2) structure is formed over a wide area or only locally using macroscopic analysis methods such as diffraction. We used non-contact atomic force microscopy, scanning tunneling microscopy, and low-energy electron diffraction at room temperature to characterize the surface. Ti2O3 rows appeared as bright spots in both NC-AFM and STM images observed in the same area. High-resolution NC-AFM images revealed that the rutile TiO2(110)-(1 × 2) reconstructed surface is composed of two domains with different types of asymmetric rows.

Beschreibung: Central nervous system diseases are a heavy burden on society and health care systems. Hence, the delivery of drugs to the brain has gained more and more interest. The brain is protected by the blood–brain barrier (BBB), a selective barrier formed by the endothelial cells of the cerebral microvessels, which at the same time acts as a bottleneck for drug delivery by preventing the vast majority of drugs to reach the brain. To overcome this obstacle, drugs can be loaded inside nanoparticles that can carry the drug through the BBB. However, not all particles are able to cross the BBB and a multitude of factors needs to be taken into account when developing a carrier system for this purpose. Depending on the chosen pathway to cross the BBB, nanoparticle material, size and surface properties such as functionalization and charge should be tailored to fit the specific route of BBB crossing.

Beschreibung: We studied in detail the in-plane magnetic properties of heterostructures based on a ferroelectric BaTiO3 overlayer deposited on a ferromagnetic La2/3Sr1/3MnO3 film grown epitaxially on pseudocubic (001)-oriented SrTiO3, (LaAlO3)0.3(Sr2TaAlO6)0.7 and LaAlO3 substrates. In this configuration, the combination of both functional perovskites constitutes an artificial multiferroic system with potential applications in spintronic devices based on the magnetoelectric effect. La2/3Sr1/3MnO3 single layers and BaTiO3/La2/3Sr1/3MnO3 bilayers using the pulsed-laser deposition technique. We analyzed the films structurally through X-ray reciprocal space maps and high-angle annular dark field microscopy, and magnetically via thermal demagnetization curves and in-plane magnetization versus applied magnetic field loops at room temperature. Our results indicate that the BaTiO3 layer induces an additional strain in the La2/3Sr1/3MnO3 layers close to their common interface. The presence of BaTiO3 on the surface of tensile-strained La2/3Sr1/3MnO3 films transforms the in-plane biaxial magnetic anisotropy present in the single layer into an in-plane uniaxial magnetic anisotropy. Our experimental evidence suggests that this change in the magnetic anisotropy only occurs in tensile-strained La2/3Sr1/3MnO3 film and is favored by an additional strain on the La2/3Sr1/3MnO3 layer promoted by the BaTiO3 film. These findings reveal an additional mechanism that alters the magnetic behavior of the ferromagnetic layer, and consequently, deserves further in-depth research to determine how it can modify the magnetoelectric coupling of this hybrid multiferroic system.

Beschreibung: We introduce a molecular dynamics (MD) coarse-grained model for the description of tripod building blocks. This model has been used by us already for linear, V-shape, and tetratopic molecules. We wanted to further extend its possibilities to trifunctional molecules to prove its versatility. For the chosen systems we have also compared the MD results with Monte Carlo results on a triangular lattice. We have shown that the constraints present in the latter method can enforce the formation of completely different structures, not reproducible with off-lattice simulations. In addition to that, we have characterized the obtained structures regarding various parameters such as theoretical diffraction pattern and average association number.

Beschreibung: Single-photon sources and their optical spin readout are at the core of applications in quantum communication, quantum computation, and quantum sensing. Their integration in photonic structures such as photonic crystals, microdisks, microring resonators, and nanopillars is essential for their deployment in quantum technologies. While there are currently only two material platforms (diamond and silicon carbide) with proven single-photon emission from the visible to infrared, a quantum spin–photon interface, and ancilla qubits, it is expected that other material platforms could emerge with similar characteristics in the near future. These two materials also naturally lead to monolithic integrated photonics as both are good photonic materials. While so far the verification of single-photon sources was based on discovery, assignment and then assessment and control of their quantum properties for applications, a better approach could be to identify applications and then search for the material that could address the requirements of the application in terms of quantum properties of the defects. This approach is quite difficult as it is based mostly on the reliability of modeling and predicting of color center properties in various materials, and their experimental verification is challenging. In this paper, we review some recent advances in an emerging material, low-dimensional (2D, 1D, 0D) hexagonal boron nitride (h-BN), which could lead to establishing such a platform. We highlight the recent achievements of the specific material for the expected applications in quantum technologies, indicating complementary outstanding properties compared to the other 3D bulk materials.

Beschreibung: The wafer-level integration of high aspect ratio silicon nanostructures is an essential part of the fabrication of nanodevices. Metal-assisted chemical etching (MACE) is a promising low-cost and high-volume technique for the generation of vertically aligned silicon nanowires. Noble metal nanoparticles were used to locally etch the silicon substrate. This work demonstrates a bottom-up self-assembly approach for noble metal nanoparticle formation and the subsequent silicon wet etching. The macroscopic wafer patterning has been done by using a poly(methyl methacrylate) masking layer. Different metals (Au, Pt, Pd, Cu, and Ir) were investigated to derive a set of technologies as platform for specific applications. Especially, the shape of the 3D structures and the resulting reflectance have been investigated. The Si nanostructures fabricated using Au nanoparticles show a perfect light absorption with a reflectance below 0.3%. The demonstrated technology can be integrated into common fabrication processes for microelectromechanical systems.

Beschreibung: The combination of scanning tunnelling microscopy (STM) and non-contact atomic force microscopy (nc-AFM) allows enhanced extraction and correlation of properties not readily available via a single imaging mode. We demonstrate this through the characterization and classification of several commonly found defects of the hydrogen-terminated silicon (100)-2 × 1 surface (H–Si(100)-2 × 1) by using six unique imaging modes. The H–Si surface was chosen as it provides a promising platform for the development of atom scale devices, with recent work showing their creation through precise desorption or placement of surface hydrogen atoms. While samples with relatively large areas of the H–Si surface are routinely created using an in situ methodology, surface defects are inevitably formed reducing the area available for patterning. By probing the surface using the different interactivity afforded by either hydrogen- or silicon-terminated tips, we are able to extract new insights regarding the atomic and electronic structure of these defects. This allows for the confirmation of literature assignments of several commonly found defects, as well as proposed classifications of previously unreported and unassigned defects. By combining insights from multiple imaging modes, better understanding of their successes and shortcomings in identifying defect structures and origins is achieved. With this, we take the first steps toward enabling the creation of superior H–Si surfaces through an improved understanding of surface defects, ultimately leading to more consistent and reliable fabrication of atom scale devices.

Beschreibung: A green and facile approach has been developed for the large-scale synthesis of nanosheets of reduced graphene oxide (rGO) and nitrogenated reduced graphene oxide (N-rGO). This has been achieved by direct thermal decomposition of sucrose and glycine at 475 °C in ca. 7 minutes, respectively. The present protocols for synthesizing rGO and N-rGO are simple and environmentally friendly as we do not use any harmful reagents, metal catalysts and solvents. Along with that, this method offers an inexpensive route with high yields to prepare rGO with a high nitrogen content (20–25 atom %). To further improve the properties of the synthesized rGO sheets, hydrogen treatment has been carried out to reduce the oxygen functional groups. Cyclic voltammograms and charge–discharge experiments have been carried out to understand the supercapacitor behavior of rGO and hydrogen treated (H-rGO) samples.

Beschreibung: Indium tin oxide (ITO) is a widely used material for transparent conductive oxide (TCO) films due to its good optical and electrical properties. Improving the optoelectronic properties of ITO films with reduced thickness is crucial and quite challenging. ITO-based multilayer films with an aluminium–silver (Al–Ag) interlayer (ITO/Al–Ag/ITO) and a pure ITO layer (as reference) were prepared by RF and DC sputtering. The microstructural, optical and electrical properties of the ITO/Al–Ag/ITO (IAAI) films were investigated before and after annealing at 400 °C. X-ray diffraction measurements show that the insertion of the Al–Ag intermediate bilayer led to the crystallization of an Ag interlayer even at the as-deposited stage. Peaks attributed to ITO(222), Ag(111) and Al(200) were observed after annealing, indicating an enhancement in crystallinity of the multilayer films. The annealed IAAI film exhibited a remarkable improvement in optical transmittance (86.1%) with a very low sheet resistance of 2.93 Ω/sq. The carrier concentration increased more than twice when the Al–Ag layer was inserted between the ITO layers. The figure of merit of the IAAI multilayer contact has been found to be high at 76.4 × 10−3 Ω−1 compared to a pure ITO contact (69.4 × 10−3 Ω−1). These highly conductive and transparent ITO films with Al–Ag interlayer can be a promising contact for low-resistance optoelectronics devices.

Beschreibung: We have investigated the structural, magnetic and superconduction properties of [Nb(1.5 nm)/Fe(x)]10 superlattices deposited on a thick Nb(50 nm) layer. Our investigation showed that the Nb(50 nm) layer grows epitaxially at 800 °C on the Al2O3(1−102) substrate. Samples grown at this condition possess a high residual resistivity ratio of 15–20. By using neutron reflectometry we show that Fe/Nb superlattices with x

Beschreibung: In a liquid-STM setup environment, the redox behavior of manganese porphyrins was studied at various solid–liquid interfaces. In the presence of a solution of Mn(III)Cl porphyrins in 1-phenyloctane, which was placed at a conductive surface, large and constant additional currents relative to a set tunneling current were observed, which varied with the magnitude of the applied bias voltage. These currents occurred regardless of the type of surface (HOPG or Au(111)) or tip material (PtIr, Au or W). The additional currents were ascribed to the occurrence of redox reactions in which chloride is oxidized to chlorine and the Mn(III) center of the porphyrin moiety is reduced to Mn(II). The resulting Mn(II) porphyrin products were identified by UV–vis analysis of the liquid phase. For solutions of Mn(III) porphyrins with non-redox active acetate instead of chloride axial ligands, the currents remained absent.

Beschreibung: We investigate superconductor–insulator quantum phase transitions in ultrathin capacitively coupled superconducting nanowires with proliferating quantum phase slips. We derive a set of coupled Berezinskii–Kosterlitz–Thouless-like renormalization group equations demonstrating that interaction between quantum phase slips in one of the wires gets modified due to the effect of plasma modes propagating in another wire. As a result, the superconductor–insulator phase transition in each of the wires is controlled not only by its own parameters but also by those of the neighboring wire as well as by mutual capacitance. We argue that superconducting nanowires with properly chosen parameters may turn insulating once they are brought sufficiently close to each other.

Beschreibung: This paper proposes the selective and ultrasensitive detection of Cd(II) ions using a cysteamine-functionalized microcantilever-based sensor with cross-linked ᴅʟ-glyceraldehyde (DL-GC). The detection time for various laboratory-based techniques is generally 12–24 hours. The experiments were performed to create self-assembled monolayers (SAMs) of cysteamine cross-linked with ᴅʟ-glyceraldehyde on the microcantilever surface to selectively capture the targeted Cd(II). The proposed portable microfluidic platform is able to achieve the detection in 20–23 min with a limit of detection (LOD) of 0.56 ng (2.78 pM), which perfectly describes its excellent performance over other reported techniques. Many researchers used nanoparticle-based sensors for the detection of heavy metal ions, but daily increasing usage and commercialization of nanoparticles are rapidly expanding their deleterious effect on human health and the environment. The proposed technique uses a blend of thin-film and microcantilever (micro-electromechanical systems) technology, which mitigate the disadvantages of the nanoparticle approaches, for the selective detection of Cd(II) with a LOD below the WHO limit of 3 μg/L.

Beschreibung: Recently, there has been growing interest in triboelectric nanogenerators (TENGs) that can effectively convert various forms of mechanical energy input into electrical energy. In the present study, a novel Teflon/vitamin B1 powder based triboelectric nanogenerator (TVB-TENG) is proposed. Paper is utilized as a supporting platform for triboelectrification between a commercial Teflon tape and vitamin B1 powder. The measured open-circuit voltage was approximately 340 V. The TVB-TENG can be applied as a humidity sensor and exhibits a linear and reversible response to the relative humidity of the environment. Moreover, the change in relative humidity is also indicated by the change in luminosity of a set of light-emitting diodes (LEDs) integrated in the TVB-TENG system. The TVB-TENG proposed in this study illustrates a cost-effective method for portable power supply and sensing devices.

Beschreibung: Colloidal systems consisting of monodomain superparamagnetic nanoparticles have been used in biomedical applications, such as the hyperthermia treatment for cancer. In this type of colloid, called a nanofluid, the nanoparticles tend to agglomeration. It has been shown experimentally that the nanoparticle coating plays an important role in the nanoparticle dispersion stability and biocompatibility. However, theoretical studies in this field are lacking. In addition, the ways in which the nanoparticle coating influences the magnetic properties of the nanoparticles are not yet understood. In order to fill in this gap, this study presents a numerical simulation model that elucidates how the nanoparticle coating affects the nanoparticle agglomeration tendency as well as the effective magnetic relaxation time of the system. To simulate the self-organization of the colloidal nanoparticles, a stochastic Langevin dynamics method was applied based on the effective Verlet-type algorithm. The Néel magnetic relaxation time was obtained via the Coffey method in an oblique magnetic field, adapted to the local magnetic field on a nanoparticle.

Beschreibung: A novel surface morphology for pipelines using transverse microgrooves was proposed in order to reduce the pressure loss of fluid transport. Numerical simulation and experimental research efforts were undertaken to evaluate the drag reduction performance of these bionic pipelines. It was found that the vortex ‘cushioning’ and ‘driving’ effects produced by the vortexes in the microgrooves were the main reason for obtaining a drag reduction effect. The shear stress of the microgrooved surface was reduced significantly owing to the decline of the velocity gradient. Altogether, bionic pipelines achieved drag reduction effects both in a pipeline and in a concentric annulus flow model. The primary and secondary order of effect on the drag reduction and optimal microgroove geometric parameters were obtained by an orthogonal analysis method. The comparative experiments were conducted in a water tunnel, and a maximum drag reduction rate of 3.21% could be achieved. The numerical simulation and experimental results were cross-checked and found to be consistent with each other, allowing to verify that the utilization of bionic theory to reduce the pressure loss of fluid transport is feasible. These results can provide theoretical guidance to save energy in pipeline transportations.

Beschreibung: High permittivity and breakdown strength are desired to improve the energy storage density of dielectric materials based on reinforced polymer composites. This article presents the synthesis of polythiophene-encapsulated BaTiO3 (BTO-PTh) nanoparticles via an in situ Cu(II)-catalyzed chemical oxidative polymerization of thiophene monomer on hydrothermally obtained tetragonal BTO nanocrystals. The formed core–shell-type BTO-PTh nanoparticles exhibit excellent dielectric properties with high permittivity (25.2) and low loss (0.04) at high frequency (106 Hz). A thick PTh encapsulation layer on the surface of the BTO nanoparticles improves their breakdown strength from 47 to 144 kV/mm and the energy storage density from 0.32 to 2.48 J/cm3. A 7.75-fold increase in the energy storage density of the BTO-PTh nanoparticles is attributed to simultaneously high permittivity and breakdown strength, which are excellent for potential energy storage applications.

Beschreibung: When considering a Li-intercalated hexagonal boron nitride bilayer (Li-hBN), the vertex corrections of electron–phonon interaction cannot be omitted. This is evidenced by the very high value of the ratio λωD/εF ≈ 0.46, where λ is the electron–phonon coupling constant, ωD is the Debye frequency, and εF represents the Fermi energy. Due to nonadiabatic effects, the phonon–induced superconducting state in Li-hBN is characterized by much lower values of the critical temperature (T LOVC C ∈ {19.1, 15.5, 11.8} K, for μ* ∈ {0.1, 0.14, 0.2}, respectively) than would result from calculations not taking this effect into account (T ME C∈ {31.9, 26.9, 21} K). From the technological point of view, the low value of T C limits the possible applications of Li-hBN. The calculations were carried out under the classic Migdal–Eliashberg formalism (ME) and the Eliashberg theory with lowest-order vertex corrections (LOVC). We show that the vertex corrections of higher order (λ3) lower the value of T LOVC C by a few percent.

Beschreibung: Multilayer capsules have been of great interest for scientists and medical communities in multidisciplinary fields of research, such as drug delivery, sensing, biomedicine, theranostics and gene therapy. The most essential attributes of a drug delivery system are considered to be multi-functionality and stimuli responsiveness against a range of external and internal stimuli. Apart from the highly explored strong polyelectrolytes, weak polyelectrolytes offer great versatility with a highly controllable architecture, unique stimuli responsiveness and easy tuning of the properties for intracellular delivery of cargo. This review describes the progress in the preparation, functionalization and applications of capsules made of weak polyelectrolytes or their combination with biopolymers. The selection of a sacrificial template for capsule formation, the driving forces involved, the encapsulation of a variety of cargo and release based on different internal and external stimuli have also been addressed. We describe recent perspectives and obstacles of weak polyelectrolyte/biopolymer systems in applications such as therapeutics, biosensing, bioimaging, bioreactors, vaccination, tissue engineering and gene delivery. This review gives an emerging outlook on the advantages and unique responsiveness of weak polyelectrolyte based systems that can enable their widespread use in potential applications.

Beschreibung: Biomass-derived carbon dots (CDs) are biocompatible and have potential for a variety of applications, including bioimaging and biosensing. In this work, we use ground soybean residuals to synthesize carbon nanoparticles by hydrothermal carbonization (HTC), annealing at high temperature, and laser ablation (LA) in a NH4OH solution. The carbon nanoparticles synthesized with the HTC process (HTC-CDs) exhibit photoluminescent characteristics with strong blue emission. The annealing of the HTC-processed carbon particles in the range of 250 to 850 °C causes a loss of the photoluminescent characteristics of the CDs without any significant change in the microstructure (amorphous structure) of the carbon particles. The LA processing of the annealed HTC-processed carbon particles introduces nitrogen-containing surface-functional groups and leads to the recovery of the photoluminescent features that are different from those of the HTC-CDs and dependent on the fraction of nitrogen in the surface-functional groups. The photoluminescence of both the HTC-CDs and LA-CDs is largely due to the presence of N-containing surface-functional groups. The quantum yield of the LA-CDs is more constant than that of the HTC-CDs under continuous UV excitation and does not exhibit a significant reduction after 150 min of excitation. The methods used in this work provide a simple and green strategy to introduce N-surface-functional groups to carbon nanoparticles made from biomass and biowaste and to produce stable photoluminescent CDs with excellent water-wettability.

Beschreibung: Ordered carbon/graphene composite nanofibers (CGCNFs) with different porous configurations were used as a material to fabricate supercapacitor electrodes. These nanofibers were synthesized by applying a modified parallel electrode to the electrospinning method (MPEM) in order to generate electrospun polyacrylonitrile (PAN) nanofibers containing graphene. After synthesis, these fibers were submitted to carbonization under a N2 atmosphere at 1100 °C. The influence of the ordering and porosity of CGCNFs on their electrochemical performance was studied. The results showed that by adding deionized water to the spinning solution one could increase the number of mesopores and the specific surface area of CGCNFs, thereby significantly increasing their specific capacitance. In addition, the ordering of CGCNFs within the electrode improved the electron transfer efficiency, resulting in a higher specific capacitance.

Beschreibung: In this work, we report on the integration of an atomic force microscope (AFM) into a helium ion microscope (HIM). The HIM is a powerful instrument, capable of imaging and machining of nanoscale structures with sub-nanometer resolution, while the AFM is a well-established versatile tool for multiparametric nanoscale characterization. Combining the two techniques opens the way for unprecedented in situ correlative analysis at the nanoscale. Nanomachining and analysis can be performed without contamination of the sample and environmental changes between processing steps. The practicality of the resulting tool lies in the complementarity of the two techniques. The AFM offers not only true 3D topography maps, something the HIM can only provide in an indirect way, but also allows for nanomechanical property mapping, as well as for electrical and magnetic characterization of the sample after focused ion beam materials modification with the HIM. The experimental setup is described and evaluated through a series of correlative experiments, demonstrating the feasibility of the integration.

Beschreibung: A small water-soluble phosphorus-containing dendrimer was engineered for the complexation of gold(I) and for its reduction under mild conditions. Gold nanoparticles were obtained as colloidal suspensions simply and only when the powdered form of this dendrimer was dissolved in water, as shown by transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDX) analyses. The dendrimers acted simultaneously as mild reducers and as nanoreactors, favoring the self-assembly of gold atoms and promoting the growth and stabilization of isolated gold nanoparticles. Thus, an unprecedented method for the synthesis of colloidal suspensions of water-soluble gold nanoparticles was proposed in this work.

Beschreibung: Currently, the patterning of innovative three-dimensional (3D) nano-objects is required for the development of future advanced electronic components. Helium ion microscopy in combination with a precursor gas can be used for direct writing of three-dimensional nanostructures with a precise control of their geometry, and a significantly higher aspect ratio than other additive manufacturing technologies. We report here on the deposition of 3D hollow tungsten carbide nanowires with tailored diameters by tuning two key growth parameters, namely current and dose of the ion beam. Our results show the control of geometry in 3D hollow nanowires, with outer and inner diameters ranging from 36 to 142 nm and from 5 to 28 nm, respectively; and lengths from 0.5 to 8.9 µm. Transmission electron microscopy experiments indicate that the nanowires have a microstructure of large grains with a crystalline structure compatible with the face-centered cubic WC1− x phase. In addition, 3D electron tomographic reconstructions show that the hollow center of the nanowires is present along the whole nanowire length. Moreover, these nanowires become superconducting at 6.8 K and show high values of critical magnetic field and critical current density. Consequently, these 3D nano-objects could be implemented as components in the next generation of electronics, such as nano-antennas and sensors, based on 3D superconducting architectures.

Beschreibung: An aluminium Josephson junction (JJ), with a critical current suppressed by a factor of three compared with the maximal value calculated from the gap, is experimentally investigated for application as a threshold detector for microwave photons. We present the preliminary results of measurements of the lifetime of the superconducting state and the probability of switching by a 9 GHz external signal. We found an anomalously large lifetime, not described by the Kramers’ theory for the escape time over a barrier under the influence of fluctuations. We explain it by the phase diffusion regime, which is evident from the temperature dependence of the switching current histograms. Therefore, phase diffusion allows for a significant improvement of the noise immunity of a device, radically decreasing the dark count rate, but it will also decrease the single-photon sensitivity of the considered threshold detector. Quantization of the switching probability tilt as a function of the signal attenuation for various bias currents through the JJ is observed, which resembles the differentiation between N and N + 1 photon absorption.

Beschreibung: A series of Zn1− x Mg x O thin films with the composition range x = 0.00–0.40 has been prepared by sol–gel spin coating on Si substrates with a post-deposition thermal treatment in the temperature range of 400–650 °C. The morphology of the films was investigated by scanning electron microscopy and atomic force microscopy while their light emission properties were studied by photoluminescence spectroscopy under excitation at 325 nm. It was found that annealing at 500 °C leads to the production of macroscopically homogeneous wurtzite phase films, while thermal treatment at higher or lower temperature results in the degradation of the morphology, or in the formation of ZnO particles embedded into the ZnMgO matrix, respectively. Local compositional fluctuations leading to the formation of deep band tails in the gap were deduced from photoluminescence spectra. A model for the band tail distribution in the bandgap is proposed as a function of the alloy composition. Thin films were also prepared by aerosol spray pyrolysis deposition using the same sol–gel precursors for the purpose of comparison. The prepared films were tested for photodetector applications.

Beschreibung: Calcite and magnesite are important mineral constituents of the earth’s crust. In aqueous environments, these carbonates typically expose their most stable cleavage plane, the (10.4) surface. It is known that these surfaces interact with a large variety of organic molecules, which can result in surface restructuring. This process is decisive for the formation of biominerals. With the development of 3D atomic force microscopy (AFM) it is now possible to image solid–liquid interfaces with unprecedented molecular resolution. However, the majority of 3D AFM studies have been focused on the arrangement of water at carbonate surfaces. Here, we present an analysis of the assembly of ethanol – an organic molecule with a single hydroxy group – at the calcite and magnesite (10.4) surfaces by using high-resolution 3D AFM and molecular dynamics (MD) simulations. Within a single AFM data set we are able to resolve both the first laterally ordered solvation layer of ethanol on the calcite surface as well as the following solvation layers that show no lateral order. Our experimental results are in excellent agreement with MD simulations. The qualitative difference in the lateral order can be understood by the differing chemical environment: While the first layer adopts specific binding positions on the ionic carbonate surface, the second layer resides on top of the organic ethyl layer. A comparison of calcite and magnesite reveals a qualitatively similar ethanol arrangement on both carbonates, indicating the general nature of this finding.

Beschreibung: Ag-based plasmonic nanostructures were manufactured by thermal annealing of thin metallic films. Structure and morphology were studied using scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HR-TEM) and X-ray photoelectron spectroscopy (XPS). SEM images show that the formation of nanostructures is influenced by the initial layer thickness as well as the temperature and the time of annealing. The Ag 3d and Ag 4d XPS spectra are characteristic of nanostructures. The quality of the nanostructures, in terms of their use as plasmonic platforms, is reflected in the UV–vis absorption spectra. The absorption spectrum is dominated by a maximum in the range of 450–500 nm associated with the plasmon resonance. As the initial layer thickness increases, an additional peak appears around 350 nm, which probably corresponds to the quadrupole resonance. For calculations leading to a better illustration of absorption, scattering and overall absorption of light in Ag nanoparticles, the Mie theory is employed. Absorbance and the distribution of the electromagnetic field around the nanostructures are calculated by finite-difference time-domain (FDTD) simulations. For calculations a novel approach based on modelling the whole sample with a realistic shape of the nanoparticles, instead of full spheres, was used. This led to a very good agreement with the experiment.

Beschreibung: For the first time, stable pillar[5]arene/Ag+ nanoparticles, consisting of water-soluble pillar[5]arene containing γ-sulfobetaine fragments and Ag+ ions without Ag–Ag bonds, were synthesized and characterized. The pillar[5]arene/Ag+ (ratio 1:10) nanoparticles obtained were cubic with a rib length of 100 nm and are less cytotoxic than Ag+ ions. The survival of the A549 model cells in the presence of pillar[5]arene/Ag+ (1:10) nanoparticles at a concentration of 30 and 40 μM was 76% and 55%, while in the absence of pillar[5]arene, the cell survival for free Ag+ ions at the same concentration was 30% and 10%, respectively. The results can be used to create new antibacterial materials and 2D biomedical coatings.

Beschreibung: Cuttlefish bones are an inexpensive source of calcium carbonate, which are produced in large amounts by the marine food industry, leading to environmental contamination and waste. The nontoxicity, worldwide availability and low production cost of cuttlefish bone products makes them an excellent calcium carbonate precursor for the fabrication of hydroxyapatite. In the present study, a novel oil-bath-mediated precipitation method was introduced for the synthesis of hydroxyapatite (Hap) nanorods using cuttlefish bone powder as a precursor (CB-Hap NRs). The obtained CB-Hap NRs were investigated using transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and thermogravimetric analysis (TGA) techniques to evaluate their physicochemical properties. The crystallite size (20.86 nm) obtained from XRD data and the elemental analysis (Ca/P molar ratio was estimated to be 1.6) showed that the Hap NRs are similar to that of natural human bone (≈1.67). Moreover, the FTIR data confirmed the presence of phosphate as a functional group and the TGA data revealed the thermal stability of Hap NRs. In addition, the antibacterial study showed a significant inhibitory effect of CB-Hap NRs against S. aureus (zone of inhibition – 14.5 ± 0.5 mm) and E. coli (13 ± 0.5 mm), whereas the blood compatibility test showed that the CB-Hap NRs exhibited a concentration-mediated hemolytic effect. These biogenic CB-Hap NRs with improved physicochemical properties, blood compatibility and antibacterial efficacy could be highly beneficial for orthopedic applications in the future.

Beschreibung: In this study, a new nanoporous material comprising NiMoO4 nanorods and Co3O4 nanoparticles derived from ZIF-67 supported by a cellulose-based carbon aerogel (CA) has been successfully synthesized using a two-step hydrothermal method. Due to its chemical composition, the large specific surface and the hierarchical porous structure, the NiMoO4@Co3O4/CA ternary composite yields electrodes with an enhanced specific capacitance of 436.9 C/g at a current density of 0.5 A/g and an excellent rate capability of 70.7% capacitance retention at 5.0 A/g. Moreover, an advanced asymmetric supercapacitor (ASC) is assembled using the NiMoO4@Co3O4/CA ternary composite as the positive electrode and activated carbon as the negative electrode. The ASC device exhibits a large capacitance of 125.4 F/g at 0.5 A/g, a maximum energy density of 34.1 Wh/kg at a power density of 208.8 W/kg as well as a good cyclic stability (84% after 2000 cycles), indicating its wide applicability in energy storage. Finally, our results provide a general approach to the construction of CA and MOF-based composite materials with hierarchical porous structure for potential applications in supercapacitors.

Beschreibung: Background: Quantum dots connected to larger systems containing a continuum of states like charge reservoirs allow the theoretical study of many-body effects such as the Coulomb blockade and the Kondo effect. Results: Here, we analyze the nonequilibrium Kondo effect and transport phenomena in a quantum dot coupled to pure monolayer graphene electrodes under external magnetic fields for finite on-site Coulomb interaction. The system is described by the pseudogap Anderson Hamiltonian. We use the equation of motion technique to determine the retarded Green’s function of the quantum dot. An analytical formula for the Kondo temperature is derived for electron and hole doping of the graphene leads. The Kondo temperature vanishes in the vicinity of the particle–hole symmetry point and at the Dirac point. In the case of particle–hole asymmetry, the Kondo temperature has a finite value even at the Dirac point. The influence of the on-site Coulomb interaction and the magnetic field on the transport properties of the system shows a tendency similar to the previous results obtained for quantum dots connected to metallic electrodes. Most remarkably, we find that the Kondo resonance does not show up in the density of states and in the differential conductance for zero chemical potential due to the linear energy dispersion of graphene. An analytical method to calculate self-energies is also developed which can be useful in the study of graphene-based systems. Conclusion: Our graphene-based quantum dot system provides a platform for potential applications of nanoelectronics. Furthermore, we also propose an experimental setup for performing measurements in order to verify our model.

Beschreibung: Inorganic hollow spheres find a growing number of applications in many fields, including catalysis and solar cells. Hence, a simple fabrication method with a low number of simple steps is desired, which would allow for good control over the structural features and physicochemical properties of titania hollow spheres modified with noble metal nanoparticles. A simple method employing sol–gel coating of nanoparticles with titania followed by controlled silver diffusion was developed and applied for the synthesis of Ag-modified hollow TiO2 spheres. The morphology of the synthesized structures and their chemical composition was investigated using SEM and X-ray photoelectron spectroscopy, respectively. The optical properties of the synthesized structures were characterized using UV–vis spectroscopy. Ag–TiO2 hollow nanostructures with different optical properties were prepared simply by a change of the annealing time in the last fabrication step. The synthesized nanostructures exhibit a broadband optical absorption in the UV–vis range.

Beschreibung: Roughening by anisotropic etching of N-face gallium nitride is the key aspect in today’s production of blue and white light emitting diodes (LEDs). Both surface area and number of surface angles are increased, facilitating light outcoupling from the LED chip. The structure of a GaN layer stack grown by metal organic chemical vapour deposition (MOCVD) was varied in the unintentionally doped u-GaN bulk region. Different sequences of 2D and 3D grown layers led to a variation in dislocation density, which was monitored by photoluminescence microscopy (PLM) and X-ray diffraction (XRD). Thin-film processing including laser lift off (LLO) was applied. The influence of epitaxial changes on the N-face etch kinetics was determined in aqueous KOH solution at elevated temperature. Inductively-coupled plasma optical emission spectroscopy (ICP-OES) was used to measure the etch progress in small time increments with high precision. Thereby, the disadvantages of other techniques such as determination of weight loss or height difference were overcome, achieving high accuracy and reproducibility.

Beschreibung: Layered materials, such as MoS2, are being intensely studied due to their interesting properties and wide variety of potential applications. These materials are also interesting as supports for low-dimensional metals for catalysis, while recent work has shown increased interest in using 2D materials in the electronics industry as a Cu diffusion barrier in semiconductor device interconnects. The interaction between different metal structures and MoS2 monolayers is therefore of significant importance and first-principles simulations can probe aspects of this interaction not easily accessible to experiment. Previous theoretical studies have focused particularly on the adsorption of a range of metallic elements, including first-row transition metals, as well as Ag and Au. However, most studies have examined single-atom adsorption or adsorbed nanoparticles of noble metals. This means there is a knowledge gap in terms of thin film nucleation on 2D materials. To begin addressing this issue, we present in this paper a first-principles density functional theory (DFT) study of the adsorption of small Cu n (n = 1–4) structures on 2D MoS2 as a model system. We find on a perfect MoS2 monolayer that a single Cu atom prefers an adsorption site above the Mo atom. With increasing nanocluster size the nanocluster binds more strongly when Cu atoms adsorb atop the S atoms. Stability is driven by the number of Cu–Cu interactions and the distance between adsorption sites, with no obvious preference towards 2D or 3D structures. The introduction of a single S vacancy in the monolayer enhances the copper binding energy, although some Cu n nanoclusters are actually unstable. The effect of the vacancy is localised around the vacancy site. Finally, on both the pristine and the defective MoS2 monolayer, the density-of-states analysis shows that the adsorption of Cu introduces new electronic states as a result of partial Cu oxidation, but the metallic character of Cu nanoclusters is preserved.

Beschreibung: The possibility of detecting genetic mutations rapidly in physiological media through liquid biopsy has attracted the attention within the materials science community. The physical properties of nanoparticles combined with robust transduction methods ensure an improved sensitivity and specificity of a given assay and its implementation into point-of-care devices for common use. Covering the last twenty years, this review gives an overview of the state-of-the-art of the research on the use of gold nanoparticles in the development of colorimetric biosensors for the detection of single-nucleotide polymorphism as cancer biomarker. We discuss the main mechanisms of the assays that either are assisted by DNA-based molecular machines or by enzymatic reactions, summarize their performance and provide an outlook towards future developments.

Beschreibung: Photodynamic therapy is a technique already used in ophthalmology or oncology. It is based on the local production of reactive oxygen species through an energy transfer from an excited photosensitizer to oxygen present in the biological tissue. This review first presents an update, mainly covering the last five years, regarding the block copolymers used as nanovectors for the delivery of the photosensitizer. In particular, we describe the chemical nature and structure of the block copolymers showing a very large range of existing systems, spanning from natural polymers such as proteins or polysaccharides to synthetic ones such as polyesters or polyacrylates. A second part focuses on important parameters for their design and the improvement of their efficiency. Finally, particular attention has been paid to the question of nanocarrier internalization and interaction with membranes (both biomimetic and cellular), and the importance of intracellular targeting has been addressed.

Beschreibung: Since the manipulation of particles using atomic force microscopy is not observable in real-time, modeling the manipulation process is of notable importance, enabling us to investigate the dynamical behavior of nanoparticles. To model this process, previous studies employed classical continuum mechanics and molecular dynamics simulations which had certain limitations; the former does not consider size effects at the nanoscale while the latter is time consuming and faces computational restrictions. To optimize accuracy and computational costs, a new nonclassical modeling of the nanomanipulation process based on the modified couple stress theory is proposed that includes the size effects. To this end, after simulating the critical times and forces that are required for the onset of nanoparticle motion on the substrate, along with the dominant motion mode, the nonclassical theory of continuum mechanics and a developed von Mises yield criterion are employed to investigate the dynamical behavior of a cylindrical gold nanoparticle during manipulation. Timoshenko and Euler–Bernoulli beam theories based on the modified couple stress theory are used to model the dynamics of cylindrical gold nanoparticles while the finite element method is utilized to solve the governing equations of motion. The results show a difference of 90% between the classical and nonclassical models in predicting the maximum deflection before the beginning of the dominant mode and a difference of more than 25% in the dynamic modeling of a 200 nm manipulation of a gold nanoparticle with a length of 25 µm and aspect ratio of 30. This difference increases with each increment of the aspect ratio and reduction of manipulation distance. Furthermore, by applying an extended von Mises criterion on the modified couple stress theory, it is found that the failure aspect ratio of a cylindrical gold nanoparticle based on nonclassical models is 212% more than that of the classical model. In the end, the results are compared with those of the classical method on polystyrene nanorods. The results for cylindrical gold nanoparticles indicate that the material length scale has a major effect on the exact positioning of cylindrical nanoparticles.

Beschreibung: The Lycurgus cup is an ancient glass artefact that shows dichroism as it looks green when a white light is reflected on it and a red colouring appears when a white light is transmitted through it. This peculiar dichroic effect is due to silver and gold nanoparticles present in the glass. In this research we show the synthesis of dichroic silver nanoparticles and their embedding in a 3D printable nanocomposite. The addition of gold nanoparticles to the silver nanoparticle composite, gave a 3D printable nanocomposite with the same dichroism effect of the Lycurgus cup.

Beschreibung: We realized integrated photonics multi-waveguide devices for optical trapping and Raman spectroscopy of particles in a fluid. In these devices, multiple beams directed towards the device center lead to a local field enhancement around this center and thus counteract the effect of light concentration near the facets, which is a disadvantage of dual-waveguide traps. Thus, a trapping region is created around the center, where a single particle of a size in a wide range can be trapped and studied spectroscopically, free from the influence of surfaces. We report the design (including simulations), fabrication and performance demonstration for multi-waveguide devices, using our Si3N4 waveguiding platform as the basis. The designed ridge waveguides, optimized for trapping and Raman spectroscopy, emit narrow beams. Multiple waveguides arranged around the central microbath result from fanning out of a single input waveguide using Y-splitters. A second waveguiding layer is implemented for detection of light scattered by the trapped particle. For reliable filling of the device with sample fluid, microfluidic considerations lead to side channels of the microbath, to exploit capillary forces. The interference of the multiple beams produces an array of hot spots around the bath center, each forming a local trap. This property is clearly confirmed in the experiments and is registered in videos. We demonstrate the performance of a 2-waveguide and a 16-waveguide device, using 1 and 3 μm polystyrene beads. Study of the confined Brownian motion of the trapped beads yields experimental values of the normalized trap stiffness for the in-plane directions. The stiffness values for the 16-waveguide device are comparable to those of tightly focused Gaussian beam traps and are confirmed by our own simulations. The Raman spectra of the beads (in this work measured via an objective) show clear peaks that are characteristic of polystyrene. In the low-wavenumber range, the spectra have a background that most likely originates from the Si3N4 waveguides.

Beschreibung: We calculate the current–phase relation (CPR) of a SN-S-SN Josephson junction based on a SN bilayer of variable thickness composed of a highly disordered superconductor (S) and a low-resistivity normal metal (N) with proximity-induced superconductivity. In such a junction, the N layer provides both a large concentration of phase in the weak link and good heat dissipation. We find that when the thickness of the S and the N layer and the length of the S constriction are about the superconducting coherence length the CPR is single-valued and can be close to a sinusoidal shape. The product I c R n can reach Δ(0)/2|e| (I c is the critical current of the junction, R n is its normal-state resistance, Δ(0) is the superconductor gap of a single S layer at zero temperature). Our calculations show, that the proper choice of the thickness of the N layer leads both to nonhysteretic current–voltage characteristics even at low temperatures and a relatively large product I c R n.

Beschreibung: Nanoparticles tend to agglomerate. The process of agglomeration is ruled by thermodynamics. Depending on the sign of the enthalpy of interaction, ensembles consist of (repelling) poorly agglomerated or (attracting) highly agglomerated particles. For these two cases different distribution functions for the agglomerates were found. The size distribution of the agglomerates is ruled by the maximum of the entropy of the ensemble of agglomerates, which is calculated using Gibbs formula of entropy. The exact determination of the size distribution of the agglomerates also gives the maximum size of the agglomerates. These considerations lead to an improved understanding of ensembles of agglomerated nanoparticles.

Beschreibung: Single-layer vanadium nitride (VN) and bilayer Pd0.96Fe0.04/VN and VN/Pd0.92Fe0.08 thin-film heterostructures for possible spintronics applications were synthesized on (001)-oriented single-crystalline magnesium oxide (MgO) substrates utilizing a four-chamber ultrahigh vacuum deposition and analysis system. The VN layers were reactively magnetron sputtered from a metallic vanadium target in Ar/N2 plasma, while the Pd1− x Fe x layers were deposited by co-evaporation of metallic Pd and Fe pellets from calibrated effusion cells in a molecular beam epitaxy chamber. The VN stoichiometry and Pd1− x Fe x composition were controlled by X-ray photoelectron spectroscopy. In situ low-energy electron diffraction and ex situ X-ray diffraction show that the 30 nm thick single-layer VN as well as the double-layer VN(30 nm)/Pd0.92Fe0.08(12 nm) and Pd0.96Fe0.04(20 nm)/VN(30 nm) structures have grown cube-on-cube epitaxially. Electric resistance measurements demonstrate a metallic-type temperature dependence for the VN film with a small residual resistivity of 9 μΩ·cm at 10 K, indicating high purity and structural quality of the film. The transition to the superconducting state was observed at 7.7 K for the VN film, at 7.2 K for the Pd0.96Fe0.04/VN structure and at 6.1 K for the VN/Pd0.92Fe0.08 structure with the critical temperature decreasing due to the proximity effect. Contrary to expectations, all transitions were very sharp with the width ranging from 25 mK for the VN film to 50 mK for the VN/Pd0.92Fe0.08 structure. We propose epitaxial single-crystalline thin films of VN and heteroepitaxial Pd1− x Fe x /VN and VN/Pd1− x Fe x (x ≤ 0.08) structures grown on MgO(001) as the materials of a choice for the improvement of superconducting magnetic random access memory characteristics.

Beschreibung: Covalent triazine frameworks (CTFs) are little investigated, albeit they are promising candidates for electrocatalysis, especially for the oxygen evolution reaction (OER). In this work, nickel nanoparticles (from Ni(COD)2) were supported on CTF-1 materials, which were synthesized from 1,4-dicyanobenzene at 400 °C and 600 °C by the ionothermal method. CTF-1-600 and Ni/CTF-1-600 show high catalytic activity towards OER and a clear activity for the electrochemical oxygen reduction reaction (ORR). Ni/CTF-1-600 requires 374 mV overpotential in OER to reach 10 mA/cm2, which outperforms the benchmark RuO2 catalyst, which requires 403 mV under the same conditions. Ni/CTF-1-600 displays an OER catalytic activity comparable with many nickel-based electrocatalysts and is a potential candidate for OER. The same Ni/CTF-1-600 material shows a half-wave potential of 0.775 V for ORR, which is slightly lower than that of commercial Pt/C (0.890 V). Additionally, after accelerated durability tests of 2000 cycles, the material showed only a slight decrease in activity towards both OER and ORR, demonstrating its superior stability.

Beschreibung: Structural colours have received a lot of attention regarding the reproduction of the vivid colours found in nature. In this study, metal–anodic aluminium oxide (AAO)–Al nanostructures were deposited using a two-step anodization and sputtering process to produce self-ordered anodic aluminium oxide films and a metal layer (8 nm Cr and 25, 17.5 and 10 nm of Au), respectively. AAO films of different thickness were anodized and the Yxy values (Y is the luminance value, and x and y are the chromaticity values) were obtained via reflectance measurements. An empirical model based on the thickness and porosity of the nanostructures was determined, which describes a gamut of colours. The proposed mathematical model can be applied in different fields, such as wavelength absorbers, RGB (red, green, blue) display devices, as well as chemical or optical sensors.

Beschreibung: Phonon dynamics is explored in mechanically exfoliated two-dimensional WSe2 using temperature-dependent and laser-power-dependent Raman and photoluminescence (PL) spectroscopy. From this analysis, phonon lifetime in the Raman active modes and phonon concentration, as correlated to the energy parameter E 0, were calculated as a function of the laser power, P, and substrate temperature, T. For monolayer WSe2, from the power dependence it was determined that the phonon lifetime for the in-plane vibrational mode was twice that of the out-of-plane vibrational mode for P in the range from 0.308 mW up to 3.35 mW. On the other hand, the corresponding relationship for the temperature analysis showed that the phonon lifetime for the in-plane vibrational mode lies within 1.42× to 1.90× that of the out-of-plane vibrational mode over T = 79 K up to 523 K. To provide energy from external stimuli, as T and P were increased, peak broadening in the PL spectra of the A-exciton was observed. From this, a phonon concentration was tabulated using the Urbach formulism, which increased with increasing T and P; consequently, the phonon lifetime was found to decrease. Although phonon lifetime decreased with increasing temperature for all thicknesses, the decay rate in the phonon lifetime in the monolayer (1L) material was found to be 2× lower compared to the bulk. We invoke a harmonic oscillator model to explain the damping mechanism in WSe2. From this it was determined that the damping coefficient increases with the number of layers. The work reported here sheds fundamental insights into the evolution of phonon dynamics in WSe2 and should help pave the way for designing high-performance electronic, optoelectronic and thermoelectric devices in the future.

Beschreibung: Cost-efficiency, durability, and reliability of catalysts, as well as their operational lifetime, are the main challenges in chemical energy conversion. Here, we present a novel, one-step approach for the synthesis of Pt/C hybrid material by plasma-enhanced chemical vapor deposition (PE-CVD). The platinum loading, degree of oxidation, and the very narrow particle size distribution are precisely adjusted in the Pt/C hybrid material due to the simultaneous deposition of platinum and carbon during the process. The as-synthesized Pt/C hybrid materials are promising electrocatalysts for use in fuel cell applications as they show significantly improved electrochemical long-term stability compared to the industrial standard HiSPEC 4000. The PE-CVD process is furthermore expected to be extendable to the general deposition of metal-containing carbon materials from other commercially available metal acetylacetonate precursors.

Beschreibung: Nano-sized materials have great potential as drug carriers for nanomedicine applications. Thanks to their size, they can exploit the cellular machinery to enter cells and be trafficked intracellularly, thus they can be used to overcome some of the cellular barriers to drug delivery. Nano-sized drug carriers of very different properties can be prepared, and their surface can be modified by the addition of targeting moieties to recognize specific cells. However, it is still difficult to understand how the material properties affect the subsequent interactions and outcomes at cellular level. As a consequence of this, designing targeted drugs remains a major challenge in drug delivery. Within this context, we discuss the current understanding of the initial steps in the interactions of nano-sized materials with cells in relation to nanomedicine applications. In particular, we focus on the difficult interplay between the initial adhesion of nano-sized materials to the cell surface, the potential recognition by cell receptors, and the subsequent mechanisms cells use to internalize them. The factors affecting these initial events are discussed. Then, we briefly describe the different pathways of endocytosis in cells and illustrate with some examples the challenges in understanding how nanomaterial properties, such as size, charge, and shape, affect the mechanisms cells use for their internalization. Technical difficulties in characterizing these mechanisms are presented. A better understanding of the first interactions of nano-sized materials with cells will help to design nanomedicines with improved targeting.

Beschreibung: In today’s modern era of medicine, macromolecular compounds such as proteins, peptides and nucleic acids are dethroning small molecules as leading therapeutics. Given their immense potential, they are highly sought after. However, their application is limited mostly due to their poor in vivo stability, limited cellular uptake and insufficient target specificity. Cell-penetrating peptides (CPPs) represent a major breakthrough for the transport of macromolecules. They have been shown to successfully deliver proteins, peptides, siRNAs and pDNA in different cell types. In general, CPPs are basic peptides with a positive charge at physiological pH. They are able to translocate membranes and gain entry to the cell interior. Nevertheless, the mechanism they use to enter cells still remains an unsolved piece of the puzzle. Endocytosis and direct penetration have been suggested as the two major mechanisms used for internalization, however, it is not all black and white in the nanoworld. Studies have shown that several CPPs are able to induce and shift between different uptake mechanisms depending on their concentration, cargo or the cell line used. This review will focus on the major internalization pathways CPPs exploit, their characteristics and regulation, as well as some of the factors that influence the cellular uptake mechanism.

Beschreibung: Rubrene (C42H28) was adsorbed with submonolayer coverage on Pt(111), Au(111), and graphene-covered Pt(111). Adsorption phases and vibronic properties of C42H28 consistently reflect the progressive reduction of the molecule–substrate hybridization. Separate C42H28 clusters are observed on Pt(111) as well as broad molecular resonances. On Au(111) and graphene-covered Pt(111) compact molecular islands with similar unit cells of the superstructure characterize the adsorption phase. The highest occupied molecular orbital of C42H28 on Au(111) exhibits weak vibronic progression while unoccupied molecular resonances appear with a broad line shape. In contrast, vibronic subbands are present for both frontier orbitals of C42H28 on graphene. They are due to different molecular vibrational quanta with distinct Huang–Rhys factors.

Beschreibung: We present the trapping and manipulation of a single nano-object in an aqueous medium by optically induced temporally varying temperature gradients. By real-time object tracking and control of the position of the heating laser focus, we can precisely employ thermophoretic drift to oppose the random diffusive motion. As a result, a nano-object is confined in a micrometer-sized trap. Numerical modeling gives a quantitative prediction of the effect. Traps can be dynamically created and relocated, which we demonstrate by the controlled independent manipulation of two nanoparticles.

Beschreibung: There is an increasing interest in the use of plant viruses as vehicles for anti-cancer therapy. In particular, the plant virus brome mosaic virus (BMV) and cowpea chlorotic mottle virus (CCMV) are novel potential nanocarriers for different therapies in nanomedicine. In this work, BMV and CCMV were loaded with a fluorophore and assayed on breast tumor cells. The viruses BMV and CCMV were internalized into breast tumor cells. Both viruses, BMV and CCMV, did not show cytotoxic effects on tumor cells in vitro. However, only BMV did not activate macrophages in vitro. This suggests that BMV is less immunogenic and may be a potential carrier for therapy delivery in tumor cells. Furthermore, BMV virus-like particles (VLPs) were efficiently loaded with small interfering RNA (siRNA) without packaging signal. The gene silencing was demonstrated by VLPs loaded with siGFP and tested on breast tumor cells that constitutively express the green fluorescent protein (GPF). After VLP-siGFP treatment, GFP expression was efficiently inhibited corroborating the cargo release inside tumor cells and the gene silencing. In addition, BMV VLP carring siAkt1 inhibited the tumor growth in mice. These results show the attractive potential of plant virus VLPs to deliver molecular therapy to tumor cells with low immunogenic response.

Beschreibung: Inorganic semiconductor oxides loaded on composite nanofibers (CNFs) have been widely applied in environmental monitoring, industry, aviation, and transportation. In this paper, heterostructured CuO–ZnO-loaded CNF membranes (CNFMs) were prepared successfully by a combination of electrospinning, heat treatment, and hydrothermal synthesis. The influence of the synthesis parameters on morphology, structure, and properties of the CNFMs was investigated, and the optimal process parameters were determined. Then, the CNFMs obtained with optimal process parameters were applied for the photocatalytic degradation of methyl orange. It was found that the CNFMs could be reused to degrade methyl orange at least three times, and the degradation rate remained above 90%.

Beschreibung: The electronic structure of molecules on metal surfaces is largely determined by hybridization and screening by the substrate electrons. As a result, the energy levels are significantly broadened and molecular properties, such as vibrations are hidden within the spectral line shapes. Insertion of thin decoupling layers reduces the line widths and may give access to the resolution of electronic and vibronic states of an almost isolated molecule. Here, we use scanning tunneling microscopy and spectroscopy to show that a single layer of MoS2 on Ag(111) exhibits a semiconducting bandgap, which may prevent molecular states from strong interactions with the metal substrate. We show that the lowest unoccupied molecular orbital (LUMO) of tetracyanoquinodimethane (TCNQ) molecules is significantly narrower than on the bare substrate and that it is accompanied by a characteristic satellite structure. Employing simple calculations within the Franck–Condon model, we reveal their vibronic origin and identify the modes with strong electron–phonon coupling.

Beschreibung: In this work, surface/interface effects for pull-in voltage and viscous fluid velocity effects on the dimensionless natural frequency of fluid-conveying multiwalled piezoelectric nanosensors (FC-MWPENSs) based on cylindrical nanoshells is investigated using the Gurtin–Murdoch surface/interface theory. The nanosensor is embedded in a viscoelastic foundation and subjected to nonlinear van der Waals and electrostatic forces. Hamilton’s principle is used to derive the governing and boundary conditions and is also the assumed mode method used for changing the partial differential equations into ordinary differential equations. The influences of the surface/interface effect, such as Lame’s constants, residual stress, piezoelectric constants and mass density, are considered for analysis of the dimensionless natural frequency with respect to the viscous fluid velocity and pull-in voltage of the FC-MWPENSs.

Beschreibung: Recent experiments suggest graphene-based materials as candidates in future electronic and optoelectronic devices. In this paper, we propose to investigate new photodetectors based on graphene nanomeshes (GNMs). Density functional theory (DFT) calculations are performed to gain insight into electronic and optical characteristics of various GNM structures. To investigate the device-level properties of GNMs, their current–voltage characteristics are explored by DFT-based tight-binding (DFTB) in combination with non-equilibrium Green’s function (NEGF) methods. Band structure analysis shows that GNMs have both metallic and semiconducting properties depending on the arrangements of perforations. Also, absorption spectrum analysis indicates attractive infrared peaks for GNMs with semiconducting characteristics, making them better photodetectors than graphene nanoribbon (GNR)-based alternatives. The results suggest that GNMs can be potentially used in mid-infrared detectors with specific detectivity values that are 100-fold that of graphene-based devices and 1000-fold that of GNR-based devices. Hence, the special properties of graphene combined with the quantum feathers of the perforation makes it suitable for optical devices.

Beschreibung: The synthesis of magnetite (Fe3O4) nanorods using reverse co-precipitation of Fe3+ and Fe2+ ions in the presence of a static magnetic field is reported in this work. The phase composition and crystal structure of the synthesized material were investigated using electron diffraction, Raman spectroscopy, and transmission electron microscopy. It was shown that the morphology of the reaction product strongly depends on the amount of OH− ions in the reaction mixture, varying from Fe3O4 nanorods to spherical Fe3O4 nanoparticles. Fe3O4 nanorods were examined using high-resolution transmission electron microscopy proving that they are single-crystalline and do not have any preferred crystallographic orientation along the axis of the rods. According to the data obtained a growth mechanism was proposed for the rods that consists of the dipole–dipole interaction between their building blocks (small hexagonal faceted magnetite nanocrystals), which are formed during the first step of the reaction. The study suggests a facile, green and controllable method for synthesizing anisotropic magnetic nanoparticles in the absence of stabilizers, which is important for further modification of their surfaces and/or incorporation of the nanoparticles into different media.

Beschreibung: On-site peroxide generation via electrochemical reduction is gaining tremendous attention due to its importance in many fields, including water treatment technologies. Oxidized graphitic carbon-based materials have been recently proposed as an alternative to metal-based catalysts in the electrochemical oxygen reduction reaction (ORR), and in this work we unravel the role of C=O groups in graphene towards sustainable peroxide formation. We demonstrate a versatile single-step electrochemical exfoliation of graphite to graphene with a controllable degree of oxygen functionalities and thickness, leading to the formation of large quantities of functionalized graphene with tunable rate parameters, such as the rate constant and exchange current density. Higher oxygen-containing exfoliated graphene is known to undergo a two-electron reduction path in ORR having an efficiency of about 80 ± 2% even at high overpotential. Bulk production of H2O2 via electrolysis was also demonstrated at low potential (0.358 mV vs RHE), yielding ≈34 mg/L peroxide with highly functionalized (≈23 atom %) graphene and ≈16 g/L with low functionalized (≈13 atom %) graphene, which is on par with the peroxide production using state-of-the-art precious-metal-based catalysts. Hence this method opens a new scheme for the single-step large-scale production of functionalized carbon-based catalysts (yield ≈45% by weight) that have varying functionalities and can deliver peroxide via the electrochemical ORR process.

Beschreibung: Polyaniline-derived carbon (PDC) was obtained via pyrolysis of polyaniline under different temperatures and applied for the purification of water contaminated with dye molecules of different sizes and charge by adsorption. With increasing pyrolysis temperature, it was found that the hydrophobicity, pore size and mesopore volume increased. A mesoporous PDC sample obtained via pyrolysis at 900 °C showed remarkable performance in the adsorption of dye molecules, irrespective of dye charge, especially in the removal of bulky dye molecules, such as acid red 1 (AR1) and Janus green B (JGB). For example, the most competitive PDC material showed a Q 0 value (maximum adsorption capacity) 8.1 times that of commercial, activated carbon for AR1. The remarkable adsorption of AR1 and JGB over KOH-900 could be explained by the combined mechanisms of hydrophobic, π–π, electrostatic and van der Waals interactions.

Beschreibung: In the present paper, we investigate the effect of heat treatment on the geometry and mobility of Au nanoparticles (NPs) on a Si substrate. Chemically synthesized Au NPs of diameter ranging from 5 to 27 nm were annealed at 200, 400, 600 and 800 °C for 1 h. A change in the geometry from faceted to more rounded shapes were observed with increasing annealing temperature. Kinetic Monte Carlo simulations indicate that the NPs become rounded due to the minimization of the surface area and the transition to lower energy surface types {111} and {100}. The NPs were manipulated on a silica substrate with an atomic force microscope (AFM) in tapping mode. Initially, the NPs were immovable by AFM energy dissipation. However, annealed NPs became movable, and less energy was required to displace the NPs annealed at higher temperature. However, after annealing at 800 °C, the particles became immovable again. This effect was attributed to the diffusion of Au into the Si substrate and to the growth of the SiO2 layer.

Beschreibung: An implementation of pump–probe Kelvin probe force microscopy (pp-KPFM) is reported that enables recording the time-resolved surface potential in single-point mode or over a 2D grid. The spectroscopic data are acquired in open z-loop configuration, which simplifies the pp-KPFM operation. The validity of the implementation is probed by measurements using electrical pumping. The dynamical photoresponse of a bulk heterojunction solar cell based on PTB7 and PC71BM is subsequently investigated by recording point-spectroscopy curves as a function of the optical power at the cathode and by mapping 2D time-resolved images of the surface photovoltage of the bare organic active layer.

Beschreibung: Nanoparticles (NPs) are considered as one of the most promising drug delivery vehicles and a next-generation solution for current medical challenges. In this context, variables related to flow of NPs such as the quantity of NPs lost during transport and flow trajectory greatly affect the clinical efficiency of NP drug delivery systems. Currently, there is little knowledge of the physical mechanisms dominating NP flow inside the human body due to the limitations of available experimental tools for mimicking complex physiological environments at the preclinical stage. Here, we report a coupled experimental and computational fluid dynamics (CFD)-based novel in vitro approach to predict the flow velocity and binding of NP drug delivery systems during transport through vasculature. Poly(hydroxyethyl)methacrylate hydrogels were used to form soft cylindrical constructs mimicking vascular sections as flow channels for synthesized iron oxide NPs in these first-of-its-kind transport experiments. Brownian dynamics and material of the flow channels played key roles in NP flow, based on the measurements of NP flow velocity over seven different mass concentrations. A fully developed laminar flow of the NPs under these conditions was simultaneously predicted using CFD. Results from the mass loss of NPs during flow indicated a diffusion-dominated flow at higher particle concentrations but a flow controlled by the surrounding fluid and Brownian dynamics at the lowest NP concentrations. The CFD model predicted a mass loss of 1.341% and 6.253% for the 4.12 g·mL−1 and 2.008 g·mL−1 inlet mass concentrations of the NPs, in close confirmation with the experimental results. This further highlights the reliability of our new in vitro technique in providing mechanistic insights of NP flow for potential preclinical stage applications.

Beschreibung: Among the patterning technologies for organic thin-film transistors (OTFTs), the fabrication of OTFT electrodes using polymer templates has attracted much attention. However, deviations in the electrode alignment occur because the coefficient of thermal expansion (CTE) of the polymer template is much higher than the CTE of the dielectric layer. Here, a novel dry-blending method is described in which SiO2 nanoparticles are filled into a grooved silicon template, followed by permeation of polydimethylsiloxane (PDMS) into the SiO2 nanoparticle gaps. The SiO2 nanoparticles in the groove are extracted by curing and peeling off PDMS to prepare a PDMS/SiO2 composite template with a nanoparticle content of 83.8 wt %. The composite template has a CTE of 96 ppm/°C, which is a reduction by 69.23% compared with the original PDMS template. Finally, we achieved the alignment of OTFT electrodes using the composite template.

Beschreibung: MoO3 is a versatile two-dimensional transition metal oxide having applications in areas such as energy storage devices, electronic devices and catalysis. To efficiently utilize the properties of MoO3 arising from its two-dimensional nature exfoliation is necessary. In this work, the exfoliation of MoO3 is carried out in 2-butanone for the first time. The achieved concentration of the dispersion is about 0.57 mg·mL−1 with a yield of 5.7%, which are the highest values reported to date. These high values of concentration and yield can be attributed to a favorable matching of energies involved in exfoliation and stabilization of MoO3 nanosheets in 2-butanone. Interestingly, the MoO3 dispersion in 2-butanone retains its intrinsic nature even after exposure to sunlight for 24 h. The composites of MoO3 nanosheets were used as an electrode material for supercapacitors and showed a high specific capacitance of 201 F·g−1 in a three-electrode configuration at a scan rate of 50 mV·s−1.

Beschreibung: Even though there have been many experimental attempts and theoretical approaches to understand the process of electromigration (EM), it has not been quantitatively understood for ultrathin structures and at grain boundaries. Nevertheless, we showed recently that it can be used reliably for the formation of single atomic point contacts after careful pre-structuring of the initial Ag nanostructures. The process of formation of nanocontacts by EM down to a single-atom point contact was investigated for ultrathin (5 nm) Ag structures at 100 K by measuring the conductance as a function of the time during EM. In this paper, we compare the process of thinning by EM of structures with constrictions below the average grain size of Ag layers (15 nm) with that of structures with much larger initial constrictions of around 150 nm having multiple grains at the centre constriction prior to the formation of a point contact. Even though clear morphological differences exist between both types of structures, quantized conductance plateaus showing the formation of single point contacts have been observed for both. Here we put emphasis on the thinning process by EM, just before a point contact is formed. To understand this thinning process, the semi-classical regime before the contact reaches the quantum regime was analyzed in detail. For this purpose, we used experimental conductance histograms in the range between 2G 0 and 15G 0 and their corresponding Fourier transforms (FTs). The FT analysis of the conductance histograms exhibits a clear preference for thinning along the [100] direction. Using well-established models, both atom-by-atom steps and ranges of stability, presumably caused by electronic shell effects, can be discriminated. Although the directional motion of atoms during EM leads to specific properties such as the instabilities mentioned, similarities to mechanically opened contacts with respect to cross-sectional stability were found.

Beschreibung: In this work, a high-resolution atomic force acoustic microscopy imaging technique is developed in order to obtain the local indentation modulus at the nanoscale level. The technique uses a model that gives a qualitative relationship between a set of contact resonance frequencies and the indentation modulus. It is based on white-noise excitation of the tip–sample interaction and uses system theory for the extraction of the resonance modes. During conventional scanning, for each pixel, the tip–sample interaction is excited with a white-noise signal. Then, a fast Fourier transform is applied to the deflection signal that comes from the photodiodes of the atomic force microscopy (AFM) equipment. This approach allows for the measurement of several vibrational modes in a single step with high frequency resolution, with less computational cost and at a faster speed than other similar techniques. This technique is referred to as stochastic atomic force acoustic microscopy (S-AFAM), and the frequency shifts of the free resonance frequencies of an AFM cantilever are used to determine the mechanical properties of a material. S-AFAM is implemented and compared with a conventional technique (resonance tracking-atomic force acoustic microscopy, RT-AFAM). A sample of a graphite film on a glass substrate is analyzed. S-AFAM can be implemented in any AFM system due to its reduced instrumentation requirements compared to conventional techniques.

Beschreibung: In this study, we used simulations as a guide for experiments in order to switch freestanding nanowire growth to a laterally aligned growth mode. By means of finite element simulations, we determined that a higher volumetric flow and a reduced process pressure will result in a preferred laterally aligned nanowire growth. Furthermore, increasing the volumetric flow leads to a higher species dilution. Based on our numerical results, we were able to successfully grow laterally aligned SnO2 nanowires out of gold film edges and gold nanoparticles on a-plane sapphire substrates. In our experiments a horizontal 2-zone tube furnace was used. The generation of Sn gas was achieved by a carbothermal reduction of SnO2 powder. However, we observed no elongation of the nanowire length with an increase of the process time. Nevertheless, an alternating gas exchange between an inert gas (Ar) and an oxygen-containing process atmosphere yielded an elongation of the laterally aligned nanowires, indicating that the nanowire growth takes place in a transient period of the gas exchange.

Beschreibung: The interaction potential between two surfaces determines the adhesive and repulsive forces between them. It also determines interfacial properties, such as adhesion and friction, and is a key input into mechanics models and atomistic simulations of contacts. We have developed a novel methodology to experimentally determine interaction potential parameters, given a particular potential form, using frequency-modulated atomic force microscopy (AFM). Furthermore, this technique can be extended to the experimental verification of potential forms for any given material pair. Specifically, interaction forces are determined between an AFM tip apex and a nominally flat substrate using dynamic force spectroscopy measurements in an ultrahigh vacuum (UHV) environment. The tip geometry, which is initially unknown and potentially irregularly shaped, is determined using transmission electron microscopy (TEM) imaging. It is then used to generate theoretical interaction force–displacement relations, which are then compared to experimental results. The method is demonstrated here using a silicon AFM probe with its native oxide and a diamond sample. Assuming the 6-12 Lennard-Jones potential form, best-fit values for the work of adhesion (W adh) and range of adhesion (z 0) parameters were determined to be 80 ± 20 mJ/m2 and 0.6 ± 0.2 nm, respectively. Furthermore, the shape of the experimentally extracted force curves was shown to deviate from that calculated using the 6-12 Lennard-Jones potential, having weaker attraction at larger tip–sample separation distances and weaker repulsion at smaller tip–sample separation distances. This methodology represents the first experimental technique in which material interaction potential parameters were verified over a range of tip–sample separation distances for a tip apex of arbitrary geometry.

Beschreibung: Plasmonic metal/semiconductor composites have attracted great attention for efficient solar energy harvesting in photovoltaic and photocatalytic applications owing to their extremely high visible-light absorption and tuned effective band gap. In this work, Ag-loaded TiO2 nanocolumn (Ag-TNC) arrays were fabricated based on anodic aluminum oxide (AAO) template by combining atomic layer deposition (ALD) and vacuum evaporation. The effects of the Ag loading position and deposition thickness, and the morphology, structure and composition of Ag-deposited TNC arrays on its optical and photocatalytic properties were studied. The Ag-filled TiO2 (AFT) nanocolumn arrays exhibited higher removal efficiency of methylene blue (MB) compared with Ag-coated TiO2 (ACT) nanocolumn arrays and pure TiO2 nanocolumns arrays. Both experimental and theoretical simulation results demonstrated that the enhanced photocatalytic performance of AFT nanocolumn arrays was attributed to the surface plasmon resonance (SPR) of Ag and the absorption of light by TiO2. These results represent a promising step forward to the development of high-performance photocatalysts for energy conversion and storage.

Beschreibung: The investigation of novel nanoparticles with antimicrobial activity has grown in recent years due to the increased incidence of nosocomial infections occurring during hospitalization and food poisoning derived from foodborne pathogens. Antimicrobial agents are necessary in various fields in which biological contamination occurs. For example, in food packaging they are used to control food contamination by microbes, in the medical field the microbial agents are important for reducing the risk of contamination in invasive and routine interventions, and in the textile industry, they can limit the growth of microorganisms due to sweat. The combination of nanotechnology with materials that have an intrinsic antimicrobial activity can result in the development of novel antimicrobial substances. Specifically, metal-based nanoparticles have attracted much interest due to their broad effectiveness against pathogenic microorganisms due to their high surface area and high reactivity. The aim of this review was to explore the state-of-the-art in metal-based nanoparticles, focusing on their synthesis methods, types, and their antimicrobial action. Different techniques used to synthesize metal-based nanoparticles were discussed, including chemical and physical methods and “green synthesis” methods that are free of chemical agents. Although the most studied nanoparticles with antimicrobial properties are metallic or metal-oxide nanoparticles, other types of nanoparticles, such as superparamagnetic iron-oxide nanoparticles and silica-releasing systems also exhibit antimicrobial properties. Finally, since the quantification and understanding of the antimicrobial action of metal-based nanoparticles are key topics, several methods for evaluating in vitro antimicrobial activity and the most common antimicrobial mechanisms (e.g., cell damage and changes in the expression of metabolic genes) were discussed in this review.