ALBERT

Description: Sabatier’s principle suggests, that for hydrogen evolution a plot of the rate constant versus the hydrogen adsorption energy should result in a volcano, and several such plots have been presented in the literature. A thorough examination of the data shows, that there is no volcano once the oxide-covered metals are left out. We examine the factors that govern the reaction rate in the light of our own theory and conclude, that Sabatier’s principle is only one of several factors that determine the rate. With the exception of nickel and cobalt, the reaction rate does not decrease for highly exothermic hydrogen adsorption as predicted, because the reaction passes through more suitable intermediate states. The case of nickel is given special attention; since it is a 3d metal, its orbitals are compact and the overlap with hydrogen is too low to make it a good catalyst.

Description: As a part of our programme to develop nanobioconjugates for the treatment of cancer, we first synthesized extracellular, protein-capped, highly stable and well-dispersed gadolinium oxide (Gd2O3) nanoparticles by using thermophilic fungus Humicola sp. The biodistribution of the nanoparticles in rats was checked by radiolabelling with Tc-99m. Finally, these nanoparticles were bioconjugated with the chemically modified anticancer drug taxol with the aim of characterizing the role of this bioconjugate in the treatment of cancer. The biosynthesized Gd2O3 nanoparticles were characterized by UV–vis spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoemission spectroscopy (XPS). The Gd2O3–taxol bioconjugate was confirmed by UV–vis spectroscopy and fluorescence microscopy and was purified by using high performance liquid chromatography (HPLC).

Description: Various types of carbon-based and non-carbon-based catalyst supports for nitric oxide (NO) removal through selective catalytic reduction (SCR) with ammonia are examined in this review. A number of carbon-based materials, such as carbon nanotubes (CNTs), activated carbon (AC), and graphene (GR) and non-carbon-based materials, such as Zeolite Socony Mobil–5 (ZSM-5), TiO2, and Al2O3 supported materials, were identified as the most up-to-date and recently used catalysts for the removal of NO gas. The main focus of this review is the study of catalyst preparation methods, as this is highly correlated to the behaviour of NO removal. The general mechanisms involved in the system, the Langmuir–Hinshelwood or Eley–Riedeal mechanism, are also discussed. Characterisation analysis affecting the surface and chemical structure of the catalyst is also detailed in this work. Finally, a few major conclusions are drawn and future directions for work on the advancement of the SCR-NH3 catalyst are suggested.

Description: A quantitative understanding of aggregation mechanisms leading to the formation of composites of inorganic nanoparticles (NPs) and proteins in aqueous media is of paramount interest for colloid chemistry. In particular, the interactions between silica (SiO2) NPs and lysozyme (LZM) have attracted attention, because LZM is well-known to adsorb strongly to silica NPs, while at the same time preserving its enzymatic activity. The inherent nature of the aggregation processes leading to NP–LZM composites involves structural changes at length scales from few to at least hundreds of nanometres but also time scales much smaller than one second. To unravel these we used in situ synchrotron-based small-angle X-ray scattering (SAXS) and followed the subtle interparticle interactions in solution at a time resolution of 50 ms/frame (20 fps). We show that if the size of silica NPs (ca. 5 nm diameter) is matched by the dimensions of LZM, the evolving scattering patterns contain a unique structure-factor contribution originating from the presence of LZM. We developed a scattering model and applied it to analyse this structure function, which allowed us to extract structural information on the deformation of lysozyme molecules during aggregation, as well as to derive the mechanisms of composite formation.

Description: This report examines the assembly of chalcogenide organic molecules on various surfaces, focusing on cases when chemisorption is accompanied by carbon–chalcogen atom-bond scission. In the case of alkane and benzyl chalcogenides, this induces formation of a chalcogenized interface layer. This process can occur during the initial stages of adsorption and then, after passivation of the surface, molecular adsorption can proceed. The characteristics of the chalcogenized interface layer can be significantly different from the metal layer and can affect various properties such as electron conduction. For chalcogenophenes, the carbon–chalcogen atom-bond breaking can lead to opening of the ring and adsorption of an alkene chalcogenide. Such a disruption of the π-electron system affects charge transport along the chains. Awareness about these effects is of importance from the point of view of molecular electronics. We discuss some recent studies based on X-ray photoelectron spectroscopy that shed light on these aspects for a series of such organic molecules.

Description: To better utilize the sunlight for efficient solar energy conversion, the research on visible-light active photocatalysts has recently attracted a lot of interest. The photosensitization of transition metal oxides is a promising approach for achieving effective visible-light photocatalysis. This review article primarily discusses the recent progress in the realm of a variety of nanostructured photosensitizers such as quantum dots, plasmonic metal nanostructures, and carbon nanostructures for coupling with wide-bandgap transition metal oxides to design better visible-light active photocatalysts. The underlying mechanisms of the composite photocatalysts, e.g., the light-induced charge separation and the subsequent visible-light photocatalytic reaction processes in environmental remediation and solar fuel generation fields, are also introduced. A brief outlook on the nanostructure photosensitization is also given.

Description: The combination of electrodeposition and polymeric templates created by heavy-ion irradiation followed by chemical track etching provides a large variety of poly- and single-crystalline nanowires of controlled size, geometry, composition, and surface morphology. Recent results obtained by our group on the fabrication, characterization and size-dependent properties of nanowires synthesized by this technique are reviewed, including investigations on electrical resistivity, surface plasmon resonances, and thermal instability.

Description: The search for and synthesis of new antimicrobial nanostructures is important to reduce microbial incidence that induces infectious diseases and to aid in the antibiotic resistance crisis, which are two of the most pressing issues in global public health. In this work, novel, hollow, calcined titanium dioxide nanospheres (CSTiO2) were successfully synthesized for the first time through the combination of electrospinning and atomic layer deposition techniques. Poly(vinylpyrrolidone) (PVP) electrosprayed spherical particles were double-coated with alumina and titanium dioxide, and after a calcination process, hollow nanospheres were obtained with a radius of approximately 345 nm and shell thickness of 17 nm. The structural characterization was performed using electron microscopy, and X-ray diffraction and small-angle X-ray diffraction evidenced an anatase titanium dioxide crystalline structure. Thermogravimetric analysis and Fourier-transform infrared spectroscopy studies demonstrated the absence of polymer residue after the calcination process. The antimicrobial properties of the developed CSTiO2 hollow nanospheres were evaluated against different bacteria, including resistant E. coli and S. aureus strains, and when compared to commercial TiO2 nanoparticles, CSTiO2 nanospheres exhibited superior performance. In addition, the positive effect of UV irradiation on the antimicrobial activity was demonstrated.

Description: A combination of a “top-down” approach (substrate-conformal imprint lithography) and two “bottom-up” approaches (dewetting and dealloying) enables fabrication of perfectly ordered 2-dimensional arrays of nanoporous gold nanoparticles. The dewetting of Au/Ag bilayers on the periodically prepatterned substrates leads to the interdiffusion of Au and Ag and the formation of an array of Au–Ag alloy nanoparticles. The array of alloy nanoparticles is transformed into an array of nanoporous gold nanoparticles by a following dealloying step. Large areas of this new type of material arrangement can be realized with this technique. In addition, this technique allows for the control of particle size, particle spacing, and ligament size (or pore size) by varying the period of the structure, total metal layer thickness, and the thickness ratio of the as-deposited bilayers.

Description: It has recently been shown that ‘sub-atomic’ contrast can be observed during NC-AFM imaging of the Si(111)-7×7 substrate with a passivated tip, resulting in triangular shaped atoms [Sweetman et al. Nano Lett. 2014, 14, 2265]. The symmetry of the features, and the well-established nature of the dangling bond structure of the silicon adatom means that in this instance the contrast cannot arise from the orbital structure of the atoms, and it was suggested by simple symmetry arguments that the contrast could only arise from the backbonding symmetry of the surface adatoms. However, no modelling of the system has been performed in order to understand the precise origin of the contrast. In this paper we provide a detailed explanation for ‘sub-atomic’ contrast observed on Si(111)-7×7 using a simple model based on Lennard-Jones potentials, coupled with a flexible tip, as proposed by Hapala et al. [Phys. Rev. B 2014, 90, 085421] in the context of interpreting sub-molecular contrast. Our results show a striking similarity to experimental results, and demonstrate how ‘sub-atomic’ contrast can arise from a flexible tip exploring an asymmetric potential created due to the positioning of the surrounding surface atoms.

Description: Background: In nanoscale layered S/F1/N/F2/AF heterostructures, the generation of a long-range, odd-in-frequency spin-projection one triplet component of superconductivity, arising at non-collinear alignment of the magnetizations of F1 and F2, exhausts the singlet state. This yields the possibility of a global minimum of the superconducting transition temperature T c, i.e., a superconducting triplet spin-valve effect, around mutually perpendicular alignment. Results: The superconducting triplet spin valve is realized with S = Nb a singlet superconductor, F1 = Cu41Ni59 and F2 = Co ferromagnetic metals, AF = CoO x an antiferromagnetic oxide, and N = nc-Nb a normal conducting (nc) non-magnetic metal, which serves to decouple F1 and F2. The non-collinear alignment of the magnetizations is obtained by applying an external magnetic field parallel to the layers of the heterostructure and exploiting the intrinsic perpendicular easy-axis of the magnetization of the Cu41Ni59 thin film in conjunction with the exchange bias between CoO x and Co. The magnetic configurations are confirmed by superconducting quantum interference device (SQUID) magnetic moment measurements. The triplet spin-valve effect has been investigated for different layer thicknesses, d F1, of F1 and was found to decay with increasing d F1. The data is described by an empirical model and, moreover, by calculations using the microscopic theory. Conclusion: The long-range triplet component of superconducting pairing is generated from the singlet component mainly at the N/F2 interface, where the amplitude of the singlet component is suppressed exponentially with increasing distance d F1. The decay length of the empirical model is found to be comparable to twice the electron mean free path of F1 and, thus, to the decay length of the singlet component in F1. Moreover, the obtained data is in qualitative agreement with the microscopic theory, which, however, predicts a (not investigated) breakdown of the triplet spin-valve effect for d F1 smaller than 0.3 to 0.4 times the magnetic coherence length, ξF1.

Description: Silver nanoparticles (AgNPs) have increasingly gained importance as antibacterial agents with applications in several fields due to their strong, broad-range antimicrobial properties. AgNP synthesis by pulsed laser ablation in liquid (PLAL) permits the preparation of stable Ag colloids in pure solvents without capping or stabilizing agents, producing AgNPs more suitable for biomedical applications than those prepared with common, wet chemical preparation techniques. To date, only a few investigations into the antimicrobial effect of AgNPs produced by PLAL have been performed. These have mainly been performed by ablation in water with nanosecond pulse widths. We previously observed a strong surface-enhanced Raman scattering (SERS) signal from such AgNPs by “activating” the NP surface by the addition of a small quantity of LiCl to the colloid. Such surface effects could also influence the antimicrobial activity of the NPs. Their activity, on the other hand, could also be affected by other parameters linked to the ablation conditions, such as the pulse width. The antibacterial activity of AgNPs was evaluated for NPs obtained either by nanosecond (ns) or picosecond (ps) PLAL using a 1064 nm ablation wavelength, in pure water or in LiCl aqueous solution, withEscherichia coliandBacillus subtilisas references for Gram-negative and Gram-positive bacteria, respectively. In all cases, AgNPs with an average diameter less than 10 nm were obtained, which has been shown in previous works to be the most effective size for bactericidal activity. The measured zeta-potential values were very negative, indicating excellent long-term colloidal stability. Antibacterial activity was observed against both microorganisms for the four AgNP formulations, but the ps-ablated nanoparticles were shown to more effectively inhibit the growth of both microorganisms. Moreover, LiCl modified AgNPs were the most effective, showing minimum inhibitory concentration (MIC) values in a restricted range of 1.0–3.7 µg/mL. An explanation is proposed for this result based on the increased surface reactivity of the metal surface due to the presence of positively charged active sites.

Description: With the worsening of the oil-product pollution problem, oil–water separation has attracted increased attention in recent years. In this study, a porous three-dimensional (3D) carbon aerogel based on cellulose nanofibers (CNFs), poly(vinyl alcohol) (PVA) and graphene oxide (GO) was synthesized by a facile and green approach. The resulting CNF/PVA/GO aerogels were synthesized through an environmentally friendly freeze-drying process and then carbonized to yield CNF/PVA/GO carbon aerogels with low density (18.41 mg cm−3), high porosity (98.98%), a water contact angle of 156° (super-hydrophobic) and high oil absorption capacity (97 times its own weight). The carbonization treatment of the CNF/PVA/GO aerogel not only improved the hydrophobic properties but also enhanced the adsorption capacity and specific surface area. Given the many good performance characteristics and the facile preparation process of carbon aerogels, these materials are viable candidates for use in oil–water separation and environmental protection.

Description: Carbon dots (CDs) and graphitic carbon nitride (g-C3N4) composites (CD/g-C3N4) were successfully synthesized by a hydrothermal method using urea and sugarcane juice as starting materials. The chemical composition, morphological structure and optical properties of the composites and CDs were characterized using various spectroscopic techniques as well as transmission electron microscopy. X-ray photoelectron spectroscopy (XPS) results revealed new signals for carbonyl and carboxyl groups originating from the CDs in CD/g-C3N4 composites while X-ray diffraction (XRD) results showed distortion of the host matrix after incorporating CDs into g-C3N4. Both analyses signified the interaction between g-C3N4 and CDs. The photoluminescence (PL) analysis indicated that the presence of too many CDs will create trap states at the CD/g-C3N4 interface, decelerating the electron (e−) transport. However, the CD/g-C3N4(0.5) composite with the highest coverage of CDs still achieved the best bisphenol A (BPA) degradation rate at 3.87 times higher than that of g-C3N4. Hence, the charge separation efficiency should not be one of the main factors responsible for the enhancement of the photocatalytic activity of CD/g-C3N4. Instead, the light absorption capability was the dominant factor since the photoreactivity correlated well with the ultraviolet–visible diffuse reflectance spectra (UV–vis DRS) results. Although the CDs did not display upconversion photoluminescence (UCPL) properties, the π-conjugated CDs served as a photosensitizer (like organic dyes) to sensitize g-C3N4 and injected electrons to the conduction band (CB) of g-C3N4, resulting in the extended absorption spectrum from the visible to the near-infrared (NIR) region. This extended spectral absorption allows for the generation of more electrons for the enhancement of BPA degradation. It was determined that the reactive radical species responsible for the photocatalytic activity were the superoxide anion radical (O2 •−) and holes (h+) after performing multiple scavenging tests.

Description: The investigation of charge transport in organic nanocrystals is essential to understand nanoscale physical properties of organic systems and the development of novel organic nanodevices. In this work, we fabricate organic nanocrystal diodes contacted by rolled-up robust nanomembranes. The organic nanocrystals consist of vanadyl phthalocyanine and copper hexadecafluorophthalocyanine heterojunctions. The temperature dependent charge transport through organic nanocrystals was investigated to reveal the transport properties of ohmic and space-charge-limited current under different conditions, for instance, temperature and bias.

Description: Silver nanoparticles were synthesized in the presence of saccharides and ammonia (NH3) in the concentration range from 10−2 to 103 ppm to develop an optical sensor for NH3 in aqueous solutions. Ammonia affects the features of the nanoparticles obtained in a concentration-dependent manner as determined by UV–vis absorption analysis and TEM observations. Structural and morphological analysis provides the basis for the production of a colorimetric label-free sensor for ammonia. Overall, surface plasmon resonance increases when ammonia concentration rises, although the functional trend is not the same over the entire investigated ammonia concentration range. Three different ranges have been identified: very low ammonia concentrations from 0.01 to 0.2 ppm, high ammonia concentrations from 20 to 350 ppm and, most importantly, the intermediate or physiological range of ammonia from 0.5 to 10 ppm.

Description: Crystalline poly- and oligosaccharides such as cellulose can form extremely robust assemblies, whereas the construction of self-assembled materials from such molecules is generally difficult due to their complicated chemical synthesis and low solubility in solvents. Enzyme-catalyzed oligomerization-induced self-assembly has been shown to be promising for creating nanoarchitectured crystalline oligosaccharide materials. However, the controlled self-assembly into organized hierarchical structures based on a simple method is still challenging. Herein, we demonstrate that the use of organic solvents as small-molecule additives allows for control of the oligomerization-induced self-assembly of cellulose oligomers into hierarchical nanoribbon network structures. In this study, we dealt with the cellodextrin phosphorylase-catalyzed oligomerization of phosphorylated glucose monomers from ᴅ-glucose primers, which produce precipitates of nanosheet-shaped crystals in aqueous solution. The addition of appropriate organic solvents to the oligomerization system was found to result in well-grown nanoribbon networks. The organic solvents appeared to prevent irregular aggregation and subsequent precipitation of the nanosheets via solvation for further growth into the well-grown higher-order structures. This finding indicates that small-molecule additives provide control over the self-assembly of crystalline oligosaccharides for the creation of hierarchically structured materials with high robustness in a simple manner.

Description: In the research field of nanoparticles, many studies demonstrated a high impact of the shape, size and surface charge, which is determined by the functionalization, of nanoparticles on cell viability and internalization into cells. This work focused on the comparison of three different nanoparticle types to give a better insight into general rules determining the biocompatibility of gold, Janus and semiconductor (quantum dot) nanoparticles. Endothelial cells were subject of this study, since blood is the first barrier after intravenous nanoparticle application. In particular, stronger effects on the viability of endothelial cells were found for nanoparticles with an elongated shape in comparison to spherical ones. Furthermore, a positively charged nanoparticle surface (NH2, CyA) leads to the strongest reduction in cell viability, whereas neutral and negatively charged nanoparticles are highly biocompatible to endothelial cells. These findings are attributed to a rapid internalization of the NH2-functionalized nanoparticles in combination with the damage of intracellular membranes. Interestingly, the endocytotic pathway seems to be a size-dependent process whereas nanoparticles with a size of 20 nm are internalized by caveolae-mediated endocytosis and nanoparticles with a size of 40 nm are taken up by clathrin-mediated internalization and macropinocytosis. Our results can be summarized to formulate five general rules, which are further specified in the text and which determine the biocompatibility of nanoparticles on endothelial cells. Our findings will help to design new nanoparticles with optimized properties concerning biocompatibility and uptake behavior with respect to the respective intended application.

Description: Nanofibers were prepared from polycaprolactone, polylactide and polyvinyl alcohol using NanospiderTM technology. Polyethylene glycols with molecular weights of 2 000, 6 000, 10 000 and 20 000 g/mol, which can be used to moderate the release profile of incorporated pharmacologically active compounds, served as model molecules. They were terminated by aromatic isocyanate and incorporated into the nanofibers. The release of these molecules into an aqueous environment was investigated. The influences of the molecular length and chemical composition of the nanofibers on the release rate and the amount of released polyethylene glycols were evaluated. Longer molecules released faster, as evidenced by a significantly higher amount of released molecules after 72 hours. However, the influence of the chemical composition of nanofibers was even more distinct – the highest amount of polyethylene glycol molecules released from polyvinyl alcohol nanofibers, the lowest amount from polylactide nanofibers.

Description: Background: When nanoparticles (NPs) are applied into a biological fluid, such as blood, proteins bind rapidly to their surface forming a so-called “protein corona”. These proteins are strongly attached to the NP surface and confers them a new biological identity that is crucial for the biological response in terms of body biodistribution, cellular uptake, and toxicity. The corona is dynamic in nature and it is well known that the composition varies in dependence of the physicochemical properties of the NPs. In the present study we investigated the protein corona that forms around poly(lactide-co-glycolide) (PLGA) NPs at different serum concentrations using two substantially different serum types, namely fetal bovine serum (FBS) and human serum. The corona was characterized by means of sodium dodecylsulfate polyacrylamide gel electrophoresis (SDS-PAGE), Bradford protein assay, zeta potential measurements, and liquid chromatography–mass spectrometry/mass spectrometry (LC–MS/MS). Additionally, the time-dependent cell interaction of PLGA NPs in the absence or presence of a preformed protein corona was assessed by in vitro incubation experiments with the human liver cancer cell line HepG2. Results: Our data revealed that the physiological environment critically affects the protein adsorption on PLGA NPs with significant impact on the NP–cell interaction. Under comparable conditions the protein amount forming the protein corona depends on the serum type used and the serum concentration. On PLGA NPs incubated with either FBS or human serum a clear difference in qualitative corona protein composition was identified by SDS-PAGE and LC–MS/MS in combination with bioinformatic protein classification. In the case of human serum a considerable change in corona composition was observed leading to a concentration-dependent desorption of abundant proteins in conjunction with an adsorption of high-affinity proteins with lower abundance. Cell incubation experiments revealed that the respective corona composition showed significant influence on the resulting nanoparticle–cell interaction. Conclusion: Controlling protein corona formation is still a challenging task and our data highlight the need for a rational future experimental design in order to enable a prediction of the corona formation on nanoparticle surfaces and, therefore, the resulting biodistribution in the body.

Description: Camptothecin (CPT; (S)-(+)-4-ethyl-4-hydroxy-1H-pyrano[3',4':6,7]indolizino[1,2-b]quinoline-3,14-(4H,12H)-dione) is a highly cytotoxic natural alkaloid that has not yet found use as chemotherapeutic agent due to its poor water-solubility and chemical instability and, as a consequence, no effective administration means have been designed. In this work, camptothecin has been successfully loaded into iron oxide superparamagnetic nanoparticles with an average size of 14 nm. It was found that surface modification of the nanoparticles by polyethylene glycol enables loading a large amount of camptothecin. While the unloaded nanoparticles do not induce apoptosis in the H460 lung cancer cell line, the camptothecin-loaded nanoparticle formulations exhibit remarkable pro-apoptotic activity. These results indicate that camptothecin retains its biological activity after loading onto the magnetic nanoparticles. The proposed materials represent novel materials based on naturally occurring bioactive molecules loaded onto nanoparticles to be used as chemotherapeutic formulations. The procedure seems apt to be extended to other active molecules extracted from natural products. In addition, these materials offer the potential of being further implemented for combined imaging and therapeutics, as magnetic nanoparticles are known to be multifunctional tools for biomedicine.

Description: The use of engineered nanoparticles has risen exponentially over the last decade. Applications are manifold and include utilisation in industrial goods as well as medical and consumer products. Gold and silver nanoparticles play an important role in the current increase of nanoparticle usage. However, our understanding concerning possible side effects of this increased exposure to particles, which are frequently in the same size regime as medium sized biomolecules and accessorily possess highly active surfaces, is still incomplete. That particularly applies to reproductive aspects, were defects can be passed onto following generations. This review gives a brief overview of the most recent findings concerning reprotoxicological effects. The here presented data elucidate how composition, size and surface modification of nanoparticles influence viablility and functionality of reproduction relevant cells derived from various animal models. While in vitro cultured embryos displayed no toxic effects after the microinjection of gold and silver nanoparticles, sperm fertility parameters deteriorated after co-incubation with ligand free gold nanoparticles. However, the effect could be alleviated by bio-coating the nanoparticles, which even applies to silver and silver-rich alloy nanoparticles. The most sensitive test system appeared to be in vitro oocyte maturation showing a dose-dependent response towards protein (BSA) coated gold–silver alloy and silver nanoparticles leading up to complete arrest of maturation. Recent biodistribution studies confirmed that nanoparticles gain access to the ovaries and also penetrate the blood–testis and placental barrier. Thus, the design of nanoparticles with increased biosafety is highly relevant for biomedical applications.

Description: Background: The development of new antiviral drugs based on nucleic acids is under scrutiny. An important problem in this aspect is to find the most vulnerable conservative regions in the viral genome as targets for the action of these agents. Another challenge is the development of an efficient system for their delivery into cells. To solve this problem, we proposed a TiO2·PL–DNA nanocomposite consisting of titanium dioxide nanoparticles and polylysine (PL)-containing oligonucleotides. Results: The TiO2·PL–DNA nanocomposites bearing the DNA fragments targeted to different conservative regions of (−)RNA and (+)RNA of segment 5 of influenza A virus (IAV) were studied for their antiviral activity in MDCK cells infected with the H1N1, H5N1, and H3N2 virus subtypes. Within the negative strand of each of the studied strains, the efficiency of DNA fragments increased in the direction of its 3’-end. Thus, the DNA fragment aimed at the 3’-noncoding region of (−)RNA was the most efficient and inhibited the reproduction of different IAV subtypes by 3–4 orders of magnitude. Although to a lesser extent, the DNA fragments targeted at the AUG region of (+)RNA and the corresponding region of (−)RNA were also active. For all studied viral subtypes, the nanocomposites bearing the DNA fragments targeted to (−)RNA appeared to be more efficient than those containing fragments aimed at the corresponding (+)RNA regions. Conclusion: The proposed TiO2·PL–DNA nanocomposites can be successfully used for highly efficient and site-specific inhibition of influenza A virus of different subtypes. Some patterns of localization of the most vulnerable regions in IAV segment 5 for the action of DNA-based drugs were found. The (−)RNA strand of IAV segment 5 appeared to be more sensitive as compared to (+)RNA.

Description: Manganese oxides are one of the most important groups of materials in energy storage science. In order to fully leverage their application potential, precise control of their properties such as particle size, surface area and Mn x + oxidation state is required. Here, Mn3O4 and Mn5O8 nanoparticles as well as mesoporous α-Mn2O3 particles were synthesized by calcination of Mn(II) glycolate nanoparticles obtained through an economical route based on a polyol synthesis. The preparation of the different manganese oxides via one route facilitates assigning actual structure–property relationships. The oxidation process related to the different MnO x species was observed by in situ X-ray diffraction (XRD) measurements showing time- and temperature-dependent phase transformations occurring during oxidation of the Mn(II) glycolate precursor to α-Mn2O3 via Mn3O4 and Mn5O8 in O2 atmosphere. Detailed structural and morphological investigations using transmission electron microscopy (TEM) and powder XRD revealed the dependence of the lattice constants and particle sizes of the MnO x species on the calcination temperature and the presence of an oxidizing or neutral atmosphere. Furthermore, to demonstrate the application potential of the synthesized MnO x species, we studied their catalytic activity for the oxygen reduction reaction in aprotic media. Linear sweep voltammetry revealed the best performance for the mesoporous α-Mn2O3 species.

Description: The biocompatibility and ease of functionalization of gold nanoparticles underlie significant potential in biotechnology and biomedicine. Eight different proteins were examined in the preparation of gold nanoparticles (AuNPs) in aqueous medium under microwave irradiation. Six of the proteins resulted in the formation of AuNPs. The intrinsic pH of the proteins played an important role in AuNPs with strong surface plasmon bands. The hydrodynamic size of the nanoparticles was larger than the values observed by TEM and ImageJ. The formation of a protein layer on the AuNPs accounts for this difference. The AuNPs exhibited sensitivity towards varying pH conditions, which was confirmed by determining the difference in the isoelectric points studied by using pH-dependent zeta potential titration. Cytotoxicity studies revealed anticancerous effects of the AuNPs at a certain micromolar concentration by constraining the growth of cancer cells with different efficacies due to the use of different proteins as capping agents. The positively charged AuNPs are internalized by the cells to a greater level than the negatively charged AuNPs. These AuNPs synthesized with protein coating holds promise as anticancer agents and would help in providing a new paradigm in area of nanoparticles.

Description: We report on an experimental study of the charge transport through tunnel gaps formed by adjustable gold electrodes immersed into different solvents that are commonly used in the field of molecular electronics (ethanol, toluene, mesitylene, 1,2,4-trichlorobenzene, isopropanol, toluene/tetrahydrofuran mixtures) for the study of single-molecule contacts of functional molecules. We present measurements of the conductance as a function of gap width, conductance histograms as well as current–voltage characteristics of narrow gaps and discuss them in terms of the Simmons model, which is the standard model for describing transport via tunnel barriers, and the resonant single-level model, often applied to single-molecule junctions. One of our conclusions is that stable junctions may form from solvents as well and that both conductance–distance traces and current–voltage characteristics have to be studied to distinguish between contacts of solvent molecules and of molecules under study.

Description: Cantilever magnetometry is a measurement technique used to study magnetic nanoparticles. With decreasing sample size, the signal strength is significantly reduced, requiring advances of the technique. Ultrathin and slender cantilevers can address this challenge but lead to increased complexity of detection. We present an approach based on the co-resonant coupling of a micro- and a nanometer-sized cantilever. Via matching of the resonance frequencies of the two subsystems we induce a strong interplay between the oscillations of the two cantilevers, allowing for a detection of interactions between the sensitive nanocantilever and external influences in the amplitude response curve of the microcantilever. In our magnetometry experiment we used an iron-filled carbon nanotube acting simultaneously as nanocantilever and magnetic sample. Measurements revealed an enhancement of the commonly used frequency shift signal by five orders of magnitude compared to conventional cantilever magnetometry experiments with similar nanomagnets. With this experiment we do not only demonstrate the functionality of our sensor design but also its potential for very sensitive magnetometry measurements while maintaining a facile oscillation detection with a conventional microcantilever setup.

Description: The study of infrared absorption by linear gold nanoantennas fabricated on a Si surface with underlying SiO2 layers of various thicknesses allowed the penetration depth of localized surface plasmons into SiO2 to be determined. The value of the penetration depth derived experimentally (20 ± 10 nm) corresponds to that obtained from electromagnetic simulations (12.9–30.0 nm). Coupling between plasmonic excitations of gold nanoantennas and optical phonons in SiO2 leads to the appearance of new plasmon–phonon modes observed in the infrared transmission spectra the frequencies of which are well predicted by the simulations.

Description: Hollow carbon spheres (HCS) with a nanoporous shell are promising for the use in lithium–sulfur batteries because of the large internal void offering space for sulfur and polysulfide storage and confinement. However, there is an ongoing discussion whether the cavity is accessible for sulfur. Yet no valid proof of cavity filling has been presented, mostly due to application of unsuitable high-vacuum methods for the analysis of sulfur distribution. Here we describe the distribution of sulfur in hollow carbon spheres by powder X-ray diffraction and Raman spectroscopy along with results from scanning electron microscopy and nitrogen physisorption. The results of these methods lead to the conclusion that the cavity is not accessible for sulfur infiltration. Nevertheless, HCS/sulfur composite cathodes with areal sulfur loadings of 2.0 mg·cm−2 were investigated electrochemically, showing stable cycling performance with specific capacities of about 500 mAh·g−1 based on the mass of sulfur over 500 cycles.

Description: Main aims of the study are a deepened understanding of the mechanically relevant (ultra-)structures and the mechanical behaviour of various arborescent and shrubby monocotyledons and obtaining the structure–function relationships of different structurally conspicuous parts in Dracaena marginata stems. The stems of five different “woody” monocotyledon species were dissected and the mechanical properties of the most noticeable tissues in the five monocotyledons and, additionally, of individual vascular bundles in D. marginata, were tested under tensile stress. Results for Young’s moduli and density of these tissues were assessed as well as the area, critical strain, Young’s modulus and tensile strength of the vascular bundles in Dracaena marginata. These analyses allowed for generating a model for the mechanical interaction of tissues and vascular bundles of the stem in D. marginata as well as filling major “white spots” in property charts for biological materials. Additionally we shortly discuss the potential significance of such studies for the development of branched and unbranched bio-inspired fibre-reinforced materials and structures with enhanced properties.

Description: This paper details the application of phosphorus monolayer doping of silicon on insulator substrates. There have been no previous publications dedicated to the topic of MLD on SOI, which allows for the impact of reduced substrate dimensions to be probed. The doping was done through functionalization of the substrates with chemically bound allyldiphenylphosphine dopant molecules. Following functionalization, the samples were capped and annealed to enable the diffusion of dopant atoms into the substrate and their activation. Electrical and material characterisation was carried out to determine the impact of MLD on surface quality and activation results produced by the process. MLD has proven to be highly applicable to SOI substrates producing doping levels in excess of 1 × 1019 cm−3 with minimal impact on surface quality. Hall effect data proved that reducing SOI dimensions from 66 to 13 nm lead to an increase in carrier concentration values due to the reduced volume available to the dopant for diffusion. Dopant trapping was found at both Si–SiO2 interfaces and will be problematic when attempting to reach doping levels achieved by rival techniques.

Description: The mucilage envelope of seeds has various functions including the provision of different ways for the dispersal of diaspores. Chemical composition and water content of the mucilage yield particular adhesive and frictional properties in the envelope that also influence the dispersal of seeds. To determine the physical properties ofPlantago lanceolataseed mucilage we studied (1) composition, (2) desiccation, (3) adhesion, and (4) friction properties of the mucilage under different hydration conditions. We revealed the presence of cellulose fibrils in the mucilage, which are responsible for a continuous and even distribution of the mucilaginous layer on the seed surface. The measured values of adhesive and frictional properties differed significantly in comparison to the previously studied pectic mucilage ofLinum usitatissimum. Also, the water loss from the cellulose mucilage was more rapid. The obtained different values can result from the presence of cellulose fibrils and their interaction with pectins in the mucilage. Because of this feature the mucilage ofP. lanceolatamay represent a more regularly ordered and stabile system than the pectic mucilage of flax, which lacks cellulose. In spite of the fact thatP. lanceolatamucilage revealed different adhesive and frictional properties than the pectic mucilage, it still demonstrates an effective system promoting zoochoric seed dispersal. Cellulose may additionally prevent the mucilage against loss from the seed surface.

Description: Zeolite pellets containing 5 wt % of binder (methylcellulose or sodium metasilicate) were formed with a hydraulic press. This paper describes a mathematical model to predict the mechanical properties (uniaxial and diametric compression) of these pellets for arbitrary dimensions (height and diameter) using a design of experiments (DOE) methodology. A second-degree polynomial equation including interactions was used to approximate the experimental results. This leads to an empirical model for the estimation of the mechanical properties of zeolite pellets with 5 wt % of binder. The model was verified by additional experimental tests including pellets of different dimensions created with different applied pressures. The optimum dimensions were found to be a diameter of 10–23 mm, a height of 1–3.5 mm and an applied pressure higher than 200 MPa. These pellets are promising for technological uses in molecular decontamination for aerospace-based applications.

Description: Heat-assisted magnetic recording (HAMR) is often considered the next major step in the storage industry: it is predicted to increase the storage capacity, the read/write speed and the data lifetime of future hard disk drives. However, despite more than a decade of development work, the reliability is still a prime concern. Featuring an inherently fragile surface-plasmon resonator as a highly localized heat source, as part of a near-field transducer (NFT), the current industry concepts still fail to deliver drives with sufficient lifetime. This study presents a method to aid conventional NFT-designs by additional grazing-incidence laser illumination, which may open an alternative route to high-durability HAMR. Magnetic switching is demonstrated on consumer-grade CoCrPt perpendicular magnetic recording media using a green and a near-infrared diode laser. Sub-500 nm magnetic features are written in the absence of a NFT in a moderate bias field of only μ0 H = 0.3 T with individual laser pulses of 40 mW power and 50 ns duration with a laser spot size of 3 μm (short axis) at the sample surface – six times larger than the magnetic features. Herein, the presence of a nanoscopic object, i.e., the tip of an atomic force microscope in the focus of the laser at the sample surface, has no impact on the recorded magnetic features – thus suggesting full compatibility with NFT-HAMR.

Description: The sensing properties of electrodes chemically modified with PEDOT/PSS towards catechol and hydroquinone sensing have been successfully improved by combining layers of PEDOT/PSS with layers of a secondary electrocatalytic material such as gold nanoparticles (PEDOT/PSS/AuNPs), copper phthalocyanine (PEDOT/PSS/CuPc) or lutetium bisphthalocyanine (PEDOT/PSS/LuPc2). Layered composites exhibit synergistic effects that strongly enhance the electrocatalytic activity as indicated by the increase in intensity and the shift of the redox peaks to lower potentials. A remarkable improvement has been achieved using PEDOT/PSS/LuPc2, which exhibits excellent electrocatalytic activity towards the oxidation of catechol. The kinetic studies demonstrated diffusion-controlled processes at the electrode surfaces. The kinetic parameters such as Tafel slopes and charge transfer coefficient (α) confirm the improved electrocatalytic activity of the layered electron mediators. The peak currents increased linearly with concentration of catechol and hydroquinone over the range of 1.5 × 10−4 to 4.0 × 10−6 mol·L−1 with a limit of detection on the scale of μmol·L−1. The layered composite hybrid systems were also found to be excellent electron mediators in biosensors containing tyrosinase and laccase, and they combine the recognition and biocatalytic properties of biomolecules with the unique catalytic features of composite materials. The observed increase in the intensity of the responses allowed detection limits of 1 × 10−7 mol·L−1 to be attained.

Description: We present a procedure to perform and interpret pull-off force measurements during the jump-off-contact process between a liquid drop and rough surfaces using a conventional atomic force microscope. In this method, a micrometric liquid mercury drop is attached to an AFM tipless cantilever to measure the force required to pull this drop off a rough surface. We test the method with two surfaces: a square array of nanometer-sized peaks commonly used for the determination of AFM tip sharpness and a multi-scaled rough diamond surface containing sub-micrometer protrusions. Measurements are carried out in a nitrogen atmosphere to avoid water capillary interactions. We obtain information about the average force of adhesion between a single peak or protrusion and the liquid drop. This procedure could provide useful microscopic information to improve our understanding of wetting phenomena on rough surfaces.

Description: The challenges and limitations in calculating free energies and entropies of adsorption and interaction of organic molecules on an insulating substrate are discussed. The adhesion of 1,3,5-tri(4'-cyano-[1,1'-biphenyl]-4-yl)benzene (TCB) and 1,4-bis(4-cyanophenyl)-2,5-bis(decyloxy)benzene (CDB) molecules to step edges on the KCl(001) surface and the formation of molecular dimers were studied using classical molecular dynamics. Both molecules contain the same anchoring groups and benzene ring structures, yet differ in their flexibility. Therefore, the entropic contributions to their free energy differ, which affects surface processes. Using potential of mean force and thermodynamic integration techniques, free energy profiles and entropy changes were calculated for step adhesion and dimer formation of these molecules. However, converging these calculations is nontrivial and comes at large computational cost. We illustrate the difficulties as well as the possibilities of applying these methods towards understanding dynamic processes of organic molecules on insulating substrates.

Description: Background: Two-dimensional (2D) transition-metal dichalcogenides (TMDCs) with intrinsically crystal inversion-symmetry breaking have shown many advanced optical properties. In particular, the valley polarization in 2D TMDCs that can be addressed optically has inspired new physical phenomena and great potential applications in valleytronics. Results: Here, we propose a TMDC–nanoantenna system that could effectively enhance and direct emission from the two valleys in TMDCs into diametrically opposite directions. By mimicking the emission from each valley of the monolayer of WSe2 as a chiral point-dipole emitter, we demonstrate numerically that the emission from different valleys is directed into opposite directions when coupling to a double-bar plasmonic nanoantenna. The directionality derives from the interference between the dipole and quadrupole modes excited in the two bars, respectively. Thus, we could tune the emission direction from the proposed TMDC–nanoantenna system by tuning the pumping without changing the antenna structure. Furthermore, we discuss the general principles and the opportunities to improve the average performance of the nanoantenna structure. Conclusion: The scheme we propose here can potentially serve as an important component for valley-based applications, such as non-volatile information storage and processing.

Description: Titania-supported palladium, gold and bimetallic nanoparticles (second-generation nanoparticles) demonstrate promising photocatalytic properties. However, due to unusual reactivity, second-generation nanoparticles can be hazardous for living organisms. Considering the ever-growing number of new types of nanoparticles that can potentially contaminate the environment, a determination of their toxicity is extremely important. The main aim of presented study was to investigate the cytotoxic effect of surface modified TiO2-based nanoparticles, to model their quantitative nanostructure–toxicity relationships and to reveal the toxicity mechanism. In this context, toxicity tests for surface-modified TiO2-based nanoparticles were performed in vitro, using Gram-negative bacteria Escherichia coli and Chinese hamster ovary (CHO-K1) cells. The obtained cytotoxicity data were analyzed by means of computational methods (quantitative structure–activity relationships, QSAR approach). Based on a combined experimental and computational approach, predictive models were developed, and relationships between cytotoxicity, size, and specific surface area (Brunauer–Emmett–Teller surface, BET) of nanoparticles were discussed.

Description: We present a fast and flexible method for the fabrication of Au nanocolumns. Au nanostructures were produced by pulsed laser deposition in air at atmospheric pressure. No impurities or Au compounds were detected in the resulting samples. The nanoparticles and nanoaggregates produced in the ablated plasma at atmospheric pressure led to the formation of chain-like nanostructures on the substrate. The dependence of the surface morphology of the samples on the deposition geometry used in the experimental set up was studied. Nanocolumns of different size and density were produced by varying the angle between the plasma plume and the substrate. The electrical, optical, and hydrophobic properties of the samples were studied and discussed in relation to their morphology. All of the nanostructures were conductive, with conductivity increasing with the accumulation of ablated material on the substrate. The modification of the electrical properties of the nanostructures was demonstrated by irradiation by infrared light. The Au nanostructures fabricated by the proposed technology are difficult to prepare by other methods, which makes the simple implementation and realization in ambient conditions presented in this work more ideal for industrial applications.

Description: The development of atomic force microscopy (AFM) has allowed wear mechanisms to be investigated at the nanometer scale by means of a single asperity contact generated by an AFM tip and an interacting surface. However, the low wear rate at the nanoscale and the thermal drift require fastidious quantitative measurements of the wear volume for determining wear laws. In this paper, we describe a new, effective, experimental methodology based on circular mode AFM, which generates high frequency, circular displacements of the contact. Under such conditions, the wear rate is significant and the drift of the piezoelectric actuator is limited. As a result, well-defined wear tracks are generated and an accurate computation of the wear volume is possible. Finally, we describe the advantages of this method and we report a relevant application example addressing a Cu/Al2O3 nanocomposite material used in industrial applications.

Description: The combination of magnetic nanoparticles with a porous silica is a composite that has attracted significant attention for potential multifunctional theranostic applications. In this study, 30 wt % CuFe2O4 was impregnated into a matrix of monodispersed spherical hydrophilic silica (HYPS) nanoparticles through a simple dry impregnation technique. The chemotherapy drug cisplatin was loaded through electrostatic equilibrium adsorption over 24 h in normal saline solution. The presence of cubic spinel CuFe2O4 on HYPS was confirmed through powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FTIR) and diffuse reflectance UV–vis spectroscopy (DR UV–vis) analysis. The HYPS particles showed a surface area of 170 m2/g, pore size of 8.3 nm and pore volume of 0.35 cm3/g. The cisplatin/CuFe2O4/HYPS nanoformulation showed the accumulation of copper ferrite nanoparticles on the surface and in the pores of HYPS with a surface area of 45 m2/g, pore size of 16 nm and pore volume of 0.18 cm3/g. Transmission electron microscopy (TEM) and energy dispersive X-ray (EDX) mapping analysis showed the presence of homogeneous silica particles with nanoclusters of copper ferrite distributed on the HYPS support. Vibrating sample magnetometry (VSM) analysis of CuFe2O4/HYPS showed paramagnetic behavior with a saturated magnetization value of 7.65 emu/g. DRS UV–vis analysis revealed the functionalization of cisplatin in tetrahedral and octahedral coordination in the CuFe2O4/HYPS composite. Compared to other supports such as mesocellular foam and silicalite, the release of cisplatin using the dialysis membrane technique was found to be superior when CuFe2O4/HYPS was applied as the support. An in vitro experiment was conducted to determine the potential of CuFe2O4/HYPS as an anticancer agent against the human breast cancer cell line MCF-7. The results show that the nanoparticle formulation can effectively target cancerous cells and could be an effective tumor imaging guide and drug delivery system.

Description: Carbon nanospheres with a high Brunauer–Emmett–Teller (BET) specific surface area were fabricated via the pyrolysis of polyacrylonitrile–poly(methyl methacrylate) (PAN–PMMA) core–shell nanoparticles. Firstly, PAN–PMMA nanoparticles at high concentration and low surfactant content were controllably synthesized by a two-stage azobisisobutyronitrile (AIBN)-initiated semicontinuous emulsion polymerization. The carbon nanospheres were obtained after the PAN core domain was converted into carbon and the PMMA shell was sacrificed via the subsequent heat treatment steps. The thickness of the PMMA shell can be easily adjusted by changing the feeding volume ratio (FVR) of methyl methacrylate (MMA) to acrylonitrile (AN). At an FVR of 1.6, the coarse PAN cores were completely buried in the PMMA shells, and the surface of the obtained PAN–PMMA nanoparticles became smooth. The thick PMMA shell can inhibit the adhesion between carbon nanospheres caused by cyclization reactions during heat treatment. The carbon nanospheres with a diameter of 35–65 nm and a high BET specific surface area of 612.8 m2/g were obtained from the PAN–PMMA nanoparticles synthesized at an FVR of 1.6. The carbon nanospheres exhibited a large adsorption capacity of 190.0 mg/g for methylene blue, thus making them excellent adsorbents for the removal of organic pollutants from water.

Description: A fabrication method of a multifunctional hybrid material is achieved by using the insoluble organic nacre matrix of the Haliotis laevigata shell infiltrated with gelatin as a confined reaction environment. Inside this organic scaffold magnetite nanoparticles (MNPs) are synthesized. The amount of MNPs can be controlled through the synthesis protocol therefore mineral loadings starting from 15 wt % up to 65 wt % can be realized. The demineralized organic nacre matrix is characterized by small-angle and very-small-angle neutron scattering (SANS and VSANS) showing an unchanged organic matrix structure after demineralization compared to the original mineralized nacre reference. Light microscopy and confocal laser scanning microscopy studies of stained samples show the presence of insoluble proteins at the chitin surface but not between the chitin layers. Successful and homogeneous gelatin infiltration in between the chitin layers can be shown. The hybrid material is characterized by TEM and shows a layered structure filled with MNPs with a size of around 10 nm. Magnetic analysis of the material demonstrates superparamagnetic behavior as characteristic for the particle size. Simulation studies show the potential of collagen and chitin to act as nucleators, where there is a slight preference of chitin over collagen as a nucleator for magnetite. Colloidal-probe AFM measurements demonstrate that introduction of a ferrogel into the chitin matrix leads to a certain increase in the stiffness of the composite material.

Description: Several new lactic acid derivatives containing the keto linkage group far from the chiral part and short alkyl chains have been synthesized and characterised by polarising optical microscopy, differential scanning calorimetry, as well as electro-optic and dielectric spectroscopy. The materials possess a self-assembling behaviour on the nanoscale level as they form polar smectic liquid crystalline mesophases, namely the orthogonal paraelectric SmA* and the tilted ferroelectric SmC* phases, in a broad temperature range down to room temperature. A short helical pitch (≈120–320 nm), relatively high spontaneous polarisation (≈150 nC/cm2) and reasonable tilt angle values have been determined within the temperature range of the tilted ferroelectric SmC* phase. The obtained results make the new materials useful for the advanced mixture design and for further utilisation in electro-optic devices based on the deformed helix ferroelectric effect.

Description: The interaction of trimethyl(methylcyclopentadienyl)platinum(IV) ((C5H4CH3)Pt(CH3)3) molecules on fully and partially hydroxylated SiO2 surfaces, as well as the dynamics of this interaction were investigated using density functional theory (DFT) and finite temperature DFT-based molecular dynamics simulations. Fully and partially hydroxylated surfaces represent substrates before and after electron beam treatment and this study examines the role of electron beam pretreatment on the substrates in the initial stages of precursor dissociation and formation of Pt deposits. Our simulations show that on fully hydroxylated surfaces or untreated surfaces, the precursor molecules remain inactivated while we observe fragmentation of (C5H4CH3)Pt(CH3)3 on partially hydroxylated surfaces. The behavior of precursor molecules on the partially hydroxylated surfaces has been found to depend on the initial orientation of the molecule and the distribution of surface active sites. Based on the observations from the simulations and available experiments, we discuss possible dissociation channels of the precursor.

Description: Two sequential transformations of the orientational structure in nematic liquid crystal droplets containing a dendrimer additive (nanosized macromolecules with light-absorbing azobenzene terminal moieties) under light irradiation in the UV–blue spectral range were investigated. The origin of these transitions is in the change of the boundary conditions due to photoisomerization of the dendrimer adsorbed onto the liquid crystal–glycerol interface. It was shown that the photoisomerization processes of dendrimer molecules in a liquid crystal are accompanied by a spatial rearrangement of their azobenzene moieties, which is the key point in the explanation of the observed effects.

Description: In this paper we consider charge current generated by maintaining a temperature difference over a nanowire at zero voltage bias. For topological insulator nanowires in a perpendicular magnetic field the current can change sign as the temperature of one end is increased. Here we study how this thermoelectric current sign reversal depends on the magnetic field and how impurities affect the size of the thermoelectric current. We consider both scalar and magnetic impurities and show that their influence on the current are quite similar, although the magnetic impurities seem to be more effective in reducing the effect. For moderate impurity concentration the sign reversal persists.

Description: The detection of single gas molecules is a highly challenging work because it requires sensors with an ultra-high level of sensitivity. By using density functional theory, here we demonstrate that the adsorption of a paramagnetic unpaired free radical gas (NO) on a monolayer of XS2 (X = Mo, W) can trigger the transition from semiconductor to half metal. More precisely, the single-layer XS2 (X = Mo, W) with NO adsorbed on it would behave like a metal in one spin channel while acting as a semiconductor in the other spin orientation. The half-metallicity is robust and independent of the NO concentration. In contrast, no half-metallic feature can be observed after the adsorption of other free radical gases such as NO2. The unique change in electronic properties after the adsorption of NO on transition-metal sulfides highlights an effective strategy to distinguish NO from other gas species by experimentally measuring spin-resolved transmission. Our results also suggest XS2 (X = Mo, W) nanosheets can act as promising nanoscale NO sensors.

Description: Carbon nanotube (CNT) yarns exhibit low tensile strength compared to conventional high-performance carbon fibers due to the facile sliding of CNTs past one another. Electron beam (e-beam) irradiation was employed for in a single-step surface modification of CNTs to improve the mechanical properties of this material. To this end, CNT yarns were simultaneously functionalized and crosslinked using acrylic acid (AA) and acrylonitrile (AN) in an e-beam irradiation process. The chemical modification of CNT yarns was confirmed by X-ray photoelectron spectroscopy (XPS), Raman spectroscopy and scanning electron microscopy (SEM). The best improvement in mechanical properties was achieved on a sample treated with an aqueous solution of AA and subsequent irradiation. CNT yarn treatment with AA enhanced the strength (444.5 ± 68.4 MPa) by more than 75% and the modulus (21.5 ± 0.6 GPa) by more than 144% as compared to untreated CNT yarn (strength 251 ± 26.5 MPa and modulus 8.8 ± 1.2 GPa).

Description: In this work, the continuum model for focused electron beam induced deposition (FEBID) is generalized to account for multilayer adsorption processes. Two types of adsorption energies, describing both physisorption and spontaneous chemisorption, are included. Steady state solutions under no diffusion are investigated and compared under a wide range of conditions. The different growth regimes observed are fully explained by relative changes in FEBID characteristic frequencies. Additionally, we present a set of FEBID frequency maps where growth rate and surface coverage are plotted as a function of characteristic timescales. From the analysis of Langmuir, as well as homogeneous and heterogeneous multilayer maps, we infer that three types of growth regimes are possible for FEBID under no diffusion, resulting into four types of adsorption isotherms. We propose the use of these maps as a powerful tool for the analysis of FEBID processes.

Description: The implementation of imaging techniques with low-energy electrons at synchrotron laboratories allowed for significant advancement in the field of spectromicroscopy. The spectroscopic photoemission and low energy electron microscope, SPELEEM, is a notable example. We summarize the multitechnique capabilities of the SPELEEM instrument, reporting on the instrumental aspects and the latest developments on the technical side. We briefly review applications, which are grouped into two main scientific fields. The first one covers different aspects of graphene physics. In particular, we highlight the recent work on graphene/Ir(100). Here, SPELEEM was employed to monitor the changes in the electronic structure that occur for different film morphologies and during the intercalation of Au. The Au monolayer, which creeps under graphene from the film edges, efficiently decouples the graphene from the substrate lowering the Dirac energy from 0.42 eV to 0.1 eV. The second field combines magnetism studies at the mesoscopic length scale with self-organized systems featuring ordered nanostructures. This example highlights the possibility to monitor growth processes in real time and combine chemical characterization with X-ray magnetic circular dichroism–photoemission electron microscopy (XMCD–PEEM) magnetic imaging by using the variable photon polarization and energy available at the synchrotron source.

Description: Measuring cellular respiration with single-cell spatial resolution is a significant challenge, even with modern tools and techniques. Here, a double-channel micropipette is proposed and investigated as a probe to achieve this goal by sampling fluid near the point of interest. A finite element model (FEM) of this perfusion probe is validated by comparing simulation results with experimental results of hydrodynamically confined fluorescent molecule diffusion. The FEM is then used to investigate the dependence of the oxygen concentration variation and the measurement signal on system parameters, including the pipette’s shape, perfusion velocity, position of the oxygen sensors within the pipette, and proximity of the pipette to the substrate. The work demonstrates that the use of perfusion double-barrel micropipette probes enables the detection of oxygen consumption signals with micrometer spatial resolution, while amplifying the signal, as compared to sensors without the perfusion system. In certain flow velocity ranges (depending on pipette geometry and configuration), the perfusion flow increases oxygen concentration gradients formed due to cellular oxygen consumption. An optimal perfusion velocity for respiratory measurements on single cells can be determined for different system parameters (e.g., proximity of the pipette to the substrate). The optimum perfusion velocities calculated in this paper range from 1.9 to 12.5 μm/s. Finally, the FEM model is used to show that the spatial resolution of the probe may be varied by adjusting the pipette tip diameter, which may allow oxygen consumption mapping of cells within tissue, as well as individual cells at subcellular resolution.

Description: The electrodeposition of graphene has drawn considerable attention due to its appealing applications for sensors, supercapacitors and lithium-ion batteries. However, there are still some limitations in the current electrodeposition methods for graphene. Here, we present a novel electrodeposition method for the direct deposition of reduced graphene oxide (rGO) with chitosan. In this method, a 2-hydroxypropyltrimethylammonium chloride-based chitosan-modified rGO material was prepared. This material disperses homogenously in the chitosan solution, forming a deposition solution with good dispersion stability. Subsequently, the modified rGO material was deposited on an electrode through codeposition with chitosan, based on the coordination deposition method. After electrodeposition, the homogeneous, deposited rGO/chitosan films can be generated on copper or silver electrodes or substrates. The electrodeposition method allows for the convenient and controlled creation of rGO/chitosan nanocomposite coatings and films of different shapes and thickness. It also introduces a new method of creating films, as they can be peeled completely from the electrodes. Moreover, this method allows for a rGO/chitosan film to be deposited directly onto an electrode, which can then be used for electrochemical detection.

Description: The properties of bulk compounds required to be suitable for photovoltaic applications, such as excellent visible light absorption, favorable exciton formation, and charge separation are equally essential for two-dimensional (2D) materials. Here, we systematically study 2D group IV–V compounds such as SiAs2 and GeAs2 with regard to their structural, electronic and optical properties using density functional theory (DFT), hybrid functional and Bethe–Salpeter equation (BSE) approaches. We find that the exfoliation of single-layer SiAs2 and GeAs2 is highly feasible and in principle could be carried out experimentally by mechanical cleavage due to the dynamic stability of the compounds, which is inferred by analyzing their vibrational normal mode. SiAs2 and GeAs2 monolayers possess a bandgap of 1.91 and 1.64 eV, respectively, which is excellent for sunlight harvesting, while the exciton binding energy is found to be 0.25 and 0.14 eV, respectively. Furthermore, band-gap tuning is also possible by application of tensile strain. Our results highlight a new family of 2D materials with great potential for solar cell applications.

Description: The determination of the negative ion yield of 2′-chloro-1,1′-biphenyl (2-Cl-BP), 2′-bromo-1,1′-biphenyl (2-Br-BP) and 2′-iodo-1,1′-biphenyl (2-I-BP) upon dissociative electron attachment (DEA) at an electron energy of 0 eV revealed cross section values that were more than ten times higher for iodide loss from 2-I-BP than for the other halogenides from the respective biphenyls (BPs). Comparison with dissociative ionization mass spectra shows that the ratio of the efficiency of electron impact ionization induced fragmentation of 2-I-BP, 2-Br-BP, and 2-Cl-BP amounts to approximately 1:0.7:0.6. Inspired by these results, self-assembled monolayers (SAMs) of the respective biphenyl-4-thiols, 2-Cl-BPT, 2-Br-BPT, 2-I-BPT as well as BPT, were grown on a Au(111) substrate and exposed to 50 eV electrons. The effect of electron irradiation was investigated by X-ray photoelectron spectroscopy (XPS), to determine whether the high relative DEA cross section for iodide loss from 2-I-BPT as compared to 2-Br-BP and 2-Cl-BP is reflected in the cross-linking efficiency of SAMs made from these materials. Such sensitization could reduce the electron dose needed for the cross-linking process and may thus lead to a significantly faster conversion of the respective SAMs into carbon nanomembranes (CNMs) without the need for an increased current density. XPS data support the notation that DEA sensitization may be used to achieve more efficient electron-induced cross-linking of SAMs, revealing more than ten times faster cross-linking of 2-I-BPT SAMs compared to those made from the other halogenated biphenyls or from native BPT at the same current density. Furthermore, the transfer of a freestanding membrane onto a TEM grid and the subsequent investigation by helium ion microscopy (HIM) verified the existence of a mechanically stable CNM created from 2-I-BPT after exposure to an electron dose as low as 1.8 mC/cm2. In contrast, SAMs made from BPT, 2-Cl-BPT and 2-Br-BPT did not form stable CNMs after a significantly higher electron dose of 9 mC/cm2.

Description: Magnetic films of magnetite (Fe3O4) with controlled defects, so-called antidot arrays, were synthesized by a new technique called AFIR. AFIR consists of the deposition of a thin film by atomic layer deposition, the generation of square and hexagonal arrays of holes using focused ion beam milling, and the subsequent thermal reduction of the antidot arrays. Magnetic characterizations were carried out by magneto-optic Kerr effect measurements, showing the enhancement of the coercivity for the antidot arrays. AFIR opens a new route to manufacture ordered antidot arrays of magnetic oxides with variable lattice parameters.

Description: A tunable fractional Fourier transform of the quantum wave function of electrons satisfying either the Schrödinger or the Dirac equation can be implemented in an atomically thin material by a parabolic potential distribution applied on a direction transverse to that of electron propagation. The difference between the propagation lengths necessary to obtain a fractional Fourier transform of a given order in these two cases could be seen as a manifestation of the Berry phase. The Fourier transform of the electron wave function is a particular case of the fractional Fourier transform. If the input and output wave functions are discretized, this configuration implements in one step the discrete fractional Fourier transform, in particular the discrete Fourier transform, and thus can act as a coprocessor in integrated logic circuits.

Description: Doxorubicin-conjugated magnetic nanoparticles containing hydrolyzable hydrazone bonds were developed using a non-toxic poly[N-(2-hydroxypropyl)methacrylamide] (PHPMA) coating, which ensured good colloidal stability in aqueous media and limited internalization by the cells, however, enabled adhesion to the cell surface. While the neat PHPMA-coated particles proved to be non-toxic, doxorubicin-conjugated particles exhibited enhanced cytotoxicity in both drug-sensitive and drug-resistant tumor cells compared to free doxorubicin. The newly developed doxorubicin-conjugated PHPMA-coated magnetic particles seem to be a promising magnetically targeted vehicle for anticancer drug delivery.

Description: Under ambient conditions, surfaces are rapidly modified and contaminated by absorbance of molecules and a variety of nanoparticles that drastically change their chemical and physical properties. The atomic force microscope tip–sample system can be considered a model system for investigating a variety of nanoscale phenomena. In the present work we use atomic force microscopy to directly image nanoscale contamination on surfaces, and to characterize this contamination by using multidimensional spectroscopy techniques. By acquisition of spectroscopy data as a function of tip–sample voltage and tip–sample distance, we are able to determine the contact potential, the Hamaker constant and the effective thickness of the dielectric layer within the tip–sample system. All these properties depend strongly on the contamination within the tip–sample system. We propose to access the state of contamination of real surfaces under ambient conditions using advanced atomic force microscopy techniques.

Description: This work is an investigation of the properties of semiconductor materials based on metal oxides, their catalytic properties, and their application as gas sensors, which were shown to exhibit high sensitivity, stability, and selectivity to target gases. The aim of this work is the comparison of gas sensing properties of tin dioxide in the form of individual nanowires and nanopowders obtained by sol–gel synthesis. This comparison is necessary because the traditional synthesis procedures of small particle, metal oxide materials seem to be approaching their limit. Because of this, there is increasing interest in the fabrication of functional materials based on nanowires, i.e., quasi-one-dimensional objects. In this work, nanocrystalline tin dioxide samples with different morphology were synthesized. The gas-transport method was used for the fabrication of well-faceted wire-like crystals with diameters ranging between 15–100 nm. The sol–gel method allowed us to obtain fragile gels from powders with grain sizes of about 5 nm. By means of X-ray photoelectron spectroscopy (XPS) it was proven that the nanowires contain considerably smaller amounts of hydroxy groups compared to the nanopowders. This leads to a decrease in the parasitic sensitivity of the sensing materials to humidity. In addition, we demonstrated that the nanowires are characterized by a nearly single-crystalline structure, ensuring higher stability of the sensor response due to the unlikelihood of sample recrystallization. The results from the ammonia detection experiments showed that the ratio of the sensor response to the surface area exhibits similar values for both the individual nanowire and nanopowders-based sensor materials.

Description: Nanocrystals are used as universal approach to improve the bioactivity of poorly soluble active ingredients. They are produced by various techniques, typically yielding aqueous nanosuspensions, which are prone to microbial contamination. Preservation of nanocrystals is possible but might not always be feasible, as preservatives might interfere with other excipients in the formulations or with chemicals used in assays, cell cultures or animal models. Therefore, to enable an easier use of nanocrystals, preservative-free nanosuspensions would be a good alternative. In this study, rutin nanocrystals were frozen and stored for three months at −20 °C. The chemical, physical and microbial stability were monitored, and the results were compared to preserved nanosuspensions. The frozen nanosuspensions remained stable and possessed excellent stability over the whole time of storage, indicating that the freeze–thaw process is suitable for the production of preservative-free nanosuspensions with excellent long-term stability. The freeze–thaw process for nanosuspensions is a simple concept and is suggested as alternative, when preserved nanosuspensions cannot be used.

Description: Ag, Pt, and Rh monometallic colloids were produced via laser ablation. Separate Ag–Rh and Ag–Pt heterostructures were formed by mixing and resulted in groupings of Rh/Pt nanoparticles adsorbing to the concavities of the larger Ag nanostructures. The 400 nm Ag plasmonic absorption peak was slightly blue-shifted for Ag–Pt and red-shifted for Ag–Rh heterostructures. Catalytic activity for the reduction of 4-nitrophenol increased significantly for Ag–Pt and Ag–Rh compared to the monometallic constituents, and persisted at lower loading ratios and consecutive reduction cycles. The enhancement is attributed to the Rh and Pt nanoparticles forming antenna–reactor-type plasmonic catalysts with the Ag nanostructures.

Description: In this contribution, the preparation of hierarchically structured ETS-10-based catalysts exhibiting notably higher activity in the conversion of triolein with methanol compared to microporous titanosilicate is presented. Triolein, together with its unsaturated analog trilinolein, represent the most prevalent triglycerides in oils. The introduction of mesopores by post-synthetic treatment with hydrogen peroxide and a subsequent calcination step results in the generation of an additional active surface with Brønsted basic sites becoming accessible for triolein and enhancing the rate of transesterification. The resulting catalyst exhibits a comparable triolein conversion (≈73%) after 4 h of reaction to CaO (≈76%), which is reportedly known to be highly active in the transesterification of triglycerides. In addition, while CaO showed a maximum conversion of 83% after 24 h, the ETS-10-based catalyst reached 100% after 8 h, revealing its higher stability compared to CaO. The following characteristics of the catalysts were experimentally addressed – crystal structure (X-ray diffraction, transmission electron microscopy), crystal shape and size (scanning electron microscopy, laser diffraction), textural properties (N2 sorption, Hg porosimetry), presence of hydroxyl groups and active sites (temperature-programmed desorption of NH3 and CO2, 29Si magic angle spinning nuclear magnetic resonance (NMR)), mesopore accessibility and diffusion coefficient of adsorbed triolein (pulsed field gradient NMR), pore interconnectivity (variable temperature and exchange spectroscopy experiments using hyperpolarized 129Xe NMR) and oxidation state of Ti atoms (electron paramagnetic resonance). The obtained results enabled the detailed understanding of the impact of the post-synthetic treatment applied to the ETS-10 titanosilicate with respect to the catalytic activity in the heterogeneously catalyzed transesterification of triglycerides.

Description: We present the successful growth of few-layer graphene on top of AlN-based solidly mounted resonators (SMR) using a low-temperature chemical vapour deposition (CVD) process assisted by Ni catalysts, and its effective bio-functionalization with antibodies. The SMRs are manufactured on top of fully insulating AlN/SiO2 acoustic mirrors able to withstand the temperatures reached during the CVD growth of graphene (up to 650 °C). The active AlN films, purposely grown with the c-axis tilted, effectively excite shear modes displaying excellent in-liquid performance, with electromechanical coupling and quality factors of around 3% and 150, respectively, which barely vary after graphene integration. Raman spectra reveal that the as-grown graphene is composed of less than five weakly coupled layers with a low density of defects. Two functionalization protocols of the graphene are proposed. The first one, based on a covalent binding approach, starts with a low-damage O2 plasma treatment that introduces a controlled density of defects in graphene, including carboxylic groups. After that, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride/N-hydroxysuccinimide (EDC/NHS) chemistry is used to covalently bind streptavidin molecules to the surface of the sensors. The second functionalization protocol is based on the non-covalent bonding of streptavidin on hydrophobic graphene surfaces. The two protocols end with the effective bonding of biotinylated anti-IgG antibodies to the streptavidin, which leaves the surface of the devices ready for possible IgG detection.

Description: We demonstrate an ultrasonication-assisted synthesis without polar solvent of CsPbBr3 and Cs4PbBr6 perovskite nanocrystals (PNCs) and their reversible transformation. The as-prepared CsPbBr3 PNCs and Cs4PbBr6 PNCs exhibit different optical properties that depend on their morphology, size, and structure. The photoluminescence (PL) emission and quantum yield (QY) of the CsPbBr3 PNCs can be tuned by changing the ultrasound power, radiation time, and the height of the vibrating spear. The optimized CsPbBr3 PNCs show a good stability and high PL QY of up to 85%. In addition, the phase transformation between CsPbBr3 PNCs and Cs4PbBr6 PNCs can be obtained through varying the amount of oleylamine (OAm) and water. The mechanism of this transformation between the CsPbBr3 PNCs and Cs4PbBr6 PNCs and their morphology change are studied, involving ions equilibrium, anisotropic growth kinetics, and CsBr-stripping process.

Description: We investigate the excitation as well as propagation of magnetic modes in plasmonic nanostructures. Such structures are particularly suited for excitation with cylindrical vector beams. We study magneto-inductive coupling between adjacent nanostructures. We utilize high-resolution lithographic techniques for the preparation of complex nanostructures consisting of gold as well as aluminium. These structures are subsequently characterized by linear optical spectroscopy. The well characterized and designed structures are afterwards studied in depth by exciting them with radial and azimuthally polarized light and simultaneously measuring their plasmonic near-field behavior. Additionally, we attempt to model and simulate our results, a project which has, to the best of our knowledge, not been attempted so far.

Description: The paper reports on the features and advantages of horizontally oriented flexible silicon nanowires (SiNWs) substrates for surface-enhanced Raman spectroscopy (SERS) applications. The novel SERS substrates are described in detail considering three main aspects. First, the key synthesis parameters for the flexible nanostructure SERS substrates were optimized. It is shown that fabrication temperature and metal-plating duration significantly influence the flexibility of the SiNWs and, consequently, determine the SERS enhancement. Second, it is demonstrated how the immersion in a liquid followed by drying results in the formation of SiNWs bundles influencing the surface morphology. The morphology changes were described by fractal dimension and lacunar analyses and correlated with the duration of Ag plating and SERS measurements. SERS examination showed the optimal intensity values for SiNWs thickness values of 60–100 nm. That is, when the flexibility of the self-assembly SiNWs allowed hot spots occurrence. Finally, the test with 4-mercaptophenylboronic acid showed excellent SERS performance of the flexible, horizontally oriented SiNWs in comparison with several other commercially available substrates.

Description: Surface-enhanced Raman spectroscopy (SERS) is a very promising analytical technique for the detection and identification of trace amounts of analytes. Among the many substrates used in SERS of great interest are nanostructures fabricated using physical methods, such as semicontinuous metal films obtained via electron beam physical vapor deposition. In these studies, we investigate the influence of morphology of semicontinuous silver films on their SERS properties. The morphologies studied ranged from isolated particles through percolated films to almost continuous films. We found that films below the percolation threshold (transition from dielectric-like to metal-like) made of isolated silver structures provided the largest SERS enhancement of 4-aminothiophenol (4-ATP) analyte signals. The substrate closest to the percolation threshold has the SERS signal about four times lower than the highest signal sample.

Description: 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.

Description: The unique photothermal properties of non-spherical gold nanoparticles under near-infrared (NIR) irradiation find broad application in nanotechnology and nanomedicine. The combination of their plasmonic features with widely used biocompatible poly(vinyl alcohol) (PVA) films can lead to novel hybrid polymeric materials with tunable photothermal properties and a wide range of applications. In this study, thin PVA films containing highly photothermally efficient gold nanostars (GNSs) were fabricated and their properties were studied. The resulting films displayed good mechanical properties and a pronounced photothermal effect under NIR irradiation. The local photothermal effect triggered by NIR irradiation of the PVA-GNS films is highly efficient at killing bacteria, therefore providing an opportunity to develop new types of protective antibacterial films and coatings.

Description: 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.

Description: We present the combined analysis of electroluminescence (EL) and current–voltage (I–V) behavior of single, freestanding (In,Ga)N/GaN nanowire (NW) light-emitting diodes (LEDs) in an unprocessed, self-assembled ensemble grown by molecular beam epitaxy. The data were acquired in a scanning electron microscope equipped with a micromanipulator and a luminescence detection system. Single NW spectra consist of emission lines originating from different quantum wells, and the width of the spectra increases with decreasing peak emission energy. The corresponding I–V characteristics are described well by a modified Shockley equation. The key advantage of this measurement approach is the possibility to correlate the EL intensity of a single-NW LED with the actual current density in this NW. This way, the external quantum efficiency (EQE) can be investigated as a function of the current in a single-NW LED. The comparison of the EQE characteristic of single NWs and the ensemble device allows for a quite accurate determination of the actual number of emitting NWs in the working ensemble LED and the respective current densities in its individual NWs. This information is decisive for a meaningful and comprehensive characterization of a NW ensemble device, rendering the measurement approach employed here a very powerful analysis tool.

Description: 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.

Description: The effect of cobalt doping on the magnetic properties of Mn1− x Co x Fe2O4 nanoparticles was investigated. All samples consist of ensembles of nanoparticles with a spherical shape and average diameter of about 10 nm, showing small structural changes due to the substitution. Besides having the same morpho-structural properties, the effect of the chemical composition, i.e., the amount of Co doping, produces marked differences on the magnetic properties, especially on the magnetic anisotropy, with evident large changes in the coercive field. Moreover, Co substitution has a profound effect on the interparticle interactions, too. A dipolar-based interaction regime is detected for all samples; in addition, the intensity of the interactions shows a possible relation with the single particle anisotropy. Finally, the sample with the strongest interaction regime shows a superspin glass state confirmed by memory effect dynamics.

Description: Lithiated thin films are necessary for the fabrication of novel solid-state batteries, including the electrodes and solid electrolytes. Physical vapour deposition and chemical vapour deposition can be used to deposit lithiated films. However, the issue of conformality on non-planar substrates with large surface area makes them impractical for nanobatteries the capacity of which scales with surface area. Atomic layer deposition (ALD) avoids these issues and is able to deposit conformal films on 3D substrates. However, ALD is limited in the range of chemical reactions, due to the required volatility of the precursors. Moreover, relatively high temperatures are necessary (above 100 °C), which can be detrimental to electrode layers and substrates, for example to silicon into which the lithium can easily diffuse. In addition, several highly reactive precursors, such as Grignard reagents or n-butyllithium (BuLi) are only usable in solution. In theory, it is possible to use BuLi and water in solution to produce thin films of LiH. This theoretical reaction is self-saturating and, therefore, follows the principles of solution atomic layer deposition (sALD). Therefore, in this work the sALD technique and principles have been employed to experimentally prove the possibility of LiH deposition. The formation of homogeneous air-sensitive thin films, characterized by using ellipsometry, grazing incidence X-ray diffraction (GIXRD), in situ quartz crystal microbalance, and scanning electron microscopy, was observed. Lithium hydride diffraction peaks have been observed in as-deposited films by GIXRD. X-ray photoelectron spectroscopy and Auger spectroscopy analysis show the chemical identity of the decomposing air-sensitive films. Despite the air sensitivity of BuLi and LiH, making many standard measurements difficult, this work establishes the use of sALD to deposit LiH, a material inaccessible to conventional ALD, from precursors and at temperatures not suitable for conventional ALD.

Description: The excellent mechanical properties of graphyne (GY) have made it an appealing candidate in the field of impact protection. We assessed the deformation mechanisms of monolayer GY nanosheets of different morphologies, including α-GY, β-GY, γ-GY and 6612-GY, under supersonic-velocity impacts (from 1 to 6 km/s) based on in silico studies. Generally, cracks initiate at the geometry center and the nanosheet experiences significant out-of-plane deformation before the propagation of cracks. Tracking the atomic von Mises stress distribution, it is found that its cumulative density function has a strong correlation with the magnitude of the Young’s modulus of the GYs. For nanosheets with a higher Young’s modulus, it tends to transfer momentum at a faster rate. Thus, a better energy dissipation or delocalization is expected during impact. This study provides a fundamental understanding of the deformation and penetration mechanisms of monolayer GY nanosheets under impact, which is crucial in order to facilitate their emerging applications for impact protection.

Description: Polyacrylonitrile (PAN)-based carbon felt was subjected to N2-plasma treatment to increase the heteroatom defects and reactive edge sites as a method to increase the performance in vanadium redox flow batteries (VRFBs). N-doping in the felt was mainly in the form of pyrrolic and pyridinic nitrogen. Even though the amount of oxygen functional groups on the N2-plasma-treated sample was very low, the felt showed enhanced electrochemical performance for both V3+/V2+ as well as V5+/V4+ redox reactions. The result is highly significant as the pristine electrode with the same amount of oxygen functional groups showed significantly less activity for the V3+/V2+ redox reaction. Overall, the single-flow cell experiments with N2-plasma-treated felt showed superior performance compared to the pristine sample. Therefore, the enhanced performance observed for the N2-plasma-treated sample should be attributed to the increase in defects and edge sites. Thus, from the present study, it can be concluded that an alternate way to increase the performance of the VRFBs is to introduce specific defects such as N-doping/substitution or to increase the edge sites. In other words, defects induced in the carbon felt such as heteroatom doping are as beneficial as the presence of oxygen functional groups for the improved performance of VRFBs. Therefore, for an optimum performance of VRFBs, defects such as N-substitution as well as oxygen functionality should be tuned.

Description: Black phosphorus (BP) has a pressure-dependent bandgap width and shows the potential for applications as a low-dimensional pressure sensor. We built two kinds of pure BP devices with zigzag or armchair conformation, and explored their pressure-dependent conductance in detail by using first principles calculations. The zigzag BP devices and the armchair BP devices exhibit different conductance–pressure relationships. For the zigzag BP devices conductance is robust against stress when the out-of-plane pressure ratio is less than 15%, and then increases rapidly until the conductive channels are fully opened. For the armchair pure BP devices conductance decreases at first by six orders of magnitude under increasing pressure and then increases quickly with further increase of pressure until the devices enter the on-state. This shows that the pure zigzag BP devices are more suitable for the application as flexible electronic devices with almost constant conductance under small pressure, while armchair BP devices can serve as bidirectional pressure sensors. Real-space distributions of band alignments were explored to understand the different pressure-related properties. We fitted a set of parameters based on the results from the empirical Wentzel–Kramers–Brillouin method, which provides an effortless approximation to quantitatively predict the pressure-related behaviors of large pure BP devices.

Description: Many recent advances in sensor technology have been possible due to nanotechnological advancements together with contributions from other research fields. Such interdisciplinary collaborations fit well with the emerging concept of nanoarchitectonics, which is a novel conceptual methodology to engineer functional materials and systems from nanoscale units through the fusion of nanotechnology with other research fields, including organic chemistry, supramolecular chemistry, materials science and biology. In this review article, we discuss recent advancements in sensor devices and sensor materials that take advantage of advanced nanoarchitectonics concepts for improved performance. In the first part, recent progress on sensor systems are roughly classified according to the sensor targets, such as chemical substances, physical conditions, and biological phenomena. In the following sections, advancements in various nanoarchitectonic motifs, including nanoporous structures, ultrathin films, and interfacial effects for improved sensor function are discussed to realize the importance of nanoarchitectonic structures. Many of these examples show that advancements in sensor technology are no longer limited by progress in microfabrication and nanofabrication of device structures – opening a new avenue for highly engineered, high performing sensor systems through the application of nanoarchitectonics concepts.

Description: A controllable ion transport including ion selectivity and ion rectification across nanochannels or porous membranes is of great importance because of potential applications ranging from biosensing to energy conversion. Here, a nanofluidic ion diode was realized by modifying carbon nitride nanotubes with different molecules yielding an asymmetric surface charge that allows for ion rectification. With the advantages of low-cost, thermal and mechanical robustness, and simple fabrication process, carbon nitride nanotubes with ion rectification have the potential to be used in salinity-gradient energy conversion and ion sensor systems.

Description: Maintaining the structural fidelity of DNA origami structures on substrates is a prerequisite for the successful fabrication of hybrid DNA origami/semiconductor-based biomedical sensor devices. Molybdenum disulfide (MoS2) is an ideal substrate for such future sensors due to its exceptional electrical, mechanical and structural properties. In this work, we performed the first investigations into the interaction of DNA origami with the MoS2 surface. In contrast to the structure-preserving interaction of DNA origami with mica, another atomically flat surface, it was observed that DNA origami structures rapidly lose their structural integrity upon interaction with MoS2. In a further series of studies, pyrene and 1-pyrenemethylamine, were evaluated as surface modifications which might mitigate this effect. While both species were found to form adsorption layers on MoS2 via physisorption, 1-pyrenemethylamine serves as a better protective agent and preserves the structures for significantly longer times. These findings will be beneficial for the fabrication of future DNA origami/MoS2 hybrid electronic structures.

Description: This work presents results of the optical and structural characterization of oleic acid-stabilized cadmium telluride nanocrystals (CdTe-NC) synthesized by an organometallic route. After being cleaned, the CdTe-NC were dispersed in toluene to obtain an ink-like dispersion, which was drop-cast on glass substrate to deposit a thin film. The CdTe-NC colloidal dispersion as well as the CdTe drop-cast thin films were characterized with regard to the optical and structural properties. TEM analysis indicates that the CdTe-NC have a nearly spherical shape (3.5 nm as mean size). Electron diffraction and XRD diffraction analyses indicated the bulk-CdTe face-centered cubic structure for CdTe-NC. An additional diffraction line corresponding to the octahedral Cd3P2 was also detected as a secondary phase, which probably originates by reacting free cadmium ions with trioctylphosphine (the tellurium reducing agent). The Raman spectrum exhibits two broad bands centered at 141.6 and 162.3 cm−1, which could be associated to the TO and LO modes of cubic CdTe nanocrystals, respectively. Additional peaks located in the 222 to 324 cm−1 range, agree fairly well with the wavenumbers reported for TO modes of octahedral Cd3P2.

Description: Nanofiltration (NF) is a capable method for the separation of dyes, which can support and even improve the applicability of photocatalysis in effluent-treatment processes. The membrane process usually will need a special pre-treatment to avoid precipitation and fouling on the membrane surface. Conceptually NF can be applied in the pre-treatment prior to the catalytic reactor or in connection with the reactor to separate the liquid phase from the reaction system and to recycle finely suspended catalysts and/or organic compounds. When concerning such reaction systems on a bigger scale, cost figures will prove the usefulness of those concepts. Different applications of photocatalysis on the lab-scale have been published in recent years. Membrane technology is used almost in all those processes and an overview will be given of those recently published systems that have been reported to be potentially useful for a further scale-up. NF membranes are mostly used for the more sophisticated separation step of these processes and the additional costs of the NF treatment, without any associated equipments, will be described and illustrated. The total specific costs of industrial NF treatment processes in usefully adjusted and designed plants range from 1 to 6 US$/m3 treated effluent. Combination concepts will have a good precondition for further development and upscaling, if the NF costs discussed here in detail will be, together with the costs of photocatalysis, economically acceptable.

Description: We report on the fabrication of thin coatings based on polylactic acid-chitosan-magnetite-eugenol (PLA-CS-Fe3O4@EUG) nanospheres by matrix assisted pulsed laser evaporation (MAPLE). Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) investigation proved that the homogenous Fe3O4@EUG nanoparticles have an average diameter of about 7 nm, while the PLA-CS-Fe3O4@EUG nanospheres diameter sizes range between 20 and 80 nm. These MAPLE-deposited coatings acted as bioactive nanosystems and exhibited a great antimicrobial effect by impairing the adherence and biofilm formation of Staphylococcus aureus (S. aureus) and Pseudomonas aeruginosa (P. aeruginosa) bacteria strains. Moreover, the obtained nano-coatings showed a good biocompatibility and facilitated the normal development of human endothelial cells. These nanosystems may be used as efficient alternatives in treating and preventing bacterial infections.

Description: Background: Non-equilibrium charge transport in superconductors has been investigated intensely in the 1970s and 1980s, mostly in the vicinity of the critical temperature. Much less attention has been paid to low temperatures and the role of the quasiparticle spin. Results: We report here on nonlocal transport in superconductor hybrid structures at very low temperatures. By comparing the nonlocal conductance obtained by using ferromagnetic and normal-metal detectors, we discriminate charge and spin degrees of freedom. We observe spin injection and long-range transport of pure, chargeless spin currents in the regime of large Zeeman splitting. We elucidate charge and spin transport by comparison to theoretical models. Conclusion: The observed long-range chargeless spin transport opens a new path to manipulate and utilize the quasiparticle spin in superconductor nanostructures.

Description: Plant surfaces showing hierarchical structuring are frequently found in plant organs such as leaves, petals, fruits and stems. In our study we focus on the level of cell shape and on the level of superimposed microstructuring, leading to hierarchical surfaces if both levels are present. While it has been shown that epicuticular wax crystals and cuticular folds strongly reduce insect attachment, and that smooth papillate epidermal cells in petals improve the grip of pollinators, the impact of hierarchical surface structuring of plant surfaces possessing convex or papillate cells on insect attachment remains unclear. We performed traction experiments with male Colorado potato beetles on nine different plant surfaces with different structures. The selected plant surfaces showed epidermal cells with either tabular, convex or papillate cell shape, covered either with flat films of wax, epicuticular wax crystals or with cuticular folds. On surfaces possessing either superimposed wax crystals or cuticular folds we found traction forces to be almost one order of magnitude lower than on surfaces covered only with flat films of wax. Independent of superimposed microstructures we found that convex and papillate epidermal cell shapes slightly enhance the attachment ability of the beetles. Thus, in plant surfaces, cell shape and superimposed microstructuring yield contrary effects on the attachment of the Colorado potato beetle, with convex or papillate cells enhancing attachment and both wax crystals or cuticular folds reducing attachment. However, the overall magnitude of traction force mainly depends on the presence or absence of superimposed microstructuring.

Description: In this work, single-asperity contact mechanics is investigated for positive and negative work of adhesion Δγ. In the latter case, finite-range repulsion acts in addition to hard-wall constraints. This constitutes a continuum model for a contact immersed in a strongly wetting fluid, which can only be squeezed out in the center of the contact through a sufficiently large normal load F N. As for positive work of adhesion, two stable solutions can coexist in a finite range of normal loads. The competing solutions can be readily interpreted as contacts with either a load-bearing or a squeezed-out fluid. The possibility for coexistence and the subsequent discontinuous wetting and squeeze-out instabilities depend not only on the Tabor coefficient μT but also on the functional form of the finite-range repulsion. For example, coexistence and discontinuous wetting or squeeze-out do not occur when the repulsion decreases exponentially with distance. For positive work of adhesion, the normal displacement mainly depends on F N, Δγ, and μT but – unlike the contact area – barely on the functional form of the finite-range attraction. The results can benefit the interpretation of atomic force microscopy in liquid environments and the modeling of multi-asperity contacts.

Description: In this paper we examine the stability of silicon tip apices by using density functional theory (DFT) calculations. We find that some tip structures - modelled as small, simple clusters - show variations in stability during manipulation dependent on their orientation with respect to the sample surface. Moreover, we observe that unstable structures can be revealed by a characteristic hysteretic behaviour present in the F(z) curves that were calculated with DFT, which corresponds to a tip-induced dissipation of hundreds of millielectronvolts resulting from reversible structural deformations. Additionally, in order to model the structural evolution of the tip apex within a low temperature NC-AFM experiment, we simulated a repeated tip–surface indentation until the tip structure converged to a stable termination and the characteristic hysteretic behaviour was no longer observed. Our calculations suggest that varying just a single rotational degree of freedom can have as measurable an impact on the tip–surface interaction as a completely different tip structure.

Description: Both fluorescence imaging and atomic force microscopy (AFM) are highly versatile and extensively used in applications ranging from nanotechnology to life sciences. In fluorescence microscopy luminescent dyes serve as position markers. Moreover, they can be used as active reporters of their local vicinity. The dipolar coupling of the tip with the incident light and the fluorophore give rise to a local field and fluorescence enhancement. AFM topographic imaging allows for resolutions down to the atomic scale. It can be operated in vacuum, under ambient conditions and in liquids. This makes it ideal for the investigation of a wide range of different samples. Furthermore an illuminated AFM cantilever tip apex exposes strongly confined non-propagating electromagnetic fields that can serve as a coupling agent for single dye molecules. Thus, combining both techniques by means of apertureless scanning near-field optical microscopy (aSNOM) enables concurrent high resolution topography and fluorescence imaging. Commonly, among the various (apertureless) SNOM approaches metallic or metallized probes are used. Here, we report on our custom-built aSNOM setup, which uses commercially available monolithic silicon AFM cantilevers. The field enhancement confined to the tip apex facilitates an optical resolution down to 20 nm. Furthermore, the use of standard mass-produced AFM cantilevers spares elaborate probe production or modification processes. We investigated tobacco mosaic viruses and the intermediate filament protein desmin. Both are mixed complexes of building blocks, which are fluorescently labeled to a low degree. The simultaneous recording of topography and fluorescence data allows for the exact localization of distinct building blocks within the superordinate structures.