The increasing interest and recent developments in nanotechnology pose previously unparalleled challenges in understanding the effects of nanoparticles on living tissues. Despite significant progress in in vitro cell and tissue culture technologies, observations on particle distribution and tissue responses in whole organisms are still indispensable. In addition to a thorough understanding of complex tissue responses which is the domain of expert pathologists, the localization of particles at their sites of interaction with living structures is essential to complete the picture. In this review we will describe and compare different imaging techniques for localizing inorganic as well as organic nanoparticles in tissues, cells and subcellular compartments. The visualization techniques include well-established methods, such as standard light, fluorescence, transmission electron and scanning electron microscopy as well as more recent developments, such as light and electron microscopic autoradiography, fluorescence lifetime imaging, spectral imaging and linear unmixing, superresolution structured illumination, Raman microspectroscopy and X-ray microscopy. Importantly, all methodologies described allow for the simultaneous visualization of nanoparticles and evaluation of cell and tissue changes that are of prime interest for toxicopathologic studies. However, the different approaches vary in terms of applicability for specific particles, sensitivity, optical resolution, technical requirements and thus availability, and effects of labeling on particle properties. Specific bottle necks of each technology are discussed in detail. Interpretation of particle localization data from any of these techniques should therefore respect their specific merits and limitations as no single approach combines all desired properties.
fluorescence lifetime imaging; fluorescence microscopy; histopathology; light microscopic autoradiography; structured illumination microscopy
This work explores the potential use of commercially obtained, carboxylated, single-walled carbon nanotubes (SWCNT–COOH) as nanocarriers for the antiparkinson drug, levodopa (LD). The resulting nanohybrid was characterized using materials characterization methods including Fourier transform infrared spectroscopy, Raman spectroscopy, elemental analysis, UV–vis spectroscopy and scanning electron microscopy. The results showed that SWCNT–COOH were able to form supramolecular complexes with LD via a π–π stacking interaction and exhibited favourable, slow, sustained-release characteristics as a drug carrier with a release period over more than 20 h. The results obtained from the drug release studies of LD at different pH values showed that the LD-loaded nanohybrid is pH activated. The release kinetics of LD from SWCNT–COOH were well-described by a pseudo-second-order kinetic model. A cytotoxicity assay of the synthesized nanohybrid was also carried out in PC12 cell lines (a widely used, in vitro Parkinson’s model for neurotoxicity studies) using 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay in order to investigate their possible effects on normal neuronal cells in vitro. It was found that the synthesized nanohybrid did not compromise the cell viability and the PC12 cells remained stable throughout the experiments up to 72 h after treatment.
carboxylic acid-functionalized single-walled carbon nanotubes; levodopa; MTT assay; nanomedicine; Parkinson’s disease; PC12 cells; sustained release
Electrospun nanofibrous scaffolds have been extensively used in several biomedical applications for tissue engineering due to their morphological resemblance to the extracellular matrix (ECM). Especially, there is a need for the cardiovascular implants to exhibit a nanostructured surface that mimics the native endothelium in order to promote endothelialization and to reduce the complications of thrombosis and implant failure. Thus, we herein fabricated poly-ε-caprolactone (PCL) electrospun nanofibrous scaffolds, to serve as coatings for cardiovascular implants and guide tissue regeneration. Oxygen plasma treatment was applied in order to modify the surface chemistry of the scaffold and its effect on cell attachment and growth was evaluated. The conditions of the surface modification were properly adjusted in order to define those conditions of the treatment that result in surfaces favorable for cell growth, while maintaining morphological integrity and mechanical behavior. Goniometry (contact angle measurements), scanning electron microscopy (SEM), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS) measurements were used to evaluate the morphological and chemical changes induced by the plasma treatment. Moreover, depth-sensing nanoindentation was performed to study the resistance of the plasma-treated scaffolds to plastic deformation. Lastly, the cell studies indicated that all scaffolds were cytocompatible, with the plasma-treated ones expressing a more pronounced cell viability and adhesion. All the above findings demonstrate the great potential of these biomimetic tissue-engineering constructs as efficient coatings for enhanced compatibility of cardiovascular implants.
cardiovascular implants; electrospun nanofibers; plasma treatment; scaffold; tissue engineering
In this short review, the main challenges in the use of hydrophobic nanoparticles in biomedical application are addressed. It is shown how to overcome the different issues by the use of a polymeric encapsulation system, based on an amphiphilic polyisoprene-block-poly(ethylene glycol) diblock copolymer. On the basis of this simple molecule, the development of a versatile and powerful phase transfer strategy is summarized, focusing on the main advantages like the adjustable size, the retained properties, the excellent shielding and the diverse functionalization properties of the encapsulated nanoparticles. Finally, the extraordinary properties of these encapsulated nanoparticles in terms of toxicity and specificity in a broad in vitro test is demonstrated.
biolable; cellular uptake; fluorescence quenching; poylmeric micelles; quantum dots
Background: The impact of gold nanoparticles on cell viability has been extensively studied in the past. Size, shape and surface functionalization including opsonization of gold particles ranging from a few nanometers to hundreds of nanometers are among the most crucial parameters that have been focussed on. Cytoxicity of nanomaterial has been assessed by common cytotoxicity assays targeting enzymatic activity such as LDH, MTT and ECIS. So far, however, less attention has been paid to the mechanical parameters of cells exposed to gold particles, which is an important reporter on the cellular response to external stimuli.
Results: Mechanical properties of confluent MDCK II cells exposed to gold nanorods as a function of surface functionalization and concentration have been explored by atomic force microscopy and quartz crystal microbalance measurements in combination with fluorescence and dark-field microscopy.
Conclusion: We found that cells exposed to CTAB coated gold nanorods display a concentration-dependent stiffening that cannot be explained by the presence of CTAB alone. The stiffening results presumably from endocytosis of particles removing excess membrane area from the cell’s surface. Another aspect could be the collapse of the plasma membrane on the actin cortex. Particles coated with PEG do not show a significant change in elastic properties. This observation is consistent with QCM measurements that show a considerable drop in frequency upon administration of CTAB coated rods suggesting an increase in acoustic load corresponding to a larger stiffness (storage modulus).
atomic force microscopy; CTAB; gold nanorods; membrane tension; MDCK II cells; QCM
Conventional closed loop-Kelvin probe force microscopy (KPFM) has emerged as a powerful technique for probing electric and transport phenomena at the solid–gas interface. The extension of KPFM capabilities to probe electrostatic and electrochemical phenomena at the solid–liquid interface is of interest for a broad range of applications from energy storage to biological systems. However, the operation of KPFM implicitly relies on the presence of a linear lossless dielectric in the probe–sample gap, a condition which is violated for ionically-active liquids (e.g., when diffuse charge dynamics are present). Here, electrostatic and electrochemical measurements are demonstrated in ionically-active (polar isopropanol, milli-Q water and aqueous NaCl) and ionically-inactive (non-polar decane) liquids by electrochemical force microscopy (EcFM), a multidimensional (i.e., bias- and time-resolved) spectroscopy method. In the absence of mobile charges (ambient and non-polar liquids), KPFM and EcFM are both feasible, yielding comparable contact potential difference (CPD) values. In ionically-active liquids, KPFM is not possible and EcFM can be used to measure the dynamic CPD and a rich spectrum of information pertaining to charge screening, ion diffusion, and electrochemical processes (e.g., Faradaic reactions). EcFM measurements conducted in isopropanol and milli-Q water over Au and highly ordered pyrolytic graphite electrodes demonstrate both sample- and solvent-dependent features. Finally, the feasibility of using EcFM as a local force-based mapping technique of material-dependent electrostatic and electrochemical response is investigated. The resultant high dimensional dataset is visualized using a purely statistical approach that does not require a priori physical models, allowing for qualitative mapping of electrostatic and electrochemical material properties at the solid–liquid interface.
diffuse charge dynamics; double layer charging; electrochemical force microscopy; electrochemistry; Kelvin probe force microscopy
Many nanofabrication methods based on scanning probe microscopy have been developed during the last decades. Local anodic oxidation (LAO) is one of such methods: Upon application of an electric field between tip and surface under ambient conditions, oxide patterning with nanometer-scale resolution can be performed with good control of dimensions and placement. LAO through the non-contact mode of atomic force microscopy (AFM) has proven to yield a better resolution and tip preservation than the contact mode and it can be effectively performed in the dynamic mode of AFM. The tip plays a crucial role for the LAO-AFM, because it regulates the minimum feature size and the electric field. For instance, the feasibility of carbon nanotube (CNT)-functionalized tips showed great promise for LAO-AFM, yet, the fabrication of CNT tips presents difficulties. Here, we explore the use of a carbon nanofiber (CNF) as the tip apex of AFM probes for the application of LAO on silicon substrates in the AFM amplitude modulation dynamic mode of operation. We show the good performance of CNF-AFM probes in terms of resolution and reproducibility, as well as demonstration that the CNF apex provides enhanced conditions in terms of field-induced, chemical process efficiency.
carbon nanofiber; dynamic mode; local anodic oxidation; nanopatterning
Tunable light filters are critical components for many optical applications in which light in-coupling, out-coupling or rejection is crucial, such as lasing, sensing, photovoltaics and information and communication technology. For this purpose, Bragg mirrors (band-pass filters with high reflectivity) represent good candidates. However, their optical characteristics are determined during the fabrication stage. Heavily doped semiconductor nanocrystals (NCs), on the other hand, deliver a high degree of optical tunability through the active modulation of their carrier density, ultimately influencing their plasmonic absorption properties. Here, we propose the design of an actively tunable light filter composed of a Bragg mirror and a layer of plasmonic semiconductor NCs. We demonstrate that the filtering properties of the coupled device can be tuned to cover a wide range of frequencies from the visible to the near infrared (vis–NIR) spectral region when employing varying carrier densities. As the tunable component, we implemented a dispersion of copper selenide (Cu2−xSe) NCs and a film of indium tin oxide (ITO) NCs, which are known to show optical tunablility with chemical or electrochemical treatments. We utilized the Mie theory to describe the carrier-dependent plasmonic properties of the Cu2−x Se NC dispersion and the effective medium theory to describe the optical characteristics of the ITO film. The transmission properties of the Bragg mirror have been modelled with the transfer matrix method. We foresee ease of experimental realization of the coupled device, where filtering modulation is achieved upon chemical and electrochemical post-fabrication treatment of the heavily doped semiconductor NC component, eventually resulting in tunable transmission properties of the coupled device.
active optical component; electronic band gap nanostructure; localized surface plasmon resonance; photonic crystal
X-ray photoelectron spectroscopy (XPS) is one of the best tools for studying the chemical modification of surfaces, and in particular the distribution and bonding of heteroatom dopants in carbon nanomaterials such as graphene and carbon nanotubes. Although these materials have superb intrinsic properties, these often need to be modified in a controlled way for specific applications. Towards this aim, the most studied dopants are neighbors to carbon in the periodic table, nitrogen and boron, with phosphorus starting to emerge as an interesting new alternative. Hundreds of studies have used XPS for analyzing the concentration and bonding of dopants in various materials. Although the majority of works has concentrated on nitrogen, important work is still ongoing to identify its precise atomic bonding configurations. In general, care should be taken in the preparation of a suitable sample, consideration of the intrinsic photoemission response of the material in question, and the appropriate spectral analysis. If this is not the case, incorrect conclusions can easily be drawn, especially in the assignment of measured binding energies into specific atomic configurations. Starting from the characteristics of pristine materials, this review provides a practical guide for interpreting X-ray photoelectron spectra of doped graphitic carbon nanomaterials, and a reference for their binding energies that are vital for compositional analysis via XPS.
carbon nanotubes; core level photoemission; graphene; substitutional doping; X-ray photoelectron spectroscopy (XPS)
Mammalian cells regulate adhesion by expressing and regulating a diverse array of cell adhesion molecules on their cell surfaces. Since different cell types express distinct sets of cell adhesion molecules, substrate-specific adhesion is cell type- and condition-dependent. Single-cell force spectroscopy is used to quantify the contribution of cell adhesion molecules to adhesion of cells to specific substrates at both the cell and single molecule level. However, the low throughput of single-cell adhesion experiments greatly limits the number of substrates that can be examined. In order to overcome this limitation, segmented polydimethylsiloxane (PDMS) masks were developed, allowing the measurement of cell adhesion to multiple substrates. To verify the utility of the masks, the adhesion of four different cell lines, HeLa (Kyoto), prostate cancer (PC), mouse kidney fibroblast and MDCK, to three extracellular matrix proteins, fibronectin, collagen I and laminin 332, was examined. The adhesion of each cell line to different matrix proteins was found to be distinct; no two cell lines adhered equally to each of the proteins. The PDMS masks improved the throughput limitation of single-cell force spectroscopy and allowed for experiments that previously were not feasible. Since the masks are economical and versatile, they can aid in the improvement of various assays.
atomic force microscopy; cell adhesion; collagen I; fibroblasts; fibronectin; HeLa; laminin; MDCK; PC3; single cell assay; single cell force spectroscopy
Nanomedicine is a rapidly growing field in nanotechnology, which has great potential in the development of new therapies for numerous diseases. For example iron oxide nanoparticles are in clinical use already in the thermotherapy of brain cancer. Although it has been shown, that tumor cells take up these particles in vitro, little is known about the internalization routes. Understanding of the underlying uptake mechanisms would be very useful for faster and precise development of nanoparticles for clinical applications. This study aims at the identification of key proteins, which are crucial for the active uptake of iron oxide nanoparticles by HeLa cells (human cervical cancer) as a model cell line. Cells were transfected with specific siRNAs against Caveolin-1, Dynamin 2, Flotillin-1, Clathrin, PIP5Kα and CDC42. Knockdown of Caveolin-1 reduces endocytosis of superparamagnetic iron oxide nanoparticles (SPIONs) and silica-coated iron oxide nanoparticles (SCIONs) between 23 and 41%, depending on the surface characteristics of the nanoparticles and the experimental design. Knockdown of CDC42 showed a 46% decrease of the internalization of PEGylated SPIONs within 24 h incubation time. Knockdown of Dynamin 2, Flotillin-1, Clathrin and PIP5Kα caused no or only minor effects. Hence endocytosis in HeLa cells of iron oxide nanoparticles, used in this study, is mainly mediated by Caveolin-1 and CDC42. It is shown here for the first time, which proteins of the endocytotic pathway mediate the endocytosis of silica-coated iron oxide nanoparticles in HeLa cells in vitro. In future studies more experiments should be carried out with different cell lines and other well-defined nanoparticle species to elucidate possible general principles.
Caveolin-1; CDC42; endocytosis inhibition; iron oxide nanoparticles; nanoparticle uptake
The nonlinear interaction between an AFM tip and a sample gives rise to oscillations of the cantilever at integral multiples (harmonics) of the fundamental resonance frequency. The higher order harmonics have long been recognized to hold invaluable information on short range interactions but their utilization has thus far been relatively limited due to theoretical and experimental complexities. In particular, existing approximations of the interaction force in terms of higher harmonic amplitudes generally require simultaneous measurements of multiple harmonics to achieve satisfactory accuracy. In the present letter we address the mathematical challenge and derive accurate, explicit formulae for both conservative and dissipative forces in terms of an arbitrary single harmonic. Additionally, we show that in frequency modulation-AFM (FM-AFM) each harmonic carries complete information on the force, obviating the need for multi-harmonic analysis. Finally, we show that higher harmonics may indeed be used to reconstruct short range forces more accurately than the fundamental harmonic when the oscillation amplitude is small compared with the interaction range.
atomic force spectroscopy; higher harmonic FM-AFM
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.
bio-inspired mineralization; biomineralization; chitin; ferrogel; hybrid materials; magnetite; nacre
The propensity of peptides and proteins to form self-assembled structures has very promising applications in the development of novel nanomaterials. Under certain conditions, amyloid protein α-synuclein forms well-ordered structures – fibrils, which have proven to be valuable building blocks for bionanotechnological approaches. Herein we demonstrate the functionalization of fibrils formed by a mutant α-synuclein that contains an additional cysteine residue. The fibrils have been biotinylated via thiol groups and subsequently joined with neutravidin-conjugated gold nanoparticles. Atomic force microscopy and transmission electron microscopy confirmed the expected structure – nanoladders. The ability of fibrils (and of the additional components) to assemble into such complex structures offers new opportunities for fabricating novel hybrid materials or devices.
α-synuclein; atomic force microscopy; gold nanoparticles; nanostructures; self-assembly
51Cr-labeled, superparamagnetic, iron oxide nanoparticles (51Cr-SPIOs) and 65Zn-labeled CdSe/CdS/ZnS-quantum dots (65Zn-Qdots) were prepared using an easy, on demand, exchange-labeling technique and their particokinetic parameters were studied in mice after intravenous injection. The results indicate that the application of these heterologous isotopes can be used to successfully mark the nanoparticles during initial distribution and organ uptake, although the 65Zn-label appeared not to be fully stable. As the degradation of the nanoparticles takes place, the individual transport mechanisms for the different isotopes must be carefully taken into account. Although this variation in transport paths can bring new insights with regard to the respective trace element homeostasis, it can also limit the relevance of such trace material-based approaches in nanobioscience. By monitoring 51Cr-SPIOs after oral gavage, the gastrointestinal non-absorption of intact SPIOs in a hydrophilic or lipophilic surrounding was measured in mice with such high sensitivity for the first time. After intravenous injection, polymer-coated, 65Zn-Qdots were mainly taken up by the liver and spleen, which was different from that of ionic 65ZnCl2. Following the label for 4 weeks, an indication of substantial degradation of the nanoparticles and the release of the label into the Zn pool was observed. Confocal microscopy of rat liver cryosections (prepared 2 h after intravenous injection of polymer-coated Qdots) revealed a colocalization with markers for Kupffer cells and liver sinusoidal endothelial cells (LSEC), but not with hepatocytes. In J774 macrophages, fluorescent Qdots were found colocalized with lysosomal markers. After 24 h, no signs of degradation could be detected. However, after 12 weeks, no fluorescent nanoparticles could be detected in the liver cryosections, which would confirm our 65Zn data showing a substantial degradation of the polymer-coated CdSe/CdS/ZnS-Qdots in the liver.
biodistribution; chromium(III); 51Cr; quantum dots; SPIOs; zinc metabolism; 65Zn
Boron nitride nanotubes (BNNTs) have been increasingly investigated for use in a wide range of applications due to their unique physicochemical properties including high hydrophobicity, heat and electrical insulation, resistance to oxidation, and hydrogen storage capacity. They are also valued for their possible medical and biomedical applications including drug delivery, use in biomaterials, and neutron capture therapy. In this review, BNNT synthesis methods and the surface modification strategies are first discussed, and then their toxicity and application studies are summarized. Finally, a perspective for the future use of these novel materials is discussed.
boron nitride nanotubes; chemical modifications; medical applications; synthesis methods; toxicity
Biosilicification sets the standard for the localized in vitro precipitation of silica at low orthosilicate concentrations in aqueous environment under ambient conditions. Numerous parameters must be controlled for the development of new technologies in designing inventive nanosilica structures, which are able to challenge the biological templates. A long neglected requirement that came into focus in the recent years are the cellular techniques of preventing unintentional lithification of cellular structures since numerous cellular components such as membranes, DNA, and proteins are known to precipitate nanosilica. The diatom metabolism makes use of techniques that restrict silicification to an armor of silica around the cell wall while avoiding the petrifying gaze of Medusa, which turns the whole cell into stone. Step by step, biochemistry unveils the hierarchical interplay of an arsenal of low-molecular weight molecules, proteins, and the cytoskeletal architecture and it becomes clearer why the organisms invest much metabolic effort for an obviously simple chemical reaction like the precipitation of amorphous silica. The discrimination between different soluble components in the silicification process (chemoselective silicification) is not only vitally important for the diatom but poses an interesting challenge for in vitro experiments. Until now, silica precipitation studies were mainly focused on the amount, the morphology, and composition of the precipitate while disregarding a quantitative analysis of the remaining soluble components. Here, we turn the tables and quantify the soluble components by 1H NMR in the progress of precipitation and present experiments which quantify the additivity, and potential cooperativity of long chain polyamines (LCPAs) and cationic peptides in the silicification process.
biomineralisation; biosilicification; NMR spectroscopy; polyamines; silaffin
Non-stoichiometric ceria nanoparticles (NPs) were obtained by a gas aggregation source with a magnetron and were mass-selected with a quadrupole mass filter. By varying magnetron power, Ar gas flow, and the length of the aggregation tube, NPs with an average diameter of 6, 9, and 14 nm were synthesized and deposited onto a substrate, thus obtaining NP films. The morphology of the films was studied with scanning electron microscopy, while high resolution transmission electron microscopy was used to gain a deeper insight into the atomic structure of individual NPs. By using X-ray photoelectron spectroscopy we analyzed the degree of reduction of the NPs of different diameters, before and after thermal treatments in vacuum (reduction cycle) and in O2 atmosphere (oxidation cycle) at different temperatures. From this analysis we inferred that the size is an important parameter only at intermediate temperatures. As a comparison, we evaluated the reducibility of an ultra-thin ceria film with the same surface to volume ratio as the 9 nm diameter NPs film, observing that NPs are more reducible than the ceria film.
CeO2 ultra-thin films; ceria nanoparticles; magnetron sputtering; reduction and oxidation; size-dependent properties; size-selected nanoparticles; X-ray photoelectron spectroscopy
The performance of high-temperature polymer electrolyte membrane fuel cells (HT-PEMFC) is critically dependent on the selection of materials and optimization of individual components. A conventional high-temperature membrane electrode assembly (HT-MEA) primarily consists of a polybenzimidazole (PBI)-type membrane containing phosphoric acid and two gas diffusion electrodes (GDE), the anode and the cathode, attached to the two surfaces of the membrane. This review article provides a survey on the materials implemented in state-of-the-art HT-MEAs. These materials must meet extremely demanding requirements because of the severe operating conditions of HT-PEMFCs. They need to be electrochemically and thermally stable in highly acidic environment. The polymer membranes should exhibit high proton conductivity in low-hydration and even anhydrous states. Of special concern for phosphoric-acid-doped PBI-type membranes is the acid loss and management during operation. The slow oxygen reduction reaction in HT-PEMFCs remains a challenge. Phosphoric acid tends to adsorb onto the surface of the platinum catalyst and therefore hampers the reaction kinetics. Additionally, the binder material plays a key role in regulating the hydrophobicity and hydrophilicity of the catalyst layer. Subsequently, the binder controls the electrode–membrane interface that establishes the triple phase boundary between proton conductive electrolyte, electron conductive catalyst, and reactant gases. Moreover, the elevated operating temperatures promote carbon corrosion and therefore degrade the integrity of the catalyst support. These are only some examples how materials properties affect the stability and performance of HT-PEMFCs. For this reason, materials characterization techniques for HT-PEMFCs, either in situ or ex situ, are highly beneficial. Significant progress has recently been made in this field, which enables us to gain a better understanding of underlying processes occurring during fuel cell operation. Various novel tools for characterizing and diagnosing HT-PEMFCs and key components are presented in this review, including FTIR and Raman spectroscopy, confocal Raman microscopy, synchrotron X-ray imaging, X-ray microtomography, and atomic force microscopy.
binder; catalysts; characterization techniques; high-temperature polymer electrolyte membrane fuel cell (HT-PEMFC); membrane electrode assembly (MEA); phosphoric acid-doped polybenzimidazole (PBI)
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 Mnx
+ 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 MnOx 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 MnOx species on the calcination temperature and the presence of an oxidizing or neutral atmosphere. Furthermore, to demonstrate the application potential of the synthesized MnOx 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.
electrocatalytic activity; in situ X-ray diffraction; manganese glycolate; manganese oxide nanoparticles; mesoporous α-Mn2O3
A variety of monodisperse superparamagnetic iron oxide particles (SPIOs) was designed in which the surface was modified by PEGylation with mono- or bifunctional poly(ethylene oxide)amines (PEG). Using 125I-labeled test proteins (transferrin, albumin), the binding and exchange of corona proteins was studied first in vitro. Incubation with 125I-transferrin showed that with increasing grade of PEGylation the binding was substantially diminished without a difference between simply adsorbed and covalently bound protein. However, after incubation with excess albumin and subsequently whole plasma, transferrin from the preformed transferrin corona was more and more lost from SPIOs in the case of adsorbed proteins. If non-labeled transferrin was used as preformed corona and excess 125I-labeled albumin was added to the reaction mixtures with different SPIOs, a substantial amount of label was bound to the particles with initially adsorbed transferrin but little or even zero with covalently bound transferrin. These in vitro experiments show a clear difference in the stability of a preformed hard corona with adsorbed or covalently bound protein. This difference seems, however, to be of minor importance in vivo when polymer-coated 59Fe-SPIOs with adsorbed or covalently bound 125I-labeled mouse transferrin were injected intravenously in mice. With both protein coronae the 59Fe/125I-labelled particles were cleared from the blood stream within 30 min and appeared in the liver and spleen to a large extent (>90%). In addition, after 2 h already half of the 125I-labeled transferrin from both nanodevices was recycled back into the plasma and into tissue. This study confirms that adsorbed transferrin from a preformed protein corona is efficiently taken up by cells. It is also highlighted that a radiolabelling technique described in this study may be of value to investigate the role of protein corona formation in vivo for the respective nanoparticle uptake.
albumin; 59Fe; 125I; organ uptake; protein corona; SPIOs; transferrin
In this letter, we report results of a hydrosilylation carried out on bifunctional molecules by using two different approaches, namely through thermal treatment and photochemical treatment through UV irradiation. Previously, our group also demonstrated that in a mixed alkyne/alcohol solution, surface coupling is biased towards the formation of Si–O–C linkages instead of Si–C linkages, thus indirectly supporting the kinetic model of hydrogen abstraction from the Si–H surface (Khung, Y. L. et al. Chem. – Eur. J.
20, 15151–15158). To further examine the probability of this kinetic model we compare the results from reactions with bifunctional alkynes carried out under thermal treatment (<130 °C) and under UV irradiation, respectively. X-ray photoelectron spectroscopy and contact angle measurements showed that under thermal conditions, the Si–H surface predominately reacts to form Si–O–C bonds from ethynylbenzyl alcohol solution while the UV photochemical route ensures that the alcohol-based alkyne may also form Si–C bonds, thus producing a monolayer of mixed linkages. The results suggested the importance of surface radicals as well as the type of terminal group as being essential towards directing the nature of surface linkage.
hydrogen abstraction; thermal hydrosilylation; UV-initated hydrosilylation; X-ray photoelectron spectroscopy
The correlation between density and specific surface area of ZrO2 nanoparticles (NPs) was studied. The NPs were produced using a hydrothermal process involving microwave heating. The material was annealed at 1100 °C which resulted in an increase in the average grain size of the ZrO2 NPs from 11 to 78 nm and a decrease in the specific surface area from 97 to 15 m2/g. At the same time, the density increased from 5.22 g/m3 to 5.87 g/m3. This effect was interpreted to be the result of the presence of a hydroxide monolayer on the NP surface. A smaller ZrO2 grain size was correlated with a larger contribution of the low density surface layer to the average density. To prove the existence of such a layer, the material was synthesized using 50% heavy water. Fourier transform infrared spectroscopy (FTIR) permitted the identification of the –OD groups created during synthesis. It was found that the –OD groups persisted on the ZrO2 surface even after annealing at 1100 °C. This hydroxide layer is responsible for the decrease in the average density of the NPs as their size decreases. This study of the correlation between particle size and density may be used to assess the quality of the NPs. In most cases, the technological aim is to avoid an amorphous layer and to obtain fully crystalline nanoparticles with the highest density possible. However, due to the effect of the surface layers, there is a maximum density which can be achieved for a given average NP diameter. The effect of the surface layer on the NP density becomes particularly evident for NPs smaller than 50 nm, and thus, the density of nanoparticles is size dependent.
density; hydrothermal synthesis; hydroxy groups; nanometrology; nanopowders; zirconia
We report a novel, practical technique for the concerted, simultaneous determination of both the adhesion force of a small structure or structural unit (e.g., an individual filament, hair, micromechanical component or microsensor) to a liquid and its elastic properties. The method involves the creation and development of a liquid meniscus upon touching a liquid surface with the structure, and the subsequent disruption of this liquid meniscus upon removal. The evaluation of the meniscus shape immediately before snap-off of the meniscus allows the quantitative determination of the liquid adhesion force. Concurrently, by measuring and evaluating the deformation of the structure under investigation, its elastic properties can be determined. The sensitivity of the method is remarkably high, practically limited by the resolution of the camera capturing the process. Adhesion forces down to 10 µN and spring constants up to 2 N/m were measured. Three exemplary applications of this method are demonstrated: (1) determination of the water adhesion force and the elasticity of individual hairs (trichomes) of the floating fern Salvinia molesta. (2) The investigation of human head hairs both with and without functional surface coatings (a topic of high relevance in the field of hair cosmetics) was performed. The method also resulted in the measurement of an elastic modulus (Young’s modulus) for individual hairs of 3.0 × 105 N/cm2, which is within the typical range known for human hair. (3) Finally, the accuracy and validity of the capillary adhesion technique was proven by examining calibrated atomic force microscopy cantilevers, reproducing the spring constants calibrated using other methods.
adhesion; AFM cantilever; air layer; capillary forces; hairs; measurement; micromechanical systems; microstructures; Salvinia effect; Salvinia molesta; sensors; stiffness; superhydrophobic surfaces
The plasmonic coupling between gold caps and holes in thin films was investigated experimentally and through finite-difference time-domain (FDTD) calculations. Sparse colloidal lithography combined with a novel thermal treatment was used to control the vertical spacing between caps and hole arrays and compared to separated arrays of holes or caps. Optical spectroscopy and FDTD simulations reveal strong coupling between the gold caps and both Bloch Wave-surface plasmon polariton (BW-SPP) modes and localized surface plasmon resonance (LSPR)-type resonances in hole arrays when they are in close proximity. The interesting and complex coupling between caps and hole arrays reveals the details of the field distribution for these simple to fabricate structures.
caps; colloidal lithography; hybridization; localized surface plasmon resonance; near field; SRO hole arrays