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Halloysite nanotubes (HNTs) and salicylic acid (SA) are natural substances widely used in different fields. HNTs are very promising as nanocarriers because of their biocompatibility, atoxicity, anti-inflammatory properties and capacity to maintain the biological activity of immobilized enzymes. Because of its bactericidal and antiseptic properties, salicylic acid (SA) is used in pharmaceutical formulations, and as an additive for preserving foods and cosmetics. In this study, we set up a procedure for the loading of HNTs with SA for their possible application in active food packaging. Pristine HNTs were studied together with acidic etched HNTs with enlarged internal lumen, and various pH values for the loading solutions were tested in order to obtain the maximum loading. The HNTs—empty and loaded with SA—were characterized by TG-FTIR, FTIR SEM, STEM, and nitrogen adsorption/desorption isotherms measurements. We obtained a maximum loading of 10.5% (w/w), using HNTs pretreated with H2SO4 2 M at 25 °C for 48...

We propose ion-induced dewetting of Au thin films as a mechanism to modify and control the morphology of Si nanowires formed through metal-assisted chemical etching. We show that the patterns formed upon irradiation resemble those typical of dewetting phenomena, with a characteristic length in the nanometer range. Irradiated Au films are then used as a template for the fabrication of Si nanowires, and we show that a long-range order exists also in etched substrates, although at much longer length scales in the micrometer range. Investigation of the optical properties reveals that the Si nanowires emit broadband photoluminescence peaked at 700 nm. The proposed synthesis method allows tuning the morphological features of the nanowire bundles at the nanoscale without affecting the optical properties. This approach can be exploited for the engineering of nanowires-based devices where the morphological features become important.

A new outgassing rate facility applying the difference method was established at KIT. This system was validated within the framework of Joint Research Project IND 12 of the European metrology Research programme by several outgassing reference probes. These served as transfer standards for comparison with three other outgassing rate systems available in the project. Two of the probes were newly developed reference devices and exhibit a known, constant outgassing rate of water. Further two probes were also newly developed outgassing reference devices which emit mixtures of gases. Additionally another probe was an elastomer which was loaded with a known gas mixture. The last probe was a commercially available plastic material whose outgassing shows a large spectrum of gases. The other outgassing rate facilities applied the in-situ calibration of quadrupole mass spectrometers by a primary method, the continuous expansion method (Physikalisch-Technische Bundesanstalt) and the known gas quantity method (Institute of Metals and Technology) or the throughput method (VACOM company). The comparison of the results shows a satisfactory agreement between the measurements.

Super Paramagnetic Iron-Oxide Nanoparticles (SPION) are currently used as magnetic resonance imaging (MRI) contrast agents. The functionalization of their surface with organic and biocompatible molecules has the purpose to produce carriers selective for different tissues and organs. In this paper, we present the preparation of new cystine-coated ultra small super paramagnetic iron-oxide nanoparticles (USPION) of different core size, from 4 nm to 11 nm. The physical-chemical characterization of these nanoparticles was performed by using several experimental techniques, such as atomic force microscopy (AFM), high resolution transmission electron microscopy (HRTEM) and magnetic measurements. 1 H NMR relaxation times at different magnetic field strengths have been measured for several water- dispersions of cystine-coated iron-oxide nanoparticles of the smallest dimensions (4 nm). These preliminary results confirm their potentialities as molecular imaging probes and MRI contrast agents.

A green and fast methodology was developed to synthesize silver nanoparticles using rosemary essential oil (EO) as a renewable reducing agent. The synthesis process was microwave (MW) assisted, using a coaxial dipole antenna immersed into the reaction medium. This configuration was used to promote both: i) rosemary EO extraction by hydrodistillation, and ii) silver nanoparticle synthesis in an aqueous solution at atmospheric pressure. The effect of two different silver salt substrates and the time reaction on the morphology of the silver nanoparticles was explored. The coaxial microwave-assisted hydrodistillation of rosemary yields 0.4% (w/w) in 30 min and contains ethers (17%), ketones (50%) and alcohols (15%). Silver nanoparticles with a tuneable particle size (from 7 to 18 nm) and morphology (from spherical to round-like shapes) were obtained in reaction times ranging from 2 to 30 min. The nanoparticle formation was followed by UV-vis spectroscopy and SEM imaging.

Several experimental techniques have been used to investigate the chemical–physical properties of new functionalized ultra-small iron-oxide nanoparticles (USPION), which are of interest for biomedical applications. The chemical composition of oleate-coated iron-oxide (OA-NPs) and cystine-coated iron-oxide (Cy-NPs) nanoparticles was investigated by means of analytical methods and Fourier transform infrared (FT-IR) spectroscopy. Atomic force microscopy (AFM) and transmission electron microscopy (TEM) investigations, at high and low resolutions, on both OA-NPs and Cy-NPs, were performed to investigate their morphology. The magnetization and susceptibility behavior of OA- and Cy-NPs were studied by SQUID magnetometry. The combination of different experimental techniques was of help in characterizing the chemical structure of both magnetic core and surface-coating of OA- and Cy-NPs. AFM/TEM images and magnetic measurements were analyzed in terms of crystallinity, polydispersity, average magnetic core size, and coating effects of these nanoparticles. These results show that the preparations reported in the present paper are effective in obtaining nanoparticles of 4 nm magnetic core size and the procedure is highly reproducible. The presence of the external cystine shell, fundamental for biomedical applications, does not affect the polidispersity, the crystallinity or the average core size. Moreover, similar values of the average core dimensions have been obtained by three different techniques (AFM and TEM images, magnetic measurements). New cystine-functionalized magnetite nanoparticles have been synthesized. Physical chemical investigations show an average core size of about 4 nm and super-paramagnetic properties.

Pristine halloysite nanotubes (HNTs) were studied by thermogravimetry (TG) up to 800 °C. Etching of alumina from inside the tube (causing a significant increase in tube lumen) was realized by treating the material with an acidic H2SO4 solution at 50 °C. Both materials were characterized by TG-FTIR techniques and their thermal behaviors were compared with that of kaolinite. The coupling of TG with FTIR enables to detect the gases evolved during the TG experiments, thus confirming that only pristine HNTs undergo dehydration with the loss of interlayer water molecules at around 245 °C, while dehydroxylation occurs in all these materials in close temperature ranges around 500 °C. TG runs at five different heating rates (2, 5, 10, 15 and 20 °C min−1), was carried out in the same experimental conditions used for the thermal analysis study with the aim to investigate dehydration and dehydroxylation kinetics using some isoconversional methods recommended by the ICTAC kinetic committee, and thermogravimetric data under a modulated rising temperature program. Finally, the results of the kinetic analysis were discussed and explained in terms of the strengths of the hydrogen bonds broken during these processes.

This work deals with the preparation and physical-chemical characterization of new ultrasmall iron oxide superparamagnetic nanoparticles (USPIONs) functionalized with titanium-N,N-dialkylcarbamato. The preparation was performed starting with monodispersed USPIONs covered with oleic acid, synthesized by thermal-decomposition, and subsequently functionalized with metal-carbamato by a ligand-exchange reaction. The surface and coating structure was characterized by infrared (FT-IR) spectroscopy on the solid powders and thermogravimetry (TG) coupled with an FT-IR detector in order to better investigate the self-assembling properties of the coating. A detailed dimensional and morphological study was carried out by transmission electron microscopy (TEM) and atomic force microscopy (AFM) analysis. Zero-field-cooled (ZFC) and field-cooled (FC) magnetic susceptibility curves as well as the magnetization behavior as a function of temperature were investigated on both the starting oleic-USPIONs and those covered by titanium-N,N-dialkylcarbamato. These results confirmed the superparamagnetic properties of the new nanoparticles (NPs), highlighting the quite high saturation value of the magnetization. Based on the results obtained by combining different experimental techniques, a model of the coating structure and ligand organization around the magnetic core is proposed for both NPs, i.e. the starting USPIONs covered by oleic acid and the new USPIONs functionalized by titanium-N,N-dialkylcarbamato.

Short tubes with diameters of the order of 200 nm were drilled into silicon nitride (Si3N4) membranes of 200 nm thickness by focused ion beam technology and examined as leak elements for vacuum technology applications. These nano-holes exhibit molecular flow in the pressure range from high vacuum up to 10 kPa and can therefore be used as predictable leak elements for any non-condensable gas species. The geometrical dimensions were determined by SEM, STEM and AFM techniques. By Direct Simulation Monte Carlo method the conductances of these short tubes were calculated from the measured dimensions. The calculated conductance agreed with the value measured by comparison with a primary gas flowmeter within their respective uncertainties.

Aims: Sensitivity, selectivity and tunability are keywords to develop effective and reliable diagnostic and bioanalytical tools. In this context, micro and nanofluidic devices constitute a powerful and versatile answer to the growing and urgent demand for innovative solutions. Nevertheless, a precise control of size and functionality of such structures is necessary for ensuring advanced manipulation and sensing capabilities, up to single molecule level. Methods: We report here on different strategies for the development of micro and nanofluidic platforms for advanced diagnostics based on the exploitation of the elastic properties of deformable materials, and on surface chemical functionalization processes. Results: We demonstrated that applying a macroscopic mechanical compression to elastomeric nanostructures it is possible to increase their confining power and vary the dynamics of DNA translocation process, while the use of the chemical functionalization allows to tune both the size and the functionality of the biosensor. Conclusion: We believe that a smart integration of these two approaches would allow a significant step forward for the fabrication of next-generation lab-on-chip devices for biomedical diagnostic applications.

Recently there has been a great develop of new antibodies immobilization procedures, that keep antibodies to retain their orientation and functionality after the binding to a solid support. This allows the formation of immune-complexes useful for the detection of biomarkers from biological samples. We have developed a new method of functionalization for solid substrates that involves an initial surface activation, then a functionalization by means of 3-aminopropyltriethoxysilane-followed by another functionalization step with a layer of very small peptides, which have a high affinity to the Antibody Fc portion, acting as antibody linkers. These antibody binding peptides can immobilize the antibodies with a proper configuration that allows an unambiguous detection of antibody-antigen complexes by means of atomic force microscopy (AFM). The AFM can act as a powerful label free detection technique, which allows to detect, in principle, single molecule interactions, with the only limitation to use substrate with low-roughness surfaces; in this case, the roughness can be interpreted as background noise in the AFM analysis. Moreover, our functionalization method can be used to obtain bioactive surfaces on a wide range of solid supports, making them capable to suitably immobilize the antibodies for the antigenic binding.

The knowledge of the effects of single-nucleotide polymorphisms (SNPs) in the human genome greatly contributes to better comprehension of the relation between genetic factors and diseases. Sequence analysis of genomic DNA in different individuals reveals positions where variations that involve individual base substitutions can occur. Single-nucleotide polymorphisms are highly abundant and can have different consequences at phenotypic level. Several attempts were made to apply atomic force microscopy (AFM) to detect and map SNP sites in DNA strands. The most promising approach is the study of DNA mutations producing heteroduplex DNA strands and identifying the mismatches by means of a protein that labels the mismatches. MutS is a protein that is part of a well-known complex of mismatch repair, which initiates the process of repairing when the MutS binds to the mismatched DNA filament. The position of MutS on the DNA filament can be easily recorded by means of AFM imaging.

Nanoindentation experiments carried out with atomic force microscopes (AFMs) open the way to understand size-related mechanical effects that are not present at the macro- or micro-scale. Several issues, currently the subject of a wide and open debate, must be carefully considered in order to measure quantities and retrieve trends genuinely associated with the material behaviour. The shape of the nanoindenter (the AFM tip) is crucial for a correct data analysis; we have recently developed a simple geometrical model to properly describe the tip effect in the nanoindentation process. Here, we demonstrate that this model is valid in indentation of both soft and hard, or relatively hard, materials carried out by two distinct, commercially available, AFM probes. Moreover, we implement the model with a data interpretation approach aimed at preventing underestimation of the tip penetration into the material. Experiments on soft polymeric materials (poly(methyl methacrylate) and polystyrene) and hard or relatively hard (Si, Au, Al) materials are reported. The results demonstrate that true hardness data can be attained also in shallow indentations and that the appearance of size effects strongly depends on data interpretation issues. In addition, we report on stiffness data measured on the considered materials during their nanoindentation.

Cocoons produced by different strains of Bombyx mori larvae were investigated by a combination of several high- and low-resolution 1H and 13C solid-state NMR techniques in order to characterize and compare their dynamic behavior at a molecular level. A detailed interpretation in terms of molecular motions in these very complex systems was possible thanks to the integrated analysis of different relaxation measurements and high-resolution selective experiments. Untreated cocoons of all strains were found to be mainly constituted by two different types of rigid domains and by a third one, more mobile, due to physisorbed water molecules. Dynamic processes in the MHz and kHz ranges were characterized by means of different 1H and 13C relaxation times. Cocoons arising from different strains exhibit a different content of physisorbed water and also slightly different dynamic behavior, especially in the MHz regime.

In order to calibrate leak-detection instruments, devices based on permeation leaks and physical leaks are used. Unfortunately, permeation leaks are very sensitive to small temperature fluctuations and can be used only with those gases for which permeating materials are available. While, physical-leaks that overcome these restrictions are susceptible to clog, in particular when the gas flow through them is in viscous regime. Furthermore, for many type of leak devices, the conductance is not predictable based on dimensional, gas species and temperature data, for this reason no estimates or only rough estimates of leak rates are possible for conditions under use where they differ from those of the calibration. Here, we present the fabrication and characterization of a new kind of physical-leak devices based on nano-holes, which overcome these problems. Nano-holes, with diameters less than or equal to 200 nm, work in molecular-flow regime up to atmospheric pressure and for this reason they do not clog. The nano-holes are manufactured by milling a silicon nitride membrane by means of Focused Ion Beam (FIB), and their shapes are characterized by both Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM). Because of the capability of the AFM to acquire surface three-dimensional images with very high resolution, it is a very useful tool to perform a topographic characterization of the nano-holes.