GC-MS profiling of volatile metabolites produced by Klebsiella pneumoniae.

Currently used methods for diagnosing ventilator-associated pneumonia (VAP) are complex, time-consuming and require invasive procedures while empirical antibacterial therapy applies broad spectrum antibiotics that may promote antimicrobial resistance. Hence, novel and fast methods based on alternative markers are needed for VAP detection and differentiation of causative pathogens. Pathogenic bacteria produce a broad range of volatile organic compounds (VOCs), some of which may potentially serve as biomarkers for microorganism identification. Additionally, monitoring of dynamically changing VOCs concentration profiles may indicate emerging pneumonia and allow timely implementation of appropriate antimicrobial treatment. This study substantially extends the knowledge on bacterial metabolites providing the unambiguous identification of volatile metabolites produced by carbapenem-resistant and susceptible strains of Klebsiella pneumoniae (confirmed with pure standards in addition to mass spectra match) but also revealing their temporary concentration profiles (along the course of pathogen proliferation) and dependence on the addition of antibiotic (imipenem) to bacteria. Furthermore, the clinical strains of K. pneumoniae isolated from bronchoalveolar lavage specimens collected from mechanically ventilated patients were investigated to reveal, whether bacterial metabolites observed in model experiments with reference strains could be relevant for wild pathogens as well. In all experiments, the headspace samples from bacteria cultures were collected on multibed sorption tubes and analyzed by GC-MS. Sampling was done under strictly controlled conditions at seven time points (up to 24 h after bacteria inoculation) to follow the dynamic changes in VOC concentrations, revealing three profiles: release proportional to bacteria load, temporary maximum and uptake. Altogether 32 VOCs were released by susceptible and 25 VOCs by resistant strain, amongst which 2-pentanone, 2-heptanone, and 2-nonanone were significantly higher for carbapenem-resistant KPN. Considerably more metabolites (n = 64) were produced by clinical isolates and in higher diversity compared to reference KPN strains.

Cuprous Oxide Thin Films Implanted with Chromium Ions-Optical and Physical Properties Studies.

Cuprous oxide is a semiconductor with potential for use in photocatalysis, sensors, and photovoltaics. We used ion implantation to modify the properties of Cu2O oxide. Thin films of Cu2O were deposited with magnetron sputtering and implanted with low-energy Cr ions of different dosages. The X-ray diffraction method was used to determine the structure and composition of deposited and implanted films. The optical properties of the material before and after implantation were studied using spectrophotometry and spectroscopic ellipsometry. The investigation of surface topography was performed with atomic force microscopy. The implantation had little influence on the atomic lattice constant of the oxide structure, and no clear dependence of microstrain or crystalline size on the dose of implantation was found. The appearance of phase change was observed, which could have been caused by the implantation. Ellipsometry measurements showed an increase in the total thickness of the sample with an increase in the amount of implanted Cr ions, which indicates the influence of implantation on the properties of the surface and subsurface region. The refractive index n, extinction coefficient k, and absorption coefficient optical parameters show different energy dependences related to implantation dose.

Influence of Cr Ion Implantation on Physical Properties of CuO Thin Films.

Cupric oxide is a semiconductor with applications in sensors, solar cells, and solar thermal absorbers. To improve its properties, the oxide was doped with a metallic element. No studies were previously performed on Cr-doping using the ion implantation technique. The research goal of these studies is to investigate how Cr ion implantation impacts the properties of the oxide thin films. CuO thin films were deposited using magnetron sputtering, and then chromium ions with different energies and doses were implanted. Structural, optical, and vibrational properties of the samples were studied using X-ray diffraction, X-ray reflectivity, infra-red spectroscopy, Raman spectroscopy, and spectrophotometry. The surface morphology and topography were studied with ellipsometry, atomic force microscopy, and scanning electron microscopy. A simulation of the range of ions in the materials was performed. Ion implantation had an impact on the properties of thin films that could be used to tailor the optical properties of the cupric oxide and possibly also its electrical properties. A study considering the influence of ion implantation on electrical properties is proposed as further research on ion-implanted CuO thin films.

Laser-Ablative Synthesis of Ultrapure Magneto-Plasmonic Core-Satellite Nanocomposites for Biomedical Applications.

The combination of magnetic and plasmonic properties at the nanoscale promises the development of novel synergetic image-guided therapy strategies for the treatment of cancer and other diseases, but the fabrication of non-contaminated magneto-plasmonic nanocomposites suitable for biological applications is difficult within traditional chemical methods. Here, we describe a methodology based on laser ablation from Fe target in the presence of preliminarily ablated water-dispersed Au nanoparticles (NPs) to synthesize ultrapure bare (ligand-free) core-satellite nanostructures, consisting of large (several tens of nm) Fe-based core decorated by small (mean size 7.5 nm) Au NPs. The presence of the Fe-based core conditions a relatively strong magnetic response of the nanostructures (magnetization of >12.6 emu/g), while the Au NPs-based satellite shell provides a broad extinction peak centered at 550 nm with a long tale in the near-infrared to overlap with the region of relative tissue transparency (650-950 nm). We also discuss possible mechanisms responsible for the formation of the magnetic-plasmonic nanocomposites. We finally demonstrate a protocol to enhance colloidal stability of the core-satellites in biological environment by their coating with different polymers. Exempt of toxic impurities and combining strong magnetic and plasmonic responses, the formed core-satellite nanocomposites can be used in biomedical applications, including photo- and magneto-induced therapies, magnetic resonance imaging or photoacoustic imaging.

Solid-State Dewetting as a Driving Force for Structural Transformation and Magnetization Reversal Mechanism in FePd Thin Films.

In this work, the process of solid-state dewetting in FePd thin films and its influence on structural transformation and magnetic properties is presented. The morphology, structure and magnetic properties of the FePd system subjected to annealing at 600 °C for different times were studied. The analysis showed a strong correlation between the dewetting process and various physical phenomena. In particular, the transition between the A1 phase and L10 phase is strongly influenced by and inextricably connected with solid-state dewetting. Major changes were observed when the film lost its continuity, including a fast growth of the L10 phase, changes in the magnetization reversal behavior or the induction of magnetic spring-like behavior.

Tuning of the Titanium Oxide Surface to Control Magnetic Properties of Thin Iron Films.

We describe the magnetic properties of thin iron films deposited on the nanoporous titanium oxide templates and analyze their dependance on nanopore radius. We then compare the results to a continuous iron film of the same thickness. Additionally, we investigate the evolution of the magnetic properties of these films after annealing. We demonstrate that the M(H) loops consist of two magnetic phases originating from the iron layer and iron oxides formed at the titanium oxide/iron interface. We perform deconvolution of hysteresis loops to extract information for each magnetic phase. Finally, we investigate the magnetic interactions between the phases and verify the presence of exchange coupling between them. We observe the altering of the magnetic properties by the nanopores as a magnetic hardening of the magnetic material. The ZFC-FC (Zero-field cooled/field cooled) measurements indicate the presence of a disordered glass state below 50 K, which can be explained by the formation of iron oxide at the titanium oxide-iron interface with a short-range magnetic order.

Electrical Transport and Magnetic Properties of Metal/Metal Oxide/Metal Junctions Based on Anodized Metal Oxides.

In this paper, we describe magnetoelectric properties of metal/metal-oxide/metal junctions based on anodized metal oxides. Specifically, we use Ti and Fe metallic layers separated by the porous metal-oxides of iron or titanium formed by the anodization method. Thus, we prepare double junctions with at least one ferromagnetic layer and measure magnetoresistance, as well as their current-voltage and magnetic characteristics. We find that magnetoresistance depends on that junction composition and discuss the nature of differential resistance calculated from I-V characteristics. Our findings show that a top metallic layer and the interface between this layer and anodized oxide, where strong interatomic diffusion is expected, have the strongest influence on this observed behavior.

Nitrogen-Vacancy Color Centers Created by Proton Implantation in a Diamond.

We present an experimental study of the longitudinal and transverse relaxation of ensembles of negatively charged nitrogen-vacancy (NV-) centers in a diamond monocrystal prepared by 1.8 MeV proton implantation. The focused proton beam was used to introduce vacancies at a 20 µµm depth layer. Applied doses were in the range of 1.5×1013 to 1.5×1017 ions/cm2. The samples were subsequently annealed in vacuum which resulted in a migration of vacancies and their association with the nitrogen present in the diamond matrix. The proton implantation technique proved versatile to control production of nitrogen-vacancy color centers in thin films.

Mechanical Properties of Different Nanopatterned TiO2 Substrates and Their Effect on Hydrothermally Synthesized Bioactive Hydroxyapatite Coatings.

Nanotechnology is a very attractive tool for tailoring the surface of an orthopedic implant to optimize its interaction with the biological environment. Nanostructured interfaces are promising, especially for orthopedic applications. They can not only improve osseointegration between the implant and the living bone but also may be used as drug delivery platforms. The nanoporous structure can be used as a drug carrier to the surrounding tissue, with the intention to accelerate tissue-implant integration as well as to reduce and treat bacterial infections occurring after implantation. Titanium oxide nanotubes are promising for such applications; however, their brittle nature could be a significantly limiting factor. In this work, we modified the topography of commercially used titanium foil by the anodization process and hydrothermal treatment. As a result, we obtained a crystalline nanoporous u-shaped structure (US) of anodized titanium oxide with improved resistance to scratch compared to TiO2 nanotubes. The US titanium substrate was successfully modified with hydroxyapatite coating and investigated for bioactivity. Results showed high bioactivity in simulated body fluid (SBF) after two weeks of incubation.

Magnetization Reversal Mechanism in Exchange-Biased Spring-like Thin-Film Composite.

Development of modern spintronic devices requires materials exhibiting specific magnetic effects. In this paper, we investigate a magnetization reversal mechanism in a [Co/Pdx]7/CoO/[Co/Pdy]7 thin-film composite, where an antiferromagnet is sandwiched between a hard and a soft ferromagnets with different coercivities. The antiferromagnet/ferromagnet interfaces give rise to the exchange bias effect. The application of soft and hard ferromagnetic films causes exchange-spring-like behavior, while the choice of the Co/Pd multilayers provides large out-of-plane magnetic anisotropy. We observed that the magnitude and the sign of the exchange bias anisotropy field are related to the arrangement of the magnetic moments in the antiferromagnetic layer. This ordering is induced by the spin orientation present in neighboring ferromagnetic films, which is, in turn, dependent on the orientation and strength of the external magnetic field.

Weak Antilocalization Tailor-Made by System Topography in Large Scale Bismuth Antidot Arrays.

Using a two-carriers model and the Hikami-Larkin-Nagaoka (HLN) theory, we investigate the influence of large area patterning on magnetotransport properties in bismuth thin films with a thickness of 50 nm. The patterned systems have been produced by means of nanospheres lithography complemented by RF-plasma etching leading to highly ordered antidot arrays with the hexagonal symmetry and a variable antidot size. Simultaneous measurements of transverse and longitudinal magnetoresistance in a broad temperature range provided comprehensive data on transport properties and enabled us to extract the values of charge carrier densities and mobilities. Weak antilocalization signatures observed at low temperatures provided information on spin-orbit scattering length ranging from 20 to 30 nm, elastic scattering length of approx. 60 nm, and strong dependence on temperature phase coherence length. We show that in the absence of antidots the charge carrier transport follow 2-dimensional behavior and the dimensionality for phase-coherent processes changes from two to three dimensions at temperature higher than 10 K. For the antidot arrays, however, a decrease of the power law dephasing exponent is observed which is a sign of the 1D-2D crossover caused by the geometry of the system. This results in changes of scattering events probability and phase coherence lengths depending on the antidot diameters, which opens up opportunity to tailor the magnetotransport characteristics.

Superparamagnetic Iron Oxide Nanoparticles Modified with Silica Layers as Potential Agents for Lung Cancer Treatment.

Superparamagnetic iron oxide nanoparticles (SPIONs) are promising drug delivery carriers and hyperthermia agents for the treatment of cancer. However, to ensure their safety in vivo, SPIONs must be modified in order to prevent unwanted iron release. Thus, SPIONs were coated with silica layers of different morphologies: non-porous (@SiO2), mesoporous (@mSiO2) or with a combination of non-porous and mesoporous layers (@SiO2@mSiO2) deposited via a sol-gel method. The presence of SiO2 drastically changed the surface properties of the nanoparticles. The zeta potential changed from 19.6 ± 0.8 mV for SPIONs to -26.1 ± 0.1 mV for SPION@mSiO2. The Brunauer-Emmett-Teller (BET) surface area increased from 7.54 ± 0.02 m2/g for SPIONs to 101.3 ± 2.8 m2/g for SPION@mSiO2. All types of coatings significantly decreased iron release (at least 10 fold as compared to unmodified SPIONs). SPIONs and SPION@mSiO2 were tested in vitro in contact with human lung epithelial cells (A549 and BEAS-2B). Both nanoparticle types were cytocompatible, although some delay in proliferation was observed for BEAS-2B cells as compared to A549 cells, which was correlated with increased cell velocity and nanoparticles uptake.

In vivo Effects of Romidepsin on T-Cell Activation, Apoptosis and Function in the BCN02 HIV-1 Kick&Kill Clinical Trial.

Romidepsin (RMD) is a well-characterized histone deacetylase inhibitor approved for the treatment of cutaneous T-cell lymphoma. in vitro and in vivo studies have demonstrated that it is able to induce HIV-1 gene expression in latently infected CD4+ T cells from HIV-1+ individuals on suppressive antiretroviral therapy. However, in vitro experiments suggested that RMD could also impair T-cell functionality, particularly of activated T cells. Thus, the usefulness of RMD in HIV-1 kick&kill strategies, that aim to enhance the immune system elimination of infected cells after inducing HIV-1 viral reactivation, may be limited. In order to address whether the in vitro observations are replicated in vivo, we determined the effects of RMD on the total and HIV-1-specific T-cell populations in longitudinal samples from the BCN02 kick&kill clinical trial (NCT02616874). BCN02 was a proof-of-concept study in 15 early treated HIV-1+ individuals that combined MVA.HIVconsv vaccination with three weekly infusions of RMD given as a latency reversing agent. Our results show that RMD induced a transient increase in the frequency of apoptotic T cells and an enhanced activation of vaccine-induced T cells. Although RMD reduced the number of vaccine-elicited T cells secreting multiple cytokines, viral suppressive capacity of CD8+ T cells was preserved over the RMD treatment. These observations have important implications for the design of effective kick&kill strategies for the HIV-1 cure.

Magnetic reversal in perpendicularly magnetized antidot arrays with intrinsic and extrinsic defects.

Defects can significantly affect performance of nanopatterned magnetic devices, therefore their influence on the material properties has to be understood well before the material is used in technological applications. However, this is experimentally challenging due to the inability of the control of defect characteristics in a reproducible manner. Here, we construct a micromagnetic model, which accounts for intrinsic and extrinsic defects associated with the polycrystalline nature of the material and with corrugated edges of nanostructures. The predictions of the model are corroborated by the measurements obtained for highly ordered arrays of circular Co/Pd antidots with perpendicular magnetic anisotropy. We found that magnetic properties, magnetic reversal and the evolution of the domain pattern are strongly determined by density of defects, heterogeneity of nanostructures, and edge corrugations. In particular, an increase in the Néel domain walls, as compared to Bloch walls, was observed with a increase of the antidot diameters, suggesting that a neck between two antidots can behave like a nanowire with a width determined by the array period and antidot size. Furthermore, the presence of edge corrugations can lead to the formation of a network of magnetic bubbles, which are unstable in non-patterned flat films.

Ion induced ferromagnetism combined with self-assembly for large area magnetic modulation of thin films.

A highly versatile and scalable path to obtain buried magnetic nanostructures within alloy thin films, while maintaining a flat topography, is described. A magnetic pattern of nanoscale periodicity is generated over ∼cm2 areas by employing a B2 → A2 structural transition in the prototype Fe60Al40 thin alloy films. The phase transition was induced in the confined regions via ion-irradiation through self-assembled nanosphere masks. In this way, large area patterns of a hexagonal symmetry of ferromagnetic nanostructures embedded within a paramagnetic Fe60Al40 thin film are realized. The depth and lateral distribution of the induced magnetization was investigated by magnetometry and microscopy methods. Magnetic contrast imaging as well as simulations shows that the obtained magnetic structures are well defined, with the magnetic behavior tunable via the mask geometry.

From monetite plate to hydroxyapatite nanofibers by monoethanolamine assisted hydrothermal approach.

Calcium phosphates offer outstanding biological adaptability. Thanks to their specific physico-chemical properties they are one of the most widely used materials in bone tissue engineering applications. The search for an innovative and economic strategy of synthesizing their different forms has been drawing considerable attention in the field. Herein, we report on a facile hydrothermal process in the presence of ethylenediamine tetraacetic acid and monoethanolamine to obtain various forms of calcium phosphates. The monoethanolamine served as an alkaline source and crystal growth modifier, while ethylenediamine tetraacetic acid was used to control the Ca2+ supersaturation level under high temperature and high pressure conditions. The obtained inorganic compounds were examined for their elemental composition, morphology, and structure using scanning electron microscopy, Raman spectroscopy, and powder x-ray diffraction. We were able to selectively synthesize monetite plate-like microcrystals as well as hydroxyapatite plates and nanofibers by simply varying the concentration of monoethanolamine.

Tailoring of Magnetic Properties of NiO/Ni Composite Particles Fabricated by Pulsed Laser Irradiation.

We present NiO/Ni composite particles with face-centered cubic (fcc) structure prepared by a pulsed laser irradiation of NiO nanoparticles dispersed in liquid. The sizes of particles and the Ni content in NiO/Ni composites were controlled by tuning the laser parameters, such as laser fluence and irradiation time. We found that the weight fraction of Ni has a significant impact on magnetic properties of composite particles. Large exchange bias (HEB) and coercivity field (HC) were observed at 5 K due to the creation of heterojunctions at interfaces of ferromagnetic Ni and antiferromagnetic NiO. For the NiO/Ni composites with 80% of NiO we have observed the largest values of exchange bias (175 Oe) and coercive field (950 Oe), but the increase of Ni weight fraction resulted in the decrease of both HC and HEB values.

Biological effect of hydrothermally synthesized silica nanoparticles within crystalline hydroxyapatite coatings for titanium implants.

Development of functional coatings for artificial bone implants that strengthen the osseointegration and accelerate bone healing processes is urgently needed in the biomedical field. In this study we present biological effect of novel composite coatings with different concentration of silica nanoparticles within crystalline hydroxyapatite matrix (HAp-SiO2) synthesized on titanium under hydrothermal conditions. Samples were analyzed for their elemental composition, structure, bioactivity and in vitro cytotoxicity. The results indicate the formation and homogeneous distribution of silica nanoparticles on the surface of hexagonal hydroxyapatite (HAp) crystals. The coatings show improved bioactivity in comparison with pure HAp after 4 days of immersion in simulated body fluid (SBF). The responses of human osteoblast-like cells (MG-63) cultured onto the synthesized materials provide evidence that HAp-SiO2 composites exhibit good biocompatibility. We propose that this is because HAp-SiO2 composites favor biomineralization process with cell proliferation remaining unaffected, regardless of the amount of silica. Furthermore, SEM and fluorescence measurements demonstrate that HAp-SiO2 had positive effect on cell morphology, favoring cell adhesion.

Exchange Bias in the [CoO/Co/Pd]10 Antidot Large Area Arrays.

Magnetic nanostructures revealing exchange bias effect have gained a lot of interest in recent years due to their possible applications in modern devices with various functionalities. In this paper, we present our studies on patterned [CoO/Co/Pd]10 multilayer where ferromagnetic material is in a form of clusters, instead of being a continuous layer. The system was patterned using nanosphere lithography technique which resulted in creation of an assembly of well-ordered antidots or islands over a large substrate area. We found that the overall hysteresis loop of the films consists of hard and soft components. The hard component hysteresis loop exhibits a large exchange bias field up to -11 kOe. The patterning process causes a slight increase of the exchange field as the antidot radius rises. We also found that the material on edges of the structures gives rise to a soft unbiased magnetization component.

Influence of Superparamagnetism on Exchange Anisotropy at CoO/[Co/Pd] Interfaces.

Magnetic systems exhibiting an exchange bias effect are being considered as materials for applications in data storage devices, sensors, and biomedicine. Because the size of new magnetic devices is being continuously reduced, the influence of thermally induced instabilities in magnetic order has to be taken into account during their fabrication process. In this study, we show the influence of superparamagnetism on the magnetic properties of an exchange-biased [CoO/Co/Pd]10 multilayer. We find that the process of progressive thermal blocking of the superparamagnetic clusters causes an unusually fast rise of the exchange anisotropy field and coercivity and promotes easy-axis switching to the out-of-plane direction.