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Diamond is increasingly popular because of its unique material properties. Diamond defects called nitrogen vacancy (NV) centers allow for measurements with unprecedented sensitivity. However, to achieve ideal sensing performance, NV centers need to be within nanometers from the surface and are thus strongly dependent on the local surface chemistry. Several attempts have been made to compare diamond surfaces. However, due to the high price of diamond crystals with shallow NV centers, a limited number of chemical modifications have been studied. Here, we developed a systematic method to investigate the continuity of different local environments with varying densities and natures of surface groups in a single experiment on a single diamond plate. To achieve this goal, we used diamonds with a shallow ensemble of NV centers and introduced a chemical gradient across the surface. More specifically, we used air and hydrogen plasma. The gradients were formed by a low-pressure plasma treatment after masking with a right-angled triangular prism shield. As a result, the surface contained gradually more oxygen/hydrogen toward the open end of the shield. We then performed wide-field relaxometry to determine the effect of surface chemistry on the sensing performance. As expected, relaxation times and thus sensing performance indeed vary along the gradient.

Pure Zn is well-known for its appropriate corrosion rate, making it suitable for use as future absorbable implants. Yet, it suffers from insufficient strength, thus, both plastic deformation and alloying are required. Hydrostatic extrusion has proven to be an efficient technique, providing high mechanical properties for zinc alloys. However, its effect on degradation rate and biocompatibility of Zn alloys remains unknown. Thus, within the present study, an attempt to evaluate those properties has been made on hydrostatically extruded pure Zn, Zn–Mg and Zn–Mg–Cu alloys. The materials were characterized by advanced microscopy techniques and uniaxial tensile tests. Corrosion properties were assessed based on electrochemical and static immersion tests. Finally, the cytotoxic effect of zinc extracts on endothelial cells were examined by standard MTT assays combined with confocal imaging.

Cumulus granulosa cells (cGCs) and mural granulosa cells (mGCs), although derived from the same precursors, are anatomically and functionally heterogeneous. They are critical for female fertility by supporting oocyte competence and follicular development. There are various techniques used to investigate the role of free radicals in mGCs and cCGs. Yet, temporospatial resolution remains a challenge. We used a quantum sensing approach to study free radical generation at nanoscale in cGCs and mGCs isolated from women undergoing oocyte retrieval during in vitrofertilization (IVF). Cells were incubated with bare fluorescent nanodiamonds (FNDs) or mitochondria targeted FNDs to detect free radicals in the cytoplasm and mitochondria. After inducing oxidative stress with menadione, we continued to detect free radical generation for 30 min. We observed an increase in free radical generation in cGCs and mGCs from 10 min on. Although cytoplasmic and mitochondrial free radical levels are indistinguishable in the physiological state in both cGCs and mGCs, the free radical changes measured in mitochondria were significantly larger in both cell types, suggesting mitochondria are sites of free radical generation. Furthermore, we observed later occurrence and a smaller percentage of cytoplasmic free radical change in cGCs, indicating that cGCs may be more resistant to oxidative stress.

The paper presents a fully recursive algorithm for building a nonlinear block-oriented model of a dynamic system on the basis of noise-corrupted data. Hidden internal signal in the Hammerstein structure is firstly predicted to compute the best possible model of the second (linear dynamic) block of the system. Asymptotically, the algorithm reaches an equilibrium point when the predictor becomes equivalent to the characteristic of the nonlinear block. Nonlinear static element is treated as a black box, and the predictor is based on non-parametric kernel regression or orthogonal expansion estimation method. The crucial contribution lies in the fact that the algorithm computes the offset (bias) between the input-output regression function and the nonlinear characteristic, which allows to get optimal model of the whole system. Experimental studies include both iterative convex optimisation procedure and its recursive version, wherein measurement data need not to be stored in memory. As a real data example - thermal analysis of chalcogenide glasses was modelled with an algorithm updated to the Hammerstein system with ARMAX block.

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Here, we present multifunctional fluorescent nanodiamonds (FNDs) for simultaneous drug delivery and free radical detection. For this purpose, we modified FNDs containing nitrogen vacancy (NV) centers with a diazoxide derivative. We found that our particles enter cells more easily and are able to deliver this cancer drug into HeLa cells. The particles were characterized by infrared spectroscopy, dynamic light scattering, and secondary electron microscopy. Compared to the free drug, we observe a sustained release over 72 h rather than 12 h for the free drug. Apart from releasing the drug, with these particles, we can measure the drug’s effect on free radical generation directly. This has the advantage that the response is measured locally, where the drug is released. These FNDs change their optical properties based on their magnetic surrounding. More specifically, we make use of a technique called relaxometry to detect spin noise from the free radical at the nanoscale with subcellular resolution. We further compared the results from our new technique with a conventional fluorescence assay for the detection of reactive oxygen species. This provides a new method to investigate the relationship between drug release and the response by the cell via radical formation or inhibition.

Cardiovascular diseases are currently the most common cause of death in developed countries. Due to lifestyle and environmental factors, this problem is only expected to increase in the future. Reactive oxygen species (ROS) are a key player in the onset of cardiovascular diseases but also have important functions in healthy cardiac tissue. Here, the interplay between ROS generation and cardiac mechanical forces is shown, and the state of the art and a perspective on future directions are discussed. To this end, an overview of what is currently known regarding ROS and mechanosignaling at a subcellular level is first given. There the role of ROS in mechanosignaling as well as the interplay between both factors in specific organelles is emphasized. The consequences at a larger scale across the population of heart cells are then discussed. Subsequently, the roles of ROS in embryogenesis, pathogenesis, and aging are further discussed, exemplifying some aspects of mechanoregulation. Finally, different models that are currently in use are discussed to study the topics above. Here, the influence of reactive oxygen species on heart physiology and cardiovascular diseases is reviewed. The effect of mechanoregulation on the heart is further investigated, and where possible a link between these two factors is provided. This article is structured to go from microscales and subcellular information up to cells, tissues, organs, and finally the whole organism.

The blood compatibility of self-assembled monolayers (SAMs) of oligoproline, a nonionic antifouling peptide, was investigated using the cone-and-plate assay imitating arterial blood flow conditions. End-capped oligoprolines composed of 6 and 9 proline residues (Pro6 and Pro9) and a Cys residue were synthesized for preparing SAMs (Pro-SAMs) on Au-sputtered glass. The surface of Pro-SAMs indicated hydrophilic property with a smooth topology. The adsorption of blood components and the adhesion of blood cells, including leukocytes and platelets, were strongly suppressed on Pro-SAMs. Moreover, Pro9-SAM did not trigger the activation of platelets (i.e., the conformational change of GPIIb/IIIa and P-selectin (CD62P) expression on platelets and the formation of aggregates). Our results demonstrate that Pro9-SAM completely inhibited acute thrombogenic responses and the activation of platelets under dynamic conditions.

The phenomenon of superior biological behavior observed in titanium processed by an unconventional severe plastic deformation method, that is, hydrostatic extrusion, has been described within the present study. In doing so, specimens varying significantly in the crystallographic orientation of grains, yet exhibiting comparable grain refinement, were meticulously investigated. The aim was to find the clear origin of enhanced biocompatibility of titanium-based materials, having microstructures scaled down to the submicron range. Texture, microstructure, and surface characteristics, that is, wettability, roughness, and chemical composition, were examined as well as protein adsorption tests and cell response studies were carried out. It has been concluded that, irrespective of surface properties and mean grain size, the (101̅0) crystallographic plane favors endothelial cell attachment on the surface of the severely deformed titanium. Interestingly, an enhanced albumin, fibronectin, and serum adsorption as well as clearly directional growth of the cells with preferentially oriented cell nuclei have been observed on the surfaces having (0001) planes exposed predominantly. Overall, the biological response of titanium fabricated by severe plastic deformation techniques is derived from the synergistic effect of surface irregularities, being the effect of refined microstructures, surface chemistry, and crystallographic orientation of grains rather than grain refinement itself.

The process of modern cardiovascular device fabrication should always be associated with an investigation of how surface properties modulate its hemocompatibility through plasma protein adsorption as well as blood morphotic element activation and adhesion. In this work, a package of novel assays was used to correlate the physicochemical properties of thin ceramic coatings with hemocompatibility under dynamic conditions. Different variants of carbon-based films were prepared on polymer substrates using the magnetron sputtering method. The microstructural, mechanical, and surface physicochemical tests were performed to characterize the coatings, followed by investigation of whole human blood quality changes under blood flow conditions using the “Impact R” test, tubes’ tester, and radial flow chamber assay. The applied methodology allowed us to determine that aggregate formation on hydrophobic and hydrophilic carbon-based coatings may follow one of the two different mechanisms dependent on the type and conformational changes of adsorbed blood plasma proteins.

Diamond-based T1relaxometry is a new technique that allows nanoscale magnetic resonance measurements. Here we present its first application in patient samples. More specifically, we demonstrate that relaxometry can determine the free radical load in samples from arthritis patients. We found that we can clearly differentiate between osteoarthritis and rheumatoid arthritis patients in both the synovial fluid itself and cells derived from it. Furthermore, we tested how synovial fluid and its cells respond to piroxicam, a common nonsteroidal anti-inflammatory drug (NSAID). It is known that this drug leads to a reduction in reactive oxygen species production in fibroblast-like synoviocytes (FLS). Here, we investigated the formation of free radicals specifically. While FLS from osteoarthritis patients showed a drastic decrease in the free radical load, cells from rheumatoid arthritis retained a similar radical load after treatment. This offers a possible explanation for why piroxicam is more beneficial for patients with osteoarthritis than those with rheumatoid arthritis.

Calibration with an internal standard was applied to eliminate particle size effects for powdered samples of copper ores, concentrates and copper slag prepared in the form of pellets. Internal standards were added in a powder form of extremely small particle size, which means that changes in their particle size could cause only negligible changes in their x-ray fluorescence intensity. The observed clear relationship between the internal standard x-ray fluorescence intensity and sample particle size was applied for the correction of x-ray fluorescence intensities of many analytes. Copyright © 2002 John Wiley & Sons, Ltd.

In the paper the internal signal in the Wiener system is recovered under nonparametric a priori knowledge about the static subsystem nonlinearity. The proposed approach is based on the observation that the impulse response of the dynamic subsystem is proportional to the MISO mapping, directly related to the considered system. Although derivation of the method involves gradient and kernel least squares techniques, the resulting algorithm possesses explicit form and does not utilize any time-consuming computational procedures. Theoretical aspects of the approach and comparison of the algorithm with other semi- and nonparametric methodsare discussed in the paper. The method is also generalized for MISO and MIMO systems.

The studies considered graphene-based biomaterials dedicated for cardiovascular therapy. Reduced graphene oxide flakes were introduced into the porous structure of the polyelectro-lyte based coatings. TEM analysis showed thepresenceofgrapheneflakes arrangedparallelto the substrate surface, firmly connected to the porous coating. Biomaterials were subjectedtoa comprehensive diagnosis ofthe biological and material properties. The material behavior was simulated using finite element method. The coatings were deposited using layer by layer method. Mechanical analysis was done using Berkovich indenter geometry.

The aim of this study was to improve properties of blood contacting materials such as polyurethane, in a form of intelligent, self-organizing and self-controlling coatings, which allow the selective mobilization and colonization of the endothelial cells on their surface. The prepared multilayer polyelectrolyte scaffolds were cross-linked chemically by EDC/NHS reagents in order to control their physicochemical properties and thus improving potential to endothelialization. Four types of coatings, i.e. non-cross-linked, cross-linked by 260mM, 400mM and 800mM EDC reagent, were investigated. Their comparison was performed based on the results of the surface topography measurements using Atomic Force Microscopy (AFM), cellular morphology and proliferation analysis using Confocal Laser Scanning Microscopy (CLSM) and the mechanical properties examinations.

Relaxometry is a technique which makes use of a specific crystal lattice defect in diamond, the so-called NV center. This defect consists of a nitrogen atom, which replaces a carbon atom in the diamond lattice, and an adjacent vacancy. NV centers allow converting magnetic noise into optical signals, which dramatically increases the sensitivity of the readout, allowing for nanoscale resolution. Analogously to T1 measurements in conventional magnetic resonance imaging (MRI), relaxometry allows the detection of different concentrations of paramagnetic species. However, since relaxometry allows very local measurements, the detected signals are from nanoscale voxels around the NV centers. As a result, it is possible to achieve subcellular resolutions and organelle specific measurements.

Free radicals play a major role in sperm development, including maturation and fertilization, but they are also linked to infertility. Since they are short-lived and reactive, they are challenging to detect with state of the art methodologies. Thus, many details surrounding their role remain unknown. One unknown factor is the source of radicals that plays a role in the sperm maturation process. Two alternative sources have been postulated: First, the NADPH-oxidase system embedded in the plasma membrane (NOX5) and second, the NADH-dependent oxidoreductase of mitochondria. Due to a lack of localized measurements, the relative contribution of each source for capacitation remains unknown. To answer this question, we use a technique called diamond magnetometry, which allows nanoscale MRI to perform localized free radical detection. With this tool, we were able to quantify radical formation in the acrosome of sperm heads. This allowed us to quantify radical formation locally in real time during capacitation. We further investigated how different inhibitors or triggers alter the radical generation. We were able to identify NOX5 as the prominent source of radical generation in capacitation while the NADH-dependent oxidoreductase of mitochondria seems to play a smaller role.

Generalized Kernel Regression Estimate for the Identification of Hammerstein SystemsA modified version of the classical kernel nonparametric identification algorithm for nonlinearity recovering in a Hammerstein system under the existence of random noise is proposed. The assumptions imposed on the unknown characteristic are weak. The generalized kernel method proposed in the paper provides more accurate results in comparison with the classical kernel nonparametric estimate, regardless of the number of measurements. The convergence in probability of the proposed estimate to the unknown characteristic is proved and the question of the convergence rate is discussed. Illustrative simulation examples are included.

Chemofiltration through zinc sulfide collected on a membrane filter was used for mercury preconcentration from water samples. Measurements of mercury radiation from the front and back sides of the sample indicate that the ion exchange proceeds on the surface and consequently mercury is collected as a thin layer of HgS on the ZnS. Therefore, filtration of mercury solutions through other sulfides, e.g., CuS, MnS and As2S3will give the same radiation intensity. The loading inhomogeneity was examined using a mapping sample with 1 mm spot size and WDXRF measurements. The mercury recovery was investigated for zinc mass per unit area from 20 to 1000 μg cm−2. Samples with mass per unit area of 200 μg cm−2of zinc were used because of their good recovery ca. 100, the fact that different flow rates between 10 mL min−1and 25 mL min−1do not influence the quantity of recovered mercury, the good precision and the ruggedness of the method. The detection limit for 1000 mL of filtered water, 100 s counting time and a molybdenum target X-ray tube operated at 50 kV and 40 mA is equal to 0.09 and 0.17 ng mL−1for Hg Lα1and Hg Lβ1, respectively. The RSD characterizing the sample preparation is ca. 3.5. The calibration was performed using standard samples in two Hg mass per unit area ranges: 0.5–20 and 0.5–3 μg cm−2. R2and residual errors RMS of 0.9998, 0.091 μg cm−2and 0.9997, 0.024 μg cm−2were obtained for the two calibrations, respectively. The selectivity was investigated by determination of mercury in test mixtures to which selected compounds such as alkali and heavy metals, phenol and bromides had been deliberately introduced.

A novel, parametric-nonparametric, methodology for Hammerstein system identification is proposed. Assuming random input and correlated output noise, the parameters of a nonlinear static characteristic and finite impulsearesponse system dynamics are estimated separately, each in two stages. First, the inner signal is recovered by a nonparametric regression function estimation method (Stage 1) and then system parameters are solved independently by the least squares (Stage 2). Convergence proper ties of the scheme are established and rates of convergence are given. [ABSTRACT FROM AUTHOR]

The Institute of Non-Ferrous Metals, Gliwice (Poland) has developed a process for uniform deposition of urban particulate matter on filter media which enables the production of reference materials for X-ray calibration by depositing certified reference materials on filters at different mass loadings. This process has been used to prepare the SRM 2783 for the National Institute of Standards and Technology, which consists of a set of five such filters based on the use of the SRM 1648 for the deposition.

Open pit mines are frequently accumulating significant amounts of material in the form of dumping grounds, landfills or forming land for reclamation. Often the form of emerging dumping grounds is determined by stability analysis of their slopes at the design stage. During the operation of the mining site and the collection of material on the pile, only the geometry of the slope is a subject of control. In many cases, after making slopes of a dozen or so meters height or even up to several tens of meters, and after a certain time has elapsed since their formation, deformation of the escarpments can be observed. At this stage, the only option is to change the geometry, i.e. inclination of a slope or, in the worst case, rebuilding of the dump. In the paper the analysis of the impact of the method of forming slopes and material quality on stability of formed slopes and their safe exploitation has been presented. It also presents a proposal to normalize the methodology of design and construction of slopes in a manner ensuring stability and taking into account the variability of the material parameters from which the slope is to be formed.