Comparison of Plasma-Polymerized Thin Films Deposited from 2-Methyl-2-oxazoline and 2-Ethyl-2-oxazoline: I Film Properties.

Poly(2-oxazoline) is a promising new class of polymeric materials due to their antibiofouling properties and good biocompatibility. Poly(2-oxazoline) coatings can be deposited on different substrates via plasma polymerization, which can be more advantageous than other coating methods. The aim of this study is to deposit poly(2-oxazoline) coatings using a surface dielectric barrier discharge burning in nitrogen at atmospheric pressure using 2-methyl-2-oxazoline and 2-ethyl-2-oxazoline vapours as monomers and compare the film properties. For the comparison, the antibacterial and cytocompatibility tests were peformed according to ISO norms. The antibacterial tests showed that all the deposited films were highly active against Staphylococcus aureus and Escherichia coli bacteria. The chemical composition of the films was studied using FTIR and XPS, and the film surface's properties were studied using AFM and surface energy measurement. The cytocompatibility tests showed good cytocompatibility of all the deposited films. However, the films deposited from 2-methyl-2-oxazoline exhibit better cytocompatibility. This difference can be explained by the different chemical compositions and surface morphologies of the films deposited from different monomers.

Antibacterial Thin Films Deposited from Propane-Butane Mixture in Atmospheric Pressure Discharge.

Antibacterial coatings on biomedical instruments are of great interest because they can suppress bacterial colonization on these instruments. In this study, antibacterial polymeric thin coatings were deposited on teflon substrates using atmospheric pressure plasma polymerization from a propane-butane mixture. The plasma polymerization was performed by means of surface dielectric barrier discharge burning in nitrogen at atmospheric pressure. The chemical composition of plasma polymerized propane-butane films was studied by energy-dispersive X-ray spectroscopy (EDX) and FTIR. The film surface properties were studied by SEM and by surface energy measurement. The EDX analysis showed that the films consisted of carbon, nitrogen and oxygen from ambient air. The FTIR analysis confirmed, in particular, the presence of alkyl, nitrile, acetylene, imide and amine groups. The deposited films were hydrophilic with a water contact angle in the range of 13-23°. The thin film deposited samples were highly active against both S. aureus and E. coli strains in general. On the other hand, the films were cytocompatible, reaching more than 80% of the cell viability threshold compared to reference polystyrene tissue.

Miniaturized bioluminescence technology for single-cell quantification of caspase-3/7.

Correct determination of the instantaneous level and changes of relevant proteins inside individual cells is essential for correct interpretation and understanding of physiological, diagnostic, and therapeutic events. Thus, single-cell analyses are important for quantification of natural cellular heterogeneity, which cannot be evaluated from averaged data of a cell population measurements. Here, we developed an original highly sensitive and selective instrumentation and methodology based on homogeneous single-step bioluminescence assay to quantify caspases and evaluate their heterogeneity in individual cells. Individual suspended cells are selected under microscope and reliably transferred into the 7 µl detection vials by a micromanipulator. The sensitivity of the method is given by implementation of photomultiplying tube with a cooled photocathode working in the photon counting mode. By optimization of our device and methodology, the limits of detection and quantitation were decreased down to 2.1 and 7.0 fg of recombinant caspase-3, respectively. These masses are lower than average amounts of caspase-3/7 in individual apoptotic and even non-apoptotic cells. As a proof of concept, the content of caspase-3/7 in single treated and untreated HeLa cells was determined to be 154 and 25 fg, respectively. Based on these results, we aim to use the technology for investigations of non-apoptotic functions of caspases.

Monitoring of the impact of road salting on spruce forest ecosystem in the vicinity of the highway D1 in the Bohemian-Moravian Highlands, Czech Republic.

Monitoring of pollution in the vicinity of roads connected to winter road maintenance is one of the important tools for optimising winter maintenance technology and reducing its environmental impact. The aim of this study was to determine the relationship between winter road maintenance and the increased concentration of sodium ion to characterise the harm caused by the de-icing agents on selected types of individual components grown in the Norway spruce ecosystem. The model area is located in the immediate vicinity of the D1 motorway connecting Prague and Brno (Czech Republic), at 103 km. The area is thus exposed to long-term contamination from automobile transport, and the monitoring was carried out for 3 consecutive years. A clear effect of the de-icing agents on conifers near the road has been demonstrated by the symptoms of salt damage visually observed in close proximity to the road (at a sampling distance of 5 m). The needles of these spruce trees also showed increased sodium concentrations, regardless of the age of the needles. The study also confirms that sodium accumulates in all selected components of the analysed ecosystem (moos, humus, soil). The sodium concentration has been found to decrease with increasing distance from the road for all of the components.

Arsenic-Doped SnSe Thin Films Prepared by Pulsed Laser Deposition.

Pulsed UV laser deposition was exploited for the preparation of thin Sn50-x As x Se50 (x = 0, 0.05, 0.5, and 2.5) films with the aim of investigating the influence of low arsenic concentration on the properties of the deposited layers. It was found that the selected deposition method results in growth of a highly (h00) oriented orthorhombic SnSe phase. The thin films were characterized by different techniques such as X-ray diffraction, scanning electron microscopy with energy-dispersive X-ray spectroscopy, atomic force microscopy, Raman scattering spectroscopy, and spectroscopic ellipsometry. From the results, it can be concluded that thin films containing 0.5 atom % of As exhibited extreme values regarding crystallite size, unit cell volume, or refractive index that significantly differ from those of other samples. Laser ablation with quadrupole ion trap time-of-flight mass spectrometry was used to identify and compare species present in the plasma originating from the interaction of a laser pulse with solid-state Sn50-x As x Se50 materials in both forms, i.e. parent powders as well as deposited thin films. The mass spectra of both materials were similar; particularly, signals of Sn m Se n + clusters with low m and n values were observed.

Atmospheric Pressure Plasma Polymerized 2-Ethyl-2-oxazoline Based Thin Films for Biomedical Purposes.

Polyoxazoline thin coatings were deposited on glass substrates using atmospheric pressure plasma polymerization from 2-ethyl-2-oxazoline vapours. The plasma polymerization was performed in dielectric barrier discharge burning in nitrogen at atmospheric pressure. The thin films stable in aqueous environments were obtained at the deposition with increased substrate temperature, which was changed from 20 ∘C to 150 ∘C. The thin film deposited samples were highly active against both S. aureus and E. coli strains in general. The chemical composition of polyoxazoline films was studied by FTIR and XPS, the mechanical properties of films were studied by depth sensing indentation technique and by scratch tests. The film surface properties were studied by AFM and by surface energy measurement. After tuning the deposition parameters (i.e., monomer flow rate and substrate temperature), stable films, which resist bacterial biofilm formation and have cell-repellent properties, were achieved. Such antibiofouling polyoxazoline thin films can have many potential biomedical applications.

The impact of tourism on extremely visited volcanic island: Link between environmental pollution and transportation modes.

The enormous tourism boom raises concern about possible negative environmental impacts worldwide. One of the risks posed by tourism may be heavy metal pollution. On the example of the volcanic island of Santorini, a popular tourist destination, pollution of soils categorized according to the tourism load was monitored. Significant anthropogenic contamination by heavy metals, especially Cu, Cr and Pb, was found out. This contamination may constitute a moderate ecological risk to the island ecosystems. Tourism has been shown to be a significant pollution factor as evidenced by the contaminated soils near the airport. Simultaneously, airport traffic has been proved to be an important emitter of Co, Cr and especially Zn. The comparison with other volcanic islands has shown that on Santorini the content of heavy metals in soils is significantly lower, despite frequently higher tourism intensity. On this basis, it can be concluded that in case of volcanic islands the dominant factor determining the content of heavy metals in the soil is the parent rock. Given high and ever-increasing intensity of tourism on the island, it can be assumed that soil contamination will continue to rise rapidly. Therefore, without proper steps reducing tourism, increase in soil degradation, growing negative impacts on local ecosystems as well as on the quality of produced wine can be expected on Santorini.

Atmospheric Pressure Plasma Polymerized Oxazoline-Based Thin Films-Antibacterial Properties and Cytocompatibility Performance.

Polyoxazolines are a new promising class of polymers for biomedical applications. Antibiofouling polyoxazoline coatings can suppress bacterial colonization of medical devices, which can cause infections to patients. However, the creation of oxazoline-based films using conventional methods is difficult. This study presents a new way to produce plasma polymerized oxazoline-based films with antibiofouling properties and good biocompatibility. The films were created via plasma deposition from 2-methyl-2-oxazoline vapors in nitrogen atmospheric pressure dielectric barrier discharge. Diverse film properties were achieved by increasing the substrate temperature at the deposition. The physical and chemical properties of plasma polymerized polyoxazoline films were studied by SEM, EDX, FTIR, AFM, depth-sensing indentation technique, and surface energy measurement. After tuning of the deposition parameters, films with a capacity to resist bacterial biofilm formation were achieved. Deposited films also promote cell viability.

Comparison of Clusters Produced from Sb2Se3 Homemade Polycrystalline Material, Thin Films, and Commercial Polycrystalline Bulk Using Laser Desorption Ionization with Time of Flight Quadrupole Ion Trap Mass Spectrometry.

This study compared Sb2Se3 material in the form of commercial polycrystalline bulk, sputtered thin film, and homemade polycrystalline material using laser desorption ionization (LDI) time of flight mass spectrometry with quadrupole ion trap mass spectrometry. It also analyzed the stoichiometry of the SbmSen clusters formed. The results showed that homemade Sb2Se3 bulk was more stable compared to thin film; its mass spectra showed the expected cluster formation. The use of materials for surface-assisted LDI (SALDI), i.e., graphene, graphene oxide, and C60, significantly increased the mass spectra intensity. In total, 19 SbmSen clusters were observed. Six novel, high-mass clusters-Sb4Se4+, Sb5Se3-6+, and Sb7Se4+-were observed for the first time when using paraffin as a protective agent.

Fast Surface Hydrophilization via Atmospheric Pressure Plasma Polymerization for Biological and Technical Applications.

Polymeric surfaces can benefit from functional modifications prior to using them for biological and/or technical applications. Surfaces considered for biocompatibility studies can be modified to gain beneficiary hydrophilic properties. For such modifications, the preparation of highly hydrophilic surfaces by means of plasma polymerization can be a good alternative to classical wet chemistry or plasma activation in simple atomic or molecular gasses. Atmospheric pressure plasma polymerization makes possible rapid, simple, and time-stable hydrophilic surface preparation, regardless of the type and properties of the material whose surface is to be modified. In this work, the surface of polypropylene was coated with a thin nanolayer of plasma-polymer which was prepared from a low-concentration mixture of propane-butane in nitrogen using atmospheric pressure plasma. A deposition time of only 1 second was necessary to achieve satisfactory hydrophilic properties. Highly hydrophilic, stable surfaces were obtained when the deposition time was 10 seconds. The thin layers of the prepared plasma-polymer exhibit highly stable wetting properties, they are smooth, homogeneous, flexible, and have good adhesion to the surface of polypropylene substrates. Moreover, they are constituted from essential elements only (C, H, N, O). This makes the presented modified plasma-polymer surfaces interesting for further studies in biological and/or technical applications.

Mass spectrometric investigation of amorphous Ga-Sb-Se thin films.

Amorphous chalcogenide thin films are widely studied due to their enhanced properties and extensive applications. Here, we have studied amorphous Ga-Sb-Se chalcogenide thin films prepared by magnetron co-sputtering, via laser ablation quadrupole ion trap time-of-flight mass spectrometry. Furthermore, the stoichiometry of the generated clusters was determined which gives information about individual species present in the plasma plume originating from the interaction of amorphous chalcogenides with high energy laser pulses. Seven different compositions of thin films (Ga content 7.6-31.7 at. %, Sb content 5.2-31.2 at. %, Se content 61.2-63.3 at. %) were studied and in each case about ~50 different clusters were identified in positive and ~20-30 clusters in negative ion mode. Assuming that polymers can influence the laser desorption (laser ablation) process, we have used parafilm as a material to reduce the destruction of the amorphous network structure and/or promote the laser ablation synthesis of heavier species from those of lower mass. In this case, many new and higher mass clusters were identified. The maximum number of (40) new clusters was detected for the Ga-Sb-Se thin film containing the highest amount of antimony (31.2 at. %). This approach opens new possibilities for laser desorption ionization/laser ablation study of other materials. Finally, for selected binary and ternary clusters, their structure was calculated by using density functional theory optimization procedure.

Variability of trace element distribution in Noccaea spp., Arabidopsis spp., and Thlaspi arvense leaves: the role of plant species and element accumulation ability.

Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) was applied for the determination of Cd and Zn distributions within the leaves of Cd- and Zn-hyperaccumulating plants, Noccaea caerulescens, N. praecox, and Arabidopsis halleri, in contrast to nonaccumulator species, Thlaspi arvense and A. thaliana. The elemental mapping of the selected leaf area was accomplished via line scans with a 110-µm-diameter laser beam at a 37-µm s-1 scan speed and repetition rate of 10 Hz. The lines were spaced 180 µm apart and ablated at an energy density of 2 J cm-2. The elemental imaging clearly confirmed that Cd was predominantly distributed within the parenchyma of the T. arvense, whereas in the Noccaea spp. and A. halleri, the highest intensity Cd signal was observed in the veins of the leaves. For Zn, higher intensities were observed in the veins for all the plant species except for A. thaliana. Close relationships between Zn and Ca were identified for the Noccaea spp. leaves. These relationships were not confirmed for A. halleri. Significant correlations were also proved between the Cd and Zn distribution in A. halleri, but not for the Noccaea spp. For both T. arvense and A. thaliana, no relevant significant relationship for the interpretation of the results was observed. Thus, the LA-ICP-MS imaging is proved as a relevant technique for the description and understanding of the elements in hyperaccumulating or highly accumulating plant species, although its sensitivity for the natural element contents in nonaccumulator plant species is still insufficient.

Gallium selenide clusters generated via laser desorption ionisation quadrupole ion trap time-of-flight mass spectrometry.

RATIONALE: Gallium selenide thin films important for electronics and phase-change materials are prepared via pulsed laser deposition (PLD); however, there are no studies concerning the analysis of gallium selenide clusters formed in the gas phase. Laser desorption ionisation (LDI) combined with time-of-flight mass spectrometry (TOF-MS) has great potential to generate charged Gam Sen clusters, to analyse them and thus to develop new materials. METHODS: LDI of Ga-Se mixtures using a pulsed laser (337 nm nitrogen) was used to generate gallium-selenide clusters. Mass spectra were recorded (in positive and negative ion mode) on a TOF mass spectrometer equipped with a quadrupole ion trap and reflectron mass analyser. RESULTS: Ga-Se mixtures were found to be suitable for laser ablation synthesis (LAS) of gallium selenide clusters, although their composition was strongly dependent on the laser energy. The effect of laser energy on the stoichiometry of the generated clusters was established. In total, over 100 gallium selenide Gam Sen clusters were generated and identified from Ga-Se mixtures. LDI of Ga2 Se3 crystals showed almost the same clusters up to m/z 1000 with lower intensities, whereas no clusters from Ga2 Se3 were observed above m/z 1000. CONCLUSIONS: A family of over 100 gallium selenide clusters, generated and identified for the first time, shows rich and complex chemistry. Some of the clusters represent new compounds that have the potential to be used in the development of advanced materials.

Laser Ablation Generation of Antimony Selenide Clusters: Laser Desorption Ionization (LDI) Quadrupole Ion Trap Time of Flight Mass Spectrometry.

The binary system Sb-Se was studied via laser ablation using antimony-selenium mixtures made from powdered elements in various ratios generating new SbmSen clusters. The results show that in addition to Sbm+ (m = 1-8) and Sen+ (n = 2-9) clusters, a series of SbmSen+ clusters such as SbSe1-8+, Sb2Se1-6+, Sb3Se1-5+, Sb4Se1-3+, and Sb5Se1,2+ is generated. In addition, some low intensity oxidized clusters like Se6O2+, Se7O2+, and SbSe2-6O5+ and partially hydroxylated clusters (SbSeO2H7+, SbSe5O4H+) are also formed. In total, 24 new antimony selenide clusters were generated. The knowledge gained can contribute to the elucidation of the structure of SbmSen glasses. Graphical Abstract.

Laser ablation synthesis of arsenic-phosphide Asm Pn clusters from As-P mixtures. Laser desorption ionisation with quadrupole ion trap time-of-flight mass spectrometry: The mass spectrometer as a synthesizer.

RATIONALE: Only a few arsenic phosphides are known. A high potential for the generation of new compounds is offered by Laser Ablation Synthesis (LAS) and when Laser Desorption Ionization (LDI) is coupled with simultaneous Time-Of-Flight Mass Spectrometry (TOFMS), immediate identification of the clusters can be achieved. METHODS: LAS was used for the generation of arsenic phosphides via laser ablation of phosphorus-arsenic mixtures while quadrupole ion trap time-of-flight mass spectrometry (QIT-TOFMS) was used to acquire the mass spectra. RESULTS: Many new Asm Pn± clusters (479 binary and 369 mono-elemental) not yet described in the literature were generated in the gas phase and their stoichiometry determined. The likely structures for some of the observed clusters arbitrary selected (20) were computed by density functional theory (DFT) optimization. CONCLUSIONS: LAS is an advantageous approach for the generation of new Asm Pn clusters, while mass spectrometry was found to be an efficient technique for the determination of cluster stoichiometry. The results achieved might inspire the synthesis of new materials.

Intact Cell Mass Spectrometry as a Quality Control Tool for Revealing Minute Phenotypic Changes of Cultured Human Embryonic Stem Cells.

The stability of in vitro cell cultures is an important issue for any clinical, bio-industrial, or pharmacological use. Embryonic stem cells are pluripotent; consequently, they possess the ability to differentiate into all three germ layers and are inherently prone to respond to differentiation stimuli. However, long-term culture inevitably yields clones that are best adapted to the culture conditions, passaging regimes, or differentiation sensitivity. This cellular plasticity is a major obstacle in the development of bio-industrial or clinical-grade cultures. At present, the quality control of cell cultures is limited by the lack of reliable (epi)genetic or molecular markers or by the focus on a particular type of instability such as karyotype abnormalities or adverse phenotypic traits. Therefore, there is an ongoing need for robust, feasible, and sensitive methods of determining or confirming cell status and for revealing potential divergences from the optimal state. We modeled both intrinsic and extrinsic changes in human embryonic stem cell (hESC) states using different experimental strategies and addressed the changes in cell status by intact cell mass spectrometry fingerprinting. The analysis of spectral fingerprints by methods routinely used in analytical chemistry clearly distinguished the morphologically and biochemically similar populations of hESCs and provided a biomarker-independent tool for the quality control of cell culture. Stem Cells Translational Medicine 2018;7:109-114.

Laser Desorption Ionization of As2Ch3 (Ch = S, Se, and Te) Chalcogenides Using Quadrupole Ion Trap Time-of-Flight Mass Spectrometry: A Comparative Study.

Laser desorption ionization using time-of-flight mass spectrometer afforded with quadrupole ion trap was used to study As2Ch3 (Ch = S, Se, and Te) bulk chalcogenide materials. The main goal of the study is the identification of species present in the plasma originating from the interaction of laser pulses with solid state material. The generated clusters in both positive and negative ion mode are identified as 10 unary (S p+/- and As m+/- ) and 34 binary (As m S p+/- ) species for As2S3 glass, 2 unary (Se q+/- ) and 26 binary (As m Se q+/- ) species for As2Se3 glass, 7 unary (Te r+/- ) and 23 binary (As m Te r+/- ) species for As2Te3 material. The fragmentation of chalcogenide materials was diminished using some polymers and in this way 45 new, higher mass clusters have been detected. This novel approach opens a new possibility for laser desorption ionization mass spectrometry analysis of chalcogenides as well as other materials. Graphical abstract ᅟ.

Analysis of Means (ANOM) as a Tool for Comparison of Sample Treatment Methods: Testing Various Mineralization Procedures for Selenium Determination in Biological Materials.

Several mineralization methods for the determination of selenium using hydride generation optical emission spectrometry with inductively coupled plasma in biological samples (whole egg powder and pork liver) were compared using the analysis of means (ANOM) method. This statistical tool is suitable for graphical representation of testing on simple comparative experiments. The results yielded by ANOM are identical with those obtained with the commonly used analysis of variance (ANOVA) method; however, the graphical output of ANOM is more illustrative in comparison to ANOVA. Both methods indicated a significant discrepancy between the results obtained using muffle furnace ashing mineralization and the results provided by other mineralization methods. This is probably due to the loss of volatile selenium compounds during the decomposition of organic matter.

Clusters of Monoisotopic Elements for Calibration in (TOF) Mass Spectrometry.

Precise calibration in TOF MS requires suitable and reliable standards, which are not always available for high masses. We evaluated inorganic clusters of the monoisotopic elements gold and phosphorus (Au n+/Au n- and P n+/P n-) as an alternative to peptides or proteins for the external and internal calibration of mass spectra in various experimental and instrumental scenarios. Monoisotopic gold or phosphorus clusters can be easily generated in situ from suitable precursors by laser desorption/ionization (LDI) or matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS). Their use offers numerous advantages, including simplicity of preparation, biological inertness, and exact mass determination even at lower mass resolution. We used citrate-stabilized gold nanoparticles to generate gold calibration clusters, and red phosphorus powder to generate phosphorus clusters. Both elements can be added to samples to perform internal calibration up to mass-to-charge (m/z) 10-15,000 without significantly interfering with the analyte. We demonstrated the use of the gold and phosphorous clusters in the MS analysis of complex biological samples, including microbial standards and total extracts of mouse embryonic fibroblasts. We believe that clusters of monoisotopic elements could be used as generally applicable calibrants for complex biological samples. Graphical Abstract ᅟ.

Laser Ablation Synthesis of Gold Selenides by using a Mass Spectrometer as a Synthesizer: Laser Desorption Ionization Time-of-Flight Mass Spectrometry.

Methods for the rapid construction of new chemical motifs have the potential to accelerate the development of nanoscience. The synthesis of new chemical entities by laser ablation has been systematically demonstrated by using mixtures of gold and selenium. The compounds generated are detected by time-of-flight mass spectrometry and, for selected compounds, the structure is investigated by using density functional theory optimization. In total, 67 new gold selenide clusters have been synthesized, demonstrating an unsuspected richness in gold chemistry. Chemical species generated in the gas phase might inspire new routes for the synthesis of novel compounds in the solid state.