The reactivity of hydrogenated graphene when treated with oxidising agents, KMnO4 and KIO4 , as well as alkylated with benzyl bromide (BnBr) was studied. The probed reactions are strictly limited to the partly hydrogenated form of graphene in which most of the hydrogen atoms are located in activated benzylic/allylic positions. This, in turn, clearly demonstrates the presence of hydrogen attached to the graphene lattice. Attachment of the benzyl group was also unequivocally demonstrated by characteristic vibrations recorded in the surface-enhanced Raman spectra, and all reactions were shown to proceed solely on hydrogenated graphene as evidenced by the comparison with pristine chemical vapour deposition-grown graphene.

• Klíčová slova
• Raman spectroscopy, functionalization, graphene, hydrogenation, surface chemistry,
• Publikační typ
• časopisecké články MeSH

The non-specific binding of non-target species to functionalized surfaces of biosensors continues to be challenge for biosensing in real-world media. Three different low-fouling and functionalizable surface platforms were employed to study the effect of functionalization on fouling resistance from several types of undiluted media including blood plasma and food media. The surface platforms investigated in this work included two polymer brushes: hydroxy-functional poly(2-hydroxyethyl methacrylate) (pHEMA) and carboxy-functional poly(carboxybetaine acrylamide) (pCBAA), and a standard OEG-based carboxy-functional alkanethiolate self-assembled monolayer (AT-SAM). The wet and dry polymer brushes were analyzed by AFM, ellipsometry, FT-IRRAS, and surface plasmon resonance (SPR). The surfaces were functionalized by the covalent attachment of antibodies, streptavidin, and oligonucleotides and the binding and biorecognition characteristics of the coatings were compared. We found that functionalization did not substantially affect the ultra-low fouling properties of pCBAA (plasma fouling of ~20 ng/cm(2)), a finding in contrast with pHEMA that completely lost its resistance to fouling after the activation of hydroxyl groups. Blocking a functionalized AT-SAM covalently with BSA decreased fouling down to the level comparable to unblocked pCBAA. However, the biorecognition capability of blocked functionalized AT-SAM was poor in comparison with functionalized pCBAA. Limits of detection of Escherichia coli O157:H7 in undiluted milk were determined to be 6×10(4), 8×10(5), and 6×10(5) cells/ml for pCBAA, pHEMA, and AT-SAM-blocked, respectively. Effect of analyte size on biorecognition activity of functionalized coatings was investigated and it was shown that the best performance in terms of overall fouling resistance and biorecognition capability is provided by pCBAA.

• Klíčová slova
• Functionalization, Low-fouling coatings, Polymer brushes, Surface chemistry, Surface plasmon resonance sensor,
• MeSH
• adsorpce MeSH
• akrylamidy chemie   MeSH
• Escherichia coli izolace a purifikace   MeSH
• limita detekce MeSH
• mléko mikrobiologie   MeSH
• polyhydroxyethylmethakrylát chemie   MeSH
• polymery chemie   MeSH
• povrchová plasmonová rezonance metody   MeSH
• povrchové vlastnosti MeSH
• sulfhydrylové sloučeniny chemie   MeSH
• zvířata MeSH
• Check Tag
• zvířata MeSH
• Publikační typ
• časopisecké články MeSH
• hodnotící studie MeSH
• práce podpořená grantem MeSH
• Research Support, U.S. Gov't, Non-P.H.S. MeSH
• Názvy látek
• akrylamidy MeSH
• poly(carboxybetaine acrylamide) MeSH Prohlížeč
• polyhydroxyethylmethakrylát MeSH
• polymery MeSH
• sulfhydrylové sloučeniny MeSH

Composite insulation materials are an inseparable part of numerous electrical devices because of synergy effect between their individual parts. One of the main aims of the presented study is an introduction of the dielectric properties of nanoscale magnesium oxide powder via Broadband Dielectric Spectroscopy (BDS). These unique results present the behavior of relative permittivity and loss factor in frequency and temperature range. Following the current trends in the application of inorganic nanofillers, this article is complemented by the study of dielectric properties (dielectric strength, volume resistivity, dissipation factor and relative permittivity) of epoxy-based composites depending on the filler amount (0, 0.5, 0.75, 1 and 1.25 weight percent). These parameters are the most important for the design and development of the insulation systems. The X-ray diffraction patterns are presented for pure resin and resin with optimal filler amount (1 wt %), which was estimated according to measurement results. Magnesium oxide nanoparticles were also treated by addition of silane coupling agent ( γ -Glycidoxypropyltrimethoxysilane), in the case of optimal filler loading (1 wt %) as well. Besides previously mentioned parameters, the effects of surface functionalization have been observed by two unique measurement and evaluation techniques which have never been used for this evaluation, i.e., reduced resorption curves (RRCs) and voltage response method (VR). These methods (developed in our departments), extend the possibilities of measurement of composite dielectric responses related to DC voltage application, allow the facile comparability of different materials and could be used for dispersion level evaluation. This fact has been confirmed by X-ray diffraction analyses.

• Klíčová slova
• broadband dielectric spectroscopy, dielectric strength, loss factor, magnesium oxide, nanocomposite, relative permittivity, surface functionalization, voltage response,
• Publikační typ
• časopisecké články MeSH

We report here on the development of tailored plasmonic AgNPs/C:H:N:O plasma polymer nanocomposites for the detection of the pathogenic bacterium Borrelia afzelii , with high selectivity and sensitivity. Silver (Ag) nanoparticles, generated by a gas aggregation source, are incorporated onto a C:H:N:O plasma polymer matrix, which is deposited by magnetron sputtering of a nylon 6.6. These anchored Ag nanoparticles propagate localized surface plasmon resonance (LSPR), optically responding to changes caused by immobilized pathogens near the nanoparticles. The tailored functionalization of AgNPs/C:H:N:O nanocomposite surface allows both high selectivity for the pathogen and high sensitivity with an LSPR red-shift Δλ > (4.20 ± 0.71) nm for 50 Borrelia per area 0.785 cm2. The results confirmed the ability of LSPR modulation for the rapid and early detection of (not only) tested pathogens.

• Klíčová slova
• C:H:N:O thin film, Lyme disease, ag nanoparticles, borrelia, localized surface plasmon resonance, magnetron sputtering, nanocomposite, nylon, plasma polymer, surface functionalization,
• MeSH
• kovové nanočástice * chemie   MeSH
• limita detekce * MeSH
• nanokompozity * chemie   MeSH
• povrchová plasmonová rezonance * metody   MeSH
• stříbro * chemie   MeSH
• Publikační typ
• časopisecké články MeSH
• Názvy látek
• stříbro * MeSH

Beyond graphene, 2D pnictogen polymers are rapidly growing among the family of 2D materials. Due to their unique properties, this group has received considerable interest in recent years. Those properties include tunable electronic band gaps, high charge carrier mobility, and in-plane anisotropic properties. This Review covers the noncovalent functionalization of pnictogen surfaces considering experimental and theoretical studies. Noncovalent functionalization is of great importance for effective modulation of the electronic structure of these materials as well as improvement of their stability toward surface oxidation. This Review highlights their noncovalent modification by organic molecules, in which enhanced surface stability of phosphorene and generated functionalized materials for applications in biomedical, supercapacitors, energy storage, and biosensors. Moreover, the noncovalent interactions with small molecules show its significance for sensing applications. Lastly, the interactions of pnictogen sheets with other 2D materials and their applications for van der Waals heterostructure formation are discussed. Current state-of-the-art as well as future perspectives in this field are covered.

• Klíčová slova
• antimonene, arsenene, noncovalent functionalization, phosphorene, pnictogens,
• Publikační typ
• časopisecké články MeSH
• přehledy MeSH

Two-dimensional transition metal carbides and nitrides (MXenes) are a promising group of materials with a broad palette of applications. Surface terminations are a result of MXene preparation, and post-processing can also lead to partial coverage. Despite applicability and fundamental properties being driven by termination patterns, it is not fully clear how they behave on MXene surfaces with various degrees of surface coverage. Here, as the first step, we used density functional theory to predict possible patterns in prototypic Ti2C MXene, demonstrating the different behavior of the two most frequent terminal atoms, oxygen, and fluorine. Oxygen (with formal charge -2e) prefers a zigzag line both-side adsorption pattern on bare Ti2C, attracting the next adsorbent at a minimal distance. Oxygen defects in fully O-terminated MXene tend to form similar zigzag line vacancy patterns. On the other hand, fluorine (with a formal charge of -1e) prefers one-side flake (island) adsorption on bare Ti2C and a similar desorption style from fully fluorinated Ti2C. The magnetic behavior of the MXene is subsequently driven by the patterns, either compensating locally and holding the global magnetic state of the MXene until some limit (oxygen case) or gradually increasing the total magnetism through summation of local effects (fluorine case). The systematic combinatoric study of Ti2CTx with various coverages (0 ≤ x ≤ 2) of distinct terminal atoms T = O or F brings encouraging possibilities of tunable behavior of MXenes and provides useful guidance for its modeling towards electronic nanodevices.

• Publikační typ
• časopisecké články MeSH

Due to their good mechanical stability compared to gelatin, collagen or polyethylene glycol nanofibers and slow degradation rate, biodegradable poly-ε-caprolactone (PCL) nanofibers are promising material as scaffolds for bone and soft-tissue engineering. Here, PCL nanofibers were prepared by the electrospinning method and then subjected to surface functionalization aimed at improving their biocompatibility and bioactivity. For surface modification, two approaches were used: (i) COOH-containing polymer was deposited on the PCL surface using atmospheric pressure plasma copolymerization of CO2 and C2H4, and (ii) PCL nanofibers were coated with multifunctional bioactive nanostructured TiCaPCON film by magnetron sputtering of TiC-CaO-Ti3POx target. To evaluate bone regeneration ability in vitro, the surface-modified PCL nanofibers were immersed in simulated body fluid (SBF, 1×) for 21 days. The results obtained indicate different osteoblastic and epithelial cell response depending on the modification method. The TiCaPCON-coated PCL nanofibers exhibited enhanced adhesion and proliferation of MC3T3-E1 cells, promoted the formation of Ca-based mineralized layer in SBF and, therefore, can be considered as promising material for bone tissue regeneration. The PCL-COOH nanofibers demonstrated improved adhesion and proliferation of IAR-2 cells, which shows their high potential for skin reparation and wound dressing.

• Klíčová slova
• XPS, mineralization, plasma modification, polycaprolactone nanofibers, tissue engineering,
• Publikační typ
• časopisecké články MeSH

Specifically designed and functionalized nanoparticles hold great promise for biomedical applications. Yet, the applicability of nanoparticles is critically predetermined by their surface functionalization and biodegradability. Here we demonstrate that amino-functionalized polystyrene nanoparticles (PS-NH2), but not amino- or hydroxyl-functionalized silica particles, trigger cell death in hepatocellular carcinoma Huh7 cells. Importantly, biodegradability of nanoparticles plays a crucial role in regulation of essential cellular processes. Thus, biodegradable silica nanoparticles having the same shape, size and surface functionalization showed opposite cellular effects in comparison with similar polystyrene nanoparticles. At the molecular level, PS-NH2 obstruct and amino-functionalized silica nanoparticles (Si-NH2) activate the mTOR signalling in Huh7 and HepG2 cells. PS-NH2 induced time-dependent lysosomal destabilization associated with damage of the mitochondrial membrane. Solely in PS-NH2-treated cells, permeabilization of lysosomes preceded cell death. Contrary, Si-NH2 nanoparticles enhanced proliferation of HuH7 and HepG2 cells. Our findings demonstrate complex cellular responses to functionalized nanoparticles and suggest that nanoparticles can be used to control activation of mTOR signaling with subsequent influence on proliferation and viability of HuH7 cells. The data provide fundamental knowledge which could help in developing safe and efficient nano-therapeutics.

• MeSH
• adsorpce MeSH
• aminy chemie   MeSH
• hepatocelulární karcinom metabolismus   patologie   MeSH
• konformace proteinů MeSH
• lyzozomy metabolismus   MeSH
• nádorové buněčné linie MeSH
• nádory jater metabolismus   patologie   MeSH
• nanočástice chemie   MeSH
• oxid křemičitý chemie   MeSH
• permeabilita MeSH
• polystyreny chemie   MeSH
• povrchové vlastnosti MeSH
• proliferace buněk MeSH
• ribonukleasy metabolismus   MeSH
• sérový albumin hovězí metabolismus   MeSH
• signální transdukce * MeSH
• skot MeSH
• TOR serin-threoninkinasy metabolismus   MeSH
• zvířata MeSH
• Check Tag
• skot MeSH
• zvířata MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• Názvy látek
• aminy MeSH
• oxid křemičitý MeSH
• polystyreny MeSH
• ribonukleasy MeSH
• sérový albumin hovězí MeSH
• TOR serin-threoninkinasy MeSH

Spatially resolved functionalization of 2D materials is highly demanded but very challenging to achieve. The chemical patterning is typically tackled by preventing contact between the reagent and material, which brings various accompanying challenges. Photochemical transformation on the other hand inherently provides remote high spatiotemporal resolution using the cleanest reagent-a photon. Herein, we combine two competing reactions on a graphene substrate to create functionalization patterns on a micrometer scale via the Mitsunobu reaction. The mild reaction conditions allow introduction of covalently dynamic linkages, which can serve as reversible labels for surface- or graphene-enhanced Raman spectroscopy characterization of the patterns prepared. The proposed methodology thus provides a pathway for local introduction of arbitrary functional groups on graphene.

• Klíčová slova
• Mitsunobu reaction, Raman spectroscopy, graphene, patterned functionalization, photochemistry,
• Publikační typ
• časopisecké články MeSH

Interactions at the solid-body fluid interfaces play a vital role in bone tissue formation at the implant surface. In this study, fully atomistic molecular dynamics (MD) simulations were performed to investigate interactions between the physiological components of body fluids (Ca2+, HPO42-, H2PO4-, Na+, Cl-, and H2O) and functionalized parylene C surface. In comparison to the native parylene C (-Cl surface groups), the introduction of -OH, -CHO, and -COOH surface groups significantly enhances the interactions between body fluid ions and the polymeric surface. The experimentally observed formation of calcium phosphate nanocrystals is discussed in terms of MD simulations of the calcium phosphate clustering. Surface functional groups promote the clustering of calcium and phosphate ions in the following order: -OH > -CHO > -Cl (parent parylene C) ≈ -COO-. This promoting role of surface functional groups is explained as stimulating the number of Ca2+ and HPO42- surface contacts as well as ion chemisorption. The molecular mechanism of calcium phosphate cluster formation at the functionalized parylene C surface is proposed.

• Klíčová slova
• calcium phosphate, functional groups, molecular dynamics, nucleation mechanism, parylene C, polymer surface,
• Publikační typ
• časopisecké články MeSH