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Ultrasensitive Impedimetric Lectin Biosensors with Efficient Antifouling Properties Applied in Glycoprofiling of Human Serum Samples

Ultrasensitive impedimetric lectin biosensors recognizing different glycan entities on serum glycoproteins were constructed. Lectins were immobilized on a novel mixed self-assembled monolayer containing 11-mercaptoundecanoic acid for covalent immobilization of lectins and betaine terminated thiol to resist nonspecific interactions. Construction of biosensors based on Concanavalin A (Con A), Sambucus nigra agglutinin type I (SNA), and Ricinus communis agglutinin (RCA) on polycrystalline gold electrodes was optimized and characterized with a battery of tools including electrochemical impedance spectroscopy, various electrochemical techniques, quartz crystal microbalance (QCM), Fourier transform infrared (FT-IR) spectroscopy, atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS) and compared with a protein/lectin microarray. The lectin biosensors were able to detect glycoproteins from 1 fM (Con A), 10 fM (Ricinus communis agglutinin (RCA), or 100 fM (SNA) with a linear range spanning 6 (SNA), 7 (RCA), or 8 (Con A) orders of magnitude. Furthermore, a detection limit for the Con A biosensor down to 1 aM was achieved in a sandwich configuration. A nonspecific binding of proteins for the Con A biosensor was only 6.1% (probed with an oxidized invertase) of the signal toward its analyte invertase and a negligible nonspecific interaction of the Con A biosensor was observed in diluted human sera (1000×), as well. The performance of the lectin biosensors was finally tested by glycoprofiling of human serum samples from healthy individuals and those having rheumatoid arthritis, which resulted in a distinct glycan pattern between these two groups.

Polypyrrole coating of inorganic and organic materials by chemical oxidative polymerisation

Polypyrrole is one of the most frequently studied conducting polymers, having high electrical conductivity and stability, suitable for multi-functionalised applications. Coatings of chemically synthesised polypyrrole applied onto various organic and inorganic materials, such as polymer particles and films, nanoparticles of metal oxides, clay minerals, and carbon nanotubes are reviewed in this paper. Its primary subject is the formation of new materials and their application in which chemical oxidative polymerisation of pyrrole was used. These combined materials are used in antistatic applications, such as anti-corrosion coating, radiation-shielding, but also as new categories of sensors, batteries, and components for organic electronics are created by coating substrates with conducting polymer layers or imprinting technologies.

Nanocarbon based ionic actuators—a review

Nanocarbons represented especially by carbon nanotubes (CNTs) and graphene have been of great interest during the last two decades, both from a fundamental point of view and for future applications. The most eye-catching features of carbon nanostructures (CNSs) are their electronic, mechanical, optical and chemical characteristics, which open a way for versatile applications. Among those future prospects, actuators are one of the promising technologies. Since 1999 when the first macroscopic actuator containing CNTs was reported, the interest of utilizing these materials as well as other CNSs in active systems has been triggered all over the world. This paper gives a thorough review as well as in-depth descriptions of the many aspects of nanocarbon-based actuators. The review covers aspects of worldwide research and development of nanocarbon ionic actuators up to 2012. Materials which are covered by this review include CNTs and their composites, carbon nanofibres (CNFs), graphene and its derivatives, microporous carbon materials (for example carbide derived carbons (CDCs) and carbon aerogels) as well as the possible combinations of these materials. The considered aspects cover the following fields: synthesis and characterization of the investigated materials, the actuation mechanism as well as modelling and simulation. Applications comprising system integration and device development are also reviewed within this paper. (Some figures may appear in colour only in the online journal)

Effect of surfactants and manufacturing methods on the electrical and thermal conductivity of carbon nanotube/silicone composites.

The effect of ionic surfactants and manufacturing methods on the separation and distribution of multi-wall carbon nanotubes (CNTs) in a silicone matrix are investigated. The CNTs are dispersed in an aqueous solution of the anionic surfactant dodecylbenzene sulfonic acid (DBSA), the cationic surfactant cetyltrimethylammonium bromide (CTAB), and in a DBSA/CTAB surfactant mixture. Four types of CNT-based composites of various concentrations from 0 to 6 vol.% are prepared by simple mechanical mixing and sonication. The morphology, electrical and thermal conductivity of the CNT-based composites are analyzed. The incorporation of both neat and modified CNTs leads to an increase in electrical and thermal conductivity. The dependence of DC conductivity versus CNT concentration shows percolation behaviour with a percolation threshold of about 2 vol.% in composites with neat CNT. The modification of CNTs by DBSA increases the percolation threshold to 4 vol.% due to the isolation/separation of individual CNTs. This, in turn, results in a significant decrease in the complex permittivity of CNT–DBSA-based composites. In contrast to the percolation behaviour of DC conductivity, the concentration dependence of thermal conductivity exhibits a linear dependence, the thermal conductivity of composites with modified CNTs being lower than that of composites with neat CNTs. All these results provide evidence that the modification of CNTs by DBSA followed by sonication allows one to produce composites with high homogeneity.

Photo-actuating materials based on elastomers and modified carbon nanotubes

Abstract. The photo-actuating behavior of new polymeric nanocomposite materials based on a commercial elastomer, an ethylene-vinylacetate copolymer (EVA), filled with multiwalled carbon nanotubes (MWCNT) was investigated. A good dispersion of the MWCNT within the elastomeric matrix was ensured by using a novel, specific compatibilizer consisting of pyrenyl and cholesteryl groups. A uniaxial orientation of the MWCNT within the matrix was induced with shear forces by employing a special custom-made punch/die system. Good dispergation and alignment of the MWCNT within the matrix were demonstrated by scanning electron microscopy. Transmission electron microscopy showed a good dispersion of the MWCNT within the composite. Photo-actuation was qualitatively characterized by atomic force microscopy and quantitatively characterized by nanoindentation. The samples prepared in the form of Braille element showed expansion upon illumination by light diodes. The maximal height deformation changes about 15% was detected when a blue diode was used.

Impact of plasma treatment on electrical properties of TiO2/RuO2 based DRAM capacitor

In this work, we systematically studied the influence of the plasma treatment (PT) on the structural and electrical properties of Pt/rutile-TiO2/RuO2 metal–insulator–metal capacitors. The leakage current of the 12 nm thick TiO2 dielectrics prepared by atomic layer deposition was reduced below 10−7 A cm−2 while the capacitance equivalent thickness was kept below 0.5 nm using oxygen PT of the bottom RuO2 electrode. Reflection high energy electron diffraction, transmission electron microscopy, atomic force microscopy and x-ray photoelectron spectroscopy analyses allowed the conclusion that O2 plasma smoothened the RuO2 surface and increased its oxygen content through plasma induced surface reconstruction. The nucleation of TiO2 on the plasma-treated surface was faster while the thickness of the capacitor dead layer at the TiO2/RuO2 interface was reduced.

A tertiary amine in two competitive processes: reduction of graphene oxide vs. catalysis of atom transfer radical polymerization

Electrically conductive graphene oxide–polystyrene hybrids (GO–PS) were prepared by reduction of graphene oxide (GO) in one step during covalent modification of graphene oxide surface using surface-initiated atom transfer radical polymerization (SI-ATRP) of styrene. The reduction of the GO surface was proven by Raman spectroscopy, electrical conductivity measurements, thermogravimetric analysis and X-ray photoelectron spectroscopy. Electrical conductivity of the synthesized GO–PS particles increased in eight orders of magnitude, depending on the polymerization period. Detailed studies were performed to determine that the tertiary amine, such as N,N,N′,N′,N′′-pentamethyldiethylenetriamine (PMDETA), used in SI-ATRP as a ligand complexing copper catalyst, was responsible for the GO surface reduction. It was shown that due to participation of PMDETA in reduction of graphene oxide, the ATRP in the presence of GO can proceed only above a certain PMDETA–GO ratio.

Elastomeric photo-actuators and their investigation by confocal laser scanning microscopy

The photo-actuation behavior of nanocomposites based on ethylene–vinylacetate copolymer (EVA) and styrene–isoprene–styrene (SIS) block copolymer filled with well-dispersed and modified multiwalled carbon nanotubes (MWCNTs) is discussed in this paper. The nanocomposites were prepared by casting from solution. To improve the dispersion of the MWCNTs in EVA, the MWCNT surface was modified with a non-covalent surfactant, cholesteryl 1-pyrenecarboxylate (PyChol). To prepare SIS nanocomposites, the MWCNT surface was covalently modified with polystyrene chains. The good dispersion of the filler was confirmed by transmission electron microscopy (TEM). Special, custom-made punch/die molds were used to create a Braille element (BE)-like shape, which under shear forces induces a uniaxial orientation of the MWCNTs within the matrix. The uniaxial orientation of MWCNTs is an essential precondition to ensure the photo-actuating behavior of MWCNTs in polymeric matrices. The orientation of the MWCNTs within the matrices was examined by scanning electron microscopy (SEM). Nanocomposite BEs were illuminated from the bottom by a red light-emitting diode (LED), and the photo-actuation was investigated by confocal laser scanning microscopy (CLSM). When the BEs were exposed to light, a temporary increase in the height of the element was detected. This process was observed to be reversible: after switching off the light, the BEs returned to their original shape and height.

Spectral characterisation of new organic fluorescent dyes with an alkoxysilane moiety and their utilisation for the labelling of layered silicates

New fluorescence dyes with an alkoxysilane moiety were synthesised by the condensation of 3-(triethoxysilyl)-1-propanamine (3-aminopropyltriethoxysilane) with 4,10-benzothioxanthene-3,1′-dicarboxylic acid anhydride (BTXA) and N,N-dimethylaminonaphthalene-1,8-dicarboxylic acid anhydride (DMANA), which was accompanied by the formation of an imidic bridge. The compounds N-(3-(triethoxysilyl)propyl)-thioxantheno[2,1,9-dej]isoquinoline-1,3-dione (BTX-S) and 4-(N′, N′-dimethyl)-N-(triethoxysilyl)propyl-1,8-naphthalene dicarboxylic acid imide (DMAN-S) were characterised by steady-state and time-resolved fluorescence spectroscopy in chloroform and ethanol. Both conjugates (BTX-S and DMAN-S) exhibited absorption and emission bands in the same region as the un-substituted BTXA and DMANA. An important Stokes shift was observed for DMAN-S in ethanol. A high fluorescence quantum yield was observed for BTX-S in both solvents and for DMAN-S in chloroform. In addition, the newly developed fluorescent silane dyes were covalently attached to the microscopic particles of layered silicates and on the surface of SiO2 wafers as a proof of concept for fluorescence particle (surface) visualisation. The surface wafer modification was precisely characterised by X-ray photoelectron spectroscopy (XPS). Successful covalent linkage onto the particles of layered silicates was proved by confocal laser scanning microscopy technique.

Release and cellular origin of extracellular vesicles during circulation of whole blood over adsorbent polymers for lipid apheresis

Whole blood lipid apheresis is clinically applied in patients with familial hypercholesterolemia to reduce low density lipoprotein and other apolipoprotein B 100 containing lipoproteins. Here, the hemocompatibility of two polyacrylate-coated polyacrylamide-based polymers for lipid apheresis by evaluating the adhesion of blood cells to the adsorbent polymers, their respective activation, as well as the release of microvesicles during circulation of whole blood over the polymers was studied. Characterization of the adsorbents by scanning electron microscopy, atomic force microscopy, and X-ray photoelectron spectroscopy revealed differences with respect to their surface morphology and their surface chemical composition. Despite these differences, equivalent amounts of leukocytes and platelets adhered to both polymers during circulation of whole blood over the adsorbent columns. The release of phosphatidylserine-exposing microvesicles, in contrast, increased significantly with increasing surface roughness and with the amount of polyacrylate groups at the adsorbent surface. The majority of microvesicles generated during blood-material contact were platelet-derived, and their release was associated with enhanced thrombin generation. Microvesicles were present in free and in cell-bound form, and 75% of all monocytes, but only 0.2% and 2.3% of red blood cells and platelets, respectively, were associated with microvesicles, pointing to a role of monocytes in the clearance of released microvesicles. Taken together, microvesicles are sensitive indicators for biomaterial-induced activation of blood cells in apheresis.