Markéta Ilčíková

Improved thermooxidation and sedimentation stability of covalently-coated carbonyl iron particles with cholesteryl groups and their influence on magnetorheology

Sedimentation of particles in magnetorheological suspensions represents a crucial problem that concerns their efficient long-term application in practice. Prepared carbonyl iron (CI) microparticles coated with a low density substance, cholesteryl chloroformate, via a two-step reaction and immersed in silicone oil, exhibit three positive aspects: (1) the CI particle modification increased the compatibility between the particles and the silicone oil resulting in improved long-term stability (reduction in sedimentation); (2) the coating provided the particles with enhanced thermal stability in the oxygen atmosphere; and (3) rheological measurements proved a promising magnetorheological performance at different particle weight fractions.

A facile controllable coating of carbonyl iron particles with poly(glycidyl methacrylate): a tool for adjusting MR response and stability properties

This study is focused on the controllable coating of the carbonyl iron (CI) particles widely applied in magnetorheology. These particles were grafted with poly(glycidyl methacrylate) (PGMA) with narrow polydispersity via surface-initiated atom transfer radical polymerization. Two types of core–shell particles differing in molecular weights of grafted polymer chains were synthesized. The effect of shell thickness on the thermo-oxidation stability of particles as well as the sedimentation stability of their silicone oil suspensions was evaluated. The successful coating process was confirmed by Fourier transform infrared spectroscopy and energy-dispersive spectrometry. The differences in the magnetic properties of bare and coated CI particles were clarified through vibrating sample magnetometry. Due to the controllable length of the PGMA grafts, the magnetic properties remain almost the same as those for bare CI. The magnetorheological (MR) behavior of silicone oil suspensions containing 60 wt% of bare CI particles as well as PGMA-coated analogues was investigated in the absence and in the presence of various magnetic field strengths, demonstrating the negligible impact of surface modification on final MR performance. Thus, the grafting of the particles with PGMA negligibly affected magnetic properties but considerably enhanced thermo-oxidation and sedimentation stabilities. Finally, a novel tensiometric method for sedimentation stability measurements of MR suspensions was successfully implemented.

Carboxybetaine Modified Interface for Electrochemical Glycoprofiling of Antibodies Isolated from Human Serum

Impedimetric lectin biosensors capable of recognizing two different carbohydrates (galactose and sialic acid) in glycans attached to antibodies isolated from human serum were prepared. The first step entailed the modification of a gold surface by a self-assembled monolayer (SAM) deposited from a solution containing a carboxybetaine-terminated thiol applied to the subsequent covalent immobilization of lectins and to resist nonspecific protein adsorption. In the next step, Sambucus nigra agglutinin (SNA) or Ricinus communis agglutinin (RCA) was covalently attached to the SAM, and the whole process of building a bioreceptive layer was optimized and characterized using a diverse range of techniques including electrochemical impedance spectroscopy, cyclic voltammetry, quartz crystal microbalance, contact angle measurements, zeta-potential assays, X-ray photoelectron spectroscopy, and atomic force microscopy. In addition, the application of the SNA-based lectin biosensor in the glycoprofiling of antibodies isolated from the human sera of healthy individuals and of patients suffering from rheumatoid arthritis (RA) was successfully validated using an SNA-based lectin microarray. The results showed that the SNA lectin, in particular, is capable of discriminating between the antibodies isolated from healthy individuals and those from RA patients based on changes in the amount of sialic acid present in the antibodies. In addition, the results obtained by the application of RCA and SNA biosensors indicate that the abundance of galactose and sialic acid in antibodies isolated from healthy individuals is age-related.

Cholesteryl-coated carbonyl iron particles with improved anti-corrosion stability and their viscoelastic behaviour under magnetic field

In principle, bare particles used in magnetorheological suspensions exhibit apparent corrosion instability. To suppress substantially this adverse phenomenon, the carbonyl iron particles modified with cholesteryl group (CI-chol) were suspended in silicone oil. There was found a deterioration of magnetorheological efficiency in comparison when only bare carbonyl iron (CI) particles are used; nevertheless, from the viewpoint of applicability, this change is fully acceptable. However, an anti-corrosion stability was significantly improved. Furthermore, dynamic oscillatory measurements and other characterizations were carried out and analyzed when both CI and CI-chol particles are applied.

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.

Simple, Reversible, and Fast Modulation in Superwettability, Gradient, and Adsorption by Counterion Exchange on Self-Assembled Monolayer

A simple fabrication method for preparation of surfaces able to switch from superhydrophobic to superhydrophilic state in a reversible and fast way is described. A self-assembled monolayer (SAM) consisting of quaternary ammonium group with aliphatic tail bearing terminal thiol functionality was created on gold nano/microstructured and gold planar surfaces, respectively. A rough nano/microstructured surface was prepared by galvanic reaction on a silicon wafer. The reversible counterion exchange on the rough surface resulted in a switchable contact angle between <5° and 151°. The prewetted rough surface with Cl(-) as a counterion possesses a superoleophobic underwater character. The kinetics of counterion exchanges suggests a long hydration process and strong electron ion pairing between quaternary ammonium group and perfluorooctanoate counterion. Moreover, a wettability gradient from superhydrophobic to superhydrophilic can be formed on the modified rough gold surface in a robust and simple way by passive incubation of the substrate in a counterion solution and controlled by ionic strength. Furthermore, adsorption of gold nanoparticles to modified plain gold surface can be controlled to a high extent by counterions present on the SAM layer.

Mixed Zwitterion-Based Self-Assembled Monolayer Interface for Impedimetric Glycomic Analyses of Human IgG Samples in an Array Format

An impedimetric lectin biosensor for the detection of changes in the glycan structure of antibodies isolated from human serum is here correlated with the progression of rheumatoid arthritis (RA). The biosensor was built up from a mixed self-assembled monolayer (SAM) on gold consisting of two different thiolated zwitterionic derivatives, carboxybetaine and sulfobetaine, to resist nonspecific interactions. The carboxyl-terminated one was applied also for the covalent immobilization of lectin Ricinus communis agglutinin I (RCA-I). The process of building a bioreceptive layer was optimized and characterized using a diverse range of techniques. Impedimetric assays were integrated on a chip consisting of eight gold working electrodes, which is an important step toward the achievement of a moderate level of multiplexing for the analysis of human serum samples. At the end, the results obtained by the impedimetric analysis of immunoglobulins G (IgGs) isolated from serum samples were compared with those of two other standard bioanalytical methods employing lectins, that is, lectin microarrays (MAs) and enzyme-linked lectin binding assays (ELLBAs). The impedimetric results agreed very well with the DAS28 index (RA disease activity score 28), suggesting that impedimetric assays could be used for the development of a new diagnostic procedure sensitive to glycosylation changes in human IgGs and thus RA progression.

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.