Effect of Modification of a Laccase-Based Electrochemical Biosensor with Carbon Nanotubes on Signal Separation of Dihydroxybenzene Isomers.

This work describes a new electrochemical biosensor for the simultaneous determination of catechol and hydroquinone. A laccase biorecognition layer was deposited using an innovative soft plasma polymerization technique onto a multiwalled carbon nanotube (MWCNT)-modified glassy carbon electrode (GCE) to sufficiently separate catechol (CT) and hydroquinone (HQ) oxidation peaks. The electrochemical analysis carried out for MWCNTs with various morphologies was supported by density functional theory (DFT) calculations showing differences in the electronic structures of both dihydroxybenzene isomers and the MWCNTs forming the biosensor interlayer. The best biosensor peak separation and biosensor analytical parameters were observed for the device containing 75 µg of MWCNTs with a higher internal diameter. For this laccase-based biosensor, a linearity range from 0.1 to 57 µM for catechol and 0.5 to 57 µM for hydroquinone as well as a sensitivity of 0.56 and 0.54 µA/µM for catechol and hydroquinone was observed, respectively. The limit of detection (LOD) values were 0.028 and 0.15 µM for CT and HQ, respectively. This biosensor was also characterized by good selectivity, stability, and reproducibility. It was successfully applied for the quantification of contaminants in the analysis of natural water samples.

Cold Plasma as an Innovative Construction Method of Voltammetric Biosensor Based on Laccase.

Development of new, faster methods of biosensor construction is a huge challenge for current science and industry. In this work, biosensor construction was carried out using a new soft plasma polymerization (SPP) method in which a bio-recognition layer of laccase enzyme was polymerized and bonded to a glassy carbon electrode (GCE) substrate under atmospheric pressure with a corona discharge jet. Laccase belongs to the oxidoreductase enzyme group with four copper atoms in its active center. Application of the corona SPP plasma method allows reduction of the time needed for biosensor construction from several hours to minutes. The presented work includes optimization of the laccase bio-recognition layer deposition time, structural studies of the deposited laccase layer, as well as study of the fabricated biosensor applicability for the determination of Rutin in real pharmaceutical samples. This method produces a biosensor with two linear ranges from 0.3 µmol/dm³ to 0.5 µmol/dm³ and from 0.8 µmol/dm³ to 16 µmol/dm³ of Rutin concentration. Results shown in this work indicate that application of the one-step, corona SPP method enables biosensor construction with comparable analytical parameters to biosensors fabricated by conventional, multi-step, wet methods.

Computational Design of Anticorrosion Properties of Novel, Low-Molecular Weight Schiff Bases.

Due to the many economic consequences and technological problems caused by the corrosion process, its inhibition is one of the most important aspects of ongoing research. Computer methods, i.e., density functional theory (DFT) methods, are of great importance to the large-scale research being conducted which allows the evaluation of the corrosion inhibition performance without conducting time-consuming, long-term and expensive experimental measurements. In this study, new corrosion inhibitors were designed in three corrosion environments on the basis of their HOMO and LUMO orbital energies-the energy difference between them and their dipole moment. In addition, their interactions with the Fe and Cu surface were modelled on the basis of the number of electrons transferred during the formation of the protective adsorption layer (ΔN) and the initial energy between inhibitor molecule and protected metal surface (Δψ). The obtained results indicate that, among the aliphatic investigated Schiff bases, the N-methylpropan-1-imine (N-MP(1)I) molecule would theoretically have the highest corrosion inhibition efficiency mainly due to its high EHOMO value, relatively low ELUMO value, high chemical reactivity and high polarity.

Chloride Ion-Selective Electrode with Solid-Contact Based on Polyaniline Nanofibers and Multiwalled Carbon Nanotubes Nanocomposite.

Use of the nanocomposite of chloride-doped polyaniline nanofibers and multiwalled carbon nanotubes (PANINFs-Cl:MWCNTs) for construction of ion-selective electrodes with solid-contact sensitive to chloride ions has been described. Many types of electrodes were tested, differing in the quantitative and qualitative composition of the layer placed between the electrode material and the ion-selective membrane. Initial tests were carried out, including tests of electrical properties of intermediate solid-contact layers. The obtained ion-selective electrodes had a theoretical slope of the electrode characteristic curve (-61.3 mV dec-1), a wide range of linearity (5 × 10-6-1 × 10-1 mol L-1) and good potential stability resistant to changing measurement conditions (redox potential, light, oxygen). The chloride contents in the tap, mineral and river water samples were successfully determined using the electrodes.

Use of New Green Bitumen Modifier for Asphalt Mixtures Recycling.

Nowadays, an increasing amount of reclaimed asphalt pavement (RAP) is being produced from the reconstruction and/or modernisation of asphalt pavements. It is necessary to recycle the obtained RAP according to principles of sustainable development. Therefore, this work includes the design of asphalt mixtures containing RAP with bio-derived modifier and evaluates their performance properties. Crosslinked sodium alginate was applied for bitumen modification. The studies were carried out for four different modifier contents, i.e., 1.0%, 2.5%, 4.0% and 5.5%, with and without crosslinking agent. On the basis of the binder test results, the optimal amount of the additive was found to be 2.5%. The nanostructure analysis for the base and modified binders indicated a dual crosslinked biopolymer effect. As a result of the bee structure size decrease, the binder softening effect was observed. The asphalt mix properties showed that application of biopolymer-modified binder is fully justified due to the functional parameters of the mixture, especially the increased resistance to water and frost by about 9%.

Metal oxide nanoparticles as solid contact in ion-selective electrodes sensitive to potassium ions.

In recent years, various types of nanomaterials and nanoparticles have been very popular, also in analytical chemistry for sensors preparation. Ion-selective electrodes with solid contact were constructed, in which a layer of nanoparticles of selected metal oxides (zinc, copper and iron oxides) obtained by pulsed laser liquid ablation (PLAL) was placed between the glassy carbon solid electrode material and the ion-selective membrane. The basic analytical parameters of the obtained sensors were determined using potentiometric methods. Additionally, the electrochemical impedance spectroscopy method (EIS) was also used to investigate the electrical properties of the sensors. The obtained results were compared for all types of electrodes, both modified and unmodified, in order to investigate the effect of the type of nanoparticles and the thickness of their layer used as solid contact. It was found that the addition of metal oxide nanoparticles improved the analytical parameters of the sensors, mainly the potential stability and electrical parameters. The best results were obtained for an electrode with an intermediate layer of zinc oxide nanoparticles. In this case, a slope of -56.07 mV/dec, a linearity range of 1 × 10-5 - 1 × 10-1 mol L-1 and a limit of detection of 3.66 × 10-6 mol L-1 were obtained. Particularly noteworthy is the significant improvement in the stability of the potential of this electrode and the long life of more than 5 months.

Quantum Chemical Analysis of the Corrosion Inhibition Potential by Aliphatic Amines.

Destructive corrosion processes lead to the loss of primary mechanical properties of metal construction materials, which generates additional costs during their maintenance connected with repairs and protection. The effectiveness of corrosion inhibitors can be determined by using many methods, in particular quantum chemical modeling. The subject of the theoretical analyses presented in this work involves the anticorrosion properties of amines with various chemical structures. Evaluation of the corrosion inhibition properties of selected amines was performed on the basis of the HOMO-LUMO energy gap, dipole moment (µ), electronegativity (χ) determined as a result of the energy of the highest occupied molecular orbital (HOMO) and the energy of the lowest unoccupied molecular orbital (LUMO). Moreover, the HSAB (Hard and Soft Acids and Bases) theory was used to explain the reactivity of the analyzed amines, while the Mulliken population analysis was used to determine their electrostatic interactions with the surface of protected metal. The obtained results indicate that the protonation reaction of aliphatic amines leads to a change in the nature of the formation of a coordination bond with the surface of the protected metal. In turn, the quantum chemical calculations showed that the protonation reaction of aliphatic amines leads to a decrease in their corrosion inhibition efficiency. Most of the analyzed parameters indicated that tertiary amines are characterized by the highest corrosion inhibition efficiency.

Methyl transfer reactions catalyzed by cobalamin-dependent enzymes: Insight from molecular docking.

Methyl transfer reactions, mediated by methyltransferases (MeTrs), such as methionine synthase (MetH) or monomethylamine: CoM (MtmBC), constitute one of the most important classes of vitamin B12-dependent reactions. The challenge in exploring the catalytic function of MeTrs is related to their modular structure. From the crystallographic point of view, the structure of each subunit has been determined, but there is a lack of understanding of how each subunit interacts with each other. So far, theoretical studies of methyl group transfer were carried out for the structural models of the active site of each subunit. However, those studies do not include the effect of the enzymatic environment, which is crucial for a comprehensive understanding of enzyme-mediated methyl transfer reactions. Herein, to explore how two subunits interact with each other and how the methyl transfer reaction is catalyzed by MeTrs, molecular docking of the functional units of MetH and MtmBC was carried out. Along with the interactions of the functional units, the reaction coordinates, including the Co-C bond distance for methylation of cob(I)alamin (CoICbl) and the C-S bond distance in demethylation reaction of cob(III)alamin (CoIIICbl), were considered. The functional groups should be arranged so that there is an appropriate distance to transfer a methyl group and present results indicate that steric interactions can limit the number of potential arrangements. This calls into question the possibility of SN2-type mechanism previously proposed for MeTrs. Further, it leads to the conclusion that the methyl transfer reaction involves some spatial changes of modules suggesting an alternate radical-based pathway for MeTrs-mediated methyl transfer reactions. The calculations also showed that changes in torsion angles induce a change in reaction coordinates, namely Co-C and C-S bond distances, for the methylation and demethylation reactions catalyzed both by MetH and MtmBC.

Application of cold plasma corona discharge in preparation of laccase-based biosensors for dopamine determination.

Laccase-based biosensors were successfully prepared using innovative, cheap, one-step Soft Plasma Polymerization technique by deposition of a bio-recognition layer on glassy carbon electrode and MWCNT (Multi-walled Carbon Nanotubes)-modified glassy carbon electrode. The Soft Plasma Polymerization technique is based on corona discharge of cold atmospheric plasma with close to room temperature. The presented work includes study of biosensor working conditions, optimization of the voltage value applied for corona discharge generation as well as applicability and interference studies for dopamine determination. The biosensor constructed under optimal conditions (corona discharge generated at a voltage of 3 kV and in 30 s time deposition, helium flow rate 10 L/min, laccase solution flow rate 200 µL/min) has two linear ranges from 0.1 µmol/dm3 to 10 µmol/dm3 and from 10 µmol/dm3 to 50 µmol/dm3 with dopamine detection sensitivities of 3.63 µA*dm3/µmol and 1.33 µA*dm3/µmol. Application of the MWCNT interlayer allows the dopamine detection sensitivity to be significantly increased to 22.35 µA* dm3/µmol for a linear range from 0.1 µmol/dm3 to 6 µmol/dm3. Additionally, the studied biosensors have stable and anti-interference ability. Both biosensors were successfully applied for dopamine determination in pharmaceutical preparation.

Particle size distribution retrieval from multiwavelength lidar signals for droplet aerosol.

A method of retrieval of the aerosol particle size distribution (APSD) from multiwavelength lidar signals is presented. Assumed distribution (usually a bimodal combination of lognormal functions) with a few free parameters is directly substituted into the lidar equations. The minimization technique allows one to find the parameters that provide the best fit of the assumed APSD by comparison of theoretically generated and experimental signals. Prior knowledge of the lidar ratio is not required. The approach was tested on a typical synthetic APSD consisting of spherical droplets. Comparison of lidar measurements with results from a condensation particle counter was also performed. For signals registered at 3-5 wavelengths from the UV to the near IR a satisfactory retrieval of synthetic APSD is possible for the particles within the 100-3000 nm range.

Laccase Enzyme Polymerization by Soft Plasma Jet for Durable Bioactive Coatings.

Conventional pin-to-point continuous wave Helium Corona plasma discharge was successfully used in Soft Plasma Polymerization (SPP) processes to immobilize into water and onto glass polymerized bioactive Cerrena unicolor laccase coatings. The coatings were tested for bioactivity and durability under water wash. The coatings showed up to 59% bioactivity relative to the native laccase in water deposition, undoubtedly due to damage to and fragmentation of monomer molecules by the active, energetic species in the plasma. However, plasma deposited laccase coatings on glass delivered 7 times the laccase activity of the same non-plasma deposition process in the coating after water wash. This latter result would seem to be due to the ability of the plasma to both crosslink monomer and more strongly bond it to the glass surface by a combination of surface cleaning and the creation of active, high energy sites in both glass and laccase molecules. FTIR analysis indicated that the core copper containing moieties at the centre of the molecule largely remain undamaged by this plasma type so that bonding and cross-linking reactions are likely to mainly involve species around the outer perimeter of the molecule. The chemical composition and structure of laccase biocoatings deposited by Corona SPP are described. The combination of the coating performance parameter values for retained activity and durability under water wash indicates that a relatively simple Corona plasma process for deposition of biocoatings, which directly polymerizes the monomer with no added matrix or encapsulant material, may offer enhanced solutions for biocatalyst, sensor or lab-on-a-chip applications.

Theoretical predictions of anti-corrosive properties of THAM and its derivatives.

We present quantum chemical theoretical estimations of the anti-corrosive properties of THAM (tris(hydroxymethyl)aminomethane) and three derivatives that differ in the number of benzene rings: THAM-1 (2-amino-3-hydroxy-2-(hydroxymethyl) propylobenzoate), THAM-2 (2-amino-2-(hydroxymetyl)prapan-1,3-diyldibenzoate) and THAM-3 (2-amino-propan-1,2,3-triyltribenzoate). Fourteen exchange-correlation functionals based on the density functional theory (DFT) were chosen for quantum chemical study of THAM derivatives. The objective was to examine the effect of benzene rings on potential anti-corrosive properties of THAM compounds. The results indicate that the addition of benzene rings in THAM derivatives is likely to significantly enhance electrostatic bonding of a THAM-based coating to a presented metal surface and, thus, its adhesion and long-term effect in corrosion inhibition. Whereas it is clear that all three derivatives appear to be superior in their bonding characteristics to pure THAM, the potential order of merit between the three is less clear, although THAM-3 presents as possibly superior.