A Comparative Study of Biocathodes Based on Multiwall Carbon Nanotube Buckypapers Modified with Three Different Multicopper Oxidases

14 Single‐ and multi‐walled carbon nanotubes from different sources were characterized in detail, and the characteristics obtained were carefully analyzed. The carbon material with the highest capacitance, and also other superior properties (“Taunit‐M” from “NanoTechCenter”, Russia), was chosen for further modification and fabrication of buckypaper based electrodes. These electrodes were biomodified with plant and fungal laccases, as well as fungal bilirubin oxidase. The designed biocathodes were investigated in simple buffers and also in a complex physiological fluid (human serum). Biocathodes based on immobilized fungal laccase were bioelectrocatalytically inactive in chloride containing media at neutral pH. In spite of the quite high current densities realized using biodevices based on plant laccase and fungal bilirubin oxidase, the limited thermal stability of the enzymes renders the biocathodes inadequate for practical applications in implanted situations.     

Reversible Control over Molecular Recognition in Surface‐Bound Photoswitchable Hydrogen‐Bonding Receptors: Towards Read–Write–Erase Molecular Printboards

The synthesis of an anthracene‐bearing photoactive barbituric acid receptor and its subsequent grafting onto azide‐terminated alkanethiol/Au self‐assembled monolayers by using an Cu^I‐catalyzed azide–alkyne reaction is reported. Monolayer characterization using contact‐angle measurements, electrochemistry, and spectroscopic ellipsometry indicate that the monolayer conversion is fast and complete. Irradiation of the receptor leads to photodimerization of the anthracenes, which induces the open‐to‐closed gating of the receptor by blocking access to the binding site. The process is thermally reversible, and polarization‐modulated IR reflection–absorption spectroscopy indicates that photochemical closure and thermal opening of the surface‐bound receptors occur in 70 and 100 % conversion, respectively. Affinity of the open and closed surface‐bound receptor was characterized by using force spectroscopy with a barbituric‐acid‐modified atomic force microscope tip.     

Metallation of the methyl group ino-nitrosotoluene: synthesis and the molecular structure of the binuclear complex [o-(NO)(CH2)C6H4)]2Pd2(μ-OOCCF3)2

The reaction of the tetranuclear cluster Pd₄(CO)₄(OOCCF₃)₄ witho-nitrosotoluene afforded the Pd¹¹-containing complex [o-(NO)(CH₂)C₆H₄]₂Pd₂(μ-OOCCF₃)₂. The elimination of CO₂ and the formation of organic products of transformation of tolylnitrene species (azotoluene, ditolylamine, and tolylisocyanate) were observed in the course of the reaction. The title complex was characterized by IR and¹H NMR spectroscopy. Its structure was established by X-ray diffraction analysis. It was suggested that the reaction proceeds through intermediate formation of nitrene complexes. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 147–150, January, 2000.     

A new method for the reduction of nitronyl nitroxides

Reduction of nitronyl nitroxides using hexamethylenetetramine is a very convenient method for preparing the corresponding imino nitroxides and 2-imidazoline N-oxides.     

Phosphorus-based SAHA analogues as histone deacetylase inhibitors

[structure: see text] Three analogues of suberoyl anilide hydroxamic acid (SAHA) with phosphorus metal-chelating functionalities were synthesized as inhibitors of histone deacetylases (HDACs). The compounds showed weak activity for HeLa nuclear extracts (IC(50) = 0.57-6.1 mM), HDAC8 (IC(50) = 0.28-0.41 mM), and histone-deacetylase-like protein (HDLP, IC(50) = 0.33-1.9 mM), suggesting that the transition state of HDAC is not analogous to zinc proteases. Antiproliferative activity against A2780 cancer cells (IC(50) = 0.11-0.12 mM), comparable to SAHA (0.15 mM), was observed.     

Electrochemical Sensor for Selective Detection of Meldonium in Urine by Voltammetry

A highly sensitive electrochemical sensor based on arenediazonium tosylates was designed to detect meldonium in urine. The effect of the concentration of ArN2⁺OTs⁻ arenediazonium tosylate modifier and various substituents was studied. Basic operating parameters for voltammetric meldonium detection were established and the procedure for urine sample preparation was developed. The following values were obtained: limit of detection (LOD) 0.005 mg ⋅ L⁻¹ (P=0.95) and limit of quantification (LOQ) 0.01 mg ⋅ L⁻¹. The relationship between the analytical signal and meldonium concentration in the solution ranging from 0.01 to 400 mg ⋅ L⁻¹ was described by a linear function. The meldonium concentration error did not exceed 18 %. The analysis time for a single urine sample was reduced to 15 minutes.     

Immunoassay based on peroxidase silver conjugate for the determination of human immunoglobulins against tick-borne borreliosis (lyme disease) by voltammetry and spectrophotometry

In this work two strategies for the synthesis of peroxidase silver conjugates for the qualitative and quantitative determination of immunoglobulins (IgG) to ixodid tick-borne borreliosis (ITBB) (Lyme disease) in human serum were proposed. The first approach for Ab-HRP@AgNP conjugate synthesis involved silver nanoparticles (Ag NPs) capped with a commercial peroxidase conjugate (Ab-HRP) by passive adsorption. The second strategy was based on the initial coupling of Ag NPs with human anti-species antibodies (Ab) by passive adsorption followed by the introduction of horseradish peroxidase (HRP) enzyme into the reaction mixture as a blocking reagent for Ab@AgNP@HRP conjugate synthesis. The formation of peroxidase silver conjugates was proved by UV/Vis spectroscopy and Transmission Electron Microscopy (TEM). The catalytic activity of Ab-HRP@AgNP and Ab@AgNP@HRP conjugates was evaluated by Michaelis-Menten kinetics. A commercially available 96-well microtiter plate with recombinant antigens to ITBB was used as a platform for immobilization of analyzed IgG. The HRP in Ab-HRP@AgNP conjugate was found to retain a sufficient level of activity for interaction with the H₂O₂ substrate to form an intensely colored reaction product. Therefore Ab-HRP@AgNP conjugate can be used in enzyme-linked immunosorbent assay (ELISA) with spectrophotometric detection of 3,3’,5,5’-Tetramethylbenzidine (TMB Ox) for quantitative determination of IgG to ITBB in human serum in the concentration range 12.5–800 ng ml⁻¹ with LOD 2 ng ml⁻¹. Ab@AgNP@HRP conjugate is recommended for the electrochemical determination of IgG to ITBB in human serum at LOD 3 ng ml⁻¹ with registration of silver oxidation by linear sweep anodic stripping voltammetry (LSASV). Ag NPs in Ab-HRP@AgNP and Ab@AgNP@HRP conjugates do not change electrochemical activity during storage and can be used as an electrochemical label in LSASV method in case of HRP inactivation. The immunoassay based on peroxidase silver conjugates expands the analytical potential for the determination of IgG to ITBB especially during the period of increasing incidence.