Designing the Molybdopterin Core through Regioselective Coupling of Building Blocks

Molybdopterin is an essential cofactor for all forms of life. The cofactor is composed of a pterin moiety appended to a dithiolene‐functionalized pyran ring, and through the dithiolene moiety it binds metal ions. Different synthetic strategies for dithiolene‐functionalized pyran precursors that have been designed and synthesized are discussed. These precursors also harbor 1,2‐diketone or osone functionality that has been condensed with 1,2‐diaminobenzene or other heterocycles resulting in several quinoxaline or pterin derivatives. Use of additives improves the regioselectivity of the complexes. The molecules have been characterized by ¹H and ¹³C NMR and IR spectroscopies, as well as by mass spectrometry. In addition, several compounds have been crystallographically characterized. The geometries of the synthesized molecules are more planar than the geometry of the cofactor found in proteins.     

Principal component analysis of the main factors of line intensity enhancements observed in oscillating direct current plasma

Enhancement of emission line intensities by induced oscillations of direct current (DC) arc plasma with continuous aerosol sample supply was investigated using multivariate statistics. Principal component analysis (PCA) was employed to evaluate enhancements of 34 atomic spectral lines belonging to 33 elements and 35 ionic spectral lines belonging to 23 elements. Correlation and classification of the elements were done not only by a single property such as the first ionization energy, but also by considering other relevant parameters. Special attention was paid to the influence of the oxide bond strength in an attempt to clarify/predict the enhancement effect. Energies of vaporization, atomization, and excitation were also considered in the analysis. In the case of atomic lines, the best correlation between the enhancements and first ionization energies was obtained as a negative correlation, with weak consistency in grouping of elements in score plots. Conversely, in the case of ionic lines, the best correlation of the enhancements with the sum of the first ionization energies and oxide bond energies was obtained as a positive correlation, with four distinctive groups of elements. The role of the gas-phase atom-oxide bond energy in the entire enhancement effect is underlined.     

Electrophoretic deposition of hydroxyapatite–CaSiO3–chitosan composite coatings

Electrophoretic deposition (EPD) method has been developed for the fabrication of hydroxyapatite (HA)–CaSiO₃ (CS)–chitosan composite coatings for biomedical applications. The use of chitosan enabled the co-deposition of HA and CS particles and offered the advantage of room temperature processing of composite materials. The coating composition was varied by the variation of HA and CS concentrations in the chitosan solutions. Cathodic deposits were obtained as HA–CS–chitosan monolayers, HA–chitosan/chitosan multilayers or functionally graded materials (FGM) containing HA–chitosan and CS–chitosan layers of different composition. The thickness of the individual layers was varied in the range of 0.1–20 μm. The deposition yield was studied at different experimental conditions and compared with the results of modeling. It was shown that the moving boundary model for the two component system can explain the non-linear increase in the deposition yield with increasing HA concentration in chitosan solutions. The obtained coatings were studied by thermogravimetric analysis (TGA), differential thermal analysis (DTA) and scanning electron microscopy (SEM). Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) studies showed that these coatings provided corrosion protection of stainless steel substrates in Ringer's physiological solution. The deposition mechanism and kinetics of deposition have been discussed.     

Enzyme-functionalized mesoporous silica for bioanalytical applications

The unique properties of mesoporous silica materials (MPs) have attracted substantial interest for use as enzyme-immobilization matrices. These features include high surface area, chemical, thermal, and mechanical stability, highly uniform pore distribution and tunable pore size, high adsorption capacity, and an ordered porous network for free diffusion of substrates and reaction products. Research demonstrated that enzymes encapsulated or entrapped in MPs retain their biocatalytic activity and are more stable than enzymes in solution. This review discusses recent advances in the study and use of mesoporous silica for enzyme immobilization and application in biosensor technology. Different types of MPs, their morphological and structural characteristics, and strategies used for their functionalization with enzymes are discussed. Finally, prospective and potential benefits of these materials for bioanalytical applications and biosensor technology are also presented. Figure Enzyme-functionalized mesoporous silica fibers and their integration in a biosensor design. The immobilization process takes place essentially in the silica micropores.     

Lab-scale testing of a low-loaded activated sludge process with membrane filtration

Two membrane bioreactors (MBRs; volume = 300 L) equipped with different types of immersed membrane modules were operated simultaneously under the same laboratory conditions as a low-loaded activated sludge process without any membrane regeneration and excess sludge uptake (sludge retention time SRT up to 170 d; activated sludge concentration MLSS up to 11 g L⁻¹). The aim was to verify the quality of treated water and to study the properties of "very old" activated sludge. Another aim was to compare different selected membrane types and choose the best one for further pilot-scale testing. Presented at the 35th International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 26–30 May 2008.     

Theoretical studies on the conformation of saccharides

Conformations of 2-methoxytetrahydropyran as a model for the six-membered ring in aldopyranosides have been calculated by the PCILO method using the algorithm of the conjugated gradient to optimize the geometry. The calculated geometry of the fourteen basic forms of 2-methoxytetrahydropyran was found to be in agreement with the available data obtained by X-ray diffraction of pyranosides. The results indicate differences in the geometry of 2-methoxytetrahydropyran resulting from the change of the axial vs. equatorial position of the methoxyl group. These changes are particularly meaningful in the values of bond angles and they are in agreement with the anomeric and exoanomeric effects. The experimentally found differences in the energies of an axial (⁴ C ₁) and equatorial (¹ C ₄) conformer, G = 2.9–3.7 kJ/mol, and the dipole moment, = 1.20 ± 0.05 D (1D = 3.33 10^–30mAs) agree well with the calculated values E = 3.18 kJ/mol and <> = 1.18 D which, in turn, suggest that the axial conformer is preferred over the equatorial one by a ratio a:e = 78:22.     

Immobilization in biotechnology and biorecognition: from macro- to nanoscale systems

Biological molecules such as enzymes, cells, antibodies, lectins, peptide aptamers, and cellular components in an immobilized form are extensively used in biotechnology, in biorecognition and in many medicinal applications. This review provides a comprehensive summary of the developments in new immobilization materials, techniques, and their practical applications previously developed by the authors. A detailed overview of several immobilization materials and technologies is given here, including bead cellulose, encapsulation in ionotropic gels and polyelectrolyte complexes, and various immobilization protocols applied onto surfaces. In addition, the review summarises the screening and design of an immobilization protocol, practical applications of immobilized biocatalysts in the industrial production of metabolites, monitoring, and control of fermentation processes, preparation of electrochemical/optical biosensors and biofuel cells.     

Membrane-bound dehydrogenases from Gluconobacter sp.: Interfacial electrochemistry and direct bioelectrocatalysis

Although membrane-bound dehydrogenases isolated from Gluconobacter sp. (mainly PQQ-dependent alcohol and fructose dehydrogenase) have been used for preparing diverse forms of bioelectronic interfaces for almost 2 decades, it is not an easy task to interpret an electrochemical behaviour correctly. Recent discoveries regarding redox properties of membrane-bound dehydrogenases along with extensive investigations of direct electron transfer (DET) or direct bioelectrocatalysis with these enzymes are summarized in this review. The main aim of this review is to draw general conclusions about possible electronic coupling paths of these enzymes on various interfaces via direct electron transfer or direct bioelectrocatalysis. A short overview of the metabolism and respiration chain in Gluconobacter relevant to interfacial electrochemistry is given. Biosensor devices based on DET or direct bioelectrocatalysis using membrane-bound dehydrogenases from Gluconobacter sp. are described briefly with the emphasis given on practical applications of preparing enzymatic biofuel cells. Moreover, interfacial electrochemistry of Gluconobacter oxydans related to the construction of microbial biofuel cells is also discussed.