Economical,Green, and Safe Route Towards Substituted Lactones by Anodic Generation of Oxycarbonyl Radicals

A new electrochemical methodology has been developed for the generation of oxycarbonyl radicals under mild and green conditions from readily available hemioxalate salts. Mono‐ and multi‐functionalised γ‐butyrolactones were synthesised through exo‐cyclisation of these oxycarbonyl radicals with an alkene, followed by the sp³–sp³ capture of the newly formed carbon‐centred radical. The synthesis of functionalised valerolactone derivatives was also achieved, demonstrating the versatility of the newly developed methodology. This represents a viable synthetic route towards pharmaceutically important fragments and further demonstrates the practicality of electrosynthesis as a green and economical method to activate small organic molecules.     

Electrochemical determination of electroinactive guests of β-cyclodextrin at a self-assembled monolayer interface

A novel determination method of electroinactive molecules by means of electrochemical technique is presented. A new self-assembled monolayer containing cyclodextrin (CD) is prepared with mono(6-o-p-tolylsulfonyl)-β-cyclodextrin. Although this derivatization process leads to a β-CD coverage of 10% of a full monolayer, this layer shows an effective host-guest response to ferrocene. The interfacial ferrocene complexation gives a response similar to that expected for a Langmuir adsorption isotherm yielding a stability constant of 4.2 ×104 mol-1· L and a maximum ferrocene coverage of 8.6×10-12 mol/cm2. The redox peak currents of the surface-confined ferrocene decrease upon addition of competing β-CD guest species to the solution, such as m-toluic acid (mTA) and sodium dodecyl sulfonate (SDS). This principle has been used for the determination of the electroinactive molecules, mTA and SDS in the concentration ranges of 0.8-2.7 μmol/L and 5-100 nmol/L, respectively.     

Interpenetrating supramolecular lattices in 4,4′-bi­pyridine–2,3,5,6-tetra­hydroxy-1,4-benzo­quinone (3/2)

4,4′-Bi­pyridine (BPY) and 2,3,5,6-tetra­hydroxy-1,4-benzo­quinone (THBQ) crystallize in a 3:2 ratio as a neutral molecular adduct, 3C₁₀H₈N₂·2C₆H₄O₆, in space group P. There are two independent and centrosymmetric THBQ mol­ecules and two different BPY mol­ecules in the asymmetric unit, one of which lies about an inversion centre. The molecules link together through O—H⃛O and O—H⃛N hydrogen bonds to form three interpenetrating networks which create a `superlattice' of three times the volume of the primitive cell.     

Substantial Influence of Temperature on Anchoring of Gold‐Nanoparticle Monolayer for Performance of DNA Biosensors

This paper presents a way of modification of crystalline gold surface with a high quality layer of gold nanoparticles (Au NPs) via self‐assembled dithiol. The application of additional Au NPs monolayer prepared at various temperatures was tested with three types of biosensors previously described in the literature. The examined DNA biosensors differed by the detection method and the way of the immobilization of DNA probe at the modified gold electrode surface. For the immobilization of DNA probe in the sensing layer either the formation of SAM or the affinity binding (biotin – sterptavidin) or covalent attachment were used. The necessary condition of successful preparation of a perfect such monolayer is the preparation temperature of 4 °C. The preparation of Au NPs layers at higher than 4 °C temperatures leads to poor repeatability and unsatisfactory precision of the measurements. The application of the perfect Au monolayer lowers the detection limit (circa by 10 to 100 times) for all tested DNA biosensors.     

Biocatalytic anode for glucose oxidation utilizing carbon nanotubes for direct electron transfer with glucose oxidase

Covalently linked layers of glucose oxidase, single-wall carbon nanotubes and poly-l-lysine on pyrolytic graphite resulted in a stable biofuel cell anode featuring direct electron transfer from the enzyme. Catalytic response observed upon addition of glucose was due to electrochemical oxidation of FADH₂ under aerobic conditions. The electrode potential depended on glucose concentration. This system has essential attributes of an anode in a mediator-free biocatalytic fuel cell.     

Os(bpy)2(PVP)10Cl]Cl polymer and Nafion dual-film modified graphite electrode for the amperometric determination of trace amounts of norepinephrine.

A chemically modified graphite electrode was prepared by using a dual film of [Os(bpy)2(PVP)10Cl]Cl polymer and Nafion. The modified electrode showed excellent electrocatalytical activity for the oxidation of norepinephrine (NE) and an ability to eliminate efficiently the interference of ascorbic acid and other anions. The catalytic peak currents obtained from the cyclic voltammograms increased linearly with increasing concentration of NE. A log-log plot of catalytic current versus NE concentration showed a dual-linear relationship in the ranges 1.8 x 10(-8)-4.4 x 10(-6) M and 4.4 x 10(-6)-2.9 x 10(-4) M with correlation coefficients of 0.990 and 0.999, respectively. The detection limit was about 18 nM (3 delta). At a potential of +500 mV the chronoamperometric response showed a linear relationship between the steady state current and NE concentration in the range 1.3-130 microM. With a further increase in NE concentration a Michaelis-Menten-shaped response was observed. The apparent Michaelis-Menten constant and the maximum current were 1.7 mM and 86 microA, respectively. The modified electrode showed excellent reproducibility, sensitivity and stability for the determination of NE at trace levels.