Biomimetic biosensor based on lipidic layers containing tyrosinase and lutetium bisphthalocyanine for the detection of antioxidants.

This paper describes the preparation of a biomimetic Langmuir-Blodgett film of tyrosinase incorporated in a lipidic layer and the use of lutetium bisphthalocyanine as an electron mediator for the voltammetric detection of phenol derivatives, which include one monophenol (vanillic acid), two diphenols (catechol and caffeic acid) and two triphenols (gallic acid and pyrogallol). The first redox process of the voltammetric responses is associated with the reduction of the enzymatically formed o-quinone and is favoured by the lutetium bisphthalocyanine because significant signal amplification is observed, while the second is associated with the electrochemical oxidation of the antioxidant and occurs at lower potentials in the presence of an electron mediator. The biosensor shows low detection limit (1.98×10(-6)-27.49×10(-6) M), good reproducibility, and high affinity to antioxidants (K(M) in the range of 62.31-144.87 µM). The excellent functionality of the enzyme obtained using a biomimetic immobilisation method, the selectivity afforded by enzyme catalysis, the signal enhancement caused by the lutetium bisphthalocyanine mediator and the increased selectivity of the curves due to the occurrence of two redox processes make these sensors exceptionally suitable for the detection of phenolic compounds.

Properties of lipophilic nucleoside monolayers at the air-water interface.

The capability of self-assembly and molecular recognition of biomolecules is essential for many nanotechnological applications, as in the use of alkyl-modified nucleosides and oligonucleotides to increase the cellular uptake of DNA and RNA. In this study, we show that a lipophilic nucleoside, which is an isomer mixture of 2'-palmitoyluridin und 3'-palmitoyluridin, forms Langmuir monolayers and Langmuir-Blodgett films as a typical amphiphile, though with a smaller elasticity. The nucleoside may be incorporated into dipalmitoyl phosphatidyl choline (DPPC) monolayers that serve as a simplified cell membrane model. The molecular-level interactions between the nucleoside and DPPC led to a remarkable condensation of the mixed monolayer, which affected both surface pressure and surface potential isotherms. The morphology of the mixed monolayers was dominated by the small domains of the nucleoside. The mixed monolayers could be deposited onto solid substrates as a one-layer Langmuir Blodgett film that displayed UV-vis absorption spectra typical of aggregated nucleosides owing to the interaction between the nucleoside and DPPC. The formation of solid films with DNA building blocks in the polar heads may open the way for devices and sensors be produced to exploit their molecular recognition properties.

Excited state absorption spectrum of chlorophyll a obtained with white-light continuum.

The study of excited state properties of chlorophyll a is a subject of foremost interest, given that it plays important roles in biological process and has also been proposed for applications in photonics. This work reports on the excited state absorption spectrum of chlorophyll a solution from 460 to 700 nm, obtained through the white-light continuum Z-scan technique. Saturation of absorption was observed due to the ground state depletion, induced by the white-light continuum region that is resonant with the Q band of chlorophyll a. The authors also observed reverse saturation of absorption related to the excitation from the first excited state to a higher energy level for wavelengths below 640 nm. An energy-level diagram, based on the electronic states of chlorophyll a, was employed to interpret their results, revealing that more states than the ones related to the Q and B bands participate in the excited state absorption of this molecule.

In situ UV-vis absorbance measurements for Langmuir films of poly[4'-[[2-(methacryloyloxy)-ethyl]ethylamino]-2-chloro-4-nitroazobenzene] (HPDR13) azopolymer.

In situ UV-vis absorbance measurements are used to investigate aggregation in Langmuir films from the azopolymer poly[4'-[[2-(methacryloyloxy)-ethyl]ethylamino]-2-chloro-4-nitroazobenzene] (HPDR13), a methacrylate derivative of DR13. The level of aggregation in a Langmuir film is intermediate between that of HPDR13 in chloroform solution and in a deposited LB film, as expected. Absorption is negligible at large areas per monomer, and starts to increase at a critical area that is the same as the one obtained in surface potential isotherms, being close to twice the area per monomer for a condensed film. This indicates that the onset for light absorption coincides with a critical packing density where monolayer structuring occurs and there is a sharp change in the effective dielectric constant of the film/water interface. Consistent with a featureless pressure-area isotherm for HPDR13, denoting no significant molecular rearrangement upon film compression, the UV-vis spectra did not vary with the surface pressure. The intensity of absorbed light increased, though, as the film was compressed owing to a higher density of chromophores. At higher subphase temperatures, larger flexibility of HPDR13 chains led to a more compact arrangement, causing the area per monomer to decrease and the absorbed light to increase-with approximately opposite trends.