Mass transport of the bulk of the analyte to the electrode and through the bioactive layer can be significantly improved by use of the nanoelectrode array and defined arrangement of protein film. This phenomenon has been studied by (i) atomic-force microscopy, (ii) electrochemical measurements of PSII activity, and (iii) digital simulations for an oriented monolayer of histidine-tagged photosystem II (PSII) immobilized on nitrilotriacetic acid (NTA)-modified gold electrodes. The output signal of the electrochemical biosensor is controlled by (i) mass transport from the bioactive layer to electrode and (ii) mass transport between the bulk of the analyte and the electrode. Mass transport through the bioactive layer was electrochemically studied for PSII self-assembled on gold screen-printed electrodes. A densely packed monolayer of PSII has a significant shielding effect toward the diffusion of redox mediator duroquinone (DQ). Mass transport to the planar electrode surface was improved by co-immobilization of bovine-serum albumin (BSA) as spacer biomolecule in the monolayer of PSII. Correlation between the electrochemical properties and surface arrangement of the resulting protein films was clearly observable and confirmed the improved mass-transport properties of structured enzyme monolayers. On the basis of this observation, the application of a bottom-up approach for improvement of electrode performance was proposed and digitally simulated for an infinite array of electrodes ranging in diameter from 50 nm to 5 microm. The nanoelectrode array, with the optimum time window selected for measurements, enables enhancement of mass transport between the bulk of the analyte and the macroelectrode by a factor of up to 50 in comparison with "classical" planar electrodes. Use of a time window enables minimization of crosstalk between individual electrodes in the array. The measurements require methods which suppress the double-layer capacity.
We report the performance of an X-ray phase contrast microscope for laboratory sources with 300 nm spatial resolution. The microscope is based on a commercial X-ray microfocus source equipped with a planar X-ray waveguide able to produce a sub-micrometer x-ray beam in one dimension. Phase contrast images of representative samples are reported. The achieved contrast and resolution is discussed for different configurations. The proposed approach could represent a simple, inexpensive, solution for sub-micrometer resolution imaging with small laboratory setups.
Experimental and theoretical studies of the mechanisms that underlay ion-pair formation, their properties and applications in various fields have been and still are focused by researchers since the introduction of the concept in 1926, by Bjerrum. Ion pairs are distinct chemical entities, electrically neutral, formed between ions of opposite charge and held together by Coulomb forces, without formation of a covalent bond. Investigation methods used are various, from classical conductometric measurements to up-to-date methods, such as spectrophotometry, chromatography and capillary electrophoresis. In the pharmaceutical field, ion pairs were used to develop methods of separation, identification and assay for the active substances in complex matrices, to obtain pharmaceutical formulations with controlled release and to explain the mechanisms of transport and action for certain drugs. The chapter is an attempt to describe new trends in the spectrophotometry of ion pairs and their applications in the pharmaceutical field. The development of the concept and types of ion pairs are first presented; further, examples of applications using molecular absorption, fluorimetry and resonance light scattering spectrophotometry are presented. Based on the literature data and the authors' experience in the field, challenges and perspectives in the ion-pair spectrophotometry are also considered.
The coupling and propagation of electromagnetic waves through planar X-ray waveguides (WG) with vacuum gap and Si claddings are analyzed in detail, starting from the source and ending at the detector. The general case of linearly tapered WGs (i.e. with the entrance aperture different from the exit one) is considered. Different kinds of sources, i.e. synchrotron radiation and laboratory desk-top sources, have been considered, with the former providing a fully coherent incoming beam and the latter partially coherent beams. It is demonstrated that useful information about the parameters of the WG can be derived, comparing experimental results with computer simulation based on analytical solutions of the Helmholtz equation which take into account the amplitude and phase matching between the standing waves created in front of the WG, and the resonance modes propagating into the WG.
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