Quantum-dot-based photoelectrochemical sensors are powerful alternatives for the detection of chemicals and biochemical molecules compared to other sensor types, which is the primary reason as to why they have become a hot topic in nanotechnology-related analytical methods. These sensors basically consist of QDs immobilized by a linking molecule (linker) to an electrode, so that upon their illumination, a photocurrent is generated which depends on the type and concentration of the respective analyte in the immediate environment of the electrode. The present review provides an overview of recent developments in the fabrication methods and sensing concepts concerning direct and indirect interactions of the analyte with quantum dot modified electrodes. Furthermore, it describes in detail the broad range of different sensing applications of such quantum-dot-based photoelectrochemical sensors for inorganic and organic (small and macro-) molecules that have arisen in recent years. Finally, a number of aspects concerning current challenges on the way to achieving real-life applications of QD-based photochemical sensing are addressed.
The combination of the biocatalytic features of enzymes with the unique physical properties of nanoparticles in a biohybrid system provides a promising approach for the development of advanced bioelectrocatalytic devices. This study describes the construction of photoelectrochemical signal chains based on CdSe/ZnS quantum dot (QD) modified gold electrodes as light switchable elements, and low molecular weight redox molecules for the combination with different biocatalysts. Photoelectrochemical and photoluminescence experiments verify that electron transfer can be achieved between the redox molecules hexacyanoferrate and ferrocene, and the QDs under illumination. Since for both redox mediators a concentration dependent photocurrent change has been found, light switchable enzymatic signal chains are built up with fructose dehydrogenase (FDH) and pyrroloquinoline quinone-dependent glucose dehydrogenase ((PQQ)GDH) for the detection of sugars. After immobilization of the enzymes at the QD electrode the biocatalytic oxidation of the substrates can be followed by conversion of the redox mediator in solution and subsequent detection at the QD electrode. Furthermore, (PQQ)GDH has been assembled together with ferrocenecarboxylic acid on top of the QD electrode for the construction of a funtional biohybrid architecture, showing that electron transfer can be realized from the enzyme over the redox mediator to the QDs and subsequently to the electrode in a completely immobilized fashion. The results obtained here do not only provide the basis for light-switchable biosensing and bioelectrocatalytic applications, but may also open the way for self-driven point-of-care systems by combination with solar cell approaches (power generation at the QD electrode by enzymatic substrate consumption).
Colloidal particles with fluorescence read-out are commonly used as sensors for the quantitative determination of ions. Calcium, for example, is a biologically highly relevant ion in signaling, and thus knowledge of its spatio-temporal distribution inside cells would offer important experimental data. However, the use of particle-based intracellular sensors for ion detection is not straightforward. Important associated problems involve delivery and intracellular location of particle-based fluorophores, crosstalk of the fluorescence read-out with pH, and spectral overlap of the emission spectra of different fluorophores. These potential problems are outlined and discussed here with selected experimental examples. Potential solutions are discussed and form a guideline for particle-based intracellular imaging of ions.
Differential Scanning Calorimetry (DSC) and optical microscopy were used to investigate the effect of the thermal history of the melt on the crystallization of a commercial sample of poly(ary1-ether-ether-ketone) (PEEK). Heating a film of PEEK at a temperature above the melt temperature for various periods of time changes the nucleation and crystal growth rate upon cooling the sample. Destruction of existing nuclei, formation of new nuclei, chain branching, cross linking, and chemical degradation of the macromolecular chains are all believed to take place at different times and to different extents during the thermal melt processing of the polymer. This study suggests that the thermal history of the melt plays a n important role in the crystallization of PEEK samples.
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