Modification of silica surface with supercritical water as a tool indicating new possibilities of existing separation methods
Silica capillaries have been an integral part of the instrumentation used in many areas of analytical chemistry for decades, especially in analytical separations. In most cases, they are used without treatment, occasionally forceless chemical surface treatments are made to suppress or enhance the activity of silanol groups. The aim of this work was to disrupt the inner surface of the capillary, perfectly smooth from manufactory, so that relatively coarse and various structures would be created, and to study their influence on the separation efficiency. The uniqueness of the used solution is based on the use of special properties of water exposed to high temperatures and pressures (supercritical water), which is able to disrupt this chemically inert material because of its aggressivity. In total, over 2000 experiments were carried out in order to define conditions suitable for the formation of various types of surface structures. Due to the high amount of resulting data, our own database application was created, allowing not only to save the picture of the structure and experimental conditions information, but also to clearly sort them out and create image reports according to the specified parameters. Samples representing individual types of structures were then selected from this database and a number of silica capillaries with a configuration suitable for electromigration analyzes were prepared. The creation of a structured surface in the input part of the separation capillary enabled the separation of some classes of substances and biosamples, which cannot be analyzed on standard capillaries with a smooth surface. An example is the complete separation of two strains of Staphyllococcus aureus bacteria (MRSA and MSSA), or the use of the absorbing capabilities of a structured surface to study the interactions of these bacteria with bacteriophages. This ability was also used in the determination of Aspergillus fungus in a sample taken directly from the patient's lungs, where there was achieved a significant increase in the sensitivity of the analysis. Structured capillaries can also be used in the analysis of food samples, i.e., for the separation of β-lactoglobulins A and B in cow's milk, which belong to its main allergens.
PVA unveiled the actual role of starch in the Briggs-Rauscher reaction
The Briggs Rauscher reaction (BR reaction) is one of the famous oscillating reactions; the aqueous mixture of KIO3, H2SO4, H2O2, C3H4O4, MnSO4, and starch exhibit color change between yellow and blue-purple repeatedly. The blue-purple color formation is due to the iodine test reaction caused by inclusions of polyiodides such as I3- and I5- in the helical structure of starch. Therefore, starch has been regarded as only an indicator in the BR reaction. But our seniors have found that the oscillation did not last without starch. They hypothesized that starch’s linear helical framework is necessary to elongate the lifetime of the oscillating reaction. If this hypothesis is correct, similar BR-type oscillations must be observed when other polymers with helical structures are used instead of starch. We found the literature which reports that polyvinyl alcohol (PVA) forms a helical structure and indicates the iodine test reaction. In our research, we studied the BR reactions using PVA, with different saponification degrees and viscosities. First, we studied the correlation between the structural features of PVA and the iodine color reaction by spectroscopic approach, exhibiting that PVA with low saponification form helical structures and show the iodine color reactions, which gives red color solutions. Second, we found that additions of the helical-structured PVA to the reaction solution instead of starch induces the BR-type oscillating reactions, while PVA without helical structure induces only a few numbers of oscillations. This is the world-first example of the oscillating reaction using PVA. The oscillation that lasted for 6 minutes with 23 oscillations was almost the same as that of the general BR reaction using starch. We concluded that the polymers with helical structures are intrinsic to elongate the lifetime of the BR reaction. Furthermore, we found that the addition of K3[Fe(CN)6], which has a high redox activity, in the reaction solution with PVA drastically elongated the lifetime (50 min) and increased the numbers of the oscillations (nearly 100 times). This result suggests that the oxidation-reduction reactions by the ferricyanide ion promotes the redox process of iodine and iodide ions.