The occurrence, mechanisms, and practicalities of the electrogeneration of chemiluminescence are described with reference to applications in analytical chemistry. The general theory of electron transfer excitation mechanisms is discussed with respect to organic reactions in aprotic media, and extended to include inorganic complexes and clusters. Analytical applications are classified according to the excitation mechanism, i.e., organic and inorganic systems, established chemiluminescence reactions initiated electrochemically, and cathodic luminescence at semiconductor electrodes.
Water is the universal solvent and plays a critical role in all known geological and biological processes. Confining water in nano-scale domains, as encountered in sedimentary rocks, in biological, and in engineered systems, leads to the deviations in water’s physicochemical properties relative to those measured for the non-confined phase. In our comprehensive analysis, we demonstrate that nano-scale confinement leads to the decrease in the melting/freezing point temperature, density, and surface tension of confined water. With increasing degree of spatial confinement the population of networked water, as evidenced by alterations in the O-H stretching modes, increases. These analyses were performed on two groups of mesoporous silica materials, which allows to separate pore size effects from surface chemistry effects. The observed systematic effects of nano-scale confinement on the physical properties of water are driven by alterations to water’s hydrogen-bonding network—influenced by water interactions with the silica surface — and has implications for how we understand the chemical and physical properties of liquids confined in porous materials.
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