Composition dependence of the optical absorption spectra of cupric ion in sodium borosilicate glass melts

Optical absorption spectra of Cu²⁺ d–d transition peak in sodium borosilicate glasses and their melts were measured from room temperature to 1100 K. In the case of borate glass free from silicon, increase of the temperature above T_g shifts the peak position to the low energy side and decreases the peak height. Peak width is gradually increased with the increase in temperature. On the other hand, in the case of silicate glass free from boron, peak width is decreased with the increase in temperature from room temperature to liquidus temperature. In addition, peak height is slightly decreased with the temperature increase in this temperature range. Further increase of the temperature makes the peak width large. In borosilicate glasses, temperature dependence of the optical absorption spectra is different both from borate and from silicate, and the temperature dependences of the peak position and of the peak height are very small. Temperature dependence of the peak width depends on the boron/silicon ratio.     

Molecular Engineering To Enhance Reactivity and Selectivity in an Ultrafast Photoclick Reaction

Light-induced 9,10-phenanthrenequinone-electron-rich alkene ( PQ-ERA ) photocycloadditions are an attractive new type of photoclick reaction, featuring fast conversions and high biocompatibility. However, the tunability of the reaction was hardly investigated up to now. To this end, we explored the influence of substituents on both reaction partners and the reaction rate between the PQs and ERAs . We identified new handles for functionalization and discovered that using enamines as ERAs leads to drastically enhanced rates (>5400 times faster), high photoreaction quantum yields ( Φ_P , up to 65 %), and multicolor emission output as well as a high fluorescence quantum yield of the adducts ( Φ_F , up to 97 %). Further investigation of the photophysical and photochemical properties provided insights to design orthogonal reaction systems both in solution and on nanoparticle surfaces for ultrafast chemoselective functionalization by photoclick reactions.