Lithium-Templated Formation of Polyhedral Oligomeric Silsesquioxanes (POSS).

A coordination complex, lithium hepta(i-butyl)silsesquioxane trisilanolate (1; Li-T7), a stable intermediate in silsesquioxane (SQ) syntheses, was successfully isolated in 65% yield and found to be highly soluble in nonpolar solvents such as hexane. The structure of Li-T7 was confirmed by NMR, IR spectroscopy, matrix-assisted laser desorption ionization time-of-flight mass spectrometry, electrospray ionization mass spectrometry, and computational simulation, providing detailed elucidation of the intermolecular self-association of the SQ cage with a box-shaped Li6O6 polyhedron through strong coordination bonds. After acid treatment, Li-T7 undergoes lithium-proton cationic exchange, yielding hepta(i-butyl)silsesquioxane trisilanol (2; H-T7) quantitatively. The high yield of H-T7 seems to be influenced by Li-O bonding in the Li-T7 complex that affects the selective formation of hepta(i-butyl)silsesquioxane trisilanolate and the bulky i-butyl groups which may prevent decomposition or SQ cage-rearrangement even at reflux under alkaline conditions. Single-crystal X-ray crystallography confirms the presence of the dumbbell-shaped SQ partial cages through strong intermolecular hydrogen bonds. Interestingly, lowering the polarity of the reaction solution by adding dichloromethane results in formation of the cubic octa(i-butyl)silsesquioxane (3; T8) cage in a good yield (47%), which is isolated by crystallization from the reaction solution.

Photo-Controlled Reversible Uptake and Release of a Modified Sulfamethoxazole Antibiotic Drug from a Pillar[5]arene Cross-Linked Gelatin Hydrogel.

Pillararene cross-linked gelatin hydrogels were designed and synthesized to control the uptake and release of antibiotics using light. A suite of characterization techniques ranging from spectroscopy (FT-IR, 1H and 13C NMR, and MAS NMR), X-ray crystallographic analysis, scanning electron microscopy (SEM), and thermogravimetric analysis (TGA) was employed to investigate the physicochemical properties of hydrogels. The azobenzene-modified sulfamethoxazole (Azo-SMX) antibiotic was noncovalently incorporated into the hydrogel via supramolecular host-guest interactions to afford the A-hydrogel. While in its ground state, the Azo-SMX guest has a trans configuration structure and forms a thermodynamically stable inclusion complex with the pillar[5]arene motif in the hydrogel matrix. When the A-hydrogel was exposed to 365 nm UV light, Azo-SMX underwent a photoisomerization reaction. This changed the structure of Azo-SMX from trans to cis, and the material was released into the environment. The Azo-SMX released from the hydrogel was effective against both Gram-positive and Gram-negative bacteria. Importantly, the A-hydrogel exhibited a striking difference in antibacterial activity when applied to bacterial colonies in the presence and absence of UV light, highlighting the switchable antibacterial activity of A-hydrogel aided by light. In addition, all hydrogels containing pillar[5]arenes have demonstrated biocompatibility and effectiveness as scaffolds for biological and medical purposes.

Eggshell-Derived Copper Calcium Hydroxy Double Salts and Their Activity for Treatment of Highly Polluted Wastewater.

By using methyl orange (MO) removal as a model reaction, the best temperatures for processing eggshells are 750 °C and above to obtain biobased CaO materials, a raw material for producing CuCa hydroxy double salt (HDS) materials with high efficiency in treatments of highly polluted wastewater (the initial concentration of MO is 500 ppm). Characterization techniques employed in this study include power X-ray diffraction, scanning electron microscopy, thermogravimetric analysis, nitrogen adsorption-desorption analysis, and the colorimetric method, as well as energy-dispersive X-ray, infrared-, and electron spin resonance spectroscopies. Complete MO removal and high chemical oxygen demand (COD) efficiencies (>90%) can be achieved after 3 min treatments of the aqueous MO with the calcined eggshell-derived CuCa HDS materials. The spent, deactivated HDS materials can be regenerated by an acid wash method. The activity of CuCa HDS materials in MO removal is unaffected by eggshell sources, implying that sorting steps may be unnecessary when eggshell food waste (duck, quail, and hen eggshells) is collected to produce biobased CaO. The findings of this study demonstrated that eggshells can be used in place of limestone and could be a more sustainable, renewable, and cost-effective source for material development and other applications.

Anion identification using silsesquioxane cages.

Anthracene-conjugated octameric silsesquioxane (AnSQ) cages, prepared via Heck coupling between octavinylsilsesquioxane (OVS) and 9-bromoanthracene, thermodynamically display intramolecular excimer emissions. More importantly, these hosts are sensitive to each anionic guest, thereby resulting in change of anthracene excimer formation, displaying the solvent-dependent fluorescence and allowing us to distinguish up to four ions such as F-, OH-, CN- and PO4 3- by fluorescence spectroscopy. Depending on the solvent polarity, for example, both F- and CN- quenched the fluorescence emission intensity in THF, but only F- could enhance the fluorescence in all other solvents. The presence of PO4 3- results in fluorescence enhancements in high polarity solvents such as DMSO, DMF, and acetone, while OH- induces enhancements only in low polarity solvents (e.g. DCM and toluene). A picture of the anion recognizing ability of AnSQ was obtained through principal component analysis (PCA) with NMR and FTIR confirming the presence of host-guest interactions. Computational modeling studies demonstrate the conformation of host-guest complexation and also the change of excimer formation. Detection of F-, CN- and OH- by AnSQ hosts in THF is noticeable with the naked eye, as indicated by strong color changes arising from charge transfer complex formation upon anion addition.

Silsesquioxane cages as fluoride sensors.

Pyrene functionalized silsesquioxane cages (PySQ) not only provide significant fluorescence from pyrene-pyrene excimers with a very large Stokes shift (Δλ = 143 nm, 69 930 cm-1) in DMSO but also exhibit fluoride capture results coincidentally with a π-π* fluorescence enhancement. On the other hand, PySQ-F- in THF significantly exhibits π-π* fluorescence quenching and a color change can be observed with the naked eye from light yellow to deep orange by forming a charge-transfer (CT) complex among the pyrenyl rings. Moreover, PySQ selectively captures F- with a response time of <2 min and with a very low detection limit (1.61 ppb), while 19F NMR is used to confirm encapsulation of F- with Δδ = 19 ppm.