Metal-ion permeation in congested nanochannels: the exposure effect of Ag plus ions on the phosphorescent properties of a gold(I)-pyrazolate complex that is confined in the nanoscopic channels of mesoporous silica

An organometallic/silica nanocomposite of a 1D cylindrical assembly of a trinuclear gold(I)pyrazolate complex ([Au3Pz3]) that was confined inside the nanoscopic channels of hexagonal mesoporous silica ([Au3Pz3]/silicahex), emitted red light with a luminescence center at 693 nm upon photoexcitation at 276 nm owing to a AuI?AuI metallophilic interaction. When a film of [Au3Pz3]/silicahex was dipped into a solution of Ag+ in tetrahydrofuran (THF), the resulting nanocomposite material (Ag@[Au3Pz3]/silicahex) emitted green light with a new luminescence center at 486 nm, which was characteristic of a AuI?AgI heterometallic interaction. Changes in the emission/excitation and XPS spectra of Ag@[Au3Pz3]/silicahex revealed that Ag+ ions permeated into the congested nanochannels of [Au3Pz3]/silicahex, which were filled with the cylindrical assembly of [Au3Pz3]

Effect of acidic aqueous alcohol solution on template sol-gel synthesis of phosphorescent hexagonal mesoporous silica film nanocomposite

Here novel mesoporous silica film nanocomposite with a hexagonal structure is successfully synthesized by using phosphorescent columnar assembly of a trinuclear gold(I) pyrazolate complex bearing amphiphilic side chains [Au3Pz3], formed via a weak Au^Au1 metallophilic interaction, as a functional template in the sol-gel synthesis. By controlling the molar ratios of alcohol to acid in an acidic aqueous alcohol solution, the sol-gel synthesis of columnar assembled [Au3Pz3] with a silica source can provide highly ordered hexagonal mesoporous silica film composite [Au3Pz3]/silicahex consisting one-dimensional molecular assembly in the nanoscopic channels. The as-fabricated silica film nanocomposite [Au3Pz3]/silicahex with red emission have phosphorescent properties with luminescence emission centered at 693nm (λext=276nm; Stokes shift, Δλ=417nm) and lifetime at 7.8jus (λext=266nm, λem=690nm)

Newly characterized interaction stabilizes DNA structure: oligoethylene glycols stabilize G-quadruplexes CH–π interactions

Oligoethylene glycols are used as crowding agents in experiments that aim to understand the effects of intracellular environments on DNAs. Moreover, DNAs with covalently attached oligoethylene glycols are used as cargo carriers for drug delivery systems. To investigate how oligoethylene glycols interact with DNAs, we incorporated deoxythymidine modified with oligoethylene glycols of different lengths, such as tetraethylene glycol (TEG), into DNAs that form antiparallel G-quadruplex or hairpin structures such that the modified residues were incorporated into loop regions. Thermodynamic analysis showed that because of enthalpic differences, the modified G-quadruplexes were stable and the hairpin structures were slightly unstable relative to unmodified DNA. The stability of G-quadruplexes increased with increasing length of the ethylene oxides and the number of deoxythymidines modified with ethylene glycols in the G-quadruplex. Nuclear magnetic resonance analyses and molecular dynamics calculations suggest that TEG interacts with bases in the G-quartet and loop via CH-pi and lone pair-pi interactions, although it was previously assumed that oligoethylene glycols do not directly interact with DNAs. The results suggest that numerous cellular co-solutes likely affect DNA function through these CH-pi and lone pair-pi interactions