81998-04-1Relevant articles and documents
An efficient ruthenium tris(bipyridine)-based luminescent chemosensor for recognition of Cu(ii) and sulfide anion in water
Li, Minna,Liang, Qichao,Zheng, Meiqing,Fang, Chenjie,Peng, Shiqi,Zhao, Ming
, p. 13509 - 13515 (2013)
A novel efficient luminescent chemosensor based on a 1,4,7,10- tetraazacyclododecane (cyclen)-tethered Ru(bpy)32+ derivative (Ru-cyclen) has been synthesized and characterized. It displays an ON-OFF-type luminescence change with excellent selectivity towards Cu(ii) amongst 16 metal ions in 100% aqueous solution. The binding stoichiometry of Ru-cyclen with Cu2+ was established by Job plot analysis and mass spectral evidence. Furthermore, the in situ generated Ru-cyclen-Cu ensemble recovered luminescence in the presence of S2-, indicating an 'OFF-ON'-type sensing process. Similar phenomena were not observed with other common anions and biothiols, making it a high selective sulfide probe. Finally, the sensing mechanism is confirmed to be displacement approach by NMR, mass and emission spectrometry.
Mechanochemical Release of Non-Covalently Bound Guests from a Polymer-Decorated Supramolecular Cage
G?stl, Robert,Küng, Robin,Pausch, Tobias,Rasch, Dustin,Schmidt, Bernd M.
supporting information, p. 13626 - 13630 (2021/05/10)
Supramolecular coordination cages show a wide range of useful properties including, but not limited to, complex molecular machine-like operations, confined space catalysis, and rich host–guest chemistries. Here we report the uptake and release of non-covalently encapsulated, pharmaceutically-active cargo from an octahedral Pd cage bearing polymer chains on each vertex. Six poly(ethylene glycol)-decorated bipyridine ligands are used to assemble an octahedral PdII6(TPT)4 cage. The supramolecular container encapsulates progesterone and ibuprofen within its hydrophobic nanocavity and is activated by shear force produced by ultrasonication in aqueous solution entailing complete cargo release upon rupture, as shown by NMR and GPC analyses.
Light-Activated Electron Transfer and Turnover in Ru-Modified Aldehyde Deformylating Oxygenases
Bains, Rajneesh K.,Miller, Jessica J.,Van Der Roest, Hannah K.,Qu, Sheng,Lute, Brad,Warren, Jeffrey J.
supporting information, p. 8211 - 8217 (2018/07/25)
Conversion of biological molecules into fuels or other useful chemicals is an ongoing chemical challenge. One class of enzymes that has received attention for such applications is aldehyde deformylating oxygenase (ADO) enzymes. These enzymes convert aliphatic aldehydes to the alkanes and formate. In this work, we prepared and investigated ADO enzymes modified with RuII(tris-diimine) photosensitizers as a starting point for probing intramolecular electron transfer events. Three variants were prepared, with RuII-modification at the wild type (WT) residue C70, at the R62C site in one mutant ADO, and at both C62 and C70 in a second mutant ADO protein. The single-site modification of WT ADO at C70 using a cysteine-reactive label is an important observation and opens a way forward for new studies of electron flow, mechanism, and redox catalysis in ADO. These Ru-ADO constructs can perform the ADO catalytic cycle in the presence of light and a sacrificial reductant. In this work, the Ru photosensitizer serves as a tethered, artificial reductase that promotes turnover of aldehyde substrates with different carbon chain lengths. Peroxide side products were detected for shorter chain aldehydes, concomitant with less productive turnover. Analysis using semiclassical electron transfer theory supports proposals for hopping pathway for electron flow in WT ADO and in our new Ru-ADO proteins.