Efficient White‐Light Generation from Ionically Self‐Assembled Triply‐Fluorescent Organic Nanoparticles

Low cost, simple, and environmentally friendly strategies for white‐light generation which do not require rare‐earth phosphors or other toxic or elementally scare species remain an essentially unmet challenge. Progress in the area of all‐organic approaches is highly sought, single molecular systems remaining a particular challenge. Taking inspiration from the designer nature of ionic‐liquid chemistry, we now introduce a new strategy toward white‐light emission based on the facile generation of nanoparticles comprising three different fluorophores assembled in a well‐defined stoichiometry purely through electrostatic interactions. The building blocks consist of the fluorophores aminopyrene, fluorescein, and rhodamine 6G which represent blue, green, and red‐emitting species, respectively. Spherical nanoparticles 16(±5) nm in size were prepared which display bright white‐light emission with high fluorescence quantum efficiency (26 %) and color coordinate at (0.29, 0.38) which lie in close proximity to pure white light (0.33, 0.33). It is noteworthy that this same fluorophore mixture in free solution yields only blue emission. Density functional theory calculations reveal H‐bond and ground‐state proton transfer mediated absolute non‐parallel orientation of the constituent units which result in frustrated energy transfer, giving rise to emission from the individual centers and concomitant white‐light emission.     

Inversion of 1JCC correlations in 1,n‐ADEQUATE spectra

ADEQUATE experiments provide an alternative to the more commonly employed GHMBC experiment for the establishment of long‐range heteronuclear connectivities. The 1,1‐ADEQUATE experiment allows the unequivocal identification of both protonated and non‐protonated carbon resonances adjacent to a protonated carbon. The 1,n‐ADEQUATE experiment establishes correlations via an initial ¹J_CH heteronuclear transfer followed by an ⁿJ_CC out‐and‐back transfer, most typically, via three carbon–carbon bonds. Hence, the 1,n‐ADEQUATE experiment allows the equivalent of ⁴J_CH heteronuclear correlations to be probed when they are not observed in a GHMBC spectrum. Aside from the lower sensitivity of the 1,n‐ADEQUATE experiment relative to GHMBC experiments, the interpretation of the former is also complicated by the ‘leakage’ of ¹J_CC correlations into the spectrum that must be identified. A method for the inversion of ¹J_CC correlations to facilitate the interpretation of 1,n‐ADEQUATE spectra is presented that allows a single experiment to be performed to access ¹J_CC and ⁿJ_CC correlation information. Copyright © 2012 John Wiley & Sons, Ltd.     

Evaluation of the impacts of gamma radiolysis on an ALSEP process solvent

Journal of Radioanalytical and Nuclear Chemistry - Separating the minor actinide elements (americium and curium) from the fission product lanthanides is an important step in closing the nuclear...     

Stochastic Stability of Lyapunov Exponents and Oseledets Splittings for Semi‐invertible Matrix Cocycles

We establish (i) stability of Lyapunov exponents and (ii) convergence in probability of Oseledets spaces for semi‐invertible matrix cocycles subjected to small random perturbations. The first part extends results of Ledrappier and Young to the semi‐invertible setting. The second part relies on the study of evolution of subspaces in the Grassmannian; the analysis developed here is based on higher‐dimensional Möbius transformations and is likely to be of wider interest. © 2015 Wiley Periodicals, Inc.     

On the Synthesis of 1,4,7-Tris(tert-butoxycarbonylmethyl)-1,4,7,10-tetraazacyclododecane

1,4,7-Tris(tert-butoxycarbonylmethyl)-1,4,7,10-tetraazacyclododecane is widely used as an intermediate in the preparation of medically important DO3A and DOTA metal chelators. Despite its commercial availability and importance, the literature describing the preparation and properties of the free base is limited and sometimes unclear. We present herein an efficient synthesis of the hydrobromide salt of 1,4,7-tris(tert-butoxycarbonylmethyl)-1,4,7,10-tetraazacyclododecane, characterize this compound spectroscopically and by X-ray crystallographic analysis, describe its simple conversion to the corresponding free base, characterize this compound spectroscopically and by X-ray crystallographic analysis, and make observations on the reactivity of this interesting and useful compound.