Time-resolved resonance Raman scattering of triplet state anthracene in supercritical CO2

The first report of time-resolved resonance Raman (TR(3)) scattering in a supercritical fluid is presented. TR(3) spectra of the lowest triplet excited state (T-1) of anthracene in supercritical (SC) CO2 have been obtained over the pressure range 90-500 bar. These data have been complemented by conventional flash photolysis measurements of the excited state lifetime, transient absorbance difference, and fluorescence spectra over a similar pressure range. The spectroscopic data show systematic changes with increasing pressure; the Delta A spectra of the TI state recorded at two different temperatures display a red shift with increasing fluid pressure, which is in agreement with earlier work carried out over a smaller range of pressures. Similar shifts in the fluorescence are also observed. The vibrational frequencies of the T-1 state of anthracene are found to be relatively insensitive to applied pressure; indeed, the transient bands are readily identified by comparison with resonance Raman (RR) spectra of the T-1 state in cyclohexane solution. Small but well-defined shifts to lower cm(-1) with increasing pressure are observed in some of the vibrational bands of SC COE. The most marked change in the excited state Raman spectra is that the intensity of the T-1 anthracene features, relative to those of CO2, increases with applied pressure. The information which each of the above spectroscopic methods gives on the question of how pressure changes affect the structure and local environment of the excited state probe molecule in the SCF is discussed. Possible explanations for the observed increase in RR band intensities in terms of increased resonance Raman enhancement arising from the spectral shifts and/or the increased solubility of anthracene in CO2 with increasing pressure are also considered.

Alkynyl-Bridged Ruthenium(II) 4 '-Diferroceny1-2,2 ':6 ',2 ''-terpyridine Electron Transfer Complexes: Synthesis, Structures, and Electrochemical and Spectroscopic Studiese

The novel ligand 4'-diferrocenylallcyne-2,2':6',2 ''-terpyridine (7; Fc-C C-Fc-tpy; tpy = terpyridyl; Fc = ferrocenyl) and its Ru2+ complexes 8-10 have been synthesized and characterized by single-crystal X-ray diffraction, cyclic voltammetry, and UV-vis and luminescence spectroscopy. Electrochemical data and UV absorption and emission spectra indicate that the insertion of an ethynyl group causes delocalization of electrons in the extended pi* orbitals. Cyclic voltammetric measurements of 7 show two successive reversible one-electron-oxidation processes with half-wave potentials of 0.53 and 0.78 V. The small variations of the E-1/2 values for the Fe2+/Fe3+ redox couples after the coordination of the Ru2+ ion suggest a weak interaction between the Ru2+ and Fe2+ centers. After insertion of an ethynyl group, UV-vis absorption spectra show a red shift of the absorption peak of the (1)[(d(pi)(Fe))(6)]->(1)[(d(pi)(Fe))(5)(pi*(Ru)(tpy))(1)] MMLCT of the Ru2+ complexes. The Ru2+ complex 8 exhibits the strongest luminescence intensity (lambda(em)(max) 712 nm, Phi(em) = 2.63 x 10(-4), tau = 323 ns) relative to analogous ferrocene-based terpyridine Ru(II) complexes in H2O/CH3CN (4/1 v/v) solution.

Nile blue-based nano-sized pH sensors for simultaneous far-red and near-infrared live bioimaging

Diblock copolymer vesicles are tagged with pH-responsive Nile Blue-based labels and used as a new type of pH-responsive colorimetric/fluorescent biosensor for far-red and near-infrared imaging of live cells. The diblock copolymer vesicles described herein are based on poly(2-(methacryloyloxy)ethyl phosphorylcholine-block-2-(diisopropylamino)ethyl methacrylate) [PMPC-PDPA]: the biomimetic PMPC block is known to facilitate rapid cell uptake for a wide range of cell lines, while the PDPA block constitutes the pH-responsive component that enables facile vesicle self-assembly in aqueous solution. These biocompatible vesicles can be utilized to detect interstitial hypoxic/acidic regions in a tumor model via a pH-dependent colorimetric shift. In addition, they are also useful for selective intracellular staining of lysosomes and early endosomes via subtle changes in fluorescence emission. Such nanoparticles combine efficient cellular uptake with a pH-responsive Nile Blue dye label to produce a highly versatile dual capability probe. This is in marked contrast to small molecule dyes, which are usually poorly uptaken by cells, frequently exhibit cytotoxicity, and are characterized by intracellular distributions invariably dictated by their hydrophilic/hydrophobic balance.