A “Dual‐Function” Photocage Releasing Nitric Oxide and an Anthrylmethyl Cation with a Single Wavelength Light

Abstract

A template‐directed sixfold dimerization of alkyne units is the final step in the synthesis of the title compound leading to nanoscale 2D rigid wheel‐shaped oligo(phenylene ethynylene)s. Solubilizing side groups allow full characterization by NMR spectroscopy, GPC, MALDI‐TOF MS, and STM. The distance between two peripheral tert‐butyl groups at opposite sites of the oligomer is estimated to be 7 nm.

Confined photo-release of nitric oxide with simultaneous two-photon fluorescence tracking in a cellular system

“…The correlation between elevated fluorescence signal and generation of NO was confirmed by the direct detection of NO through amperometric method upon 1PE of a H 2 O:MeOH solution of CPA 1 (Fig. 3a insert) in agreement with previous results 22 , implying that the system could be applied as an optical reporter system for NO release. The figure also demonstrates an increase in 2PE induced fluorescence after sequential scanning of CPA in FBS free cell media using fs-pulsed near infrared light in the multiphoton microscope.…”

“…2 . As shown by the figure, the absorption spectra in this spectral range exhibit three absorption peaks, corresponding to the peaks observed for anthracene in methanol solution 22 . Also shown in the figure are the emission spectra acquired for 1PE and 2PE.…”

“…Cupferron-antracene (CPA) was synthesized and characterized as previously described 22 using the procedure introduced by Hou et al . 21 .…”

“…Cupferrons (CP) are spontaneous NO donors at room temperature, while their O -alkylated counterparts have been found stable 21 . Inspired by initial work by Wang and co-workers 21 , we have previously shown 22 that CP O -alkylated with anthracene (CPA, compound 1 , Fig. 1 ) is stable at room temperature.…”

“…In addition, an antrylmethyl carbocation is simultaneously formed as key intermediate in the photodecomposition. The precursor for this photo-reactivity pathway was demonstrated to be a charge transfer state which is also responsible for the strong fluorescence quenching of the anthracene moiety 22 .

Figure 1 Cupferron (CP) O -alkylated with anthracene (CPA, compound 1) which, upon light activation, one-photon (1PE) or two-photon (2PE) excitation, forms anthrylmethyl carbocation and CP.

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