Characterization of Triphenylamine and Ferrocenyl Donor-π-donor Vinyl BODIPY Derivatives as Photoacoustic Contrast Agents.

The photophysical and electrochemical properties for a series of BODIPY dyes with incremental 3- and 3,5-vinyl conjugation, as well as incremental electron-donating groups (anisole < triphenylamine < ferrocenyl), are presented. Insight into the influence of each vinyl-conjugated electron-donating group on both vis-NIR absorption and fluorescence emission properties is provided. These trends are further corroborated by density functional theory computational analysis. Two of this series containing the 3,5-bis(vinyltriphenylamine) and 3,5-bis(vinylferrocenyl) substituents exhibit significant absorption cross sections in the biological transparency window justifying further investigation of their photoacoustic emission properties via both optical photoacoustic z-scan and photoacoustic tomography experiments. Both the 3,5-bis(vinyltriphenylamine) and 3,5-bis(vinylferrocenyl) substituted BODIPY dyes exhibit quantitative photoacoustic quantum yields. Relative to the commercially available methylene blue and indocyanine green molecular photoacoustic contrast agents, the 3,5-bis(vinyltriphenylamine)-derived BODIPY exhibits the greatest photoacoustic emission and contrast upon excited-state absorption at 685 nm excitation at a low power laser fluence (<20 mJ cm-2 ).

Repetitive optical coherence elastography measurements with blinking nanobombs.

Excitation of dye-loaded perfluorocarbon nanoparticles (nanobombs) can generate highly localized axially propagating longitudinal shear waves (LSW) that can be used to quantify tissue mechanical properties without transversal scanning of the imaging beam. In this study, we used repetitive excitations of dodecafluoropentane (C5) and tetradecafluorohexane (C6) nanobombs by a nanosecond-pulsed laser to produce multiple LSWs from a single spot in a phantom. A 1.5 MHz Fourier-domain mode-locked laser in combination with a phase correction algorithm was used to perform elastography. Multiple nanobomb activations were also monitored by detecting photoacoustic signals. Our results demonstrate that C6 nanobombs can be used for repetitive generation of LSW from a single spot for the purpose of material elasticity assessment. This study opens new avenues for continuous quantification of tissue mechanical properties using single delivery of the nanoparticles.

Photophysical and Photoacoustic Properties of π-Extended Curcumin Dyes. Effects of the Terminal Dimethylamino Electron-donor and the Bridging Aryl Ring.

The synthesis, photophysical and photoacoustic characterization for a series of nine π-extended quadrupolar curcumin dyes is presented. A systematic evaluation of the π-bridging unit including the p-phenyl, naphth-4-yl, thien-2-yl and hybrid 4-naphthathien-2-yl groups is presented. Furthermore, evaluation of the strongly donating donor-π-acceptor-π-donor quadrupolar dimethylamino terminated derivatives is also included. Select dyes exhibit excited state absorption at increased laser fluence which translates to the production of a nonlinear enhanced photoacoustic response. In particular, the bis-4-dimethylaminonaphtha-2-thien-5-yl curcuminBF2 contrast agent DMA-5 exhibits an excellent molar photoacoustics (PA) emission at both low (9.4 × 103  V M-1 ) and high (1.47 × 105  V M-1 ) laser fluence which is confirmed by its strong contrast by photoacoustic tomography (PAT). In summary, the strong absorbance and enhanced photoacoustic properties of naphthyl and thienyl curcuminoids here presented provides great promise for future photoacoustic imaging applications as demonstrated by preliminary PAT studies.

Characterization of a NIR absorbing thienyl curcumin contrast agent for photoacoustic imaging.

The synthesis and characterization of a bis(2-dimethylaminothien-5-yl)curcumin boron difluoride chromophore is presented. Photophysical, electrochemical and computational investigations establish the properties of its absorption in the Vis-NIR spectral range relative to established curcumin dyes. Application of this thienyl curcumin dye as a photoacoustic contrast agent is investigated against the dicarbocyanine Cy5 dye in the 675-735 nm excitation range.

Photophysical and Photoacoustic Properties of Quadrupolar Borondifluoride Curcuminoid Dyes.

The synthesis and characterization of a series of donor-π-acceptor-π-donor (D-A-D) curcuminoid molecules is presented herein that incorporates π-extended aryl and electron-donating amino terminal functionalization. Computational evaluation shows these molecules possess quadrupolar character with the lowest energy transitions displaying high molar extinction coefficients with broad tunability through manipulation of terminal donating groups. Consistent with their quadrupolar nature, these molecules show varying degrees of solvatochromic behavior in both their absorption and emission spectra, which has been analyzed by Lippert-Mataga and Kamlet-Taft analysis. Photophysical and photoacoustic (PA) properties of these molecules have been investigated by the optical photoacoustic z-scan (OPAZ) method. Selected curcuminoid molecules display nonlinear behavior at a high laser fluence through excited state absorption that translates to the production of an enhanced photoacoustic emission. A relative comparison of "molar PA emission" is also presented with the crystal violet linear optical absorbing/linear PA emitting system being utilized as a standard reference material for OPAZ experiments. Furthermore, PA tomography experiments are presented to illustrate the enhanced PA contrast obtainable via an excited state absorption.

Shining light on the dark side of imaging: excited state absorption enhancement of a bis-styryl BODIPY photoacoustic contrast agent.

A first approach toward understanding the targeted design of molecular photoacoustic contrast agents (MPACs) is presented. Optical and photoacoustic Z-scan spectroscopy was used to identify how nonlinear (excited-state) absorption contributes to enhancing the photoacoustic emission of the curcuminBF2 and bis-styryl (MeOPh)2BODIPY dyes relative to Cy3.

Nonlinear optical properties of multipyrrole dyes.

The nonlinear optical properties of a series of pyrrolic compounds consisting of BODIPY and aza-BODIPY systems are investigated using 532 nm nanosecond laser and the Z-scan technique. Results show that 3,5-distyryl extension of BODIPY to the red shifted MeO2BODIPY dye has a dramatic impact on its nonlinear absorption properties changing it from a saturable absorber to an efficient reverse saturable absorbing material with a nonlinear absorption coefficient of 4.64 × 10-10 m/W. When plotted on a concentration scale per mole of dye in solution MeO2BODIPY far outperforms the recognized zinc(II) phthalocyanine dye and is comparable to that of zinc(II) tetraphenylporphyrin.