ABSTRACT
In vivo fluorescence imaging in the shortwave infrared (SWIR, 1,000-1,700 nm) and extended SWIR (ESWIR, 1,700-2,700 nm) regions has tremendous potential for diagnostic imaging. Although image contrast has been shown to improve as longer wavelengths are accessed, the design and synthesis of organic fluorophores that emit in these regions is challenging. Here we synthesize a series of silicon-RosIndolizine (SiRos) fluorophores that exhibit peak emission wavelengths from 1,300-1,700 nm and emission onsets of 1,800-2,200 nm. We characterize the fluorophores photophysically (both steady-state and time-resolved), electrochemically and computationally using time-dependent density functional theory. Using two of the fluorophores (SiRos1300 and SiRos1550), we formulate nanoemulsions and use them for general systemic circulatory SWIR fluorescence imaging of the cardiovascular system in mice. These studies resulted in high-resolution SWIR images with well-defined vasculature visible throughout the entire circulatory system. This SiRos scaffold establishes design principles for generating long-wavelength emitting SWIR and ESWIR fluorophores.
Subject(s)
Fluorescent Dyes , Infrared Rays , Optical Imaging , Silicon , Fluorescent Dyes/chemistry , Fluorescent Dyes/chemical synthesis , Silicon/chemistry , Animals , Mice , Indolizines/chemistry , Indolizines/chemical synthesis , Density Functional TheoryABSTRACT
The design of bright short-wave infrared fluorophores remains a grand challenge. Here we investigate the impact of deuteration on the properties in a series of heptamethine dyes, the absorption of which spans near-infrared and SWIR regions. We demonstrate that it is a generally applicable strategy that leads to enhanced quantum yields of fluorescence, longer-lived singlet excited states and suppressed rates of non-radiative deactivation processes.
ABSTRACT
Rational design of bright near and shortwave infrared (NIR: 700-1000 SWIR: 1000- 2000 nm) emitters remains an open question with applications spanning imaging and photonics. Combining experiment and theory, we derive an energy gap quantum yield master equation (EQME), describing the fundamental limits in SWIR quantum yields (Ï F ) for organic chromophores. Evaluating the photophysics of 21 polymethine NIR/SWIR chromophores to parameterize the EQME, we explain the precipitous decline of Ï F past 900 nm through decreasing radiative rates and increasing nonradiative losses via high frequency vibrations relating to the energy gap. Using the EQME we develop an energy gap independent Ï F NIR/SWIR chromophore comparison metric. We show electron donating character on polymethine heterocycles results in relative increases in radiative efficiency obscured by a simultaneous redshift. Finally, the EQME yields rational chromophore design insights shown by how deuteration (backed by our experimental results) or molecular aggregation increases SWIR Ï F .
ABSTRACT
Despite broad applications in imaging, energy conversion, and telecommunications, few nanoscale moieties emit light efficiently in the shortwave infrared (SWIR, 1000-2000 nm or 1.24-0.62 eV). We report quantum-confined mercury chalcogenide (HgX, where X = Se or Te) nanoplatelets (NPLs) can be induced to emit bright (QY > 30%) and tunable (900-1500+ nm) infrared emission from attached quantum dot (QD) "defect" states. We demonstrate near unity energy transfer from NPL to these QDs, which completely quench NPL emission and emit with a high QY through the SWIR. This QD defect emission is kinetically tunable, enabling controlled midgap emission from NPLs. Spectrally resolved photoluminescence demonstrates energy-dependent lifetimes, with radiative rates 10-20 times faster than those of their PbX analogues in the same spectral window. Coupled with their high quantum yield, midgap emission HgX dots on HgX NPLs provide a potential platform for novel optoelectronics in the SWIR.
ABSTRACT
We describe and implement an interferometric approach to decay-associated photoluminescence spectroscopy, which we term decay-associated Fourier spectroscopy (DAFS). In DAFS, the emitted photon stream from a substrate passes through a variable path length Mach-Zehnder interferometer prior to detection and timing. The interferometer encodes spectral information in the intensity measured at each detector enabling simultaneous spectral and temporal resolution. We detail several advantages of DAFS, including wavelength-range insensitivity, drift-noise cancellation, and optical mode retention. DAFS allows us to direct the photon stream into an optical fiber, enabling the implementation of superconducting nanowire single photon detectors for energy-resolved spectroscopy in the shortwave infrared spectral window (λ = 1-2 µm). We demonstrate the broad applicability of DAFS, in both the visible and shortwave infrared, using two Förster resonance energy transfer pairs: a pair operating with conventional visible wavelengths and a pair showing concurrent acquisition in the visible and the shortwave infrared regime.
