High sensitivity and specificity are two desirable features in biomedical imaging. Raman imaging has surfaced as a promising optical modality that offers both. Here, we report the design and synthesis of a group of near infrared absorbing 2-thienyl-substituted chalcogenopyrylium dyes tailored to have high affinity for gold. When adsorbed onto gold nanoparticles, these dyes produce biocompatible SERRS-nanoprobes with attomolar limits of detection amenable to ultrasensitive in vivo multiplexed tumor and disease marker detection.
This is the first report of the use of a hand-held 1064 nm Raman spectrometer combined with red-shifted surface-enhanced Raman scattering (SERS) nanotags to provide an unprecedented performance in the short-wave infrared (SWIR) region. A library consisting of 17 chalcogenopyrylium nanotags produce extraordinary SERS responses with femtomolar detection limits being obtained using the portable instrument. This is well beyond previous SERS detection limits at this far red-shifted wavelength and opens up new options for SERS sensors in the SWIR region of the electromagnetic spectrum (between 950 and 1700 nm).
Hollow Gold Nanospheres (HGNs) exhibit a unique combination of properties which provide great scope for their use in many biomedical applications. However, they are highly unstable to changes in their surrounding environment and have a tendency to aggregate, particularly when exposed to high salt concentrations or changes in pH which is not ideal for applications such as cell imaging and drug delivery where stable solutions are required for efficient cellular uptake. Therefore there is a significant need to find a suitable stabilising agent for HGNs, however potential stabilising agents for these nanostructures have not previously been compared. Within this work we present an improved method for stabilising HGNs which simultaneously shifts the SPR from around 700 nm to 800 nm or greater. Herein, we compare three different materials which are commonly used as stabilising agents; polymers, sugars and silica in order to determine the optimum stabilising agent for HGNs. Analysis was performed using extinction spectroscopy and dynamic light scattering, supported with SEM imaging. Results showed PEG to be the most suitable stabilising agent for HGNs displaying both an increased stability to changes in salt concentration and pH as well as increased long term stability in solution. Furthermore, we demonstrate that in addition to increased stability, SERS detection can be achieved at both 1064 nm and 785 nm excitation. This combination of improved stability with a SPR in the NIR region along with SERS detection demonstrates the great potential for these nanostructures to be used in applications such as biological SERS imaging and drug delivery.
Chalcogenopyrylium monomethine dyes were prepared via condensation of a 4-methylchalcogenopyrylium compound with a chalcogenopyran-4-one bearing a 4-(diethoxyphosphoryl)phenyl substituent (or the phosphonic acid derivative). The dyes have absorbance maxima of 603-697 nm in the window where the solar spectrum is most intense. The dyes formed H-aggregates on TiO2, increasing the light-harvesting efficiency of the dyes. Shortcircuit photocurrent action spectra were acquired to evaluate the influence of dye structure on the photoelectrochemical performance.
Chalcogenopyrylium
monomethine (CGPM) dyes represent a class of
environmentally activated singlet oxygen generators with applications
in photodynamic therapy (PDT) and photoassisted chemotherapy (PACT).
Upon binding to genomic material, the dyes are presumed to rigidify,
allowing for intersystem crossing to outcompete excited state deactivation
by internal conversion. This results in large triplet yields and hence
large singlet oxygen yields. To understand the nature of the internal
conversion process that controls the activity of the dyes, femtosecond
transient absorption experiments were performed on a series of S-,
Se-, and Te-substituted CGPM dyes. For S- and Se-substituted species
in methanol, rapid internal conversion from the singlet excited state,
S1, occurs in ∼5 ps, deactivating the optically
active excited state. The internal conversion produces a distorted
ground-state species that returns to its equilibrium structure in
∼20 ps. For Te-substituted species, the internal conversion
competes with rapid intersystem crossing to the lowest triplet state,
T1, which occurs with a ∼ 100 ps time constant in
methanol. In more viscous methanol/glycerol mixtures, the internal
conversion to the ground state slows by 2 orders of magnitude, occurring
in 500–600 ps. For Se- and Te-substituted species in viscous
environments, the slower internal conversion rate allows a larger
triplet yield. Using femtosecond stimulated Raman spectroscopy (FSRS)
and time-dependent density functional theory (TD-DFT), the internal
conversion is determined to occur by twisting of the pyrylium rings
about the monomethine bridge. Evolution from the distorted ground
state occurs by twisting back to the S0 equilibrium structure.
The environmentally dependent photoactivity of CGPM dyes is discussed
in the context of PDT and PACT applications.
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