We report a surprising discovery that Prussian blue (PB) can be employed as a highly sensitive and background-free resonant Raman reporter. Conventional Raman reporters show multiple spectral bands in the fingerprint region, which are generally overlapped with those from dominant endogenous biomolecules, and are thus difficult to be separated. Herein, we found that PB only possesses a strong and sharp single-band in the cellular Raman-silent region, where no Raman signals from biological species were observed. Therefore, the Raman spectra from PB and endogenous biomolecules are completely resolved without resorting to complicated spectral unmixing. Moreover, PB holds a strong UV-vis absorption band between 500 and 900 nm, which is resonant with the incident detection lasers, providing extremely high sensitivity. Through assembly of PB onto plasmonic cores, a new surface-enhanced resonance Raman scattering (SERRS) probe was achieved with a high signal-to-background ratio (SBR). We demonstrated the performance of the PB-based SERRS tags for high-sensitivity immunoassay and cancer cell imaging.
In recent years, cancer phototherapy has been extensively studied as noninvasive cancer treatment. To present efficient recognition toward cancer cells, most photosensitizers (PSs) are required to couple with tumor-targeted ligands. Interestingly, the heptamethine cyanine IR780 displays an intrinsic tumor-targeted feature even without modification. However, the photothermal efficacy and photostability of IR780 are not sufficient enough for clinical use. Herein, we involve a twisted structure of tetraphenylethene (TPE) between two molecules of IR780 to improve the photothermal conversion efficiency (PCE). The obtained molecule T780T shows strong near-infrared (NIR) fluorescence and improved PCE (38.5%) in the dispersed state. Also, the photothermal stability and ROS generation capability of T780T at the NIR range (808 nm) are both promoted. In the aqueous phase, the T780T was formulated into uniform nanoaggregates (∼200 nm) with extremely low fluorescence and PTT response, which would reduce in vivo imaging background and side effect of PTT response in normal tissues. After intravenous injection into tumor-bearing mice, the T780T nanoaggregates display high tumor accumulation and thus remarkably inhibit the tumor growth. Moreover, the enhanced photostability of the T780T allows for twice irradiation after one injection and leads to more significant tumor inhibition. In summary, our study presents a tumor-targeted small-molecule PS for efficient cancer therapy and brings a new design of heptamethine cyanine PS for potential clinical applications.
In this research, we developed a multianalyte fluorescence sensing system through a carbon dots (CDs)-based fluorescent probe that can specifically recognize Fe(III) by fluorescence quenching. The CDs prepared using black tea by a hydrothermal method show outstanding properties like low cytotoxicity, high photostability, excellent biocompatibility, and high sensitivity. It was found that the fluorescence of CDs can be quenched by micromolar concentrations of Fe(III) in both aqueous solutions as well as living cells. It is well known that glucose can be oxidized by glucose oxidase (GOx) to release H 2 O 2 , which, in turn, can oxidize Fe(II) to Fe(III). Based on this consideration, a multianalyte sensing system was established. Therefore the quantitative analysis of Fe(III), H 2 O 2 , and glucose with detection limits of 0.25 mM, 0.82 mM, and 1.71 mM, respectively, was achieved by the simple and cost-effective multianalyte CDs sensing system constructed. The sensing system showed high photostability and negligible cytotoxicity toward HeLa cells, which enables it to be applied in the visualization of Fe(III) or H 2 O 2 in living cells. The system was further applied in the detection of Fe(III) or glucose in human serum, and satisfactory results were obtained.
Near-infrared
(NIR) fluorescent probes can deeply penetrate through tissues with
little damage. To facilitate image-guided theranostics, researchers
usually apply a desired amount of photosensitizers to achieve effective
photothermal responses. However, these probes could easily suffer
from low photostability and aggregated-caused quenching effect in
high concentrations. In this paper, the rational incorporation of
an aggregated-induced emission (AIE) unit into the structure of heptamethine
cyanine IR-780 is reported. Using tetraphenylethene (TPE) as an AIE
core, we synthesize three TPE-modified IR-780 probes (IR-780 AIEgens)
via different linkages. The IR-780 derivatives all show enhanced AIE
features, in which the probe with an ether linkage (IR780-O-TPE) is
superior in rapid cell uptake, high targeting capacity, and good photostability.
Moreover, IR780-O-TPE exhibits the strongest cytotoxicity to HeLa
cells (IC50 = 3.3 μM). The three IR-780 derivatives
displayed a photothermal response in a concentration-dependent manner,
in which IR-780 AIEgens are more cytotoxic than IR-780, with IC50 of 0.3 μM under 808 nm laser irradiation. In tumor-bearing
mice, the optimal probe IR780-O-TPE also showed a more effective photothermal
response than IR-780. By illustrating the relationship between aggregation
state with photophysical properties, cell imaging, and cytotoxicity,
this work is helpful in modulating NIR-based photosensitizers into
AIE features for efficient image-guided theranostics.
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