Al(III) and Ga(III) Bisphenolate Azadipyrromethene-Based “N2O2” Complexes as Efficient NIR-Fluorophores (original) (raw)
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Water-Soluble Aza-BODIPYs: Biocompatible Organic Dyes for High Contrast In Vivo NIR-II Imaging
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Materials and Methods Reactions were carried out in analytical reagent grade solvents from Carlo Erba under normal atmosphere. Non-stabilized dry solvents were purchased from Carlo Erba and dried using a MB-SPS-800 (MBraun) or PureSolv-MD-5 (Inert®). All other reagents were purchased from Sigma Aldrich™ or ACROS Organics™ and used as received without further purification. Reactions were monitored by thin-layer chromatography and RP-HPLC-MS. Analytical thinlayer chromatography was performed with Merck 60 F254 silica gel (precoated sheets, 0.2 mm thick). Column chromatography was carried out using silica gel (Sigma Aldrich; 40-63 µm 230-400 mesh 60Å). (1 H, 13 C, 11 B, 19 F) were recorded at 300K on Bruker 500 Avance III. Chemical shifts are given relative to TMS (1 H, 13 C), BF 3 *Et 2 O (11 B), CFCl 3 (19 F) and were referenced to the residual solvent signal. High-resolution mass spectra were recorded on a Thermo LTQ Orbitrap XL ESI-MS spectrometer. NMR and Mass-analyses were performed at the "Plateforme d'Analyse
N2O2" Metal-azaDIPY complexes: a new class of NIR-fluorophores
Aza-BODIPYs are an increasingly studied class of fluorophores. They can be seen as an "aza-DIPY" ligand rigidified by a metalloid, a boron atom. Based on this idea, a series of complexes of group 13 metals (aluminum and gallium) have been synthesized and characterized. Impact of the metal and of the nature of the substituents of aza-DIPY core were investigated. The photophysical and electrochemical properties were determined and an X-ray structure of an azaGaDIPY was obtained. These data reveal that azaGaDIPY and azaAlDIPY exhibit significant red-shifted fluorescence compared to their analogue aza-BODIPY. Their emission can go up to 800 nm for the maximum emission length and up to NIR-II for the emission tail. This, associated with their electrochemical stability (no metal release whether oxidized or reduced) make them a promising class of fluorophores for optical medical imaging. Moreover, X-ray structure and molecular modeling studies have shown that this red shift seems...
The Mechanisms and Biomedical Applications of an NIR BODIPY-Based Switchable Fluorescent Probe
International journal of molecular sciences, 2017
Highly environment-sensitive fluorophores have been desired for many biomedical applications. Because of the noninvasive operation, high sensitivity, and high specificity to the microenvironment change, they can be used as excellent probes for fluorescence sensing/imaging, cell tracking/imaging, molecular imaging for cancer, and so on (i.e., polarity, viscosity, temperature, or pH measurement). In this work, investigations of the switching mechanism of a recently reported near-infrared environment-sensitive fluorophore, ADP(CA)₂, were conducted. Besides, multiple potential biomedical applications of this switchable fluorescent probe have been demonstrated, including wash-free live-cell fluorescence imaging, in vivo tissue fluorescence imaging, temperature sensing, and ultrasound-switchable fluorescence (USF) imaging. The fluorescence of the ADP(CA)₂ is extremely sensitive to the microenvironment, especially polarity and viscosity. Our investigations showed that the fluorescence of A...
Journal of Porphyrins and Phthalocyanines, 2019
Since their discovery in 1968, the BODIPYs dyes (4,4-difluoro-4-bora-3a, 4a diaza-s-indacene) have found an exponentially increasing number of applications in a large variety of scientific fields. In particular, studies reporting bioapplications of BODIPYs have increased dramatically. However, most of the time, only in vitro investigations have been reported. The in vivo potential of BODIPYs and aza-BODIPYs is more recent, but considering the number of in vivo studies with BODIPY and aza-BODIPY which have been reported in the last five years, we can now affirm that this family of fluorophores can be considered important as cyanine dyes for future in vivo and even clinical applications. This review aims to present representative examples of recent in vivo applications of BODIPYs or aza-BODIPYs, and to highlight the potential of these dyes for optical molecular imaging.
Design of Promising aza-BODIPYs for Bioimaging and Sensing
Designs
The obtainment of new luminophores for molecular sensorics of biosystems is becoming one of the urgent tasks in the field of chemical synthesis. The solution to each practical problem imposes its own limitations in the design of new structures with practically useful properties. The relationship between the structure and spectral properties is still to be unveiled. Three aza-BODIPY complexes with substituents of different natures were studied using time-resolved and steady-state fluorescence and absorption spectroscopy. The solvatochromic properties of aza-BODIPYs were studied with the use of a combined polyparametric approach and analysis by chemoinformatics methods for the first time. It was found that red shift of aza-BODIPY dyes was due to the increase of their structural lability. Predictive and experimental methods showed that the investigated aza-BODIPYs exhibited a positive solvatochromic effect, in contrast to classic BODIPYs (bearing C in the meso-position of the dipyrrome...
Advanced Materials, 2009
Two-photon absorption (TPA) is a resonant third-order nonlinear optical (NLO) process in which an electron is promoted from its ground state to an excited state by simultaneous absorption of two photons of half-energy in an intense focused light beam such as that generated by a laser source. This phenomenon, theoretically predicted in 1929 by Göppert-Mayer, was experimentally evidenced in 1961 in a TPA-induced fluorescence of Eu 2þ -doped CaF 2 crystals under ruby-laser irradiation. Since then, the intrinsic advantages of TPA excitation, that is, long wavelength and confocal 3D-resolved absorption, led to numerous applications in the fields of material sciences and biology following the availability of tunable laser sources. In particular, the development of femtosecond (fs)-Ti-sapphire lasers triggered numerous studies in the 700-1000 nm spectral range. For instance, TPA was successfully involved in the fabrication of microstructures or high-density optical memories with a 3D sub-micrometer resolution, in signal processing, or for the design of optical limiting devices devoted to the protection of sensors against laser damages. In life sciences, the long-wavelength TPA excitation is located in the biologically transparent spectral range (800-1000 nm), and is therefore able to penetrate more deeply into biological tissues. Combined with the above mentioned spatial resolution, TPA found exciting applications for bioimaging using nonlinear microscopy, and also for drug delivery or dynamic phototherapy. All these applications encouraged the scientific community to design a large variety of chromophores with optimized two-photon cross-sections (s 2 ) in this 700-1000 nm spectral range, such as organic dyes, organometallic or coordination complexes, polymers, dendrimers, or nanonoparticles and quantum-dots, compiled in a recent exhaustive review. However, the near-infrared (NIR) spectral range has been less studied, and in particular the telecommunications-wavelengths spectral range (1.3-1.55 mm), where applications in signal processing (optical power stabilization, pulse suppression, optical limiting) are very attractive. Since 2005, inspired by the Marder-Van Stryland and Osuka-Kim groups, there is a great interest in the design of chromophores exhibiting strong TPA properties in the NIR. Maximal TPA cross-section of ca. 1500 GM at 1.44 mm and 1600 GM at 1.3 mm have been reported for dipolar and quadrupolar squarine-type chromophores, respectively, whereas nickel (bisdithiolene) complexes and singlet diradical systems exhibit significant s 2 over the entire telecommunication range. On the other hand, numerous fused-, extended-, or organizedporphyrin complexes have been reported with very large TPA crosssections ranging from 10 3 to 10 4 GM. Finally, we reported the TPA properties of cyanine-type chromophores (s 2 of 750 GM at 1450 nm) that present enough solubility to carry out additional nonlinear transmittance experiments at telecommunications wavelengths. Herein, we report the synthesis and X-ray structures of aza boron-dipyrromethane (Bodipy) NIR dyes functionalized in the a position by donor-p-conjugated systems, and their TPA and nonlinear transmittance properties in the 1.2-1.6 mm spectral range.
Chemistry (Weinheim an der Bergstrasse, Germany), 2016
A new generation of MOnomolecular Imaging Probes (MOMIP) based on a distyryl-BODIPY coupled with three DOTA macrocycles has been prepared. The MOMIP presents good fluorescence properties and is very stable in serum. The bimodal probe was conjugated to trastuzumab, and optical in-vivo study showed high accumulation of the imaging agent at the tumor site. 111In radiometallation of the bioconjugate was performed in high radiochemical yield, highlighting the potential of this new BODIPY-chelators derivative as a bimodal imaging probe.