Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Access to 2,6-Dipropargylated BODIPYs as "Clickable" Congeners of Pyrromethene-567 Dye: Photostability and Synthetic Versatility.

ABSTRACT: Hitherto unreported 2,6-dipropargyl-1,3,5,7-tetramethyl BODIPYs can be efficiently prepared by a Nicholas reaction/decomplexation protocol from 1,3,5,7-tetramethyl BODIPYs. The title compounds, which improve the BODIPY photostability by retaining their inherent photophysical and photochemical properties, can be engaged in efficient copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) "click-type" reactions with azido derivatives to provide all-BODIPY-triads or conjugated BODIPYs.

SUBMITTER: Uriel C

PROVIDER: S-EPMC8419863 | biostudies-literature | 2021 Sep

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Access to 2,6-Dipropargylated BODIPYs as "Clickable" Congeners of Pyrromethene-567 Dye: Photostability and Synthetic Versatility.

Uriel Clara C Gómez Ana M AM García Martínez de la Hidalga Enrique E Bañuelos Jorge J Garcia-Moreno Inmaculada I López J Cristobal JC

Organic letters 20210817 17

Hitherto unreported 2,6-dipropargyl-1,3,5,7-tetramethyl BODIPYs can be efficiently prepared by a Nicholas reaction/decomplexation protocol from 1,3,5,7-tetramethyl BODIPYs. The title compounds, which improve the BODIPY photostability by retaining their inherent photophysical and photochemical properties, can be engaged in efficient copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) "click-type" reactions with azido derivatives to provide all-BODIPY-triads or conjugated BODIPYs. ...[more]

PMID: 34403255

Similar Datasets

Carbazole- and Fluorene-Fused Aza-BODIPYs: NIR Fluorophores with High Brightness and Photostability.

Project description:Three new aza-BODIPY dyes incorporating fused fluorene or carbazole moieties have been prepared. The dyes show significant enhancement of photophysical properties compared to the parent 1,3,5,7-tetraphenyl aza-BODIPY (TPAB): a bathochromic shift of the absorption maximum (up to 2700 cm-1 ) and emission maximum (up to 2270 cm-1 ); an almost threefold increase in molar absorption coefficients (to ca. 230 000 M-1 cm-1 ) and a significant increase in the fluorescence quantum yield to 49-66 %. Owing to the combination of these properties, the new aza-BODIPY dyes belong to the brightest NIR dyes reported. The dyes also show excellent photostability. Due to their outstanding properties, the new dyes represent a promising platform for further exploration in biomedical research. A pH indicator containing only one fused carbazole unit was also prepared and shows absorption and emission spectra that are bathochromically shifted by about 110 and 100 nm, respectively, compared to the indicator dye based on the TPAB chromophore.

| S-EPMC8362076 | biostudies-literature

Synthesis, spectroscopic, and in vitro investigations of 2,6-diiodo-BODIPYs with PDT and bioimaging applications.

Project description:A series of five mono-styryl and their corresponding symmetric di-styryl-2,6-diiodo-BODIPYs containing indolyl, pyrrolyl, thienyl or tri(ethylene glycol)phenyl groups were synthesized using Knoevenagel condensations. The yields for the condensation reactions were improved up to 40% using microwave irradiation (90°C for 1h at 400W) due to lower decomposition of BODIPYs upon prolonged heating. The spectroscopic, structural (including the X-ray of a di-styryl-2,6-diiodo-BODIPY) and in vitro properties of the BODIPYs were investigated. The extension of π-conjugation through the 3,5-dimethyls of the known phototoxic 2,6-diiodo-BODIPY 1 produced bathochromic shifts in the absorption and emission spectra, in the order of 63-125nm for the mono-styryl- and 128-220nm for the di-styryl-BODIPYs in DMSO. The largest red-shifts were observed for the indolyl-containing BODIPYs while the largest fluorescence quantum yields were observed for the tri(ethyleneglycol)phenylstyryl-BODIPYs. Among this series, only the mono-styryl-BODIPYs were phototoxic (IC50=2-15μM at 1.5J/cm(2)), and were observed to localize preferentially in the cell ER and mitochondria. On the other hand, the di-styryl-BODIPYs were found to have low or no phototoxicity (IC50>100μM at 1.5J/cm(2)). Among this series of compounds BODIPY 2a shows the most promise for application as photosensitizer in PDT.

| S-EPMC4369175 | biostudies-literature

Synthetic Exploration of Bis(phenolate) Aza-BODIPYs and Heavier Group 13 Chelates.

Project description:A series of boron, aluminum, gallium, and indium chelates containing the underexplored bis(phenolate) aza-dipyrromethene (aza-DIPY) core were prepared. These compounds were found to possess near-infrared absorption and emission profiles in the 710 to 770 nm domain and exhibit quantum yield values up to 14%. X-ray diffraction analysis revealed that heavier group 13 bis(phenolate) aza-DIPY chelates possessed octahedral geometries with either THF or pyridine groups occupying the axial positions as opposed to the tetrahedral geometry of the boron chelate.

| S-EPMC9737893 | biostudies-literature

On the photostability and luminescence of dye-sensitized upconverting nanoparticles using modified IR820 dyes.

Project description:Dye sensitization is a promising route to enhance luminescence from lanthanide-doped upconverting nanoparticles (LnUCNPs) by improving the photon harvesting capability of LnUCNPs through the use of dye molecules, characterized by higher absorption coefficients. The literature does not fully address the poor photostability of NIR dyes, hindering solution-based applications. The improvements achieved by dye-sensitized LnUCNPs are usually obtained by comparison with non-dye sensitized LnUCNPs. This comparison results in exciting the LnUCNPs at different wavelengths with respect to the dye-sensitized LnUCNPs or at the same wavelengths, where, however, the non-dye sensitized LnUCNPs do not absorb. Both these comparisons are hardly conclusive for a quantification of the improvements achieved by dye-sensitization. Both shortcomings were addressed by studying the photodegradation via thorough spectroscopic evaluations of a 4-nitrothiophenol-modified and unmodified IR820-LnUCNP system. The modified IR820 dye system exhibits a 200% enhancement in the emission of NaGdF4:Er3+,Yb3+/NaGdF4:Yb3+ nanoparticles relative to the unmodified IR820-sensitized LnUCNPs and emits for over twice the duration, demonstrating a substantial improvement over previous dye-LnUCNP systems. Upconversion dynamics between the dyes and Er3+ establish the importance of back-transfer dynamics in modulating the dye-LnUCNP luminescence. Quantum yield measurements further illustrate the mechanism of sensitization and increased efficiency of this new nanosystem.

| S-EPMC9419735 | biostudies-literature

Phase-transfer-catalyst enabled enantioselective C-N coupling to access chiral boron-stereogenic BODIPYs.

Project description:Tetracoordinate boron-based fluorescent materials have shown extensively applications in chemistry, biology and materials science owing to their unique optoelectronic properties. However, constructing chiral boron-stereogenic fluorophores through practical and universal strategies remains rare and challenging. Herein, as a proof of concept, we report an enantioselective postfunctionalization of boron dipyrromethene dyes (BODIPYs), to acess boron-stereogenic BODIPYs in moderate to good yields with commendable enantioselectivity. Chiral BODIPYs have attracted increasing attention owing to not only their distinctively photophysical properties and applications in circularly polarized luminescence (CPL) materials, but also diversely structural modification. In this·work, we present a phase-transfer-catalyst enabled enantioselective C-N coupling reaction of BODIPYs with diverse nucleophiles. This method serves as a practical SNAr (nucleophilic aromatic substitution reaction) route to achieve a series of boron-stereogenic amido/amino BODIPYs as well as demonstrates their promising CD and·CPL·activities, excellent biocompatibility, and high specificities, showing potential applications as chiral fluorescent imaging agents.

| S-EPMC11923064 | biostudies-literature

4,4'-Dicyano- versus 4,4'-Difluoro-BODIPYs in Chemoselective Postfunctionalization Reactions: Synthetic Advantages and Applications.

Project description:The presence of F or CN substituents at boron in BODIPYs causes a dramatic effect on their reactivity, which allows their chemoselective postfunctionalization. Thus, whereas 1,3,5,7-tetramethyl B(CN)2-BODIPYs displayed enhanced reactivity in Knoevenagel condensations with aldehydes, the corresponding BF2-BODIPYs can experience selective aromatic electrophilic substitution (SEAr) reactions in the presence of the former. These (selective) reactions have been employed in the preparation of BODIPY dimers and tetramers, with balanced fluorescence and singlet oxygen formation, and all-BODIPY trimers and heptamers, with potential application as light-harvesting systems.

| S-EPMC10127263 | biostudies-literature

8(<i>meso</i>)-Pyridyl-BODIPYs: Effects of 2,6-Substitution with Electron-Withdrawing Nitro, Chloro, and Methoxycarbonyl Groups.

Project description:The introduction of electron-withdrawing groups on 8(meso)-pyridyl-BODIPYs tends to increase the fluorescence quantum yields of this type of compound due to the decrease in electronic charge density on the BODIPY core. A new series of 8(meso)-pyridyl-BODIPYs bearing a 2-, 3-, or 4-pyridyl group was synthesized and functionalized with nitro and chlorine groups at the 2,6-positions. The 2,6-methoxycarbonyl-8-pyridyl-BODIPYs analogs were also synthesized by condensation of 2,4-dimethyl-3-methoxycarbonyl-pyrrole with 2-, 3-, or 4-formylpyridine followed by oxidation and boron complexation. The structures and spectroscopic properties of the new series of 8(meso)-pyridyl-BODIPYs were investigated both experimentally and computationally. The BODIPYs bearing 2,6-methoxycarbonyl groups showed enhanced relative fluorescence quantum yields in polar organic solvents due to their electron-withdrawing effect. However, the introduction of a single nitro group significantly quenched the fluorescence of the BODIPYs and caused hypsochromic shifts in the absorption and emission bands. The introduction of a chloro substituent partially restored the fluorescence of the mono-nitro-BODIPYs and induced significant bathochromic shifts.

| S-EPMC10303842 | biostudies-literature

Synthesis and Photophysics Characterization of Boronic Styril and Distyryl BODIPYs for Water-Based Dye-Sensitized Solar Cells.

Project description:In this study, two boronic acid BODIPYs are obtained through a microwave-assisted Knoevenagel reaction. The aim is to use them for the first time as dyes in a photosensitized solar cell (DSSC) to mimic chlorophyll photosynthesis, harvesting solar light and converting it into electricity. The microwave-assisted Knoevenagel reaction is a straightforward approach to extending the molecular conjugation of the dye and is applied for the first time to synthesize BODIPY's boronic acid derivatives. These derivatives have proved to be very useful for covalent deposition on titania. This work studies the photo-physical and electrochemical properties. Moreover, the photovoltaic performances of these two new dyes as sensitizers for DSSC are discussed. Experimental data show that both dyes exhibit photosensitizing activities in acetonitrile and water. In particular, in all the experiments, distyryl BODIPY was more efficient than styryl BODIPY. In this study, demonstrating the use of a natural component as a water-based electrolyte for boronic BODIPY sensitizers, we open new possibilities for the development of water-based solar cells.

| S-EPMC9397057 | biostudies-literature

Terminal Uridylyl Transferase Mediated Site-Directed Access to Clickable Chromatin Employing CRISPR-dCas9.

Project description:Locus-specific interrogation of target genes employing functional probes such as proteins and small molecules is paramount in decoding the molecular basis of gene function and designing tools to modulate its downstream effects. In this context, CRISPR-based gene editing and targeting technologies have proved tremendously useful, as they can be programmed to target any gene of interest by simply changing the sequence of the single guide RNA (sgRNA). Although these technologies are widely utilized in recruiting genetically encoded functional proteins, display of small molecules using CRISPR system is not well developed due to the lack of adequate techniques. Here, we have devised an innovative technology called sgRNA-Click (sgR-CLK) that harnesses the power of bioorthogonal click chemistry for remodeling guide RNA to display synthetic molecules on target genes. sgR-CLK employs a novel posttranscriptional chemoenzymatic labeling platform wherein a terminal uridylyl transferase (TUTase) was repurposed to generate clickable sgRNA of choice by site-specific tailoring of multiple azide-modified nucleotide analogues at the 3' end. The presence of a minimally invasive azide handle assured that the sgRNAs are indeed functional. Notably, an azide-tailed sgRNA targeting the telomeric repeat served as a Trojan horse on the CRISPR-dCas9 system to guide synthetic tags (biotin) site-specifically on chromatin employing copper-catalyzed or strain-promoted click reactions. Taken together, sgR-CLK presents a significant advancement on the utility of bioorthogonal chemistry, TUTase, and the CRISPR toolbox, which could offer a simplified solution for site-directed display of small molecule probes and diagnostic tools on target genes.

| S-EPMC7611130 | biostudies-literature

Structure Based Modulation of Electron Dynamics in meso-(4-Pyridyl)-BODIPYs: A Computational and Synthetic Approach.

Project description:The effects of structural modification on the electronic structure and electron dynamics of cationic meso-(4-pyridyl)-BODIPYs were investigated. A library of 2,6-difunctionalized meso-(4-pyridyl)-BODIPYs bearing various electron-withdrawing substituents was designed, and DFT calculations were used to model the redox properties, while TDDFT was used to determine the effects of functionalization on the excited states. Structural modification was able to restructure the low-lying molecular orbitals to effectively inhibit d-PeT. A new meso-(4-pyridyl)-BODIPY bearing 2,6-dichloro groups was synthesized and shown to exhibit enhanced charge recombination fluorescence. The fluorescence enhancement was determined to be the result of functionalization modulating the kinetics of the excited state dynamics.

| S-EPMC6693353 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data