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Photophysical and Cellular Studies of pH-Sensitive Boron-Functionalised Far-Red Fluorophores
Anita Marfavi ; Liam D. Adair ; Elizabeth J. New , et al. J. Organomet. Chem.,2024,123132. DOI: 10.1016/j.jorganchem.2024.123132
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Abstract: Two novel chromenylium-based probes were developed by functionalisation of the 5-position of the xanthene core with either a para-N-methyldiaminoacetic acid (MIDA) boronate ester (CRpMD) or closo?1,7-carborane (CRmCB). CRpMD revealed near-infrared emission at 655 nm, demonstrating a bathochromic shift compared to the analogous phenyl derivative (CRPh). Both boron-containing probes were found to be sensitive to changes in acidic pH, with CRpMD also displaying a dual fluorescence response at alkaline pH (pKa1 = 2.40 and pKa2 = 9.16). CRmCB showed a ca. 3-fold increase in fluorescence intensity at 638 nm from pH 7.01 to 2.00, with a pKa = 2.08. Moreover, CRpMD and CRmCB were successfully taken up by A549 lung cancer cells to assess their intracellular biodistributions, thereby showcasing the future potential of these probes for time-resolved pH measurements using confocal microscopy.
Keywords: Near-infrared ; Fluorescence microscopy ; Fluorescent probes ; BoronpH sensor
Purchased from AmBeed: 4408-64-4 ; 5809-23-4 ; 87199-17-5
CAS No. : | 5809-23-4 | MDL No. : | MFCD00134669 |
Formula : | C18H19NO4 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | FQNKTJPBXAZUGC-UHFFFAOYSA-N |
M.W : | 313.35 | Pubchem ID : | 79878 |
Synonyms : |
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Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H315-H319 | Packing Group: | N/A |
GHS Pictogram: |
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* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With sulfuric acid; at 90℃; for 8h; | Compound b (1.05 g, 3.35 mmol) was placed in a 75 ml pressurized bottle, 10 ml of concentrated sulfuric acid was added, and Compound 5a (500 mg, 3.35 mmol) was added portionwise to the reaction solution. 90 C reaction 8h. After cooling to room temperature, the reaction solution was poured into 300 ml of ice and neutralized with saturated sodium hydroxide solution until neutral. A solid precipitated out, was filtered, washed with water, the cake was dried and purified by column chromatography. Obtained red solid 1.30g, yield 91% |
91% | With sulfuric acid; for 24h;Sealed tube; Heating; | Compound 1 (1.05 g, 3.35 mmol) and 2 (0.50 g, 3.35 mmol) were dissolvedin concentrated H2SO4 in pressure tube and stirred at 90oC for 24 h. After the completion ofthe reaction, the reaction mixture was poured into ice and neutralized with NaOH aqueoussolution, then extracted with dichloromethane 3 times and dried over Na2SO4. Evaporation ofthe solvent resulted in a red solid. The crude material was purified by flash columnchromatography to yield the product as a red solid (1.30 g) in a 91% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
47.6% | With potassium carbonate; In N,N-dimethyl-formamide; at 100 - 110℃; for 4h;Large scale; | 2- (4-N, N-diethylamino-2-hydroxybenzoyl) benzoic acid (1.1 kg, 3.51 mol) synthesized in Preparation Example 1,Hexyl 4-methylbenzenesulfonate (1.1 kg, 4.22 mol), K2CO3 (0.9 kg, 7.02 mol) synthesized in Preparation Example 2-4 was stirred with 1.65 L of DMF.After raising the internal temperature to 100 ~ 110 and stirred for 4 hours, cooled and extracted with 3.5 L of ethyl acetate and 3.5 L of purified water.The separated organic layer was concentrated under reduced pressure after decolorizing for 1 hour using 5% charcoal at an internal temperature of 30-50 C.The concentrated residue was crystallized by the crystallization method of Example 3 to obtain the title compound (0.66 kg, 47.6%) in the form of crystalline particles. |
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