研究目的
To perform nucleophilic substitution of fluorine atoms in perfluorinated zinc(II) octaphenylporphyrazine with alkoxy groups and monosaccharide residues, and to obtain water-soluble glycoconjugated derivatives with enhanced fluorescence properties.
研究成果
Nucleophilic substitution successfully modified perfluorinated zinc octaphenylporphyrazine, introducing up to 12 butoxy groups or up to 8 monosaccharide residues. Substitution led to bathochromic shifts in absorption spectra and increased fluorescence quantum yields, particularly for glycosylated derivatives (from 0.19 to 0.29). The removal of protecting groups yielded a water-soluble glycoconjugate, demonstrating potential for biomedical applications due to improved solubility and fluorescence. Future studies should focus on isolating pure compounds, evaluating biological activity, and optimizing synthesis for higher yields.
研究不足
Steric hindrance limits the substitution degree to a maximum of eight monosaccharide residues in glycosylated derivatives, preventing higher functionalization. The glycosylated products were obtained as mixtures (n=6-8) and individual fractions could not be isolated, complicating precise characterization. The water-soluble glycoconjugate's aggregation behavior in aqueous solutions was not fully explored, and scalability or biological applicability were not addressed.
1：Experimental Design and Method Selection:
The study involved nucleophilic aromatic substitution reactions to modify the periphery of perfluorinated zinc octaphenylporphyrazine. Reactions were conducted with sodium butoxide in butanol for alkoxy substitution and with 1,2:3,4-di-O-isopropylidene-α-D-galactopyranose in toluene with sodium hydride for glycosylation. Protecting group removal was done using trifluoroacetic acid to achieve water solubility.
2：Sample Selection and Data Sources:
The starting material was synthesized zinc octa(pentafluorophenyl)porphyrazine [ZnPAF40]. Reagents included sodium butoxide, sodium hydride, and protected galactose.
3：0]. Reagents included sodium butoxide, sodium hydride, and protected galactose. List of Experimental Equipment and Materials:
3. List of Experimental Equipment and Materials: Equipment included MALDI-TOF mass spectrometer (Shimadzu Biotech Axima Confidence), NMR spectrometers (Bruker Avance, Bruker AC-300), UV-Vis spectrophotometer (Cary-60), spectrofluorometer (Shimadzu RF-6000). Materials included solvents (butanol, toluene, dichloromethane, chloroform, THF, water), reagents (sodium, sodium hydride, trifluoroacetic acid, citric acid, sodium bicarbonate), and chromatography materials (Al2O3, silica gel, Molselect G-25).
4：0). Materials included solvents (butanol, toluene, dichloromethane, chloroform, THF, water), reagents (sodium, sodium hydride, trifluoroacetic acid, citric acid, sodium bicarbonate), and chromatography materials (Al2O3, silica gel, Molselect G-25). Experimental Procedures and Operational Workflow:
4. Experimental Procedures and Operational Workflow: For alkoxy substitution, [ZnPAF40] was reacted with sodium butoxide in butanol under reflux, followed by chromatography. For glycosylation, [ZnPAF40] was reacted with protected galactose and sodium hydride in toluene under argon in the dark, followed by extraction and chromatography. Protecting groups were removed with trifluoroacetic acid, and the product was purified using column chromatography.
5：Data Analysis Methods:
Products were characterized using mass spectrometry (MALDI-TOF), NMR spectroscopy (1H, 13C, 19F), electronic absorption spectroscopy, and fluorescence spectroscopy. Quantum yields were determined relative to a reference compound.
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