Decorating Metal Oxide Surfaces with Fluorescent Chlorosulfonated Corroles

Abstract

ExperimentalMaterials. 2 M AlMe 3 in toluene (Aldrich), GaCl 3 (Aldrich), HSO 3 Cl (Aldrich), 21 nm nanopowder TiO 2 (Aldrich), 30% H 2 O 2 (EMD) were obtained commercially and used as received. The starting material 5,10, corrole (H 3 tpfc) was prepared based on the literature method.1 The solvents pyridine and toluene were dried over a column. Acetone and dichloromethane used were both of reagent and spectroscopic grades depending on the applications.Chemical Preparation. All preparations were carried out under Ar(g) atmosphere unless otherwise noted. ,17-bischlorosulfonato-5,10,15-tris(pentafluorophenyl) corrole (H 3 tpfc(SO 2 Cl) 2 ; 1) was performed according to the literature procedure. 2 The metallocorroles described in this study were prepared in the following manner. Corrole Preparation. Preparation of 2 Preparation of 1-Al.To the 20-mL toluene solution of 0.32 g of 1 (0.32 mmol) in a round bottom flask was added 0.8 mL of 2 M AlMe 3 (1.6 mmol) in toluene solution at an icebath temperature. The solution was stirred for 10 min followed by the addition of 1 mL anhydrous pyridine. The solution was allowed to stir for another 10 min over ice. The reaction was quenched by an addition of ice chips. The dark green solution was then extracted with CH 2 Cl 2 and washed with water. The solvent was removed in vacuo and the dry deep green solid was redissolved in CH 2 Cl 2 followed by filtration. The filtrate was brought to dryness to afford the dark green solid (0. Preparation of 1-Ga.To a heavy-walled Schlenk flask were added 0.20 g of 1 (0.20 mmol) and 0.57 g GaCl 3 (3.3 mmol) under Ar(g). The flask was chilled in N 2 (l) and evacuated. 15 mL Degassed anhydrous pyridine (15mL) was added to the flask via vacuum transfer. The

Cellular uptake and cytotoxicity of a near-IR fluorescent corrole–TiO2 nanoconjugate

“…Preparation of Al(III)tpfc(SO 2 Cl) 2 ( 1-Al ) and the nanoconjugate 1-Al -TiO 2 was reported previously[32]. D-Luciferin potassium salt (Promega), Hoechst 34580 (Invitrogen™), Hoechst 33258 (Invitrogen™), Sytox Green (Invitrogen™), and FM ® 1–43FX (Invitrogen™) were used as received according to the provider’s instruction.…”

“…Characterization of 1-Al was performed by 1 H NMR, 19 F NMR, electronic absorption, and fluorescence spectroscopies, and was reported previously[32]. Surface characterization of 1-Al -TiO 2 is outlined as follows.…”

“…Previously we reported the syntheses, spectroscopic characterizations, and spectral confocal fluorescence imaging results for a family of corrole-TiO 2 nanoconjugates, namely 1 -TiO 2 , 1-Al -TiO 2 , and 1-Ga -TiO 2 [32]. The TiO 2 nanoparticle surfaces were covalently labeled with chlorosulfonated corroles through a sulfonic ester linkage (Scheme 1).…”

“…Because 1-Al -TiO 2 exhibits the brightest fluorescence, consistent with the emission properties of related molecular Al corroles[26,32,33], we chose this nanoconjugate as a model to study cellular uptake and cytotoxic effects.…”

Primary Ammonium Monocarboxylate Synthon in Designing Supramolecular Gels: A New Series of Chiral Low‐Molecular‐Weight Gelators Derived from Simple Organic Salts that are Capable of Generating and Stabilizing Gold Nanoparticles

“…Owing to fundamental work on the original syntheses of corroles from Gross and co‐workers, the field has grown enormously 1,2. Corroles have found applications in molecular tumor imaging and treatment,3 solar fuels chemistry,4 chemical catalysis,5 and nanomaterial development 6…”