A New Lysosome-Targetable Turn-On Fluorogenic Probe for Carbon Monoxide Imaging in Living Cells

A lysosome-targetable fluorogenic probe, LysoFP-NO₂, was designed and synthesized based on a naphthalimide fluorophore that can detect selectively carbon monoxide (CO) in HEPES buffer (pH 7.4, 37 °C) through the transformation of the nitro group into an amino-functionalized system in the presence of CO. LysoFP-NO₂ triggered a “turn-on” fluorescence response to CO with a simultaneous increase of fluorescence intensity by more than 75 times. The response is selective over a variety of relevant reactive nitrogen, oxygen, and sulfur species. Also, the probe is an efficient candidate for monitoring changes in intracellular CO in living cells (MCF7), and the fluorescence signals specifically localize in the lysosome compartment

Synthesis, Structure, Spectroscopic Characterization, and Protein Binding Affinity of New Water-Soluble Hetero- and Homometallic Tetranuclear [Cu^II₂Zn^II₂] and [Cu^II₄] Clusters

Two new water-soluble hetero- and homometallic tetranuclear clusters, Na₄[Cu₂Zn₂(ccdp)₂(μ-OH)₂]·CH₃OH·6H₂O (<b>1</b>) and K₃[Cu₄(ccdp)₂(μ-OH)­(μ-OH₂)]·14H₂O (<b>2</b>), have been synthesized in methanol–water at room temperature by exploiting the flexibility, chelating ability, and bridging potential of a carboxylate-rich dinucleating ligand, <i>N</i>,<i>N</i>′-bis­(2-carboxybenzomethyl)-<i>N</i>,<i>N</i>′-bis­(carboxymethyl)-1,3 diaminopropan-2-ol (H₅ccdp). Complex <b>1</b> is obtained through the self-assembly of two monoanionic [CuZn­(ccdp)]⁻ fragments, which are, in turn, exclusively bridged by two μ-OH^– groups. Similarly, complex <b>2</b> is formed through the self-assembly of two monoanionic [Cu₂(ccdp)]⁻ species exclusively bridged by one μ-OH^– and one μ-OH₂ groups. Complexes <b>1</b> and <b>2</b> are fully characterized in the solid state as well as in solution using various analytical techniques including a single-crystal X-ray diffraction study. The X-ray crystal structure of <b>1</b> reveals that two Cu^II centers are in a distorted square-pyramidal geometry, whereas two Zn^II centers are in a distorted trigonal-bipyramidal geometry. The solid-state structure of <b>2</b> contains two dinuclear [Cu₂(ccdp)]⁻ units having one Cu^II center in a distorted square-pyramidal geometry and another Cu^II center in a distorted trigonal-bipyramidal geometry within each dinuclear unit. In the powder state, the high-field EPR spectrum of complex <b>1</b> indicates that two Cu^II ions are not spin-coupled, whereas that of complex <b>2</b> exhibits at least one noninteracting Cu^II center coordinated to a nitrogen atom of the ligand. Both complexes are investigated for their binding affinity with the protein bovine serum albumin (BSA) in an aqueous medium at pH ∼7.2 using fluorescence spectroscopy. Synchronous fluorescence spectra clearly reveal that complexes <b>1</b> and <b>2</b> bind to the active sites in the protein, indicating that the effect is more pronounced toward tyrosine than tryptophan. Density functional theory calculations have been carried to find the Fukui functions at the metal sites in complexes <b>1</b> and <b>2</b> to predict the possible metal centers involved in the binding process with BSA protein

Synthesis, Structure, Spectroscopic Characterization, and Protein Binding Affinity of New Water-Soluble Hetero- and Homometallic Tetranuclear [Cu^II₂Zn^II₂] and [Cu^II₄] Clusters

Two new water-soluble hetero- and homometallic tetranuclear clusters, Na₄[Cu₂Zn₂(ccdp)₂(μ-OH)₂]·CH₃OH·6H₂O (<b>1</b>) and K₃[Cu₄(ccdp)₂(μ-OH)­(μ-OH₂)]·14H₂O (<b>2</b>), have been synthesized in methanol–water at room temperature by exploiting the flexibility, chelating ability, and bridging potential of a carboxylate-rich dinucleating ligand, <i>N</i>,<i>N</i>′-bis­(2-carboxybenzomethyl)-<i>N</i>,<i>N</i>′-bis­(carboxymethyl)-1,3 diaminopropan-2-ol (H₅ccdp). Complex <b>1</b> is obtained through the self-assembly of two monoanionic [CuZn­(ccdp)]⁻ fragments, which are, in turn, exclusively bridged by two μ-OH^– groups. Similarly, complex <b>2</b> is formed through the self-assembly of two monoanionic [Cu₂(ccdp)]⁻ species exclusively bridged by one μ-OH^– and one μ-OH₂ groups. Complexes <b>1</b> and <b>2</b> are fully characterized in the solid state as well as in solution using various analytical techniques including a single-crystal X-ray diffraction study. The X-ray crystal structure of <b>1</b> reveals that two Cu^II centers are in a distorted square-pyramidal geometry, whereas two Zn^II centers are in a distorted trigonal-bipyramidal geometry. The solid-state structure of <b>2</b> contains two dinuclear [Cu₂(ccdp)]⁻ units having one Cu^II center in a distorted square-pyramidal geometry and another Cu^II center in a distorted trigonal-bipyramidal geometry within each dinuclear unit. In the powder state, the high-field EPR spectrum of complex <b>1</b> indicates that two Cu^II ions are not spin-coupled, whereas that of complex <b>2</b> exhibits at least one noninteracting Cu^II center coordinated to a nitrogen atom of the ligand. Both complexes are investigated for their binding affinity with the protein bovine serum albumin (BSA) in an aqueous medium at pH ∼7.2 using fluorescence spectroscopy. Synchronous fluorescence spectra clearly reveal that complexes <b>1</b> and <b>2</b> bind to the active sites in the protein, indicating that the effect is more pronounced toward tyrosine than tryptophan. Density functional theory calculations have been carried to find the Fukui functions at the metal sites in complexes <b>1</b> and <b>2</b> to predict the possible metal centers involved in the binding process with BSA protein

Synthesis, Structure, Spectroscopic Characterization, and Protein Binding Affinity of New Water-Soluble Hetero- and Homometallic Tetranuclear [Cu^II₂Zn^II₂] and [Cu^II₄] Clusters

Two new water-soluble hetero- and homometallic tetranuclear clusters, Na₄[Cu₂Zn₂(ccdp)₂(μ-OH)₂]·CH₃OH·6H₂O (<b>1</b>) and K₃[Cu₄(ccdp)₂(μ-OH)­(μ-OH₂)]·14H₂O (<b>2</b>), have been synthesized in methanol–water at room temperature by exploiting the flexibility, chelating ability, and bridging potential of a carboxylate-rich dinucleating ligand, <i>N</i>,<i>N</i>′-bis­(2-carboxybenzomethyl)-<i>N</i>,<i>N</i>′-bis­(carboxymethyl)-1,3 diaminopropan-2-ol (H₅ccdp). Complex <b>1</b> is obtained through the self-assembly of two monoanionic [CuZn­(ccdp)]⁻ fragments, which are, in turn, exclusively bridged by two μ-OH^– groups. Similarly, complex <b>2</b> is formed through the self-assembly of two monoanionic [Cu₂(ccdp)]⁻ species exclusively bridged by one μ-OH^– and one μ-OH₂ groups. Complexes <b>1</b> and <b>2</b> are fully characterized in the solid state as well as in solution using various analytical techniques including a single-crystal X-ray diffraction study. The X-ray crystal structure of <b>1</b> reveals that two Cu^II centers are in a distorted square-pyramidal geometry, whereas two Zn^II centers are in a distorted trigonal-bipyramidal geometry. The solid-state structure of <b>2</b> contains two dinuclear [Cu₂(ccdp)]⁻ units having one Cu^II center in a distorted square-pyramidal geometry and another Cu^II center in a distorted trigonal-bipyramidal geometry within each dinuclear unit. In the powder state, the high-field EPR spectrum of complex <b>1</b> indicates that two Cu^II ions are not spin-coupled, whereas that of complex <b>2</b> exhibits at least one noninteracting Cu^II center coordinated to a nitrogen atom of the ligand. Both complexes are investigated for their binding affinity with the protein bovine serum albumin (BSA) in an aqueous medium at pH ∼7.2 using fluorescence spectroscopy. Synchronous fluorescence spectra clearly reveal that complexes <b>1</b> and <b>2</b> bind to the active sites in the protein, indicating that the effect is more pronounced toward tyrosine than tryptophan. Density functional theory calculations have been carried to find the Fukui functions at the metal sites in complexes <b>1</b> and <b>2</b> to predict the possible metal centers involved in the binding process with BSA protein