Cd²⁺-Specific Fluorescence Response of Methoxy-Substituted <i>N</i>,<i>N</i>‑Bis(2-quinolylmethyl)-2-methoxyaniline Derivatives

The N3O1 tetradentate ligand, TriMeOBQMOA (N,N-bis(5,6,7-trimethoxy-2-quinolylmethyl)-2-methoxyaniline), was developed as a Cd2+-specific fluorescent sensor. The structure of TriMeOBQMOA is half of TriMeOBAPTQ (N,N,N′,N′-tetrakis(5,6,7-trimethoxy-2-quinolylmethyl)-1,2-bis(2-aminophenoxy)ethane), which is a tetrakisquinoline derivative of the well-known calcium chelator BAPTA (1,2-bis(2-aminophenoxy)ethane-N,N,N′,N′-tetraacetic acid). The fluorescent Cd2+ selectivity of TriMeOBAPTQ (IZn/ICd = 5.3% in the presence of 3 equiv of metal ions in MeOH–HEPES buffer (9:1)) comes from the formation of fluorescent dinuclear cadmium (M2L) and nonfluorescent OH-bridged dizinc ((μ-OH)M2L) complexes. TriMeOBQMOA also exhibits excellent Cd2+ specificity in fluorescence enhancement (IZn/ICd = 2.3% in the presence of 5 equiv of metal ions in DMF–HEPES buffer (1:1, HEPES 50 mM, KCl 0.1 M, pH = 7.5)) via substantial formation of a highly fluorescent bis(μ-chloro)dinuclear cadmium complex ([Cd2(μ-Cl)2L2]2+), which is in equilibrium with the mononuclear Cd2+ complex ([CdLCl]+), and extremely poor stability of the TriMeOBQMOA-Zn2+ complex. The all-nitrogen derivatives of BQMOA and BAPTQ, namely, N,N-BQDMPHEN (N,N-bis(2-quinolylmethyl)-N′,N′-dimethyl-1,2-phenylenediamine) and BPDTQ (N,N,N′,N′-tetrakis(2-quinolylmethyl)-2,2′-(N,N′-dimethylethylenediamino)dianiline), respectively, and their methoxy-substituted derivatives were also prepared, and the fluorescent metal ion sensing properties are discussed

Sandglass-Typed Single Chameleon Luminophore for Water Mapping Measurements: Intramolecular Energy Migrations in the Hydrophilic Tb(III)/Sm(III) Cluster

Novel hydrophilic and color-changeable single chameleon luminophores composed of Tb(III)/Sm(III) nona-nuclear clusters [TbxSm9–x(Sal-PEG-n)16(μ-OH)10]+(NO3)− (x = 1, 2, 3, and 9; Sal-PEG-n: salicylate polyethylene glycolmethylester, n = 2 and 4) are reported for water mapping measurements. Their characteristic sandglass structures and aggregates were analyzed using X-ray single crystal analysis and dynamic light scattering (DLS) measurements. The green- and yellow-luminescence of [Tb3Sm6(Sal-PEG-4)16(μ-OH)]+(NO3)− in water were observed at 20 and 50 °C, respectively. The ratio-metric luminescence analysis using green Tb(III) and orange Sm(III) emission bands is a promising candidate for exact temperature distribution measurements in fluid dynamics. The effective temperature-sensing property based on the competitive intramolecular energy transfer processes between Tb(III)-to-ligand and Tb(III)-to-Sm(III) in a non-a-nuclear cluster is explained using temperature-dependent kinetic analyses in the excited state

Nanotubes of Biomimetic Supramolecules Constructed by Synthetic Metal Chlorophyll Derivatives

Various supramolecular nanotubes have recently been built up by lipids, peptides, and other organic molecules. Major light-harvesting (LH) antenna systems in a filamentous anoxygenic phototroph, <i>Chloroflexus</i> (<i>Cfl.</i>) <i>aurantiacus</i>, are called chlorosomes and contain photofunctional single-wall supramolecular nanotubes with approximately 5 nm in their diameter. Chlorosomal supramolecular nanotubes of <i>Cfl. aurantiacus</i> are constructed by a large amount of bacteriochlorophyll­(BChl)-<i>c</i> molecules. Such a pigment self-assembles in a chlorosome without any assistance from the peptides, which is in sharp contrast to the other natural photosynthetic LH antennas. To mimic chlorosomal supramolecular nanotubes, synthetic models were prepared by the modification of naturally occurring chlorophyll­(Chl)-<i>a</i> molecule. Metal complexes (magnesium, zinc, and cadmium) of the Chl derivative were synthesized as models of natural chlorosomal BChls. These metal Chl derivatives self-assembled in hydrophobic environments, and their supramolecules were analyzed by spectroscopic and microscopic techniques. Cryo-transmission electron microscopic images showed that the zinc and cadmium Chl derivatives could form single-wall supramolecular nanotubes and their outer and inner diameters were approximately 5 and 3 nm, respectively. Atomic force microscopic images suggested that the magnesium Chl derivative formed similar nanotubes to those of the corresponding zinc and cadmium complexes. Three chlorosomal single-wall supramolecular nanotubes of the metal Chl derivatives were prepared in the solid state and would be useful as photofunctional materials