A Simple Turn-off Schiff Base Fluorescent Sensor for Copper (II) Ion and Its Application in Water Analysis

An aniline-functionalized naphthalene dialdehyde Schiff base fluorescent probe L with aggregation-induced enhanced emission (AIEE) characteristics was synthesized via a simple one-step condensation reaction and exhibited excellent sensitivity and selectivity towards copper(II) ions in aqueous media with a fluorescence “ turn-off ” phenomenon. The detection limit of the probe is 1.64 × 10−8 mol·L−1. Furthermore, according to the results of the UV-vis/fluorescence titrations, Job’s plot method and 1H-NMR titrations, a 1:2 stoichiometry was identified. The binding constant between L and Cu2+ was calculated to be Ka = 1.222 × 103. In addition, the AIEE fluorescent probe L could be applied to detection in real water samples with satisfactory recoveries in the range 99.10–102.90% in lake water and 98.49–102.37% in tap water.

1,1′-Bis(diphenylphosphino)ferrocene Platinum(II) Complexes as a Route to Functionalized Multiporphyrin Systems

In this study, the cationic complex [PtMe(Me2SO)(dppf)]CF3SO3 (PtFc) (dppf = 1,1′-bis(diphenylphosphino)ferrocene) was exploited as a precursor to functionalize the multi-chromophoric system hexakis(pyridyl-porphyrinato)benzene (1). The final adduct [PtFc]18-1, containing eighteen platinum(II) organometallic [PtMe(dppf)] fragments, was prepared and characterized through UV/Vis absorption, 31P{1H}-NMR spectroscopy, and fluorescence emission. UV/vis and fluorescence titrations confirmed the coordination between the platinum(II) center and all the pyridyl moieties of the peripheral substituent groups of the porphyrin. The drop casting of diluted dichloromethane solution of [PtFc]18-1 onto a glass surface afford micrometer-sized emissive porphyrin rings.

On the Different Mode of Action of Au(I)/Ag(I)-NHC Bis-Anthracenyl Complexes Towards Selected Target Biomolecules

Gold and silver N-heterocyclic carbenes (NHCs) are emerging for therapeutic applications. Multiple techniques are here used to unveil the mechanistic details of the binding to different biosubstrates of bis(1-(anthracen-9-ylmethyl)-3-ethylimidazol-2-ylidene) silver chloride [Ag(EIA)2]Cl and bis(1-(anthracen-9-ylmethyl)-3-ethylimidazol-2-ylidene) gold chloride [Au(EIA)2]Cl. As the biosubstrates, we tested natural double-stranded DNA, synthetic RNA polynucleotides (single-poly(A), double-poly(A)poly(U) and triple-stranded poly(A)2poly(U)), DNA G-quadruplex structures (G4s), and bovine serum albumin (BSA) protein. Absorbance and fluorescence titrations, mass spectrometry together with melting and viscometry tests show significant differences in the binding features between silver and gold compounds. [Au(EIA)2]Cl covalently binds BSA. It is here evidenced that the selectivity is high: low affinity and external binding for all polynucleotides and G4s are found. Conversely, in the case of [Ag(EIA)2]Cl, the binding to BSA is weak and relies on electrostatic interactions. [Ag(EIA)2]Cl strongly/selectively interacts only with double strands by a mechanism where intercalation plays the major role, but groove binding is also operative. The absence of an interaction with triplexes indicates the major role played by the geometrical constraints to drive the binding mode.

Biophysical and X-ray structural studies of the (GGGTT)3GGG G-quadruplex in complex with N-methyl mesoporphyrin IX

The G-quadruplex (GQ) is a well-studied non-canonical DNA structure formed by G-rich sequences found at telomeres and gene promoters. Biological studies suggest that GQs may play roles in regulating gene expression, DNA replication, and DNA repair. Small molecule ligands were shown to alter GQ structure and stability and thereby serve as novel therapies, particularly against cancer. In this work, we investigate the interaction of a G-rich sequence, 5’-GGGTTGGGTTGGGTTGGG-3’ (T1), with a water-soluble porphyrin, N-methyl mesoporphyrin IX (NMM) via biophysical and X-ray crystallographic studies. UV-vis and fluorescence titrations, as well as a Job plot, revealed a 1:1 binding stoichiometry with an impressively tight binding constant of 30–50 μM-1 and ΔG298 of -10.3 kcal/mol. Eight extended variants of T1 (named T2 –T9) were fully characterized and T7 was identified as a suitable candidate for crystallographic studies. We solved the crystal structures of the T1- and T7-NMM complexes at 2.39 and 2.34 Å resolution, respectively. Both complexes form a 5’-5’ dimer of parallel GQs capped by NMM at the 3’ G-quartet, supporting the 1:1 binding stoichiometry. Our work provides invaluable details about GQ-ligand binding interactions and informs the design of novel anticancer drugs that selectively recognize specific GQs and modulate their stability for therapeutic purposes.

Dihomooxacalix[4]arene-Based Fluorescent Receptors for Anion and Organic Ion Pair Recognition

Fluorescent dihomooxacalix[4]arene-based receptors 5a–5c, bearing two naphthyl(thio)ureido groups at the lower rim via a butyl spacer, were synthesised and obtained in the cone conformation in solution. The X-ray crystal structures of 1,3- (5a) and 3,4-dinaphthylurea (5b) derivatives are reported. Their binding properties towards several anions of different geometries were assessed by 1H-NMR, UV-Vis absorption and fluorescence titrations. Structural and energetic insights of the naphthylurea 5a and 5b complexes were also obtained using quantum mechanical calculations. The data showed that all receptors follow the same trend, the association constants increase with the anion basicity, and the strongest complexes were obtained with F−, followed by the oxoanions AcO− and BzO−. Proximal urea 5b is a better anion receptor compared to distal urea 5a, and both are more efficient than thiourea 5c. Compounds 5a and 5b were also investigated as heteroditopic receptors for biologically relevant alkylammonium salts, such as the neurotransmitter γ-aminobutyric acid (GABA·HCl) and the betaine deoxycarnitine·HCl. Chiral recognition towards the guest sec-butylamine·HCl was also tested, and a 5:2 selectivity for (R)-sec-BuNH3+·Cl− towards (P) or (M) enantiomers of the inherently chiral receptor 5a was shown. Based on DFT calculations, the complex [(S)-sec-BuNH3+·Cl−/(M)-5a] was indicated as the more stable.

Color-tunable white-light of binary tris-β-diketonate-(Dy3+, Gd3+ ) complexes’ blend under single wavelength excitation

Based on the Dy³⁺-centered yellow-light and the ligands-based blue-light of the iso-structural two complexes [Ln(acac)3(5-Br-2,2′-bpy)] (Ln³⁺ = Dy³⁺ (2) or Gd³⁺ (3); Hacac = acetylacetone, 5-Br-2,2′-bpy = 5-bromo-2,2′-bipyridine), respectively, the stoichiometric fluorescence titrations of their tris-β-diketonate-(Dy³⁺, Gd³⁺x)-mixed complex, show that it is capable of the smooth color-tuning (yellow- to white- and to blue-light) under single wavelength excitation. Moreover, through the dichromatic integration, the binary tris-β-diketonate-(Dy³⁺, Gd³⁺x) complex exhibits the straightforward white-light in solid-state.

Vibrio campbellii chitoporin: thermostability study and implications for the development of therapeutic agents against Vibrio infections

Vibrio campbellii (formerly Vibrio harveyi) is a bacterial pathogen that causes vibriosis, which devastates fisheries and aquaculture worldwide. V. campbellii expresses chitinolytic enzymes and chitin binding/transport proteins, which serve as excellent targets for antimicrobial agent development. We previously characterized VhChiP, a chitooligosaccharide-specific porin from the outer membrane of V. campbellii BAA-1116. This study employed far-UV circular dichroism and tryptophan fluorescence spectroscopy, together with single channel electrophysiology to demonstrate that the strong binding of chitoligosaccharides enhanced thermal stability of VhChiP. The alanine substitution of Trp136 at the center of the affinity sites caused a marked decrease in the binding affinity and decreased the thermal stability of VhChiP. Tryptophan fluorescence titrations over a range of temperatures showed greater free-energy changes on ligand binding (ΔG°binding) with increasing chain length of the chitooligosaccharides. Our findings suggest the possibility of designing stable channel-blockers, using sugar-based analogs that serve as antimicrobial agents, active against Vibrio infection.

Interactions of Small-Molecule Guests with Interior and Exterior Surfaces of a Coordination Cage Host

Coordination cages are well-known to act as molecular containers that can bind small-molecule guests in their cavity. Such cavity binding is associated with interactions of the guests with the surrounding set of surfaces that define the cavity; a guest that is a good fit for the cavity will have many favourable interactions with the interior surfaces of the host. As cages have exterior as well as interior surfaces, possibilities also exist for ‘guests’ that are not well-bound in the cavity to interact with the exterior surface of the cage where spatial constraints are fewer. In this paper, we report a combined solid-state and solution study using an octanuclear cubic M8L12 coordination cage which illustrates the occurrence of both types of interaction. Firstly, crystallographic studies show that a range of guests bind inside the cavity (either singly or in stacked pairs) and/or interact with the cage exterior surface, depending on their size. Secondly, fluorescence titrations in aqueous solution show how some flexible aromatic disulfides show two separate types of interaction with the cage, having different spectroscopic consequences; we ascribe this to separate interactions with the exterior surface and the interior surface of the host cage with the former having a higher binding constant. Overall, it is clear that the idea of host/guest interactions in molecular containers needs to take more account of external surface interactions as well as the obvious cavity-based binding.

Comparison of two rhodamine-based polystyrene solid-phase fluorescent sensors for mercury(II) determination

Two novel rhodamine-based polystyrene solid-phase fluorescent sensors PS-AC-I and PS-AC-II with different coordination atoms (O or S) are synthesized and shown to be able to detect Hg(II) ions. They are characterized by Fourier-transform infrared spectroscopy and by scanning electron microscopy analysis. Their fluorescent properties, including response time, pH effects, fluorescence titrations, metal ion competition and recycling, are investigated and compared. Sensor PS-AC-II displayed higher selectivity and sensitivity to Hg(II), with a lower detection limit of 0.032 µM, which was 15 times better than PS-AC-I. A detection mechanism involving the Hg(II) chelation-induced ring-opening of the rhodamine spirolactam is proposed with the aid of theoretical calculations.

Novel Schiff Base of E-2-(((4-Aminophenyl)imino)methyl)-5-(difluoromethoxy)phenol Fluorescence Chemosensor for Detection of Al3+, Fe2+, Cu2+ Ions and its Application towards Live Cell Imaging

A Schiff base compound E-2-(((4-aminophenyl)imino)methyl)-5-(difluoromethoxy)phenol was synthesized and characterized by FT-IR, 1H and 13C NMR, ESI-mass spectroscopy. The synthesized compound also selectively detects Al3+, Fe2+ and Cu2+ without any interference of other metal ions. Fluorescence titrations carried out to find the selectivity of Al3+, Fe2+ and Cu2+ in turn-on system, with binding modes of 2:1 complex, confirmed by Job′s plot. The presence of metal ions Al3+, Fe2+ and Cu2+ with receptor conformed by ESI-MS spectrum, which changed the base value at 298.00 m/z. Moreover, among the binding constant of three metals calculated (20 μM), Al3+ showed a high value of 5.7 × 104 M-1 compared to Fe2+ and Cu2+ metal ions. Prominently, the cytotoxicity activities of probe with HeLa cells were also calculated