A series of asymmetric, homoleptic Fe(II) compounds based on the facially-binding tridentate ligand -methyl-1,1-di(pyridin-2-yl)C-amine (LC) (C = butyl, hexyl, octyl, decyl, dodecyl, tetradecyl and hexadecyl alkyl chains) with formula [Fe(LC)](X)·solvate, where = 4, 14 and X = BF (1C4 and 1C14) or = 6, 8, 10, 12, 16 and X = CFSO (1C6-1C12 and 1C16), are reported. Complexes 1C6 to 1C16 pack in crystalline bilayers in the solid state, forming hydrophobic and hydrophilic regions between adjacent layers of complexes. The combination of short Fe-N bond distances (∼2.
View Article and Find Full Text PDFA 1,8-naphthalimide-based tripodal fluorescent ligand (L3) was synthesized through the copper (I) catalyzed Huisgen azide-alkyne cycloaddition reaction of 2-(2-azidoethyl)-6-morpholino-1 H-benzo[de]isoquinoline-1,3(2 H)-dione with triproparagylamine. Naphthalimide acts as the fluorophore while the triazole and amine nitrogens chelate the metal ion. L3 showed a selective fluorescence turn-off for Cu(II) over other metal ions in aqueous acetonitrile solution.
View Article and Find Full Text PDFOrg Biomol Chem
December 2023
Two quinidine-functionalized coumarin molecular probes have been synthesized and have been found to bind metal cations (Cd, Co, Cu, Fe, Hg, Ni, and Zn) with high affinity in organic-aqueous media (DMSO-HEPES). The chemodosimeters coordinate with the Zn ions in a two-to-one ratio (molecular probe : Zn) with a log of 10.0 M.
View Article and Find Full Text PDFThe binding behaviour of two ureido-hexahomotrioxacalix[3]arene derivatives bearing naphthyl () and pyrenyl () fluorogenic units at the lower rim towards selected nitroaromatic compounds (NACs) was evaluated. Their affinity, or lack of it, was determined by UV-Vis absorption, fluorescence and NMR spectroscopy. Different computational methods were also used to further investigate any possible complexation between the calixarenes and the NACs.
View Article and Find Full Text PDFPolymer self-healing films containing fragments of pillar[5]arene were obtained for the first time using thiol/disulfide redox cross-linking. These films were characterized by thermogravimetric analysis and differential scanning calorimetry, FTIR spectroscopy, and electron microscopy. The films demonstrated the ability to self-heal through the action of atmospheric oxygen.
View Article and Find Full Text PDFPillar[5]arenes containing sulfonate fragments have been shown to form supramolecular complexes with therapeutic proteins to facilitate targeted transport with an increased duration of action and enhanced bioavailability. Regioselective synthesis was used to obtain a water-soluble pillar[5]arene containing the fluorescent label FITC and nine sulfoethoxy fragments. The pillar[5]arene formed complexes with the therapeutic proteins binase, bleomycin, and lysozyme in a 1:2 ratio as demonstrated by UV-vis and fluorescence spectroscopy.
View Article and Find Full Text PDFIn addition to a variety of viral-glycoprotein receptors (e.g., heparan sulfate, Niemann-Pick C1, etc.
View Article and Find Full Text PDFLangmuir
March 2021
Decasubstituted pillar[5]arenes containing amidopyridine fragments have been synthesized for the first time. As was shown by UV-vis spectroscopy, the pillar[5]arenes with -amidopyridine fragments form supramolecular associates with Cu(II) and Pd(II) cations in methanol in a 2:1 ratio. Using a sol-gel approach these associates are transformed into metallo-supramolecular coordination polymers (supramolecular gels) which were characterized as amorphous powders by scanning electron microscopy (SEM) and dynamic light scattering (DLS).
View Article and Find Full Text PDFIn the last decade, the chemistry of meroterpenoids-conjugated molecules formed from isoprenyl fragments through biosynthetic pathways-has developed rapidly. The class includes some natural metabolites and fully synthetic fragments formed through nonbiological synthesis. In the field of synthetic receptors, a range of structures can be achieved by combining fragments of different classes of organic compounds into one hybrid macrocyclic platform which retains the properties of these fragments.
View Article and Find Full Text PDFCalixarenes and related macrocycles have been shown to have antimicrobial effects since the 1950s. This review highlights the antimicrobial properties of almost 200 calixarenes, resorcinarenes, and pillararenes acting as prodrugs, drug delivery agents, and inhibitors of biofilm formation. A particularly important development in recent years has been the use of macrocycles with substituents terminating in sugars as biofilm inhibitors through their interactions with lectins.
View Article and Find Full Text PDFNovel water-soluble, deca-substituted pillar[5]arenes containing thiasulfate and thiacarboxylate fragments were synthesized and characterized. UV-vis, 2D 1H-1H NOESY and DOSY NMR spectroscopy revealed the ability of pillar[5]arenes containing thiasulfate fragments to form an inclusion complex with cholecalciferol (vitamin D3) in a 1 : 2 ratio (lg Kass = 2.2).
View Article and Find Full Text PDFThe alkyl chain carrying ligands N,N-di(pyridin-2-yl)butanamide (LC4) and N,N-di(pyridin-2-yl)decanamide (LC10) were combined with NCS- co-ligands to form the neutral heteroleptic Fe(ii) complexes trans-[FeII(LC4)2(NCS)2] (1C4) and trans-[FeII(LC10)2(NCS)2] (1C10). Variable temperature crystallographic studies revealed that 1C4 is in the orthorhombic space group Pna21 between 85-200 K whereas 1C10 is in the monoclinic space group P21/c between 85-140 K. The average Fe-N bond lengths suggest that at 85 K 1C4 contains LS Fe(ii) centres; however, the ca.
View Article and Find Full Text PDFA water-soluble pillar[5]arene, decafunctionalized with thioether and carboxylate fragments, was synthesized as a structural analogue of Sugammadex. Its ability to restore the contraction of the diaphragm muscle by encapsulating the muscle relaxant rocuronium bromide was demonstrated. Using UV-vis, NMR and fluorescence spectroscopy, it was shown that the muscle relaxant is associated with the pillar[5]arene with an association constant of 4500 M-1 and a stoichiometry of 1 : 1.
View Article and Find Full Text PDFOpportunistic Gram-negative uses adhesins (e.g., LecA and LecB lectins, type VI pili and flagella) and iron to invade host cells with the formation of a biofilm, a thick barrier that protects bacteria from drugs and host immune system.
View Article and Find Full Text PDFGlycan-protein interactions control numerous biological events from cell-cell recognition and signaling to pathogen host cell attachment for infections. To infect cells, some viruses bind to immune cells with the help of DC-SIGN (dendritic cell [DC]-specific ICAM3-grabbing nonintegrin) C-type lectin expressed on dendritic and macrophage cell membranes, via their envelope protein. Prevention of this infectious interaction is a serious therapeutic option.
View Article and Find Full Text PDFThe formation of inclusion complexes of the water-soluble -sulfonatocalix[]arenes, where = 4 or 6, with the Chemical Warfare Agent (CWA) GD, or Soman, and commonly used dialkyl methylphosphonate simulants has been studied by experimental solution NMR methods and by Molecular Mechanics (MMFF) and semi-empirical (PM6) calculations. Complex formation in non-buffered and buffered solutions is driven by the hydrophobic effect, and complex stoichiometry determined as 1:1 for all host:guest pairs. Low affinity complexes ( < 100 M) are observed for all guests, attributed to poor host-guest complementarity and the role of buffer cation species accounts for the low affinity of the complexes.
View Article and Find Full Text PDFThe detection and monitoring of lithium in environmental and clinical settings is becoming increasingly important. In this review, sensors incorporating conductive polymers and lithium bronzes are discussed, together with electrochemical and spectroscopic approaches. Ionophore-based methods have been employed extensively, with varying degrees of selectivity and sensitivity, and these are discussed in depth.
View Article and Find Full Text PDFEffective technologies are required to remove organic micropollutants from large fluid volumes to overcome present and future challenges in water and effluent treatment. A novel hierarchical composite filter material for rapid and effective removal of polar organic contaminants from water was developed. The composite is fabricated from phenolic resin-derived carbon microbeads with controllable porous structure and specific surface area embedded in a monolithic, flow permeable, poly(vinyl alcohol) cryogel.
View Article and Find Full Text PDFThe iteroselective "all-but-one" carbamatation methodology has been successfully extended to homooxacalixarenes and used for the selective and controlled synthesis of homooxacalixarene-monoquinones and calixarene-monoquinones. These moquinone derivatives constitute interesting molecular platforms that, until now, were inaccessible through any efficient means.
View Article and Find Full Text PDFAn esterified pillar[5]arene has been incorporated into a PVC electrochemical membrane. The resulting pH-responsive sensor functions in the range of pH 1 to 4 in a non-linear manner.
View Article and Find Full Text PDFAn N,N-carbonyl-bridged dipyrrinone oxime has been synthesized and studied as a potential sensor for organophosphates. The molecular sensor underwent a drastic colorimetric response upon formation of the adduct. The pesticide dimethoate was found to produce the biggest spectral response, with a limit of detection equal to 4.
View Article and Find Full Text PDFHexahomotrioxacalix[3]arenes, commonly called oxacalix[3]arenes, were first reported in 1962. Since then, their chemistry has been expanded to include numerous derivatives and complexes. This review describes the syntheses of the parent compounds, their derivatives, and their complexation behaviour towards cations.
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