Complexes of a novel N-(diisopropxythiophosphoryl)thiourea derivative of 1,4,8,11-tetraazacyclotetradecane with Na+, K+ and Cu (PPh3)2 + cations

The reaction between 1,4,8,11-tetraazacyclotetradecane (cyclam) and O,O′-diisopropyl-isothiocyanatothiophosphoric acid (iPrO)2P(S)NCS gives the tetra-functional thiourea H4L with four C(S)NHP(S)(OPri)2 groups attached to the intracyclic nitrogen atoms. The tetra-substituted product has been obtained in the solid state, while partial dissociation with elimination of isothiocyanate (iPrO)2P(S)NCS takes place in CCl4 and CDCl3 solutions. Deprotonation of the exocyclic groups prevents the dissociation, and alkali metal salts of M4L formula (M = Na+, K+) were obtained by treatment with MOH. The potassium salt K4L was used to synthesize the Cu(I) complex [{Cu(PPh3)2}4L] by reaction with Cu(PPh3)3I. © 2006 Elsevier Ltd. All rights reserved

Rich magnetic chemistry of cobalt(II) complexes with N-phosphorylthioureas. Crystal structure and solution1H NMR spectral properties

Structure and magnetic properties of CoII complexes with N-phosphorylthiourea derivatives [RC(S)NHP(O)(OiPr)2] (HL) [Co {Et2NC(S)NP(O)(OzPr)2}2] (1), [Co [(PrNHC(S)NP(O)-(OiPr)2}2] (2), [Co {[/BuNHC(S)NP(O)(OiPr) 2}2] (3), [Co{p-MeOC6H4NHC(S)NP(O) (O(Pr)2}2] (4), [Co{P-BrC6H4NHC-(S) NP(O)(O(Pr)2}2] (5) were investigated. Paramagnetic shifts in the 1H NMR spectrum were observed for high-spin CoII complexes with HL, incorporating amidophosphate moiety C(S)NP(O). The thermal dependence of the magnetic susceptibility has shown that the extended materials 2, 3 and 5 show ferromagnetic exchange between distorted tetrahedral metal atoms, while in complex 4 antiferromagnetic behavior takes place. Compound 1 behaves as a spincanted ferromagnet, an antiferromagnetic ordering taking place below a critical temperature, Tc = 175 K. Complex 2 was investigated by single crystal X-ray diffraction. The cobalt(II) atom in complex 2 is in distorted tetrahedral CoO2S2 environment formed by the C=S sulfur atoms and the P=O oxygen atoms of two deprotonated ligands. © 2007 WILEY-VCH Verlag GmbH & Co. KGaA

Complexes of N-thiophosphorylthioureas (HL) with copper(I). Crystal structures of [Cu3L3] and [Cu(PPh3) 2L] chelates

Reaction of the potassium salts of N-thiophosphorylated thioureas of common formula RC(S)NHP(S)(OiPr)2 [R = morpholin-N-yl (HLa), piperidin-N-yl (HLb), NH2 (HLc), PhCH 2NH (HLd)] with Cu(PPh3)3I in aqueous EtOH/CH2Cl2 leads to mononuclear [Cu(PPh 3)2L-S,S′] complexes. Using copper(i) iodide instead of Cu(PPh3)3I, polynuclear complexes [Cu n(L-S,S′)n] were obtained. The structures of these compounds were investigated by ES-MS, elemental analyses, 1H and 31P NMR in solution, IR and 31P solid-state MAS NMR spectroscopy. The crystal structures of [Cu3L3 a] and [Cu(PPh3)2Lb] were determined by single-crystal X-ray diffraction. © The Royal Society of Chemistry 2007

N,N '-Ethylenediaminobis(benzylphosphonic acids) as a potent class of chelators for metal ions

Aminophosphonates were found to be effective metal ion chelators. Ethylenediamine (EN) itself binds strongly to a series of metal ions forming efficient five-membered chelate ring using two nitrogen donors. Combination of EN with phosphonate function results in the family of low molecular chelating agents. Introduction of a pyridine moiety into EN -phosphonate structure results in the very effective ligands involving a four-nitrogen donor set to coordinate the metal ion. In this work, the potentiometric and spectroscopic data for two analogues 2,2'-(ethylenedi-imino)bis(3-pyridylphosphonic-acid)-L(2) and 2,2'-(ethylenedi-imino)bis(2-pyridylphosphonic-acid) - L(3), comprising EN, two phosphonates and two pyridines with Cu(II), Ni(II) and Zn(II) ions are presented showing very high efficacy of one of the ligands studied

Complexes of a novel N-(diisopropxythiophosphoryl)thiourea derivative of 1,4,8,11-tetraazacyclotetradecane with Na+, K+ and Cu (PPh3)2 + cations

The reaction between 1,4,8,11-tetraazacyclotetradecane (cyclam) and O,O′-diisopropyl-isothiocyanatothiophosphoric acid (iPrO)2P(S)NCS gives the tetra-functional thiourea H4L with four C(S)NHP(S)(OPri)2 groups attached to the intracyclic nitrogen atoms. The tetra-substituted product has been obtained in the solid state, while partial dissociation with elimination of isothiocyanate (iPrO)2P(S)NCS takes place in CCl4 and CDCl3 solutions. Deprotonation of the exocyclic groups prevents the dissociation, and alkali metal salts of M4L formula (M = Na+, K+) were obtained by treatment with MOH. The potassium salt K4L was used to synthesize the Cu(I) complex [{Cu(PPh3)2}4L] by reaction with Cu(PPh3)3I. © 2006 Elsevier Ltd. All rights reserved

Complexes of a novel N-(diisopropxythiophosphoryl)thiourea derivative of 1,4,8,11-tetraazacyclotetradecane with Na+, K+ and Cu (PPh3)2 + cations

The reaction between 1,4,8,11-tetraazacyclotetradecane (cyclam) and O,O′-diisopropyl-isothiocyanatothiophosphoric acid (iPrO)2P(S)NCS gives the tetra-functional thiourea H4L with four C(S)NHP(S)(OPri)2 groups attached to the intracyclic nitrogen atoms. The tetra-substituted product has been obtained in the solid state, while partial dissociation with elimination of isothiocyanate (iPrO)2P(S)NCS takes place in CCl4 and CDCl3 solutions. Deprotonation of the exocyclic groups prevents the dissociation, and alkali metal salts of M4L formula (M = Na+, K+) were obtained by treatment with MOH. The potassium salt K4L was used to synthesize the Cu(I) complex [{Cu(PPh3)2}4L] by reaction with Cu(PPh3)3I. © 2006 Elsevier Ltd. All rights reserved

Studies on zinc(II) complexes with N-thioacylamidophosphates: X-ray crystal structure of the [Zn(RC(S)NP(O)(OiPr)2)2] (R = NH2, tBuNH, c-C6H11NH)

The photoluminescent properties of 17 zinc(II) chelates [Zn(RC(S)NP(O)(OiPr)2-O,S)2] (R = Ph (1a), PhNH (1b), p-BrPh (1c), p-MeOC6H4NH (1d), p-BrC6H4NH (1e), NH2 (1f), iPrNH (1g), tBuNH (1h), Et2N (1i), c-C5H10N (1j), c-OC4H8N (1k), c-C6H11NH (1l), aminobenzo-15-crown-5 (1m)) and [Zn(B)(RC(S)NP(O)(OiPr)2-O,S)2] (R = Ph, B = 2,2′-bipyridine (2a); R = Ph, B = 1,10-phenanthroline (2b); R = PhNH, B = 2,2′-bipyridine (2c); R = PhNH, B = 1,10-phenanthroline (2d)), are reported. Colorless and air/moisture stable chelate complexes of divalent zinc show blue emission in the solid state when excited with UV light. Complexes 1f, 1h, 1l were investigated by single crystal X-ray diffraction. The zinc(II) atom in complexes 1f, 1h, 1l is in a distorted tetrahedral O2S2 environment formed by the C{double bond, long}S sulphur atoms and the P{double bond, long}O oxygen atoms of two deprotonated ligands. © 2008 Elsevier Ltd. All rights reserved

Physicochemical study of biomolecular interactions between lysosomotropic surfactants and bovine serum albumin

The interactions between two cationic lysosomotropic surfactants (2-dodecanoyloxyethyl)trimethylammonium bromide (DMM-11) and (2-dodecanoyloxypropyl)trimethylammonium bromide (DMPM-11) with bovine serum albumin (BSA) in Hepes buffer (pH = 7.4) were systematically studied by surface tension, fluorescence and circular dichroism (CD) spectroscopy and isothermal titration calorimetry (ITC). Furthermore, the size of the micellar aggregates and the polydispersity indexes of both cationic surfactants were studied by dynamic light scattering technique (DLS). The hydrodynamic radii, micellar volumes and aggregation numbers were calculated using a method based on density functional theory (DFT). The results showed that, in both cases, the surface tension was modified upon addition of BSA, and the critical micelle concentration (CMC) values of DMM-11 and DMPM-11 were higher in the presence of BSA. The fluorescence intensity of BSA decreased significantly as the concentration of both cationic surfactants increased and this effect was attributed to the formation of surfactant-BSA complexes. Synchronous fluorescence spectrometry showed the binding-induced conformational changes in BSA. Finally, CD and DLS results revealed the occurrence of changes in the secondary structure of the protein in the presence of both surfactants. In conclusion, understanding the interactions between lysosomotropic surfactants and BSA is required to explore their potential applications in medicine.Author Żaneta Czyżnikowska gratefully acknowledge the allotment of the CPU time in Wroclaw Center of Networking and Supercomputing (WCSS). All the ITC experiments were performed by Joanna Gałęzowska in the Laboratory of Elemental Analysis and Structural Research, Faculty of Pharmacy and the Division of Laboratory Diagnostics, Wroclaw Medical University, supported by the ERDF Project within the Innovation Economy Operational Programme POIG.02.01.00-14-122/09”. Ligia R. Rodrigues and Eduardo J. Gudiña acknowledge the Portuguese Foundation for Science and Technology (FCT) for the financial support under the scope of the strategic funding of UID/BIO/04469/2013 unit and COMPETE 2020 (POCI-01-0145-FEDER-006684) and BioTecNorte operation (NORTE-01-0145-FEDER-000004) funded by the European Regional Development Fund under the scope of Norte2020 − Programa Operacional Regional do Norte. The authors also thank the FCT for the financial support under the scope of the Project RECI/BBB-EBI/0179/2012 (FCOMP-01-0124-FEDER-027462). This work was supported by Polish-Portugal Executive Program for years 2017-2018.info:eu-repo/semantics/publishedVersio

Studies on zinc(II) complexes with N-thioacylamidophosphates: X-ray crystal structure of the [Zn(RC(S)NP(O)(OiPr)2)2] (R = NH2, tBuNH, c-C6H11NH)

The photoluminescent properties of 17 zinc(II) chelates [Zn(RC(S)NP(O)(OiPr)2-O,S)2] (R = Ph (1a), PhNH (1b), p-BrPh (1c), p-MeOC6H4NH (1d), p-BrC6H4NH (1e), NH2 (1f), iPrNH (1g), tBuNH (1h), Et2N (1i), c-C5H10N (1j), c-OC4H8N (1k), c-C6H11NH (1l), aminobenzo-15-crown-5 (1m)) and [Zn(B)(RC(S)NP(O)(OiPr)2-O,S)2] (R = Ph, B = 2,2′-bipyridine (2a); R = Ph, B = 1,10-phenanthroline (2b); R = PhNH, B = 2,2′-bipyridine (2c); R = PhNH, B = 1,10-phenanthroline (2d)), are reported. Colorless and air/moisture stable chelate complexes of divalent zinc show blue emission in the solid state when excited with UV light. Complexes 1f, 1h, 1l were investigated by single crystal X-ray diffraction. The zinc(II) atom in complexes 1f, 1h, 1l is in a distorted tetrahedral O2S2 environment formed by the C{double bond, long}S sulphur atoms and the P{double bond, long}O oxygen atoms of two deprotonated ligands. © 2008 Elsevier Ltd. All rights reserved

Cobalt(II) complexes with N-thioacylamidophosphates and 2,2′-bipyridyl and 1,10-phenathroline. Crystal structures, solution 11H NMR spectral and magnetic properties

Structure and magnetic properties of N-diisopropoxyphosphorylthiobenzamide PhC(S)-N(H)-P(O)(OiPr) 2 (HL I) and N- diisopropoxyphosphoryl-N′-phenylthiocarbamide PhN(H)-C(S)-N(H)-P(O)(OiPr) 2 (HL II) complexes with the Co II cation of formulas [Co {PhC(S)-N-P(O)(OiPr) 2} 2] (1), [Co(PhN(H)-C(S)-N-P(O)(OiPr) 2] 2] (2), [Co{PhC(S)-N(H)-P(O) (OiPr) 2} 2{PhC(S)-N-P(O)(OiPr) 2} 2] (1a) and [Co{PhC(S)-N-P(O)(OiPr) 2} 2}(2,2′-bipy)] (3), [Co{PhC(S)-N-P(O)(OiPr) 2} 2(1,10-phen)] (4), [Co{PhN(H)-C(S)-N-P(O)(OiPr) 2] 2(2,2′-bipy)] (5), [Co(PhN(H)-C(S)-N-P(O)(OiPr) 2} 2(1,10-phen)] (6) were investigated. Paramagnetic shifts in the 1H NMR spectrum were observed for high-spin Co II complexes with HL I,II, incorporating the S-C-N-P-O chelate moiety and two aromatic chelate ligands. Investigation of the thermal dependence of the magnetic susceptibility has shown that the extended materials 1-2 and 6 show ferromagnetic exchange between distorted tetrahedral (1, 2) or octahedral (la, 6) metal atoms whereas 3 and 5 show antiferromagnetic properties. Compound 4 behaves as a spin-canted ferromagnet, an antiferromagnetic ordering taking place below a critical temperature, T c = 115 K. Complexes 1 and 1a were investigated by single crystal X-ray diffraction. The cobalt(II) atom in complex 1 resides a distorted tetrahedral O 2S 2 environment formed by the C=S sulfur atoms and the P=O oxygen atoms of two deprotonated ligands. Complex la has a tetragonal-bipyramidal structure, Co(O ax) 2(O eq) 2(S eq) 2, and two neutral ligand molecules are coordinated in the axial positions through the oxygen atoms of the P=O groups. The base of the bipyramid is formed by two anionic ligands in the typical 1,5-O,S coordination mode. The ligands are in a trans configuration. © 2007 WILEY-VCH Verlag GmbH & Co. KGaA