Search

Your search keyword '"Szyrwiel Ł"' showing total 26 results
Start Over Author "Szyrwiel Ł"
26 results on '"Szyrwiel Ł"'

1. Dinuclear complexes of copper(I) with crown ether-containing N-thiophosphorylated bis-thioureas and 2,2'-bipyridine or 1,10-phenanthroline: Synthesis, characterization, and picrate extraction properties

Author

Babashkina M., Shakirova E., Safin D., Sokolov F., Klein A., Szyrwiel Ł., Kubiak M., Kozlowski H., and Krivolapov D.

Subjects
2-2'-Bipyridine, 1-10-Phenanthroline, N-Thiophosphoryl bis-thiourea, Copper, X-ray diffraction
Abstract

Reaction of O,O'-diisopropylthiophosphoric acid isothiocyanate (iPrO) 2P(S)NCS with 1,10-diaza-18-crown-6, 1,7-diaza-18-crown-6, or 1,7-diaza-15-crown-5 leads to the N-thiophosphorylated bis-thioureas N,N'-bis[C(S)NHP(S)(OiPr)2]-1,10-diaza-18-crown-6 (H 2LI), N,N'-bis[C(S)NHP(S)(OiPr)2]-1,7-diaza-18- crown-6 (H2LII) and N,N'-bis[C(S)NHP(S)(OiPr) 2]-1,7-diaza-15-crown-5 (H2LIII). Reaction of the potassium salts of H2LI-III with a mixture of CuI and 2,2'-bipyridine (bpy) or 1,10-phenanthroline (phen) in aqueous EtOH/CH 2Cl2 leads to the dinuclear complexes [Cu 2(bpy)2LI-III] and [Cu2(phen) 2LI-III]. The structures of these compounds were investigated by 1H, 31P{1H} NMR spectroscopy, and elemental analysis. The crystal structures of H2LI and [Cu2(phen)2LI] were determined by single-crystal X-ray diffraction. Extraction capacities of the obtained compounds in comparison to the related compounds 1,10-diaza-18-crown-6, N,N'-bis[C(=CMe2)CH2P(O)(OiPr)2]-1,10-diaza-18- crown-6, N,N'-bis[C(S)NHP(O)(OiPr)2]-1,10-diaza-18-crown-6 towards the picrate salts LiPic, NaPic, KPic. and NH4Pic were also studied. Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Published
2010

2. Intramolecular hydrogen bond controlled monodentate S-coordination of N-phosphoryl-N′-(R)-thioureas with Pd(II)

Author

Safin D., Szyrwiel Ł., Baranov S., Sokolov F., Babashkina M., and Kozlowski H.

Subjects
Complex, Palladium(II), Thiourea, Monodentate coordination, Crown-ether
Abstract

Reaction of N-phosphorylated thioureas RNHC(S)NHP(O)(OiPr)2 (R = tBu, HLI; R = Ph, HLII; R = 4′-benzo-15-crown-5, HLIII) with Pd(PhCN)2Cl2 in acetonitrile leads to complexes of formulae Pd(HLI-S)2Cl2 (1), Pd(HLII-S)2Cl2 (2) and Pd(HLIII-S)2Cl2 (3). The crystal structure of complex 1 has been investigated by X-ray crystallography. It was established that the thiourea ligands are in a trans-configuration and the palladium(II) cation is coordinated by the sulfur atoms of the C{double bond, long}S groups and the chlorine atoms. Complex 1 is the first example of palladium(II) complex in which the potentially chelating N-phosphorylated thiourea ligand is bound through the sulfur atom only. © 2008 Elsevier B.V. All rights reserved.

Published
2008

3. Coordination mode of the nickel(II) cation with N-diisopropoxyphosphinyl-p- bromothiobenzamide

Author

Safin D., Sokolov F., Baranov S., Szyrwiel Ł., Babashkina M., Shakirova E., Hahn F., and Kozlowski H.

Subjects
Amidophosphate, Nickel, Crystal structure, Chelates
Abstract

Reaction of the potassium salt of N-diisopropoxyphosphinyl-p- bromothiobenzamide p-BrC6H4C(S)NHP(O)(OiPr)2 (HL) with Ni(NO3)2 in aqueous EtOH leads to complex of formula [Ni(HL-O)2(L-O,S)2] (1). The structure of 1 was investigated by single crystal X-ray diffraction analysis, IR, 1H and 31P{1H} NMR spectroscopy, MALDI and microanalysis. The nickel(II) ion in 1 has a tetragonal-bipyramidal environment, (O ax)2(Oeq)2(Seq) 2, with two neutral ligand molecules coordinated in axial positions through the oxygen atoms of the P=O groups. The equatorial plane of bipyramide is formed by two anionic ligands involving 1,5-O,S-coordination mode. The chelating ligands are bound in trans configuration. © 2008 Wiley-VCH Verlag GmbH & Co. KGaA.

Published
2008

4. Nickel(II) complexes with N-(thio)phosphorylthioureas AdNHC(S)NHP(X)(OiPr)2: Versatile coordination of phosphoryl (X = O) and thiophosphoryl (X = S) derivatives

Author

Safin D., Sokolov F., Szyrwiel Ł., Babashkina M., Gimadiev T., Hahn F., Kozlowski H., Krivolapov D., and Litvinov I.

Subjects
Chelate, Hydrogen bond, N-(Thio)phosphorylthiourea, Crystal structures, Nickel complexes
Abstract

The reaction of the potassium salts of N-(thio)phosphorylated thioureas of the common formula AdN(H)C(S)N(H)P(X)(OiPr)2 (X = O, HLI; X = S, HLII) with the Ni(II) cation in aqueous EtOH leads to [Ni(LI,II)2] chelate complexes. The molecular structures of the thioureas HLI,II and the complexes [Ni(LI-N,S)2] and [Ni(LII-S,S′)2] were elucidated by single crystal X-ray diffraction analysis, IR, 1H and 31P NMR spectroscopy and microanalysis. In the complex [Ni(LI)2], the metal center is found to be in a square-planar N2S2 environment formed by the C{double bond, long}S sulfur atoms and the P-N nitrogen atoms of two deprotonated LI ligands. The ligands are in a trans configuration. The Ni(II) atom in complex [Ni(LII)2], with the deprotonated thiourea LII, is coordinated in a square-planar fashion by the C{double bond, long}S and P{double bond, long}S sulfur atoms of two anionic ligands. The ligands are in a cis configuration. © 2008 Elsevier Ltd. All rights reserved.

Published
2008

5. Monodentate S-vs. bidentate 1,5-O,S-coordination of N-phosphoryl-N′-(R)-thioureas with Pd(II)

Author

Safin D., Sokolov F., Szyrwiel Ł., Baranov S., Babashkina M., Gimadiev T., and Kozlowski H.

Subjects
Complex, Palladium(II), Thiourea, Monodentate coordination, Crown-ether
Abstract

Reaction of N-phosphorylated thioureas of common formula RNHC(S)NHP(O)(OiPr)2 (R = tBu, HLI; R = Ph, HLII; R = 4′-benzo-15-crown-5, HLIII) with Pd(PhCN)2Cl2 in acetonitrile leads to complexes of the structure Pd(HLI-S)2Cl2 (1), Pd(HLII-S)2Cl2 (2) and Pd(HLIII-S)2Cl2 (3). Reaction of N-phosphorylated thioureas of common formula RC(S)NHP(O)(OiPr)2 (R = Et2N, HLIV; R = morpholine-N-yl, HLV) in the same conditions leads to complexes Pd(LIV-O,S)2 (4) and Pd(LV-O,S)2 (5), where the palladium(II) atoms are coordinated in a square-planar fashion by the C{double bond, long}S sulfur atoms and the P{double bond, long}O oxygen atoms of two anionic ligands. The crystal structure of complex 1 has been investigated by X-ray crystallography. It was established that the thiourea ligands are in a trans-configuration and the palladium(II) cation is coordinated by the sulfur atoms of the C{double bond, long}S groups and the chlorine atoms. Complex 1 is the first example of palladium(II) complex in which the potentially chelating N-phosphorylated thiourea ligand is bound through the sulfur atom only. © 2008 Elsevier Ltd. All rights reserved.

Published
2008

6. Complexes of N-thiophosphorylthiourea α-naphthylnhc(S)NHP(S)(OiPr)2 (HL) with copper(I). crystal structures of HL and Cu(PPh3)2L

Author

Babashkina M., Safin D., Szyrwiel Ł., Kubiak M., Sokolov F., Starikov Y., Kozlowski H., Babashkina M., Safin D., Szyrwiel Ł., Kubiak M., Sokolov F., Starikov Y., and Kozlowski H.

Abstract

Reaction of the potassium salt of N-thiophosphorylated thiourea α-naphthylNHC(S)NHP(S)(OiPr)2 (HL) with Cu(PPh3)3I in aqueous EtOH/CH2Cl2 leads to the mononuclear complex [Cu(PPh3)2L-S,S′]. By using copper(I) iodide instead of Cu(PPli3)3I, the polynuclear complex [Cun(L-S,S′)n was obtained. The structures of these compounds were investigated by elemental analysis, H and 31P{1H} NMR and IR spectroscopy. The crystal structures of HL and Cu(PPh3)2-L were determined by singlecrystal X-ray diffraction. © 2009 Wiley-VCH Verlag GmbH & Co. KGaA.

7. Complexes of N-thiophosphorylthiourea α-naphthylnhc(S)NHP(S)(OiPr)2 (HL) with copper(I). crystal structures of HL and Cu(PPh3)2L

Author

Babashkina M., Safin D., Szyrwiel Ł., Kubiak M., Sokolov F., Starikov Y., Kozlowski H., Babashkina M., Safin D., Szyrwiel Ł., Kubiak M., Sokolov F., Starikov Y., and Kozlowski H.

Abstract

Reaction of the potassium salt of N-thiophosphorylated thiourea α-naphthylNHC(S)NHP(S)(OiPr)2 (HL) with Cu(PPh3)3I in aqueous EtOH/CH2Cl2 leads to the mononuclear complex [Cu(PPh3)2L-S,S′]. By using copper(I) iodide instead of Cu(PPli3)3I, the polynuclear complex [Cun(L-S,S′)n was obtained. The structures of these compounds were investigated by elemental analysis, H and 31P{1H} NMR and IR spectroscopy. The crystal structures of HL and Cu(PPh3)2-L were determined by singlecrystal X-ray diffraction. © 2009 Wiley-VCH Verlag GmbH & Co. KGaA.

8. Dinuclear complexes of copper(I) with crown ether-containing N-thiophosphorylated bis-thioureas and 2,2'-bipyridine or 1,10-phenanthroline: Synthesis, characterization, and picrate extraction properties

Author

Babashkina M., Shakirova E., Safin D., Sokolov F., Klein A., Szyrwiel Ł., Kubiak M., Kozlowski H., Krivolapov D., Babashkina M., Shakirova E., Safin D., Sokolov F., Klein A., Szyrwiel Ł., Kubiak M., Kozlowski H., and Krivolapov D.

Abstract

Reaction of O,O'-diisopropylthiophosphoric acid isothiocyanate (iPrO) 2P(S)NCS with 1,10-diaza-18-crown-6, 1,7-diaza-18-crown-6, or 1,7-diaza-15-crown-5 leads to the N-thiophosphorylated bis-thioureas N,N'-bis[C(S)NHP(S)(OiPr)2]-1,10-diaza-18-crown-6 (H 2LI), N,N'-bis[C(S)NHP(S)(OiPr)2]-1,7-diaza-18- crown-6 (H2LII) and N,N'-bis[C(S)NHP(S)(OiPr) 2]-1,7-diaza-15-crown-5 (H2LIII). Reaction of the potassium salts of H2LI-III with a mixture of CuI and 2,2'-bipyridine (bpy) or 1,10-phenanthroline (phen) in aqueous EtOH/CH 2Cl2 leads to the dinuclear complexes [Cu 2(bpy)2LI-III] and [Cu2(phen) 2LI-III]. The structures of these compounds were investigated by 1H, 31P{1H} NMR spectroscopy, and elemental analysis. The crystal structures of H2LI and [Cu2(phen)2LI] were determined by single-crystal X-ray diffraction. Extraction capacities of the obtained compounds in comparison to the related compounds 1,10-diaza-18-crown-6, N,N'-bis[C(=CMe2)CH2P(O)(OiPr)2]-1,10-diaza-18- crown-6, N,N'-bis[C(S)NHP(O)(OiPr)2]-1,10-diaza-18-crown-6 towards the picrate salts LiPic, NaPic, KPic. and NH4Pic were also studied. Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

9. Coordination mode of the nickel(II) cation with N-diisopropoxyphosphinyl-p- bromothiobenzamide

Author

Safin D., Sokolov F., Baranov S., Szyrwiel Ł., Babashkina M., Shakirova E., Hahn F., Kozlowski H., Safin D., Sokolov F., Baranov S., Szyrwiel Ł., Babashkina M., Shakirova E., Hahn F., and Kozlowski H.

Abstract

Reaction of the potassium salt of N-diisopropoxyphosphinyl-p- bromothiobenzamide p-BrC6H4C(S)NHP(O)(OiPr)2 (HL) with Ni(NO3)2 in aqueous EtOH leads to complex of formula [Ni(HL-O)2(L-O,S)2] (1). The structure of 1 was investigated by single crystal X-ray diffraction analysis, IR, 1H and 31P{1H} NMR spectroscopy, MALDI and microanalysis. The nickel(II) ion in 1 has a tetragonal-bipyramidal environment, (O ax)2(Oeq)2(Seq) 2, with two neutral ligand molecules coordinated in axial positions through the oxygen atoms of the P=O groups. The equatorial plane of bipyramide is formed by two anionic ligands involving 1,5-O,S-coordination mode. The chelating ligands are bound in trans configuration. © 2008 Wiley-VCH Verlag GmbH & Co. KGaA.

10. Intramolecular hydrogen bond controlled monodentate S-coordination of N-phosphoryl-N′-(R)-thioureas with Pd(II)

Author

Safin D., Szyrwiel Ł., Baranov S., Sokolov F., Babashkina M., Kozlowski H., Safin D., Szyrwiel Ł., Baranov S., Sokolov F., Babashkina M., and Kozlowski H.

Abstract

Reaction of N-phosphorylated thioureas RNHC(S)NHP(O)(OiPr)2 (R = tBu, HLI; R = Ph, HLII; R = 4′-benzo-15-crown-5, HLIII) with Pd(PhCN)2Cl2 in acetonitrile leads to complexes of formulae Pd(HLI-S)2Cl2 (1), Pd(HLII-S)2Cl2 (2) and Pd(HLIII-S)2Cl2 (3). The crystal structure of complex 1 has been investigated by X-ray crystallography. It was established that the thiourea ligands are in a trans-configuration and the palladium(II) cation is coordinated by the sulfur atoms of the C{double bond, long}S groups and the chlorine atoms. Complex 1 is the first example of palladium(II) complex in which the potentially chelating N-phosphorylated thiourea ligand is bound through the sulfur atom only. © 2008 Elsevier B.V. All rights reserved.

11. Nickel(II) complexes with N-(thio)phosphorylthioureas AdNHC(S)NHP(X)(OiPr)2: Versatile coordination of phosphoryl (X = O) and thiophosphoryl (X = S) derivatives

Author

Safin D., Sokolov F., Szyrwiel Ł., Babashkina M., Gimadiev T., Hahn F., Kozlowski H., Krivolapov D., Litvinov I., Safin D., Sokolov F., Szyrwiel Ł., Babashkina M., Gimadiev T., Hahn F., Kozlowski H., Krivolapov D., and Litvinov I.

Abstract

The reaction of the potassium salts of N-(thio)phosphorylated thioureas of the common formula AdN(H)C(S)N(H)P(X)(OiPr)2 (X = O, HLI; X = S, HLII) with the Ni(II) cation in aqueous EtOH leads to [Ni(LI,II)2] chelate complexes. The molecular structures of the thioureas HLI,II and the complexes [Ni(LI-N,S)2] and [Ni(LII-S,S′)2] were elucidated by single crystal X-ray diffraction analysis, IR, 1H and 31P NMR spectroscopy and microanalysis. In the complex [Ni(LI)2], the metal center is found to be in a square-planar N2S2 environment formed by the C{double bond, long}S sulfur atoms and the P-N nitrogen atoms of two deprotonated LI ligands. The ligands are in a trans configuration. The Ni(II) atom in complex [Ni(LII)2], with the deprotonated thiourea LII, is coordinated in a square-planar fashion by the C{double bond, long}S and P{double bond, long}S sulfur atoms of two anionic ligands. The ligands are in a cis configuration. © 2008 Elsevier Ltd. All rights reserved.

12. Monodentate S-vs. bidentate 1,5-O,S-coordination of N-phosphoryl-N′-(R)-thioureas with Pd(II)

Author

Safin D., Sokolov F., Szyrwiel Ł., Baranov S., Babashkina M., Gimadiev T., Kozlowski H., Safin D., Sokolov F., Szyrwiel Ł., Baranov S., Babashkina M., Gimadiev T., and Kozlowski H.

Abstract

Reaction of N-phosphorylated thioureas of common formula RNHC(S)NHP(O)(OiPr)2 (R = tBu, HLI; R = Ph, HLII; R = 4′-benzo-15-crown-5, HLIII) with Pd(PhCN)2Cl2 in acetonitrile leads to complexes of the structure Pd(HLI-S)2Cl2 (1), Pd(HLII-S)2Cl2 (2) and Pd(HLIII-S)2Cl2 (3). Reaction of N-phosphorylated thioureas of common formula RC(S)NHP(O)(OiPr)2 (R = Et2N, HLIV; R = morpholine-N-yl, HLV) in the same conditions leads to complexes Pd(LIV-O,S)2 (4) and Pd(LV-O,S)2 (5), where the palladium(II) atoms are coordinated in a square-planar fashion by the C{double bond, long}S sulfur atoms and the P{double bond, long}O oxygen atoms of two anionic ligands. The crystal structure of complex 1 has been investigated by X-ray crystallography. It was established that the thiourea ligands are in a trans-configuration and the palladium(II) cation is coordinated by the sulfur atoms of the C{double bond, long}S groups and the chlorine atoms. Complex 1 is the first example of palladium(II) complex in which the potentially chelating N-phosphorylated thiourea ligand is bound through the sulfur atom only. © 2008 Elsevier Ltd. All rights reserved.

13. Coordination mode of the nickel(II) cation with N-diisopropoxyphosphinyl-p- bromothiobenzamide

Author

Safin D., Sokolov F., Baranov S., Szyrwiel Ł., Babashkina M., Shakirova E., Hahn F., Kozlowski H., Safin D., Sokolov F., Baranov S., Szyrwiel Ł., Babashkina M., Shakirova E., Hahn F., and Kozlowski H.

Abstract

Reaction of the potassium salt of N-diisopropoxyphosphinyl-p- bromothiobenzamide p-BrC6H4C(S)NHP(O)(OiPr)2 (HL) with Ni(NO3)2 in aqueous EtOH leads to complex of formula [Ni(HL-O)2(L-O,S)2] (1). The structure of 1 was investigated by single crystal X-ray diffraction analysis, IR, 1H and 31P{1H} NMR spectroscopy, MALDI and microanalysis. The nickel(II) ion in 1 has a tetragonal-bipyramidal environment, (O ax)2(Oeq)2(Seq) 2, with two neutral ligand molecules coordinated in axial positions through the oxygen atoms of the P=O groups. The equatorial plane of bipyramide is formed by two anionic ligands involving 1,5-O,S-coordination mode. The chelating ligands are bound in trans configuration. © 2008 Wiley-VCH Verlag GmbH & Co. KGaA.

14. Nickel(II) complexes with N-(thio)phosphorylthioureas AdNHC(S)NHP(X)(OiPr)2: Versatile coordination of phosphoryl (X = O) and thiophosphoryl (X = S) derivatives

Author

Safin D., Sokolov F., Szyrwiel Ł., Babashkina M., Gimadiev T., Hahn F., Kozlowski H., Krivolapov D., Litvinov I., Safin D., Sokolov F., Szyrwiel Ł., Babashkina M., Gimadiev T., Hahn F., Kozlowski H., Krivolapov D., and Litvinov I.

Abstract

The reaction of the potassium salts of N-(thio)phosphorylated thioureas of the common formula AdN(H)C(S)N(H)P(X)(OiPr)2 (X = O, HLI; X = S, HLII) with the Ni(II) cation in aqueous EtOH leads to [Ni(LI,II)2] chelate complexes. The molecular structures of the thioureas HLI,II and the complexes [Ni(LI-N,S)2] and [Ni(LII-S,S′)2] were elucidated by single crystal X-ray diffraction analysis, IR, 1H and 31P NMR spectroscopy and microanalysis. In the complex [Ni(LI)2], the metal center is found to be in a square-planar N2S2 environment formed by the C{double bond, long}S sulfur atoms and the P-N nitrogen atoms of two deprotonated LI ligands. The ligands are in a trans configuration. The Ni(II) atom in complex [Ni(LII)2], with the deprotonated thiourea LII, is coordinated in a square-planar fashion by the C{double bond, long}S and P{double bond, long}S sulfur atoms of two anionic ligands. The ligands are in a cis configuration. © 2008 Elsevier Ltd. All rights reserved.

15. Intramolecular hydrogen bond controlled monodentate S-coordination of N-phosphoryl-N′-(R)-thioureas with Pd(II)

Author

Safin D., Szyrwiel Ł., Baranov S., Sokolov F., Babashkina M., Kozlowski H., Safin D., Szyrwiel Ł., Baranov S., Sokolov F., Babashkina M., and Kozlowski H.

Abstract

Reaction of N-phosphorylated thioureas RNHC(S)NHP(O)(OiPr)2 (R = tBu, HLI; R = Ph, HLII; R = 4′-benzo-15-crown-5, HLIII) with Pd(PhCN)2Cl2 in acetonitrile leads to complexes of formulae Pd(HLI-S)2Cl2 (1), Pd(HLII-S)2Cl2 (2) and Pd(HLIII-S)2Cl2 (3). The crystal structure of complex 1 has been investigated by X-ray crystallography. It was established that the thiourea ligands are in a trans-configuration and the palladium(II) cation is coordinated by the sulfur atoms of the C{double bond, long}S groups and the chlorine atoms. Complex 1 is the first example of palladium(II) complex in which the potentially chelating N-phosphorylated thiourea ligand is bound through the sulfur atom only. © 2008 Elsevier B.V. All rights reserved.

16. Monodentate S-vs. bidentate 1,5-O,S-coordination of N-phosphoryl-N′-(R)-thioureas with Pd(II)

Author

Safin D., Sokolov F., Szyrwiel Ł., Baranov S., Babashkina M., Gimadiev T., Kozlowski H., Safin D., Sokolov F., Szyrwiel Ł., Baranov S., Babashkina M., Gimadiev T., and Kozlowski H.

Abstract

Reaction of N-phosphorylated thioureas of common formula RNHC(S)NHP(O)(OiPr)2 (R = tBu, HLI; R = Ph, HLII; R = 4′-benzo-15-crown-5, HLIII) with Pd(PhCN)2Cl2 in acetonitrile leads to complexes of the structure Pd(HLI-S)2Cl2 (1), Pd(HLII-S)2Cl2 (2) and Pd(HLIII-S)2Cl2 (3). Reaction of N-phosphorylated thioureas of common formula RC(S)NHP(O)(OiPr)2 (R = Et2N, HLIV; R = morpholine-N-yl, HLV) in the same conditions leads to complexes Pd(LIV-O,S)2 (4) and Pd(LV-O,S)2 (5), where the palladium(II) atoms are coordinated in a square-planar fashion by the C{double bond, long}S sulfur atoms and the P{double bond, long}O oxygen atoms of two anionic ligands. The crystal structure of complex 1 has been investigated by X-ray crystallography. It was established that the thiourea ligands are in a trans-configuration and the palladium(II) cation is coordinated by the sulfur atoms of the C{double bond, long}S groups and the chlorine atoms. Complex 1 is the first example of palladium(II) complex in which the potentially chelating N-phosphorylated thiourea ligand is bound through the sulfur atom only. © 2008 Elsevier Ltd. All rights reserved.

17. Dinuclear complexes of copper(I) with crown ether-containing N-thiophosphorylated bis-thioureas and 2,2'-bipyridine or 1,10-phenanthroline: Synthesis, characterization, and picrate extraction properties

Author

Babashkina M., Shakirova E., Safin D., Sokolov F., Klein A., Szyrwiel Ł., Kubiak M., Kozlowski H., Krivolapov D., Babashkina M., Shakirova E., Safin D., Sokolov F., Klein A., Szyrwiel Ł., Kubiak M., Kozlowski H., and Krivolapov D.

Abstract

Reaction of O,O'-diisopropylthiophosphoric acid isothiocyanate (iPrO) 2P(S)NCS with 1,10-diaza-18-crown-6, 1,7-diaza-18-crown-6, or 1,7-diaza-15-crown-5 leads to the N-thiophosphorylated bis-thioureas N,N'-bis[C(S)NHP(S)(OiPr)2]-1,10-diaza-18-crown-6 (H 2LI), N,N'-bis[C(S)NHP(S)(OiPr)2]-1,7-diaza-18- crown-6 (H2LII) and N,N'-bis[C(S)NHP(S)(OiPr) 2]-1,7-diaza-15-crown-5 (H2LIII). Reaction of the potassium salts of H2LI-III with a mixture of CuI and 2,2'-bipyridine (bpy) or 1,10-phenanthroline (phen) in aqueous EtOH/CH 2Cl2 leads to the dinuclear complexes [Cu 2(bpy)2LI-III] and [Cu2(phen) 2LI-III]. The structures of these compounds were investigated by 1H, 31P{1H} NMR spectroscopy, and elemental analysis. The crystal structures of H2LI and [Cu2(phen)2LI] were determined by single-crystal X-ray diffraction. Extraction capacities of the obtained compounds in comparison to the related compounds 1,10-diaza-18-crown-6, N,N'-bis[C(=CMe2)CH2P(O)(OiPr)2]-1,10-diaza-18- crown-6, N,N'-bis[C(S)NHP(O)(OiPr)2]-1,10-diaza-18-crown-6 towards the picrate salts LiPic, NaPic, KPic. and NH4Pic were also studied. Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

18. In vitro SOD-like activity of mono- and di-copper complexes with a phosphonate substituted SALAN-type ligand.

Author

Székács I, Tokarz P, Horvath R, Kovács K, Kubas A, Shimura M, Brasun J, Murzin V, Caliebe W, Szewczuk Z, Paluch A, Wojnárovits L, Tóth T, Pap JS, and Szyrwiel Ł

Subjects
3T3-L1 Cells, Animals, Antioxidants chemistry, Antioxidants pharmacology, Cell Survival drug effects, Cells, Cultured, Copper chemistry, Ligands, Mice, Molecular Conformation, Organometallic Compounds chemistry, Organometallic Compounds pharmacology, Oxidation-Reduction, Antioxidants metabolism, Copper pharmacology, Organometallic Compounds metabolism, Superoxide Dismutase metabolism
Abstract

SALEN- and SALAN-based complexes with catalytically active metal centers are very promising small molecules to be utilized as part of antioxidant therapies. Here we discuss a modified SALAN-type molecule armed with two phosphonate groups that significantly increase its water solubility and aid to furnish mono- or dinuclear complexes with Cu 2+ ions. The regulation of the SOD-mimicking (i.e., catalytic) disproportionation reaction of the superoxide radical anion (O 2 •- ) at pH ~7.5 could be achieved by adjusting the metal-to-ligand stoichiometry as confirmed by McCord-Fridovich and pulse radiolysis tests. The higher antioxidant activity of the dicopper complex can be explained by the better access of O 2 •- to the copper centers and their more positive Cu(II)/Cu(I) redox potential. Simultaneously the analysis of in vitro effect on cells morphology indicates that cytotoxicity is also affected by the metal-to-ligand ratio, however, the active complex molecules do not show notable cytotoxicity that, together with the observed SOD-like activities, makes them potential candidates for antioxidant therapies., (Copyright © 2019. Published by Elsevier B.V.)

Published
2019
Full Text
View/download PDF

19. Self-assembled, nanostructured coatings for water oxidation by alternating deposition of Cu-branched peptide electrocatalysts and polyelectrolytes.

Author

Farkas E, Srankó D, Kerner Z, Setner B, Szewczuk Z, Malinka W, Horvath R, Szyrwiel Ł, and Pap JS

Abstract

This work demonstrates the heterogenization of homogeneous water oxidation electrocatalysts in surface coatings produced by combining the substances with a suitable polyelectrolyte. The electrocatalysts i.e. Cu(ii)-branched peptide complexes involving a 2,3-l-diaminopropionic acid junction unit are heterogenized by building composite layers on indium-tin-oxide (ITO) electrode surface. Alternating deposition of the peptide complexes and poly(l-lysine) or poly(allylamine hydrochloride) were carried out in the presence of phosphate in a pH range of 7.5-10.5. Discussion of the results is divided to (1) characteristics of composite layer buildup and (2) electrocatalytic water oxidation and accompanying changes of these layers. For (1), optical waveguide lightmode spectroscopy (OWLS) has been applied to reveal the layer-by-layer formation of a Cu-ligand/polyelectrolyte/phosphate coating. The fabricated structures had a nanoporous topography (atomic force microscopy). As for (2), electrochemistry employing coated ITO substrates indicated improved water oxidation electrocatalysis vs. neat ITO and dependence of this improvement on the presence or absence of a histidine ligand in the deposited Cu(ii)-complexes equally, as observed in homogeneous systems. Electrochemical OWLS revealed changes in the coatings in operando , upon alternating positive-zero-positive etc. polarization: after some initial loss of the coating mass steady-state electrolysis was sustained by a compact and stable layer. According to X-ray photoelectron spectroscopy Cu remains in an N-donor ligand environment after electrolysis.

Published
2016
Full Text
View/download PDF

20. In vitro induction and proteomics characterisation of a uranyl-protein interaction network in bovine serum.

Author

Szyrwiel Ł, Liauchuk V, Chavatte L, and Lobinski R

Subjects
Animals, Cattle, Protein Binding, Protein Interaction Maps, Blood Proteins chemistry, Blood Proteins metabolism, Protein Interaction Mapping methods, Proteomics methods, Uranium Compounds chemistry, Uranium Compounds metabolism
Abstract

Uranyl ions (UO2(2+)) were shown to interact with a number of foetal serum proteins, leading to the formation of a complex that could be isolated by ultracentrifugation. The molecular weight of the complex was estimated based on size-exclusion chromatography as 650 000 Da. Online ICP AES detection indicated that UO2(2+) in the complex co-eluted with minor amounts of calcium and phosphorous, but not with magnesium. A 1D gel electrophoresis of the U-complex produced more than 10 bands of similar intensity compared with only 2-3 intense bands corresponding to the main serum proteins in the control serum, indicative of the specific interaction of UO2(2+) with minor proteins. A proteomics approach allowed for the identification of 74 proteins in the complex. Analysis of the protein-protein interaction network in the UO2(2+) complex identified 32 proteins responsible for protein-protein complex formation and 34 with demonstrated ion-binding function, suggesting that UO2(2+) stimulates the formation of protein functional networks rather than using a particular molecule as its target.

Published
2015
Full Text
View/download PDF

21. A novel branched TAT(47-57) peptide for selective Ni(2+) introduction into the human fibrosarcoma cell nucleus.

Author

Szyrwiel Ł, Shimura M, Shirataki J, Matsuyama S, Matsunaga A, Setner B, Szczukowski Ł, Szewczuk Z, Yamauchi K, Malinka W, Chavatte L, and Łobinski R

Subjects
Amino Acid Sequence, Carcinogens chemistry, Carcinogens metabolism, Carcinogens toxicity, Cell Line, Tumor, Cell Nucleus genetics, Cell Nucleus pathology, DNA Damage drug effects, Fibrosarcoma genetics, Fibrosarcoma pathology, Humans, Nickel administration & dosage, Optical Imaging, Peptide Fragments chemistry, tat Gene Products, Human Immunodeficiency Virus chemistry, Cell Nucleus metabolism, Fibrosarcoma chemically induced, Fibrosarcoma metabolism, Nickel metabolism, Nickel toxicity, Peptide Fragments metabolism, tat Gene Products, Human Immunodeficiency Virus metabolism
Abstract

A TAT47-57 peptide was modified on the N-terminus by elongation with a 2,3-diaminopropionic acid residue and then by coupling of two histidine residues on its N-atoms. This branched peptide could bind to Ni under physiological conditions as a 1 : 1 complex. We demonstrated that the complex was quantitatively taken up by human fibrosarcoma cells, in contrast to Ni(2+) ions. Ni localization (especially at the nuclei) was confirmed by imaging using both scanning X-ray fluorescence microscopy and Newport Green fluorescence. A competitive assay with Newport Green showed that the latter displaced the peptide ligand from the Ni-complex. Ni(2+) delivered as a complex with the designed peptide induced substantially more DNA damage than when introduced as a free ion. The availability of such a construct opens up the way to investigate the importance of the nucleus as a target for the cytotoxicity, genotoxicity or carcinogenicity of Ni(2+).

Published
2015
Full Text
View/download PDF

22. Electrocatalytic water oxidation by Cu(II) complexes with branched peptides.

Author

Pap JS, Szyrwiel Ł, Srankó D, Kerner Z, Setner B, Szewczuk Z, and Malinka W

Subjects
Catalysis, Electrochemistry, Oxidation-Reduction, Copper chemistry, Organometallic Compounds chemistry, Peptides chemistry, Water chemistry
Abstract

Two mononuclear Cu(II) complexes with tetrapeptides incorporating a L-2,3-diaminopropionic acid (dap) branching unit are reported to undergo PCET and catalyse water oxidation. C-terminal His extension of dap (L = 2GH) instead of Gly (L = 3G) lowers the pKa for Cu(III)H-2L (9.36 vs. 9.98) and improves the TOF at pH 11 (53 vs. 24 s(-1)).

Published
2015
Full Text
View/download PDF

23. The Cu²⁺ binding properties of branched peptides based on L-2,3-diaminopropionic acid.

Author

Szyrwiel Ł, Szczukowski Ł, Pap JS, Setner B, Szewczuk Z, and Malinka W

Subjects
Hydrogen-Ion Concentration, Potentiometry, Spectrometry, Mass, Electrospray Ionization, beta-Alanine chemistry, Copper chemistry, Peptides chemical synthesis, beta-Alanine analogs & derivatives
Abstract

Three new branched peptides, namely, H-Gly-Dap(H-Gly)-Gly-NH2 (3G), H-His-Dap(H-His)-Gly-NH2 (2HG), and H-Gly-Dap(H-Gly)-His-NH2 (2GH), where Dap stands for the 2,3-diaminopropionic acid residue, were synthesized by solid phase procedures. Because of the junction at Dap these peptides have three available pending arms for metal chelation. The complex formation between these peptides and 1 equiv of Cu(2+) was investigated as a function of pH by potentiometry ultraviolet-visible absorption, circular dichroism, and X-band electron paramagnetic resonance spectroscopy in aqueous medium. Our results clearly demonstrate that cooperation between all three peptide arms essentially contributes to the stability of copper(II) complexes.

Published
2014
Full Text
View/download PDF

24. The cyclopeptides with the multi-His motif as ligands for copper(II).

Author

Czapor H, Bielińska S, Kamysz W, Szyrwiel Ł, and Brasuń J

Subjects
Animals, Coordination Complexes chemical synthesis, Ligands, Models, Molecular, Oligopeptides chemical synthesis, Peptides, Cyclic chemical synthesis, Potentiometry, Spectrometry, Mass, Electrospray Ionization, Structure-Activity Relationship, Coordination Complexes chemistry, Copper, Histidine chemistry, Oligopeptides chemistry, Peptides, Cyclic chemistry
Abstract

The coordination properties of cyclic octapeptides with multi-His motif: c(His-Gly-His-Xaa-His-Gly-His-Xaa) where Xaa = Asp or Lys, were investigated. The binding abilities of this peptides towards Cu(II) ions were studied by using different analytic methods as: potentiometry, spectroscopy and mass spectrometry. The obtained results show that the studied peptides in physiological related pH prefer formation of the species with the {4N(Im)} binding mode. The efficiency of Cu(II) binding depends on additional side chain groups Asp or Lys. Additionally the analysis of results for His containing cyclopeptides with different numbers of amino acid residues in cyclopeptide ring e.g. four, eight shows that in higher pH in both cases the binding by four amide nitrogens is not observed in the case of α-amino acid peptides., (Copyright © 2010 Elsevier Inc. All rights reserved.)

Published
2011
Full Text
View/download PDF

25. One-pot synthesis of a new magnetically coupled heterometallic Cu(2)Mn(2) [2 x 2] molecular grid.

Author

Moroz YS, Szyrwiel Ł, Demeshko S, Kozłowski H, Meyer F, and Fritsky IO

Subjects
Crystallography, X-Ray, Cyclization, Models, Molecular, Molecular Structure, Organometallic Compounds chemistry, Copper chemistry, Magnetics, Manganese chemistry, Organometallic Compounds chemical synthesis
Abstract

The heterometallic [2 x 2] grid-type complex [Cu(2)Mn(2)(pop)(4)(OAc)(4)].7H(2)O (1) has been selectively synthesized in a targeted one-pot reaction. Single-crystal X-ray analysis shows the expected structure with identical metal ions located at diagonal vertices of the grid. Magnetochemical studies reveal that 1 has a ferrimagnetic spin ground state with some admixture of low-lying excited states.

Published
2010
Full Text
View/download PDF

26. Heteronuclear and homonuclear Cu2+ and Zn2+ complexes with multihistidine peptides based on zebrafish prion-like protein.

Author

Valensin D, Szyrwiel Ł, Camponeschi F, Rowińska-Zyrek M, Molteni E, Jankowska E, Szymanska A, Gaggelli E, Valensin G, and Kozłowski H

Subjects
Animals, Circular Dichroism, Copper metabolism, Histidine chemistry, Histidine metabolism, Isomerism, Nuclear Magnetic Resonance, Biomolecular, Peptides metabolism, Prions metabolism, Protein Binding, Zinc metabolism, Copper chemistry, Peptides chemistry, Prions chemistry, Zebrafish metabolism, Zinc chemistry
Abstract

The homeostasis of metal ions, especially copper and zinc, is a major factor that may influence the prion diseases and the biological function of prion protein (PrP). The His-rich regions are basic sites for metal binding and antioxidant activity of the PrP structures. Animal prion-like proteins contain also His-rich domains, and their coordination chemistry may provide better insight into the chemistry and biology of PrP structures and related diseases. Herein, we report an equilibrium study on heteronuclear Zn(2+)-Cu(2+) complexes with zrel-PrP fragments from zebrafish. Potentiometric, spectroscopic, and mass spectrometric methods showed that the binding of copper is much more effective than the binding of zinc. At physiological pH, both metals bind to the histidine imidazole N donors of the studied peptides.

Published
2009
Full Text
View/download PDF

Catalog

Books, media, physical & digital resources
See catalog results