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1

Modele eksperymentalne w badaniach zewnątrzkomórkowego transportu miedzi

Bal Wojciech

Wiadomości Chemiczne

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2022

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[Z] 76, 5-6

456-466

EN

The biological relevance of proteins and peptides for Cu(II) biology, including the extracellular transport of this element, is commonly estimated by studying stabilities and structures of their complexes. However, our experimental studies on the kinetics of formation of Cu(II) complexes of ATCUN/NTS and Xaa-His-R peptides, considered to be key actors in extracellular copper biology, revealed novel long-lived reaction intermediates. These intermediates, rather than the final reaction products fulfil the chemical criteria for actual biocomplexes derived from biological studies. Our research clearly demonstrated that understanding of the kinetic aspect of interactions is indispensable for realistic modeling of biological interactions of metal ions.

2

Selective transport of copper(II) ions across polymer inclusion membrane with aromatic β–diketones as carriers

Radzymińska-Lenarcik E., Witt K., Bożejewicz D.

Physicochemical Problems of Mineral Processing

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2018

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Vol. 54, iss. 3

741--750

EN

The transport of Cu(II) ions from an equimolar mixture of Co(II), Ni(II), and Cu(II) ions as well as from solutions containing only Cu(II) ions in the feed phase through polymer inclusion membranes (PIMs) with aromatic β–diketones as carriers has been investigated. The polymer membranes consisted of polyvinylchloride (PVC) as the support, bis(2-ethylhexyl)adipate (ADO) as plasticizer, and aromatic β–diketones (benzoylacetone (1) and dibenzoylmethane (2)) as ion carriers. The transport selectivity of PIMs with 1 and 2 was: Cu(II) > Co(II) > Ni(II). The highest recovery factors of Cu(II) ions were observed for 1 (94.0%), whereas for Co(II) and Ni(II) the factors were 21.4 and 7.3%, respectively. The Cu(II)/Co(II) and Cu(II)/Ni(II) selectivity coefficients were equal to 8.9 and 33.7 (for 1), 6.4 and 28.3 (for 2), respectively.

3

Adsorpcja fenolu i jonów miedzi(II) na sferycznym węglu aktywnym utlenianym nadtlenodisiarczanem(VI) diamonu

Dąbek L., Kuśmierek K., Świątkowski A.

Ochrona Środowiska

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2018

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Vol. 40, nr 4

3--8

PL

Zbadano adsorpcję fenolu i jonów miedzi(II) z modelowych roztworów wodnych na sferycznym węglu aktywnym utlenianym nadtlenodisiarczanem(VI) diamonu w różnych warunkach. Do oceny stopnia modyfikacji węgla wykorzystano analizę elementarną oraz izotermy adsorpcji pary wodnej i benzenu. Wykazano, że adsorpcję fenolu i jonów Cu(II) z roztworów wodnych można dobrze opisać modelami izoterm Freundlicha i Langmuira. Stwierdzono, że adsorpcja fenolu zmniejszała się wraz ze wzrostem stopnia utlenienia węgla i spadkiem jego powierzchni właściwej. Adsorpcja jonów Cu(II) zwiększała się wraz ze wzrostem stopnia utlenienia powierzchni węgla aktywnego, wykazując dużą rolę kwasowych grup tlenowych w adsorpcji jonów metalu na drodze wymiany jonowej. Wykazano również, że nadtlenodisiarczan(VI) diamonu okazał się bardzo skutecznym utleniaczem, gdyż nawet utlenianie węgla w najbardziej łagodnych warunkach (stężenie 0,1 mol/dm3, czas 30 min) dało znaczące zwiększenie ilości związanego tlenu (ok. 3,4-krotne) oraz znaczące zwiększenie ilości adsorbowanych jonów miedzi(II), przy stosunkowo niedużym zmniejszeniu ilości adsorbowanego fenolu.

EN

Adsorption of phenol and copper(II) ions from model aqueous solutions on spherical activated carbon oxidized with ammonium persulfate under various conditions was investigated. Elemental analysis and adsorption isotherms of water and benzene vapors were employed to assess the extent of modifications of the activated carbon surface. It was demonstrated that adsorption of phenol and Cu(II) ions from aqueous solutions could be well described by the Freundlich and Langmuir isotherm models. Adsorption of phenol decreased with the increasing degree of carbon oxidation as well as its decreasing specific surface area. Adsorption of the Cu(II) ions increased with the increasing degree of carbon surface oxidation indicating an important role of acidic groups in adsorption of metal ions by ion-exchange mechanism. Furthermore, ammonium persulfate was demonstrated to be an efficient oxidizing agent as carbon oxidation under even the mildest conditions (0.1 mol/dm3, 30 min) led to a significant increase in the oxygen bound (about 3-4 times) as well as the Cu(II) ions adsorbed. The amount of the adsorbed phenol decreased only slightly.

4

Badanie własności związków kompleksowych wybranych biopierwiastków ze składnikami napojów energetyzujących

Giełzak-Koćwin K., Poroś P.

Chemistry, Environment, Biotechnology

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2017

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Vol. 20

43--50

PL

Napoje energetyzujące cieszą się w Polsce znaczną popularnością, zwłaszcza wśród studentów podczas wzmożonej pracy umysłowej czy sportowców intensywnie trenujących. Produkty te mogą mieć zarówno pozytywne, jak i negatywne oddziaływanie, stąd konieczność prowadzenia badań nad ich optymalnym składem i działaniem na organizm. W tej publikacji badano zdolności kompleksowania wybranych składników napojów energetyzujących, tauryny i L-karnityny z jonami metali bioaktywnych, miedzi(II) i oksowanadu(IV). Przeprowadzono pomiary spektrofotometryczne w zakresie widzialnym promieniowania elektromagnetycznego dla roztworów wodnych zawierających różne stężenia jonów metali oraz tauryny i L-karnityny oraz pomiary pH-metryczne roztworów. Wykazano możliwości tworzenia trwałych połączeń koordynacyjnych L-karnityny z Cu2+ i VO2+ oraz bardzo słabe oddziaływania z tauryną. Wprowadzenie słabej zasady (amoniaku) i słabego kwasu (kwasu octowego), zmieniających pH roztworów badanych, miało zasadniczy wpływ na stany równowagowe w roztworach kompleksów z tauryną i L-karnityną.

EN

Energy drinks sustain considerable level of popularity in Poland, especially among students doing intense mental work or intensively training sportsmen. These products can have both positive and negative influence, hence the need to conduct research on their optimal composition and effects on the body. In this paper the complexation abilities of selected components of energy drinks, taurine and L-carnitine with bioactive metal ions, copper(II) and oxovanadium(IV) have been tested. Spectrophotometric measurements were made in aqueous solutions containing varying amounts of metals and taurine or L-carnitine, without any buffer solutions, and without stabilization of ionic strength in the visible range of electromagnetic radiation as well as the solutions pH-metric measurements. The ability to create persistent coordination bonds of L-carnitine with Cu2+ and VO2+ has been shown as well as a very weak interactions with taurine. Addition of components altering pH of the solutions had a major effect on the equilibrium states in the solution of ammonia and of acetic acid complexes with taurine and L-carnitine.

5

Separation of palladium(II) from mixtures of non-ferrous metal ions by solvent extraction

Radzyminska-Lenarcik E., Witt K.

Challenges of Modern Technology

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2016

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Vol. 7, no. 1

17-22

EN

The possibility of Pd(II) ions separation from mixtures of Co(II), Ni(II), Cu(II) and Pd(II) ions by solvent extraction was studied, using 1-hexyl-2methylimidazole in chloroform as the extractant. The initial concentration of each ion was 10 mM. The tests were carried out at a temperature of 25°C, at a constant strength of the aqueous solution of I = 0.5, as maintained by the KCl solution. It was demonstrated that differences in the stability and structure of their coordination sphere as well as solubility of complexes with the extractant could be used for separating the Co(II), Ni(II), Cu(II) and Pd(II) ions by solvent extraction. Pd(II), which forms flat-square complexes in the solutions, passes easily into the organic phase and is easier separated from the mixture of Co(II), Ni(II), Cu(II) ions, which form octahedral or tetrahedral complexes. Extraction percentages were calculated. For the respective metals, their values increase for increasing concentrations of the extractant in the aqueous phase. The extraction percentage decreases in the following order: Pd(II) > Cu(II) > Co(II) > Ni(II). In the case of the quaternary mixture, the highest extraction percentage for Pd(II) (70%) was obtained at a pH=7.33. Separation coefficients were also calculated. The highest separation coefficients were obtained for the system: Pd(II)/Ni(II), Pd(II)/Co(II); at a pH of 5.4 for an aqueous solution, their values are 13.3 and 7.7, respectively.

6

The use of the steric effect of the carrier molecule in the polymer inclusion membranes for the separation of cobalt(II), nickel(II), copper(II), and zinc(II) ions

Radzyminska-Lenarcik E., Ulewicz M.

Polish Journal of Chemical Technology

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2015

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Vol. 17, nr 2

51--56

EN

In this study, palladium-modified nickel foam substrate was applied to examine ethanol oxidation reaction (EOR) in 0.1 The transport of cobalt(II), nickel(II), copper(II), and zinc(II) ions from chloride solutions across polymer inclusion membranes (PIMs), which 1-heptylimidazole (1̲) or 1-heptyl-2-methylimidazole (2̲) or 1-heptyl-4-methylimidazole (3̲) as the ion carrier was reported. The steric effect for carriers 2̲&enspand 3̲&enspdecreases the transport of all ions except Cu(II). The initial fluxes of metal ions transport across PIMs with the 1̲- 2̲&enspdecrease in the sequence: Cu(II) > Zn(II) > Co(II) > Ni(II), whereas for 3 they were Cu(II) > Zn(II) > Ni(II) > Co(II). The highest recovery values were obtained for Cu(II), this being 99 and 85% for carrier 1̲&enspand 2̲, respectively. In both membranes the degree of deposition of the Zn(II) ions was comparable. Zn(II), Co(II) and Cd(II) ions, which form complexes with coordination numbers 4 and 6, are more easily recovered with the use of carriers 2̲&enspand 3̲. Ni(II) ions, which form complexes with coordination number 6 only, practically remain in the feeding phase. PIMs with alkylimidazoles were characterized by non-contact atomic force microscopy.

7

Selective removal of Ag(I) and Cu(II) by plasticizer membranes with n-(diethylthiophosphoryl)-aza[18]crown-6 as a carrier

Kolodziejska M., Kozlowski C., Kozlowska J., Ulewicz M.

Physicochemical Problems of Mineral Processing

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2014

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Vol. 50, iss. 1

237--247

EN

The competitive transport of equimolar mixtures of Ag(I) and Cu(II) ions from aqueous source phase (cMe = 0.001 mol/dm3) across polymer inclusion membranes PIMs with N-(diethylthiophosphoryl)aza[18]crown-6 as ion carriers, was studied. The influence of pH of source phase and metal concentration on an efficiency of silver(I) transport through polymer inclusion membranes containing cellulose triacetate as the support and o-nitrophenyl pentyl ether as the plasticizer was studied. The transport selectivity order for the PIM with N-(diethylthiophosphoryl)-aza[18]crown-6 was: Ag(I) >> Cu(II). The metal cations transport rate can be explained by size and nature of substituent in lariat ether molecule, which prefer formation of Ag(I) complex in the membrane phase.

8

Separation of lead(II) and copper(ii) by plasticizer membranes with sulphur ana-logus of phosphinic acids as carriers

Kolodziejska M., Kozlowski C., Ulewicz M.

Physicochemical Problems of Mineral Processing

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2013

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Vol. 49, iss. 1

267--276

EN

Investigation of selective removal of Pb(II) and Cu(II) from acidic nitrate aqueous solutions using transport across polymer inclusion membranes PIMs was performed. The sulphur analogus of phosphinic acids, i.e. bis(2,4,4-trimethylpentyl)monothiophosphinic acid (1) and tert-butyl(phenyl)- phosphinothioic acid (2) as well as their mixture were incorporated into polymer inclusion membranes composed of cellulose triacetate as a support and o-nitrophenyl octyl ether as a plasticizer. In the experi-ments the transport of Cu(II) across PIM with 1 was rapid and complete, however the lead(II) removal increased with increased membrane saturation. Selective transport of Cu(II) over Pb(II) through PIMs with binary carrier system (1 + 2) was observed; the selectivity order was: Cu(II) >> Pb(II). At tempera-ture of 50C the selectivity coefficient Cu(II)/Pb(II) for membrane with binary carriers was the highest and was equal to 758.

9

Application of supported and polymer membrane with 1 decyl-2-methylimidazole for separation of transition metal ions

Ulewicz M., Radzyminska-Lenarcik E.

Physicochemical Problems of Mineral Processing

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2012

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Vol. 48, iss. 1

91-102

EN

The facilitated transport of Cu(II), Zn(II), Co(II), and Ni(II) ions from different aqueous nitrate source phases (cMe = 0.001M, pH 6.0) across polymer inclusion membranes (PIMs) consisting of cellulose triacetate (support) and 2-nitrophenylpentyl ether (plasticizer) doped with 1-decyl-2-methylimidazol as ion carrier was reported. The membrane is characterised by atomic force microscopy (AFM) and thermal analysis (DTA and TG) techniques. The results show that Cu2+ can be separated very effectively from other transition metal cations as Zn2+, Co2+, and Ni2+ from different equimolar mixtures of these ions. The recovery factor of Cu2+ ions during transport across PIM from different mixture is equal to 92-95.1%. The comparative transport of Cu(II), Zn(II), Co(II), and Ni(II) ions from aqueous nitrate source phase across supported (SLMs) containing 1-decyl-2-methylimidazol as ion carrier was reported.

10

Transport of metal ions across polymer inclusion membrane with 1-alkylimidazole

Ulewicz M., Radzymińska-Lenarcik E.

Physicochemical Problems of Mineral Processing

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2011

|

Vol. 46

119-130

EN

The facilitated transport of copper(II), zinc(II), cobalt(II), and nickel(II) ions across polymer inclusion membranes (PIMs), which consist of cellulose triacetate as polymeric support, o-nitrophenyl pentyl ether as plasticizer and 1-alkylimidazole as ion carrier was reported. PIM was characterized by using atomic force microscopy (AFM) technique. The results show that Cu2+ can be separated very effectively from others heavy and transition metal cations as Zn2+, Co2+, and Ni2+ (at concentration of 10-3 M each). Alkyl substituents in position 1 of imidazole ring have an effect on hydrophobic properties and the initial flux of the transported metal ions. Also, the influence of the chloride ions concentration on the separation process was investigated. To explain the mechanism of membrane transport the diffusion of metal ions complexes with 1-alkylimidazole was also measured.

PL

Zbadano selektywność transportu jonów Cu(II), Zn(II), Co(II) i Ni(II) (cMe=0,001M, każdy) przez polimerowe membrany inkluzyjne składające się z trójoctanu celulozy (suportu), eteru o-nitrofenylooktylu (plastyfikatora) i przenośnika jonów (1 alkiloimidazole). Polimerowa membrana została scharakteryzowana przy pomocy mikroskopii sił atomowych (AFM). Wykazano, że podstawnik alkilowy w pozycji 1 pierścienia imidazolu zmieniając własności hydrofobowe przenośnika wpływa na strumień początkowy transportu jonów metali. Wartości strumienia początkowego transportu jonów przy użyciu przenośnika 1 i 2 maleją w szeregu: Cu(II) > Zn(II) > Co(II) > Ni(II), natomiast dla 3 - 5 w szeregu: Cu(II) > Zn(II) > Ni(II), Co(II). Strumień transportu Cu(II) wzrasta w szeregu użytych przenośników: 1 < 2 < 3 < 4 ɝ, osiągając najwyższą wartość 6,36 µµmol/m2 · s (dla 5). Na selektywność transportu wpływ również stężenie jonów chlorkowych w fazie zasilającej. Czynnikiem limitującym szybkości transportu Cu2+ przez PIM jest współczynnik dyfuzji kompleksu przenoszonego kationu przez membranę.

11

Synthesis and Properties of New Bimetallic Complexes of General Formula: [Cu(diamine)2][Cr(NCS)4(NH3)2]2

Wrzeszcz G., Grzebielucha T.

Polish Journal of Chemistry

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2009

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Vol. 83, nr 9

1575-1582

EN

Four new thiocyanato bridged heteronuclear com plexes of general formula [Cu(diamine)2][Cr(NCS)4(NH3)2]2, where diamine = ethylenediamine (en) (1), 1,2-di -amino propane (pn) (2), 1,3-diaminopropane (tn) (3) and N-methylethylenediamine (men) (4) have been prepared in solid state by treatment of [Cr(NCS)4(NH3)2]– with corresponding cationic [Cu(diamine)2]2+ complex in anaqueous solutions. They have been characterized by elemental and thermal analysis, spectroscopic methods (IR, UV-Vis, EPR), and variable-temperature magnetic susceptibility measurements. The formation of end-to-end thiocyanato bridges between tetragonal (elongated octahedral) Cu(II) and octahedral Cr(III) is evident from IR and electronic spectra. The EPR spectra measured at room temperature on solid samples (1 and 3) show very broad and symmetric signal at g = 2.02 and 2.07, respectively. Magnetic data reveal the absence of significant exchange inter actions between the Cr(III) and Cu(II) ions in all studied complexes (1–4). Thermal decomposition after ammonia release is multistage and yields CuO, and Cr2O3 as final products.

12

Hexacyanochromates(III) and Hexacyanocobaltates(III) of Copper(II) with Tridentate and Tetradentate N-donor Ligands. Crystal Structure of [{Cu(ept)}3{Co(CN)6}2]źH2O (ept = N-(2-aminoethyl)-1,3-propandiamine)

Mamulová Kutláková K., Smékal Z., Neels A., Önal M., Šindelář Z.

Polish Journal of Chemistry

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2009

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Vol. 83, nr 10

1707-1716

EN

The following complexes [{Cu(ept)}3{Cr(CN)6}2]ź5H2O, [{Cu(hatce)}3{Cr(CN)6}2]ź ź15H2O, [{Cu(hatco)}3{Cr(CN)6}2]ź14H2O, [{Cu(ept)}3{Co(CN)6}2]ź5H2O, [{Cu(hatce)}3{Co(CN)6}2]ź18H2O and [{Cu(medpt)}3{Co(CN)6}2]źH2O (ept = N-(2-amino ethyl)-1,3-propandiamine, hatce = 1,3,6,10,12,15-hexaaza tricyclo [13.3.1.16,10]eicosane, hatco = 1,3,6,9,11,14-hexaaza tricyclo[12.2.1.16,9]octadecane and medpt = N,N-bis-(3-aminopropyl)methylamine) have been synthesized by the reactions of Cu(ClO4)2ź6H2O or Cu(NO3)2ź3H2O and ept or medpt, or [Cu(hatce)](ClO4)2ź2H2O and [Cu(hatco)Cl]ClO4źH2O, and K3[Cr(CN)6] or K3[Co(CN)6] in aqueous solution, respectively. All the compounds have been characterized by elemental analyses, IR and UV-Vis spectroscopies and magnetic measurements and the three selected complexes were studied using thermal analysis. The crystal structure of [{Cu(ept)}3{Co(CN)6}2]ź źH2O has been determined by single-crystal X-ray analysis – the studied compound can be for mulated as [{Cu(ept)}6{Co(CN)6}3][Co(CN)6]ź2H2O. The copper atom is five-coordinated by two cyanide-nitrogen and three ept-nitrogen atoms, in a distorted square-pyramidal arrangement. The structure of the other complexes with cyanide bridges between hexacoordinated chromium(III) (S = 3/2) or cobalt(III) (S = 0) and penta- or hexacoordinated copper(II) (S = 1/2) is proposed.

13

Structure and characterization of copper(II) perchlorate with diethyl(pyridin-2-ylmethyl) phosphonate (2-pmpe) ligand: [Cu(2-pmpe)2(ClO4)2]

Żurowska B., Białońska A., Ochocki J.

Materials Science Poland

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2009

|

Vol. 27, No. 4/1

987--998

EN

Copper(II) mononuclear compound [Cu(2-pmpe)2(ClO4)2] (2-pmpe = diethyl(pyridin-2-ylmethyl) phosphonate was synthesized and studied. Examination of the crystal structure by the X-ray diffraction method revealed two crystallographically unrelated molecules, [Cu(1)(2-pmpe)2(ClO4)2] (1) and [Cu(2)(2-pmpe)2(ClO4)2] (2) in an asymmetric part of the unit cell. The geometry about the Cu(1) and Cu(2) chromophores shows elongated octahedra, resulting from the didentate N,O-bonded two chelate 2-pmpe ligands and two coordinated perchlorate ions around the Cu(II) cations (CuN2O4 chromophore). Similarly to 1, molecules 2 are linked to each other by weak C-HoooO hydrogen bonds and ?ooo? stacking interactions. Additionally, both 1 and 2 molecules are linked to each other through weak C-HoooO hydrogen bonds and C-Hooo? contacts, resulting in a 3D polymeric network arrangement. Magnetic data indicate a very weak intermolecular exchange interaction between copper(II) ions (zJ´ = -0.20 cm-1) transmitted through non-covalent interactions in the crystal lattice. The spectral properties are in accordance with the structural and magnetic data.

14

Rhodamine-6G hydrazide probe for selective determination of Cu(II) in aqueous media

Wang P., Wu G., Gu Z., Wu D., He C.

Chemia Analityczna

|

2009

|

Vol. 54, No. 2

151-162

EN

A new fluorescence method for selective determination of Cu24 using rhodamine 6G hydra-zide (R6GH) as a probe has been developed. The probe has shown selective and sensitive fluorescence response toward Cu2+ in aqueous media. In the proposed reaction mechanism the hydrazide group of R6GH binds to Cu2+ exhibiting a behavior similar to a-amino esters, which results in a redox hydrolysis of the hydrazide moiety with the release of highly fluorescent rhodamine 6G. Under the optimal conditions the fluorescence enhancement at 545 nm was linearly related to the concentration of Cu2+ in the range 0.1-10 μ mol L-1 The proposed method has been applied to the determination of trace Cu-2 in water samples with satisfactory results.

PL

Opracowano nową fluorescencyjną metodę selektywnego oznaczania Cu-2 używając hydrazydku rodaminy 6G (R6GH) jako sondy. Sonda wykazała selektywną i czułą fluoroscencyjną reakcję na obecność Cu-2 w wodnym roztworze. Zaproponowano mechanizm reakcji, w którym grupa hydrazydkowa w R6GH łączy się z Cu-1 i wykazuje zachowanie podobne do a-amino estrów co prowadzi do hydrolizy red-oks i wydzielenia wysoko fluoryzującej rodaminy 6G. W warunkach optymalnych wzrost fluorescencji przy 545 nm był liniowo zależny od stężenia Cu-2 w zakresie 0,1-10 μ mol L-1. Zaproponowaną metodę zastosowano do oznaczania śladów Cu-2 w próbkach wód uzyskując dobre wyniki.

15

Korelacje magnetyczno-strukturalne dla układów molekularnych Cu-pikolinian oraz Cu-chinaldynian

Żurowska B.

Wiadomości Chemiczne

|

2008

|

[Z] 62, 1-2

9-48

EN

This article concerns information on a synthesis, and structural and magnetic characterization of copper(II) compounds based on two classes of carboxylate ligands containing heterocyclic nitrogen atom of pyridine and quinoline i.e. pyridylo-2-carboxylate (2-picolinate, 2-pic) and quinolilo-2-carboxylate (2-chinaldynate, 2-qic), (Fig. 1, Tab. 1). Such compounds are products of a direct reaction of picolinate or chinaldynate acids with copper(II) salts [19, 37, 45, 48, 50, 51] and the hydrolytic [20, 52] and non hydrolytic [53] decomposition of ligands. Picolinate ion forms compounds of the general formula Cu(2-pic)2ź2H2O (1) or [Cu(2-pic)2Br2][(2-picH)2] (2). The compound of the formula Cu(pyridylo-2-carboxylate)2 exists in three polymorphic forms: monomeric (Cu(N2O2) chromophore) (3), and two (4 and 5) polymeric (1D) (Cu(N2O4) chromophore). With halide ions isostructural polymeric (2D) compounds of the formula Cu(2-pic)X, X= Cl (6) or Br (10) are formed (Cu(N2O2X) chromophore). However, with chinaldynate ion exist compounds of the stoichiometries: two isomeric forms of Cu(2-qic)2źH2O (7 and 8), which involve the same CuN2O3 chromophore (distortion isomers), and Cu(2-qic)X, X = Cl (9) and Br (11) compounds. The chloride and bromide (9 and 11) polymeric (2D) Cu(2-qic)X compounds, which crystal structure consists of two different chromophore Cu(N2O2X) and Cu(O2X2) are isostructural. Crystal structure of these copper-picolinate and copper-quinaldinate systems indicate, that carboxylate group in both ligands offers a variety of coordination modes leading to the formation of mononuclear and polynuclear compounds. The monomeric form of Cu(2-pic)2 (3) is an example of a square-planar copper(II) compound in which structure is achieved by important ?-? stacking intermolecular interaction. This interaction leads to antiferromagnetic coupling (J = -0.76 cm-1) [129]. The polymeric compounds of the formula Cu(2-pic)2 (4 and 5) are an example of an out-of-plane double carboxylato-bridged copper(II) compound resulting in the formation of an infinite chain. The magnetic properties revealed a weak intrachain antiferromagnetic coupling in both compounds (J = -0.73 and -1.04 cm-1 for 4 [48] and 5 [49], respectively). The structures of Cu(2-pic)X (6 and 10) and Cu(2-qic)X (9 and 11) compounds are based on syn-anti carboxylate bridge and additionally on halido-bridge. The carboxylate bridges transmit a weak ferromagnetic exchange (J < 0.5 cm-1) in both compounds [46, 47, 50]. For Cu(2-pic)X observed ferromagnetic coupling through dichloro-bridge (J = 15 cm-1) [46] is stronger than that through dibromo-bridge in bromide analog (J = 8.31 cm-1) [50]. For Cu(2-qic)X observed strong antiferromagnetic coupling through the single chloro-bridge (J = -57 cm-1) [47] is much weaker than that transmitted by the single bromo-bridge (J = -102.5 cm-1) [50]. The magnitude of the magnetic coupling through the non-covalent interactions (hydrogen bonds and ?-? stacking) is also discussed on the basis of the structural data [48, 49, 129, 130]. The magnitude of the exchange interactions between copper(II) ions are discussed on the basis of the molecular and crystal structures, in terms of bond properties and known theory of exchange [62-65, 100-104]. Keywords: copper(II), carboxylate ligands, halide ligands, structure, magnetism

16

Metallo-Supramolecular Assemblies Incorporating 1,3- and 1,4-Aryl Linked Bis-beta-Diketones - Some Recent Studies

Clegg J. K., Jolliffe K. A., Lindoy L. F., Meehan G. V.

Polish Journal of Chemistry

|

2008

|

Vol. 82, nr 6

1131-1144

EN

A review of recent work in the authors laboratories in volving the interaction of 1,3- and 1,4-aryl linked bis-beta-diketone derivatives with divalent and trivalent metal ions is presented. In some in stances, bifunctional bridging ligands have been employed to extend the resulting structures from two to three dimensions. Examples of metallosupra molecular dinuclear 'platforms', tetranuclear cofacial dimers, dinuclear helicates, trinuclear triangles, stepped metallo-polymers, a prismatic columnar polymer and large cavity-containing, tetranuclear tetrahedra are all discussed.

17

Synthesis and Properties of a Trinuclear Copper(II) Complex with Trithiocyanurate Bridge

Kopel P., Čermáková S., Dolezal K., Kalińska B., Bieńko A., Mroziński J.

Polish Journal of Chemistry

|

2007

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Vol. 81, nr 3

327-335

EN

Mixed-ligand trinuclear Cu(II) complex involving trithiocyanurate(3-) anion (ttc3-) and N,N,N',N' , N'-pentamethyldiethylenetriamine (pmdien) in the coordination sphere of composition [Cu3(pmdien)3(mi-ttc)](ClO4)3 has been prepared. The complex has been characterized by EA, IR, UV-Vis, and mass spectroscopy. We can assume, that the complex is trinuclear with central atoms connected by trithiocyanurate(3-) bridges. Each central atom is in deformed trigonal bypiramidal arrangement formed by chelating S,N atoms of ttc(3-) and by three N atoms of pmdien. Temperature dependence of magnetic susceptibility and EPR spectroscopy have also been employed to characterize the compound. Magnetic susceptibility measurements over the 1.8-300 K temperature range revealed antiferromagnetic interactions among central atoms. The antitumor activity in vitro against G-361 (human malignant melanoma), HOS (human osteogenic sarcoma), K-562 (human chronic myelogenous leukaemia) and MCF-7 (human breast adenocarcinoma) tumor cell lines have been tested but unfortunately the complexes showed no cytotoxic activity against the four cell lines.

18

Magnetic Interactions in Cu(pyridine-2-carboxylate)2

Żurowska B., Mroziński J., Ciunik Z.

Polish Journal of Chemistry

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2007

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Vol. 81, nr 3

403-410

EN

The magnetic properties of the compound of the formula Cu(2-pca)2, (2-pca = 2-picolinate ion) were studied in the light of its known X-ray structure. The crystal structure consists of a copper atom lying in the centre of symmetry, trans square-planar coordinated via two pyridine nitrogens and the carboxylate oxygen atoms of the two picolinate anions. The crystal packing is due to short pi-pi stacking interactions between pyridine rings belonging to different molecules giving rise to a one-dimensional polymeric network arrangement. Additional CH-O hydrogen bonds form a three-dimensional polymeric network. The variable-temperature (1.8-300 K) magnetic susceptibility data of the complex were interpreted with the Bonner-Fisher expression with molecular field approximation, yielding J, zJ' and g values of -0.76, -0.47 cm-1, 2.09, respectively. The magnitude of the magnetic interaction through the pi-pi stacking interaction and hydrogen bond, and the nature of the exchange coupling is discussed on the basis of the structural data results.

19

Cloud point extraction and spectrophotometric determination of copper(II) in natural waters

Shemirani F., Jamali M. R., Kozani R. R.

Chemia Analityczna

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2007

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Vol. 52, No. 2

327-336

EN

Copper(Il) was determined spectrophotometrically as a complex with 4-benzylpiperidine-ditiocarbamate (4-BPDC). Prior to determination, the anaKte was preconcetitrated applying cloud point extraction with Triton X-114 as a surfactant. Chemical conditions influencing sensitivity ofextractive-spectrophotometric procedure were optimized. Molar absorptivity of Cu-(4-BPDC), complex was determined as 2.75x 10 L mol-1 cm-1 at λmax=435nm.Under optimum conditions (pH = 6.0, 3.0 x 10 mol L-1 4-BPDC. 0.2 % (m/v) Triton X-l14. 50°C equilibrium temperature) calibration plot was constructed and found linear in the analyte's concentration range 5-200 ng mL-1: the corresponding detection limit was 1.6 ng niL-1. In the presence of foreign ions no significant interference was observed. Precision (% RSD) of ten replicate determinations of 50.0 ng mL-1Cu(ll) was better than 2.8%.The proposed procedure was successfully applied to the determination of Cu(Il) in natural water samples.

PL

Opracowano spektrofotometryczną metodę oznaczania miedzi(Il) w postaci kompleksu z 4-benzylopipery dynoditiokarbarninianem (4-BPDC). Przed oznaczeniem analit zależano stosując ekstrakcje w punkcie zmętnienia oraz Triton X-114 jako środek pov\ ierzchniowo czynny. Zoptymalizowano warunki wpływające na czułość ekstrakcyjno-spektro foto metrycznej procedury. Molowy współczynnik absorpcji kompleksu: Cu-(4-BPDC}, wynosił 2.75x 10 L mol-1 cm-1 at λmax=435nm. W optymalnych warunkach (pH = 6.0, 3.0 x 10 mol L-1 4-BPDC. 0.2 % (m/v) Triton X-l 14; temperatura 50°C) przebieg krzywej kalibracji był liniowy w zakresie stężenia analitu od 5 do 200 ng mL-1 granicawykrywalności wynosiła 1.6 ng mL-1 nie zaobserwowano znaczącego wpływu obcych jonów. Precyzja (% RSD) obliczona na podstawie 10-u oznaczeń Cu(II) o stężeniu 50 ng L-1 nie przekraczała 2.8%. Opracowaną metodę z powodzeniem zastosowano do oznaczania Cu(II) wód naturalnych.

20

A new chemiluminescence method for determination of EDTA in ophthalmic drugs

Sorouraddin M.-H., Iranifam M.

Chemia Analityczna

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2007

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Vol. 52, No. 3

481-490

EN

A new chemiluminescence (CL) method for determination of ethyienediaminetetraacetic acid (EDTA) at a micromolar level in a batch-type system has been proposed. The method is based on inhibition of CLemission accompanying oxidation of thiosemicarbazide (TSC) by H2O2, in alkaline medium in the presence of Cu(II) as a catalyst. Inhibition was caused by the formation of a robust complex between EDTA and the catalyst. Light emission was observed using a conventional fluorescence detector. Experimental variables affecting CL inhibition were optimized applying the Taguchi method. Under the optimum conditions, calibration plot was linear in the analyte concentration range 4x102-6>-4x 10-5 mol L-1 Limit of detection was 1.6 x 10-6 mol L-1 and relative standard deviation for five replicate determinations of 10-5mol L-1 EDTA was 2.58%. The method affords recoveries in the range 95-101 %. It was successfully applied to the determination of EDTA in some pharmaceutical dosage forms.

PL

Opracowano nową, chemiluminescencyjnąmetodę oznaczania mikromolowych ilości kwasu etylenodiamonotetraoctowego (EDTA). W metodzie wykorzystano zjawisko wygaszania chemiluminescencji towarzyszącej utlenianiu tiosemikarbazydu (TSC) przez H2O2 w środowisku alakalicznym i w obecności jonów Cu(II) jako katalizatorów. Wygaszanie zachodziło w wyniku powstawania trwałego kompleksu między EDTA. a katalizatorem. Emisje promieniowania obserwowano za pomocą tradycyjnego detektora fluorescencyjnego.Warunki eksperymentu zoptymalizowano stosując metodę Taguchi. W optymalnych warunkach krzywa kalibracji wykazywała charakter liniowy w zakresie stężeń analitu 4x102-6>-4x 10-5 mol L-1. Granica wykrywalności wynosiła 1.6 x 10-6 mol L-1, względne odchylenie stndardowe, obliczone na podstawie 5-krotnie powtórzonych oznaczeń, przy stężeniu EDTA l x 10-5mol L-1 wynosiło 2,58%, a odzysk zawierał się w granicach 95-100%. Metodę z powodzeniem zastosowano do oznaczania EDTA w niektórych formach farmaceutycznych.