Małgorzata Kaczmarek

Chemiluminescence of systems containing lanthanide ions

A review of the chemiluminescent reactions in the systems containing lanthanide ions as emitters and different chemical compounds is presented. The systems in which lanthanide ions enhance the chemiluminescence intensity, thanks to the energy transfer processes, as well as the systems in which redox reactions involving lanthanide ions cause chemiluminescence and the systems showing electrogenerated luminescence and lyoluminescence are discussed.

Chemiluminescence determination of tetracyclines using Fenton system in the presence europium(III) ions

A new simple chemiluminescent method for the determination of chlortetracycline (Chlor-TC), oxytetracycline (Oxy-TC) and doxycycline (Doxy-TC) is described. This method is based on the europium(III) emission as a result of the energy transfer process from the excited product of the tetracyclines oxidation to the uncomplexed Eu(III). Under the optimum conditions, calibration graphs were obtained for 4x10(-7) to 2x10(-5) mol L(-1) of Chlor-TC; 2x10(-7) to 2x10(-5) mol L(-1) of Oxy-TC and 1x10(-7) to 3x10(-5) mol L(-1) of Doxy-TC. The method was successfully applied to the determination of these drugs in pharmaceutical and veterinary formulation and honey.

New supramolecular dinuclear rare earth Schiff base podates

Abstract The metal-promoted reactions between 2,6-diacetylpyridine and 4-methyl-1,2-phenylenediamine, 3-azaoctane-1,8-diamine (spermidine) or N,N′-bis(2-aminoethyl)-1,3-propanediamine in the presence of lanthanide(III) ions acting as template agents afford new supramolecular dinuclear complexes of podate type with terminal acetylpyridyl groups and N4O2, N5O2 or N6O2 set of donor atoms as a result of [2+1] Schiff base condensation. The complexes were characterized by spectral data (IR, 1 H NMR, FAB-MS), thermogravimetric and elemental analysis.

THE NATURE OF THE EMITTERS IN EU(II)/(III)-CORONAND-H2O2 CHEMILUMINESCENT SYSTEMS

Abstract The kinetics and chemiluminescent (CL) spectral properties of the systems, Eu(II)/(III)-H 2 O 2 and Eu(II)/(III)-coronand-H 2 O 2 were investigated. In the former the dominant emitters were found to be excited Eu(III) ions. Although emission both from Eu(III) and dimers of singlet oxygen were recorded. Introduction of a macrocycle caused an increase in the luminescence of the system. The intensity and shape of the decay as well as the spectral distribution of the chemiluminescence were found to depend on the number of nitrogen atoms in the ring of the macrocycle and the size match between the cavity of the macrocycle and the europium ion. Our interpretation of the results suggests that radical reactions play a dominant role in these systems.

The Template Synthesis of the New Macrocyclic and Acyclic Metal Ion Complexes Derived from Putrescine

The template reaction of 2,6-diacetylpyridine with biogenic diamine–putrescine in the presence of cadmium(II), mercury(II) or lead(II) ions produces the complexes of 22-membered macrocyclic ligand L1 with an N6 set of donor atoms as a result of [2 + 2] Schiff base cyclocondensation. The lead(II) complex containing Schiff base acyclic ligand L2 terminated by one carbonyl and one amine group as product of the partial [2 + 2] condensation has been also isolated and might be regarded as possible intermediate in the formation of the macrocyclic L1 complex. Analogous reaction involving the uranyl nitrate generates the complex containing the same Schiff base acyclic ligand L2 as a final product of template reaction. The complexes were characterized by spectral data (IR, 1H NMR, FAB-MS), thermogravimetric and elemental analyses. A notable feature of the FAB mass spectrum of the uranyl complex is the appearance of the clusters of the form [(UO2)nO]+(n= 1–7) along with the peak corresponding to molecular ion.

Chemiluminescence determination of ibuprofen and ketoprofen using the Fenton system in the presence of europium(III) ions

A simple new chemiluminescent method for the determination of ibuprofen (IB) and ketoprofen (KP) is described. The method for the determination of ibuprofen is based on the europium(III) emission as a result of the energy transfer process from the excited product of the ibuprofen oxidation in the Fenton system to the uncomplexed Eu(III). The detection limit of ibuprofen is 6 × 10−8 mol L−1. The method was successfully applied to the determination of IB in a mixture of non-steroidal anti-inflammatory drugs, pharmaceutical formulations and urine.

Spectral analysis in ultraweak emissions of chemi- and electrochemiluminescence systems

Investigation of ultraweak emissions in the processes of chemiluminescence, CL, and electrochemiluminesce, ECL, requires special techniques of their recording and spectral analysis. From among the hitherto proposed methods of detection of the emission spectra of these processes, that of the cut-off filter was most sensitive. The usefulness of this method in interpretation of the CL and ECL systems of the quantum yields in the range 1×10−9−1×10−11 containing ions and complexes of Eu(III), Tb(III) and Dy(III) was shown. Exceptional character of the emission bands of lanthanide ions, being a result of the f-f electron transitions and in particular their low FWHM, permitted the application of the cut-off filter method to their analysis. The results obtained for CL and ECL on the basis of analysis of ultraweak emission proved to be successful in analytical applications. The systems containing Eu(III) ions hydrated or complexed with organic ligands enabled inferring changes in the coordination sphere of the ions.

New supramolecular dinuclear Schiff base complexes of yttrium and lanthanides

Abstract The metal-promoted reactions between 2,6-diacetylpyridine and 3,6-dioxaoctane-1,8-diamine, 4,9-dioxadodecane-1,12-diamine or 4,7,10-trioxatridecane-1,13-diamine in the presence of yttrium(III) and lanthanide(III) ions acting as template agents afford new supramolecular dinuclear complexes of podate type with terminal acetylpyridyl groups and N 4 O 4 and N 4 O 5 set of donor atoms as a result of [2+1] Schiff base condensation. The complexes were characterized by spectral data (IR, 1 H NMR, FAB-MS) and elemental analysis.

Energy Transfer Processes of Chemiluminescence Reaction Systems with Cerium(IV) Ions and Their Analytical Application: A Review

This review is devoted to a thorough discussion of chemiluminescence of the systems containing Ce(IV) ions as oxidising agents, with particular emphasis on the energy transfer processes in such systems. The influence of sensitisers such as: rhodamines, quinine, lanthanide ions and their complexes and quantum-dots has been analysed and the practical use of reaction systems for development of new chemiluminescence methods for determination of therapeutic drugs and substances of biological importance in different matrices such as human urine or serum is indicated. The types of emitters and excited reaction products taking part in energy transfer to sensitisers and processes taking place in the chemiluminescence reaction systems containing Ce(IV) ions are presented on the basis of recent literature.

Stabilization of Eu(II) Ions by Macrocyclic Compounds in the Oxidation Reaction with Hydrogen Peroxide

Summary. The influence of coronands 15C5 and 18C6 and cryptands 2.2.1 and 2.2.2 on the chemiluminescence (CL) of the system Eu(II)/(III)-H2O2 was studied. Analysis of the chemiluminescence spectra revealed that the excited Eu(III) ions are the dominant emitter in all cases. The stabilizing effect of the macrocyclic compounds was manifested in an extension of the CL duration and was particularly strong in the systems with cryptands. The protective activity of ligands is explained by the matching of the ligand’s cavity with the size of Eu(II) ions. Measurement of the Eu(II) absorption band decay (γ=248 nm) upon oxidation by hydrogen peroxide confirmed the results of the CL studies according to which the stabilizing properties of the macrocyclic ligands towards Eu(II) ions increase in the order 15C5 < 18C6 < 2.2.1 < 2.2.2 in aqueous solution.Zusammenfassung. Der Einfluß der Kronenether 15C5 und 18C6 und der Kryptanden 2.2.1 und 2.2.2 auf die Chemolumineszenz (CL) des Systems Eu(II)/Eu(III)-H2O2 wurde untersucht. Die Analyse der Chemolumineszenzspektren zeigt, daß in allen Fällen angeregte Eu(III)-Ionen als Emitter dominieren. Der stabilisierende Effekt der makrocyclischen Verbindungen äußerte sich in einer Verlängerung der CL-Dauer und war im Fall der Kryptanden besonders ausgeprägt. Die inhibierende Wirkung wird mit der Übereinstimmung der Größe der Hohlräume der Liganden und des Eu(II)-Ions erklärt. Messungen der Abnahme der Intensität der Absorptionsbande von Eu(II) (λ=248 nm) während der Oxidation mit Wasserstoffperoxid bestätigten die Ergebnisse der CL-Untersuchungen, nach denen die stabilisierende Wirkung der makrocyclischen Liganden gegenüber Eu(II) in wäßriger Lösung in der Reihenfolge 15C5 < 18C6 < 2.2.1 < 2.2.2 ansteigt.