Chemiluminescence and catalysis of the decomposition of dispiro(diadamantane-1,2-dioxetane) in solutions of lanthanide perchlorates

Decomposition of dispiro(diadamantane-1,2-dioxetane) (1) in acetonitrile solutions of Eu^III, Gd^III, Tb^III, Pr^III, and Ce^III perchlorates was studied by tile chemiluminescence method. The rate constants of decomposition of1 in complexes of composition1 · Ln^III and stability constants of these complexes, as well as activation parameters of the decomposition of1 and thermodynamic parameters of the complexation were determined. A correlation between the thermodynamic parameters of complexation and ionic radii of Ln^III was found.Translated fromIzvestiya Nauk. Seriya Khimicheskaya, No. 10, pp. 2479–2483, October, 1996.     

Mechanically induced chemiluminescence in the dispiro(adamantane-1,2-dioxetane)—Eu(fod)3 system

Luminescence accompanying an impact mechanical treatment of solid particles of the complex of Eu(fod)₃ (fod is 1,1,1,2,2,3,3-heptafluoro-7,7-dimethyloctane-4,6-dione) with dispiro(adamantane-1,2-dioxetane) (1) was discovered and studied. The luminescence has a complex structure, and its spectrum belongs to the excited Eu^III ions. The emission of light is observed only in a mechanical mixture of the Eu(fod)₃ with dioxetane1 and in their cocrystallized form, but not in the case of the components taken separately. The mechanism by which the impacts cause the luminescence is considered. It was shown that the luminescence is not triboluminescence, but is chemiluminescence induced by the decomposition of compound1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1159–1162, May, 1996.     

Chemiluminescence initiated by complex formation in solutions of 1,2-dioxetane and lanthanide perchlorates

The spectral and activation parameters of chemiluminescence in the thermal decay of 1,2-dioxetane based on adamantylideneadamantane in acetonitrile in the presence of Tb^III, Eu^III, Pr^III, Ce^III, and Gd^III perchlorates and UO₂(NO₃)₂ have been studied. Two types of catalysis by metals, luminescent and nonluminescent, can be distinguished in the framework of one mechanism of dioxetane decay initiated by metal-peroxide complex formation. The mode of catalysis depends both on the presence of suitable energy levels in the metal ion to which the intracomplex transfer of excitation from the³n,^*-state of the ketone that appears in the decay of dioxetane in a catalytic complex can occur and on the ratio of the quantum yields of luminescence of the ketone and the metal ion that is the catalytic activator of luminescence.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1588–1592, September, 1994.The authors are grateful to S. S. Ostakhov for measuring the spectra and the duration of photoluminescence of terbium in dioxetane solutions and for participation in discussions of the results.     

Photocatalytic decomposition of dispiro(diadamantane-1,2-dioxetane) initiated by Ce(CIO4)3 in the excited state

Photocatalytic decomposition of dispiro(diadamantane-1,2-dioxetane) (1) to adamantanone (2) initiated by Ce(ClO₄)₃ in the excited state in the MeCN−CHCl₃ (2∶1) mixture was studied. The bimolecular rate constants of quenchingk _q were determined from the kinetics of quenching of Ce^3+* by dioxetane at different temperatures. The Arrhenius parameters of the quenching were calculated from the temperature dependence ofk _q:E _a=3.2±0.3 kcal mol⁻¹ and logA=11.6±6. The quantum yields of photolysis of 1 depending on its concentration and the rate constant of the chemical reaction of Ce^3+* with 1 were determined. The latter coincides withk _q:k _ch=(2.6±0.3)·10⁹ L mol⁻¹ s⁻¹ (T=298 K). The fact that the maximum quantum yield of decomposition of dioxetane is equal to 1 indicates the absence of physical quenching of Ce^3+* with 1. Nonradiative deactivation of Ce^3+* in solutions of MeCN and in MeCN−CHCl₃ mixtures was studied. It is caused by the replacement of H₂O molecules in the nearest coordination surroundings of Ce³⁺ by solvent molecules and reversible transfer of an electron to the ligand. The activation parameters of the nonradiative deactivation of Ce^+* were determined. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 724–729, April, 1997.     

Chemiluminescence and catalysis of decomposition of dispiro(diadamantane-1,2-dioxetane) in the presence of EuIII and TbIII tris(benzoyltrifluoroacetonate) complexes

Catalysis of decomposition of dispiro(diadamantane-1,2-dioxetane) (1) in the presence of Eu^III and Tb^III tris(benzoyltrifluoroacetonate) complexes (Ln(btfa)₃) accompanied by the formation of adamantanone (2) and chemiluminescence (CL) was studied. The rate constants (k ₂) of decomposition of compound1 in the1·Ln(btfa)₃ complexes and their stability constants (K ₁) have been determined. The Arrhenius parameters of decomposition of1 (E _a= 22.4±0.7 kcal mol^?1, logA=10.2±0.8 for1·Tb(btfa)₃ andE _a=23.4±0.6 kcal mol^?1, logA=10.6±0.8 for1·Eu(btfa)₃) and thermodynamic parameters of complex formation (ΔH=?5.5±0.5 kcal mol^?1, ΔS=?10.4±0.7 e.u. for1·Tb(btfa)₃ and ΔH=?5.8±0.5 kcal mol^?1, ΔS=?10.9±0.7 e.u. for1·Eu(btfa)₃) have been calculated from the temperature dependences ofk ₂ andK ₁. The yields of excitation of the Ln(btfa)₃ chelates φ _Eu ^* =0.021±0.006 and φ _Tb ^* =0.12±0.04 have been determined. A higher efficiency of the occupation of the⁵D₄-level of Tb³⁺ compared to those of the⁵D₁- and⁵D₀-levels of Eu³⁺ is caused by different efficiencies of the non-radiative energy dissipation in the Ln³⁺ ion after the intracomplex energy transfer from the³n,π^*-state of2 to the resonance excited levels of lanthanides.     

Mechanism of activation and catalysis of chemiluminescence by Eu(fod)3 chelate in thermal decomposition of adamantylideneadamantane-1,2-dioxetane

Complexation of the chelate both with dioxetane and with adamantanone (2), the product of decomposition of dioxetane, have an important effect on chemiluminescence (CL) in thermal decomposition of adamantylideneadamantane-1,2-dioxetane (1) in the presence of Eu(fod)₃ chelate. The stability constants of Eu(fod)₃·1 and Eu(fod)₃·2 complexes were obtained. It was found that Eu(fod)₃ catalyzes and activates chemiluminescent decomposition of1. The rate constant (k₂) of decomposition of the Eu(III)·1 complex was determined from the kinetics of quenching of CL, and the activation parameters were determined from the temperature curve. Luminescence from the⁵D_1-level of the Eu(III) ion was detected in the CL spectrum and was correlated with direct (bypassing the triplet of the ligand) transfer of excitation energy from2 _t* to the luminescent levels of Eu(III) in the geometrically distorted complex Eu(fod)₃·2.Institute of Organic Chemistry, Ural Branch, Russian Academy of Sciences, 450054 Ufa. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 5, pp. 1056–1063, May, 1992.     

The chemiluminescence of dispiro(1,2-dioxetane-diadamantane) sorbed on silipore activated by a phenanthroline complex of Eu(iii)

The thermal decomposition of dispiro(1,2-dioxetane-diadamantane) (1) sorbed on silipore containing EuCl₃ ando-phenanthroline was investigated. The observed chemiluminescence is caused by radiative deactivation of EU^*(iii) formed according to an energy transfer mechanism. Chemiluminescence decay in the course of the decomposition of1 is exponential with the rate constantk. The activation parameters of the decomposition of1 sorbed on silipore were determined from the temperature dependence ofk. These parameters are independent of the Eu(iii) content. A kinetic compensating effect was found: the dependence of logA onE _a as a function of the content of1. The mechanism of the compensating effect is discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 447–451, March, 1995.     

Design and Synthesis of Chemiluminescent Cassettes Based on Energy Transfer

Chemiluminescent probes are being considered as a convenient option for optical imaging. Several strategies were reported to increase the probe chemiluminescence efficiency. In this study, a series of chemiluminescent cassettes based on adamantyl stabilized 1,2-dioxetanes (“Schaap's dioxetane”) linked to a fluorophore (BODIPY or dicyanoisophorone fluorophore) by a conjugated linker have been synthetized. Their chemiluminescent decomposition and the photoluminescence properties of their respective emissive species were investigated.     

Thermal decomposition of Y,La and lanthanide benzene-1,2-dioxyacetates in an air atmosphere

The thermal decompositions of Y, La and lanthanide (from Ce(III) to Lu(III) benzene-1,2-dioxyacetates with general formula Ln₂(C₁₀H₈O₆)₃·nH₂O were studied. The hydrated complexes first lose water of crystallization in one or two steps to yield anhydrous compounds or hydrates containing coordination water molecules, and then decompose to the oxides Ln₂O₃, CeO₂, Pr₆O₁₁ and Tb₄O₇ with formation of intermediates, carbonates and oxycarbonates (La, Pr-Eu), oxycarbonates (Y, Tb-Lu) or carbonate (Gd) only. Anhydrous cerium(III) benzene-1,2-dioxyacetate decomposes on heating directly to CeO₂.     

Application of Multi-step Excitation Schemes for Detection of Actinides and Lanthanides in Solutions by Luminescence/Chemiluminescence Laser Spectroscopy

The use of laser radiation with tunable wavelength allows the selective excitation of actinide/lanthanide species with subsequent registration of luminescence/chemiluminescence for their detection. This work is devoted to applications of the time-resolved laser-induced luminescence spectroscopy and time-resolved laser-induced chemiluminescence spectroscopy for the detection of lanthanides and actinides. Results of the experiments on U, Eu, and Sm detection by TRLIF method in blood plasma and urine are presented. Data on luminol chemiluminescence in solutions containing Sm(III), U(IV), and Pu(IV) are analyzed. It is shown that appropriate selectivity of lanthanide/actinide detection can be reached when chemiluminescence is initiated by transitions within 4f- or 5f-electron shell of lanthanide/actinide ions corresponding to the visible spectral range. In this case chemiluminescence of chemiluminogen (luminol) arises when the ion of f element is excited by multi-quantum absorption of visible light. The multi-photon scheme of chemiluminescence excitation makes chemiluminescence not only a highly sensitive but also a highly selective tool for the detection of lanthanide/actinide species in solutions.     

Synthesis of 1,2-bis(methoxyamino)cycloalkanes from alicyclic 1,2-bis(hydroxyamines)

Derivatives of 1,4-dihydroxypiperazine-2,3-dione were obtained by reaction of cis-1,2-bis(hydroxyamino)cycloalkanes with diethyl oxalate. Their alkylation with CH₂N₂ or Mel afforded 1,4-dimethoxypiperazine-2,3-diones. Hydrolysis of the latter gave 1,2-bis(methoxyamino)cycloalkanes.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 925–929, April, 1996.     

Chemiluminescence and catalysis of decomposition of dimethyldioxirane adsorbed from the gas phase on silipore containing tris(bipyridyl)ruthenium complex Ru(bpy)3Cl2 and 9,10-diphenylanthracene

The kinetics of decomposition of dimethyldioxirane (DMD) adsorbed from the gas phase on the silipore surface was studied by the chemiluminescence (CL) technique. The lower boundary of the CL yield in the reaction of DMD decomposition (4·10⁻⁹ Einstein mol⁻¹) and chemiexcitation yield of methyl acetate (4·10⁻⁴) were estimated. Chemiluminescence upon decomposition of DMD on the silipore surface in the presence of activators of CL such as tris(bipyridyl)ruthenium complex Ru(bpy)₃Cl₂ and 9,10-diphenylanthracene was revealed. Ru(bpy)₃Cl₂ activates the luminescence according to chemically induced electron exchange mechanism. Devoted to Prof. R. W. Murray on his 70th birthday. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1516–1521, August, 1998.     

Chemiluminescence in the thermal decomposition of di(tert-butyl) trioxide

Intense chemiluminescence (CL) in the visible and IR regions arising during the thermal decomposition of di(tert-butyl) trioxide has been observed. The decomposition rate constants have been determined. The emitter of CL in the IR region is singlet oxygen, that of CL in the visible region is triplet excited acetone. Kinetic and spectral data and thermochemical and MNDO calculations point to a homolytic mechanism of decomposition. The formation of the CL emitters occurs in the reactions of radicals that arise upon the decay of di(tert-butyl) trioxide.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2056–2059, December, 1993.     

联吡啶钌电化学发光研究进展

联吡啶钌电化学发光在免疫分析、核酸分析、共反应物分析和适配子传感器等方面具有广泛的应用前景,成为在诸多电化学发光体系如9,10-二苯基蒽、光泽精、联吡啶钌、过氧化草酸酯、鲁米诺、石墨烯和量子点等之中近年来国际上研究最多的电化学发光体系之一.本综述对已发表的绝大多数联吡啶钌电化学发光成果加以归纳总结,简要介绍联吡啶钌电化学发光的概况,并尝试展望其今后的研究趋势.     

Thermal decomposition of lanthanide(III) and Y(III) 3,4,5-trihydroxybenzoates: Preparation, properties

Complexes of lanthanides(III) (La-Lu) and Y(III) with 3,4,5-trihydroxybenzoic acid (gallic acid) were obtained and their thermal decomposition, IR spectra and solubility in water have been investigated. When heated, the complexes with a general formula Ln(C₇H₅O₅)(C₇H₄O₅)·nH₂O (n=2 for La-Ho and Y: n=0 for Er-Lu) lose their crystallization water and decompose to the oxides Ln₂O₃, CeO₂, Pr₆O₁₁, and Tb₄O₇, except of lanthanum and neodymium complexes, which additionally form stable oxocarbonates such as Ln₂O₂CO₃. The complexes are sparingly soluble in water (0.3·10^–5–8.3·10^–4 mol dm^–3).This revised version was published online in November 2005 with corrections to the Cover Date.     

Chemiluminescence Determination of Sulfite and Sulfur Dioxide Using Tris(1,10-Phenanthroline)Ruthenium-KMnO4 System

Abstract

The emission produced by sulfite after oxidation by potassium permanganate in acidic solution in the presence of Ru(phen)₃ ²⁺ is used to determine 1.0 × 10^?7 to 2.5 × 10^?5 mol/L sulfite. The limit of detection is 4.5 × 10^?9 mol/L and the relative standard deviation is 3.1% for a 1 × 10^?5 mol/L sulfite solution (n=8). The method was also applied satisfactorily to the determination of sulfur dioxide in air by using triethanolamine (TEA) as absorbent material.