LONG-LIVED AFTERGLOW OF PHOTOSYNTHETIC PIGMENTS IN SOLUTION: PHOTOCHEMILUMINESCENCE

Abstract —Our recent research on photochemiluminescence (PCL) of pigments in solutions is reviewed. PCL was observed in the course of photooxidation by oxygen of chlorophyll a , bacteriochlorophyll, protochlorophyll, their analogs, synthetic dyes and aromatic hydrocarbons. The PCL of chlorophyll was studied in detail. It depends on oxygen concentration, intensity of exciting light, pH, nature of pigments, solvents etc. The thermochemiluminescence was observed after illumination of liquid and solid pigment solutions at low temperature (down to - 170C). The excitation spectra of PCL coincide with the pigment absorption spectra. The PCL emission spectra in most cases differ from those of pigment fluorescence. Electron acceptors, electron donors, radical inhibitors and β-carotene quench PCL. The quenching efficiency of electron acceptors is similar to their action on the chlorophyll triplet state. The quenching effect of radical inhibitors and β-carotene correlates with their activity in reaction with singlet oxygen. The effect of quenchers on the chlorophyll fluorescence, photobleaching and pigment sensitized oxygenation was studied. Analysis of experimental data allowed the assumption that chemiluminescence accompanies the decomposition of labile pigment peroxides. The accumulation of peroxides is probably due to the reaction in the complex of pigment and singlet oxygen, formed as a result of energy transfer from photoexcited (triplet) pigment molecules to oxygen. The terminal chemiluminescence emission proceeds from the singlet excited states of molecules of pigments and products of their oxidation.     

N1-Substitution in 2-methyl-4(5)nitroimidazole. III. New syntheses of 1-(2′-(ethylsulfonyl)ethyl)-2-methyl-5-nitroimidazole

Some new syntheses of 1-[2′-(ethylsulfonyl)ethyl]-2-methyl-5-nitroimidazole (IV), a new antitrichomonal agent are described. The most successful method proved to be alkylation of sodium ethanesulfinate (XXI) with 1-(2′-haloethyl)-2-methyl-5-nitroimidazoles (1a,b) in dimethylformamide.     

Photochemical chlorination of 2-trichloromethyl-1,3-dioxolane

The photochemical chlorination of 2-trichloromethyl-1,3-dioxolane proceeds only at the carbon atoms in the 4 and 5 positions. The structures of the resulting 2-trichloromethyl-4-chloro-and 2-trichloromethyl-4,5-dichloro-1,3-dioxolanes were proved by means of the IR spectra and chemical transformations.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1611–1613, December, 1973.     

Trialkyl-n-(2-vinyloxyethyl)ammonium salts — New systems akin to acetylcholine

Conclusions Vinyloxyethyltrialkylammonium salts possessing strong hypertensive activity were prepared by reacting 2-(dialkylamino)ethyl vinyl ethers with alkyl iodides and 2-halogenoethyl vinyl ethers with tertiary amines.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1178–1180, May, 1969.     

The temperature dependence of the d-electron dipole strengths of cobalt(II) tetrahalides

The dipole strengths of the ⁴A₂ → ⁴T₁(F), ⁴T₁(P), d-electron transitions of the cobalt(II) tetrahalides are found to decrease with an increase in temperature, in agreement with a dynamic ligand-polarisation model for the absorption mechanism. The reduction in dipole strength is accounted for by a decrease in the coulombic coupling between the quadrupole moment of the d-electron transition of the metal ion and the transient electric dipole moment induced in the ligands, due to the anharmonic increase in the mean bond length and the progressively larger mean-square amplitudes of the bending modes of the complex ion in its ground electronic state as the temperature is raised.     

Determination of 5-methoxyindoles in pineal gland and plasma samples by high-performance liquid chromatography with electrochemical detection.

A liquid chromatographic analysis with electrochemical detection of 5-methoxytryptamine, 5-methoxytryptophol, 5-methoxyindoleacetic acid and melatonin is described. Optimal elution conditions were determined by studying several variables: pH, buffer salt, counter ion and organic modifier. Measurement of 5-methoxyindoles in the pineal gland and plasma of hamsters has been performed after extraction. This method is specific and sensitive, and enables detection of 5-methoxyindoles in a pool of two hamster pineal glands. This is also the first time that these three 5-methoxyindoles have been measured simultaneously in plasma.     

Photolysis of (η5-C5H5)2V(CH3)2: II . Photo-induced formation of ethane

Photolysis of (η⁵-C₅H₅)₂V(CH₃)₂ results in the formation of methane and ethane. The percentage of ethane detected in the evolved gas can vary from a trace to 70%. The percentage of ethane formed is dependent on the solvent, the concentration of (η⁵-C₅H₅)₂V(CH₃)₂, time and temperature. The results of oxidation and reduction reactions involving (η⁵-C₅H₅)₂V(CH₃)₂ are also presented.     

Untersuchungen über Phenthiazinderivate, 17. Mitt.: Über Strukturfragen bei der LiAlH4-Reduktion des 4, 10-(α-Hydroximino-trimethylen)-phenthiazins

Zusammenfassung Je nach den Reaktionsbedingungen entstehen verschiedene Produkte bei der Reduktion des 4,10-(-Hydroximino-trimethylen)-phenthiazins. Durch Vergleich mit Verbindungen bekannter Struktur wurde der Beweis erbracht, daß die von uns schon früher für das Produkt der Natriumamalgamreduktion angenommene Struktur richtig ist.Mit 2 Abbildungen     

Quantum chemical study of the appearance of the “α-effect” in35Cl NQR spectra of chloromethylsilanes

We consider the connection between the electron distribution in ClCH₂MX₁X₂X₃ molecules (M = C, Si) calculated by the CNDO/2 method and the experimental³⁵Cl NQR frequencies. We show that the ratio of the NQR frequencies for chloromethylsilanes and their organic analogs can be explained on the basis of ideas concerning the totality of induction and conjugation effects influencing the population of the orbital of the chlorine atom which participates in formation of the C-Cl bond.Translated from Teoreticheskaya i Eksperimental'naya Khimiya, Vol. 26, No. 2, pp. 241–244, March–April, 1990.     

Extractive fluorimetric determination of ultratraces of lead with cryptand 2.2.2 and eosin

A new speetrofluorimetric method for determination of ultratraces of lead is based on solvent extraction into chloroform of the ion-pair formed between the positively-charged cryptate of lead with cryptand 2.2.2 and the eosinate anion. The detection limit for lead is 1 ng ml , and the linear working range is from the detection limit to 250 ng ml . The relative standard deviation is 3.7% at the 100 ng ml level. The method is highly selective for the extraction and determination of lead in the presence of other cations, and has been tested for direct determination of lead contamination in soft drinks. Aggregation of the extracted ion-pair in the organic phase has been demonstrated in fundamental extraction studies.