In this work, the luminescence properties of three europium complexes with ligands based on 2,2’–bipyridyldicarboxylic acid with various counterions (TFA, NO3, Cl) were studied in the form of powders and acetonitrile solutions. Their luminescence spectra were recorded at room temperature and in liquid nitrogen. We obtained and calculated the following luminescence characteristics: luminescence lifetime, relative intensities of each luminescence peak, asymmetry coefficient, radiative lifetime, internal quantum yield, luminescence quantum yield, and the effectiveness of sensitization.
The luminescent properties of two water-soluble europium complexes and two organo-soluble terbium and europium complexes with ligands based on different N-heterocyclic ligands in various mixed solvents (light and heavy water, glycerol, methanol and ethanol) were studied in this work. The absorption, emission, and excitation luminescence spectra were obtained and analyzed. We calculated the asymmetry coefficient, the luminescence quantum yield, and the luminescence lifetime at various concentrations of mixed solvents. The luminescence quenching was found more noticeable in methanol than in ethanol for all studied complexes. We observed that the luminescence quantum yield in the water-containing solvents (methanol/water, methanol/heavy water, ethanol/heavy water) is almost independent of the water or heavy water concentration. We received that heavy water has less influence on luminescence quenching than water, since the vibrational frequencies of OH groups are higher than that of OD groups. Luminescence quenching by adding glycerol to the solvent is more effective for the studied organo-soluble complexes than for water-soluble ones. This effect can be explained by the fact that the ligand of organo-soluble complexes surrounds the rare earth ion more closely, thus preventing glycerol OH groups from entering the coordination zone of the ligand.
The influence of the water on the stability of complexes of 6,6′-Bis(diphenylphosphinoyl)-2,2′-bipyridyl with lanthanide ions was studied. An increase in the stability value of the complexes is observed with a decrease in the ionic radius of the metal. An increasing of the water content in acetonitrile leads to decrease the stability of the complexes. Moreover the stability of the complexes became independent on ionic radii of metals.
In this work, the luminescent properties of three europium salts with various counterions (trifluoroacetate, nitrate and chloride) are studied. Their luminescence excitation spectra at room temperature and in liquid nitrogen have been recorded and studied. Their luminescence lifetime is determined when excited in the UV and visible regions of the spectrum. The influence of counterions and the number of water molecules in the structure of europium salts on their luminescent characteristics is determined.
New types of europium complexes with 2,2’-bipyridyl-based ligands were synthesized and their photophysical properties were studied in detail. The influence of the amidic-group substituents on the stability of their complexes with lanthanides also investigated. The branching of the substituent at the amidic group decreases both the quantum yields and stability of complexes.
Investigation of proteins interactions with luminescent europium complex is interesting for the practical task of sensitive protein detection, as well as to study fundamental problems of peptide-lanthanide interplay. Presented work is devoted to examine the spectroscopic properties of europium complex (europium trinitrate (2,2'-bipyridyl-6,6'- dikarbonilazandiil)tetrakis (methylene) phosphonate) and to study its interaction with human serum albumin using various spectroscopic techniques. This complex has unique optical ability such as high values of the phosphorescence intensity in aqueous solutions, which exceeds the intensity of many other known coordination complexes of rare earth elements.
Imaging techniques in biology and medicine are crucial tools to obtain information on structural and functional properties of living cells and organisms. To fulfill the requirements associated with application of these techniques it appears necessary to design markers with specific characteristics. Luminescent complexes of trivalent lanthanide ions with chelating ligands are of increasing importance in biomedical applications because of their millisecond luminescence lifetime, narrow emission band, high signal-to-noise ratio and minimal photodamage to biological samples. In order to extend the available emission wavelength range the luminescent samarium chelates are highly desirable. In this study the ligands with diamides of 2,2’-bipyridin-6,6’-dicarboxylic acid were used to improve photophysical characteristics of samarium complexes. We report the luminescence characteristics of samarium complexes with novel ligands. All complexes exhibited the characteristic emission of Sm (III) ion with the lines at 565, 597, 605, 645 and 654 nm, the intensity strongly depended on the ligand. Absorption and luminescence excitation spectra of Sm (III) complexes showed main peaks in the UV range demonstrating lanthanide coordination to the ligand. The absolute lumenescence quantum yield was measured for solutions in acetonitrile with excitation at 350 nm. The largest luminescence quantum yield was found for the samarium complex Bipy 6MePy Sm (3%) being much higher that for samarium complexes reported in the literature earlier. These results prove as well that samarium chelates are potential markers for multiparametric imaging techniques.
Hydrophobic components of cromophoric dissolved organic matter (CDOM) extracted from water samples and sediments taken in several relic basins located on Karelian shoreline of the White Sea were analyzed using spectroscopic techniques. Those water reservoirs exist at various stages of isolation from the White Sea and represent complex stratified systems of fresh and marine water layers not completely mixing trough the year. Basins separating from the White Sea are the unique natural objects for investigations of properties CDOM, its transformation in the process of turning the marine ecosystem into freshwater environment. CDOM occurring in all types of natural water represents a significant reservoir of organic carbon and plays a key role in the carbon cycle on the Earth. However, aquatic CDOM and nonliving organic matter in sediments from relic separating basins still have not been studied. The target of this work was to study absorption and fluorescence spectra of hydrophobic components of aquatic CDOM from different water depth and sediments in several separated basins of the Kandalaksha Gulf of the White Sea located near the N.A. Pertsov White Sea Biological Station.
We analyze the results received from two expeditions performed in August-September 2013, August-September 2014 and February 2015 in the Kandalaksha Bay of the White Sea. Depth profiles of hydrological characteristics and optical properties of water were recorded for five marine lakes being on different stages of isolation from the White Sea. Those relic lakes demonstrate a tendency to meromixis and are characterized by apparent stratification of the water bodies from the brackish top layer to the bottom salt water. Maximal concentrations of anoxygenic phototrophs (green sulfur bacteria) were found at depths close to the redox interface in all the studied lakes. To discriminate differently pigmented groups of microorganisms the fluorescence emission spectra of bacteriochlorophylls from the living cells were used. We puzzle out the data on light spectrum propagation through the water body in each lake using optical properties of water (attenuation spectra) in the UV, visible and NIR ranges, as well as direct measurements of the total irradiances at various depths. The changes in optical characteristics of water in the stratified reservoirs due to cromophoric dissolved organic matter (CDOM) and microbial pigments affect the light intensity and its spectral distribution at each water layer thus influencing the living conditions for differently pigmented phototrophic microorganisms and determining the composition of microbial community.
Detection of phototropic organisms in their natural habitat using optical instruments operating under water is urgently needed for many tasks of ecological monitoring. While fluorescence methods are widely applied nowadays to detect and characterize phytoplankton communities, the techniques for detection and recognition of anoxygenic phototrophs are considered challenging. Differentiation of the forms of anoxygenic green sulfur bacteria in natural water using spectral techniques remains problematic. Green sulfur bacteria could be found in two forms, green-colored (containing BChl d in pigment compound) and brown-colored (containing BChl e), have the special ecological niche in such reservoirs. Separate determination of these microorganisms by spectral methods is complicated because of similarity of spectral characteristics of their pigments. We describe the novel technique of quantification of two forms of green sulfur bacteria directly in water using bacteriochlorophyll fluorescence without pigment extraction. This technique is noninvasive and could be applied in remote mode in the water bodies with restricted water circulation to determine simultaneously concentrations of two forms of green sulfur bacteria in their natural habitat.
As a result of a recent years study on the Karelia shore of the White Sea more than ten relict lakes in different stages of separation from the sea have been discovered. Five of them are located close to the Nikolai Pertsov White Sea Biological Station of Moscow State University. Such separated lakes are interesting to explore for their firm vertical stratification. Water layers differ not only by temperature, salinity and other physic and chemical characteristics and optical properties, but also by ibhabiting microorganisms and by the quality of dissolved organic matter. To study phototropic organisms in water sampled from different depths we used spectroscopic techniques. Identification of the main bands in the absorption and fluorescence spectra showed that there are two main groups of photosynthetic organisms in the redox zone (chemocline): unicellular algae containing chlorophyll a and green sulfur bacteria with bacteriochlorophylls c, d, e. Spectral data were compared with physical and chemical characteristics of the water layer (temperature, salinity, pH, dissolved oxygen and sunlight illumination at certain depth). It gave an opportunity to compare vertical profiles of oxygen and hydrogen sulphide concentration with the number and distribution of oxygenic and anoxygenic phototrophic microorganisms. Maximum abundance of both algae and green sulfur bacteria were achieved within the redox zone. Typical thickness of the layer with the highest concentration of microorganisms did not exceed 10-20 cm.
The development of new complexes of rare earth elements (REE) with chelating organic ligands opens up the possibility of purposeful alteration in the composition and structure of the complexes, and therefore tuning their optical properties. New ligands possessing two pyridine rings in their structure were synthesized to improve coordination properties and photophysical characteristics of REE compounds. Complexes of trivalent europium with novel chelating ligands were investigated using luminescence and absorption spectroscopy, as well as atomic force microscopy. Luminescence properties of new compounds were studied both for solutions and films deposited on the solid support. All complexes exhibit the characteristic red luminescence of Eu (III) ion with the absolute lumenescence quantum yield in polar acetonitrile solution varying from 0.21 to 1.45 % and emission lifetime ranged from 0.1 to 1 ms. Excitation spectra of Eu coordination complexes correspond with absorption bands of chelating ligand. The energy levels of the triplet state of the new ligands were determined from the phosphorescence at 77 K of the corresponding Gd (III) complexes. The morphology of films of europium complexes with different substituents in the organic ligands was investigated by atomic force microscopy (AFM). It strongly depends both on the type of substituent in the organic ligand, and the rotation speed of the spin-coater. New europium complexes with chelating ligands containing additional pyridine fragments represent outstanding candidates for phosphors with improved luminescence properties.
Research is initiated to study water samples from stratified water basins in the Kandalaksha Gulf of the White Sea at
different stages of their separation from the sea. The objects of research are lakes Elovoe and Nizhnee Ershovskoe
located close to the Nikolai Pertsov White Sea Biological Station. Depth profiles of physico-chemical characteristics
such as temperature, salinity, pH and dissolved oxygen were measured. Brightly colored green water layers were found
in both lakes. Concentrations of photosynthetic organisms were estimated using absorption and fluorescence spectra of
water samples from various depths.
The work is devoted to the spectral measurements of maple leaves. Fresh green leaves of maple were investigated in
spring and summer, healthy leaves and leaves affected by fungal diseases - during the fall color change. F685/F740
parameter values for healthy and diseased maple leaves were found, as well as the change of this parameter during the
growing season. The concentration of chlorophylls a and b and carotenoids in ethanol extracts of maple leaves with
different pigmentation were calculated by absorption spectroscopy and the ratio of Chl a / Chl b was found.
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