Efficient Excitation Energy Transfer Research Articles

Adaptation processes in Halomicronema hongdechloris, an example of the light-induced optimization of the photosynthetic apparatus on hierarchical time scales

Oxygenic photosynthesis in Halomicronema hongdechloris, one of a series of cyanobacteria producing red-shifted Chl f, is adapted to varying light conditions by a range of diverse processes acting over largely different time scales. Acclimation to far-red light (FRL) above 700 nm over several days is mirrored by reversible changes in the Chl f content. In several cyanobacteria that undergo FRL photoacclimation, Chl d and Chl f are directly involved in excitation energy transfer in the antenna system, form the primary donor in photosystem I (PSI), and are also involved in electron transfer within photosystem II (PSII), most probably at the ChlD1 position, with efficient charge transfer happening with comparable kinetics to reaction centers containing Chl a. In H. hongdechloris, the formation of Chl f under FRL comes along with slow adaptive proteomic shifts like the rebuilding of the D1 complex on the time scale of days. On shorter time scales, much faster adaptation mechanisms exist involving the phycobilisomes (PBSs), which mainly contain allophycocyanin upon adaptation to FRL. Short illumination with white, blue, or red light leads to reactive oxygen species-driven mobilization of the PBSs on the time scale of seconds, in effect recoupling the PBSs with Chl f-containing PSII to re-establish efficient excitation energy transfer within minutes. In summary, H. hongdechloris reorganizes PSII to act as a molecular heat pump lifting excited states from Chl f to Chl a on the picosecond time scale in combination with a light-driven PBS reorganization acting on the time scale of seconds to minutes depending on the actual light conditions. Thus, structure–function relationships in photosynthetic energy and electron transport in H. hongdechloris including long-term adaptation processes cover 10−12 to 106 seconds, i.e., 18 orders of magnitude in time.

Water-dispersable photoreactors based on core–shell mesoporous silica particles

Robust solid-core silica particles with submicrometer size and anthracene-containing mesoporous shell were obtained and studied as model water-dispersable photoreactors. An anthracene derivative containing a triethoxysilyl group was synthesized and co-condensed with tetraethoxysilane in various ratios to form a photoactive mesoporous shell with a thickness up to approximately 80 nm on previously prepared solid silica particles. Mesopores of as-synthesized particles, without a commonly applied removal of the micellar templates, offered a confined space for solubilization of hydrophobic molecules. Efficient excitation energy transfer from anthracene chromophores to both hydrophobic (perylene) and hydrophilic (fluoresceine) encapsulated acceptors was observed in an aqueous dispersion of the particles. Photosensitized oxidation of encapsulated perylene was shown to proceed efficiently in such systems serving as water-dispersable photoreactors. Importantly, the designed core–shell systems were found to be stable for a long time (at least 24 months) and robust enough, thanks to the presence of solid cores, to be handled by centrifugation in aqueous dispersions. All these features make them promising candidates for reusable systems for the photosensitized degradation of water pollutants, especially hydrophobic pollutants.

Architecture of symbiotic dinoflagellate photosystem I–light-harvesting supercomplex in Symbiodinium

Symbiodinium are the photosynthetic endosymbionts for corals and play a vital role in supplying their coral hosts with photosynthetic products, forming the nutritional foundation for high-yield coral reef ecosystems. Here, we determine the cryo-electron microscopy structure of Symbiodinium photosystem I (PSI) supercomplex with a PSI core composed of 13 subunits including 2 previously unidentified subunits, PsaT and PsaU, as well as 13 peridinin-Chl a/c-binding light-harvesting antenna proteins (AcpPCIs). The PSI–AcpPCI supercomplex exhibits distinctive structural features compared to their red lineage counterparts, including extended termini of PsaD/E/I/J/L/M/R and AcpPCI-1/3/5/7/8/11 subunits, conformational changes in the surface loops of PsaA and PsaB subunits, facilitating the association between the PSI core and peripheral antennae. Structural analysis and computational calculation of excitation energy transfer rates unravel specific pigment networks in Symbiodinium PSI–AcpPCI for efficient excitation energy transfer. Overall, this study provides a structural basis for deciphering the mechanisms governing light harvesting and energy transfer in Symbiodinium PSI–AcpPCI supercomplexes adapted to their symbiotic ecosystem, as well as insights into the evolutionary diversity of PSI–LHCI among various photosynthetic organisms.

Efficient two-step excitation energy transfer in artificial light-harvesting antenna based on bacteriochlorophyll aggregates

Chlorosomes of green photosynthetic bacteria are large light-harvesting complexes enabling these organisms to survive at extremely low-light conditions. Bacteriochlorophylls found in chlorosomes self-organize and are ideal candidates for use in biomimetic light-harvesting in artificial photosynthesis and other applications for solar energy utilization. Here we report on the construction and characterization of an artificial antenna consisting of bacteriochlorophyll c co-aggregated with β-carotene, which is used to extend the light-harvesting spectral range, and bacteriochlorophyll a, which acts as a final acceptor for excitation energy. Efficient energy transfer between all three components was observed by means of fluorescence spectroscopy. The efficiency varies with the β-carotene content, which increases the average distance between the donor and acceptor in both energy transfer steps. The efficiency ranges from 89 to 37% for the transfer from β-carotene to bacteriochlorophyll c, and from 93 to 69% for the bacteriochlorophyll c to bacteriochlorophyll a step. A significant part of this study was dedicated to a development of methods for determination of energy transfer efficiency. These methods may be applied also for study of chlorosomes and other pigment complexes.

Structural Diversity in Eukaryotic Photosynthetic Light Harvesting.

Photosynthesis has been using energy from sunlight to assimilate atmospheric CO2 for at least 3.5 billion years. Through evolution and natural selection, photosynthetic organisms have flourished in almost all aquatic and terrestrial environments. This is partly due to the diversity of light-harvesting complex (LHC) proteins, which facilitate photosystem assembly, efficient excitation energy transfer, and photoprotection. Structural advances have provided Ångström-level structures of many of these proteins and have expanded our understanding of the pigments, lipids, and residues that drive LHC function. In this review, we compare and contrast recently observed cryo-electron microscopy structures across photosynthetic eukaryotes to identify structural motifs that underlie various light-harvesting strategies. We discuss subtle monomer changes that result in macroscale reorganization of LHC oligomers. Additionally, we find recurring patterns across diverse LHCs that may serve as evolutionary stepping stones for functional diversification. Advancing our understanding of LHC protein-environment interactions will improve our capacity to engineer more productive crops. Expected final online publication date for the Annual Review of Plant Biology, Volume 75 is May 2024. Please see http://www.annualreviews.org/page/journal/pubdates for revised estimates.

Impact of Structure, Coupling Scheme, and State of Interest on the Energy Transfer in CP29.

The Qy and Bx excitation energy transfer (EET) in the minor light-harvesting complex CP29 (LHCII B4.1) antenna complex of Pisum sativum was characterized using a computational approach. We applied Förster resonance energy transfer (FRET) and the transition density cube (TDC) method to estimate the Coulombic coupling, based on a combination of classical molecular dynamics and quantum mechanics/molecular mechanics calculations. Employing TDC instead of FRET mostly affects the EET between chlorophylls (Chls) and carotenoids (Crts), as expected due to the Crts being spatially more challenging for FRET. Only between Chls, effects are found to be small (about only 0.1 EET efficiency change when introducing TDC instead of FRET). Effects of structural sampling were found to be small, illustrated by a small average standard deviation for the Qy state coupling elements (FRET/TDC: 0.97/0.94 cm-1). Due to the higher flexibility of the Bx state, the corresponding deviations are larger (FRET/TDC between Chl-Chl pairs: 17.58/22.67 cm-1, between Crt-Chl pairs: 62.58/31.63 cm-1). In summary, it was found for the Q band that the coupling between Chls varies only slightly depending on FRET or TDC, resulting in a minute effect on EET acceptor preference. In contrast, the coupling in the B band spectral region is found to be more affected. Here, the S2 (1Bu) states of the spatially challenging Crts may act as acceptors in addition to the B states of the Chls. Depending on FRET or TDC, several Chls show different Chl-to-Crt couplings. Interestingly, the EET between Chls or Crts in the B band is found to often outcompete the corresponding decay processes. The individual efficiencies for B band EET to Crts vary however strongly with the chosen coupling scheme (e.g., up to 0.29/0.99 FRET/TDC efficiency for the Chl a604/neoxanthin pair). Thus, the choice of the coupling scheme must involve a consideration of the state of interest.

Assembling Artificial Photosynthetic Models in Water Using β-Cyclodextrin-Conjugated Phthalocyanines as Building Blocks.

Two water-soluble zinc(II) phthalocyanines substituted with two or four permethylated β-cyclodextrin (β-CD) moieties at the α positions have been utilized as building blocks for the construction of artificial photosynthetic models in water. The hydrophilic and bulky β-CD moieties not only can increase the water solubility of the phthalocyanine core and prevent its stacking in water but can also bind with a tetrasulfonated zinc(II) porphyrin (ZnTPPS) and/or sodium 2-anthraquinonesulfonate (AQ) in water through host-guest interactions. The binding interactions of these species have been studied spectroscopically, while the photoinduced processes of the resulting complexes have been investigated using steady-state and time-resolved spectroscopic methods. In the ternary complexes, the ZnTPPS units serve as light-harvesting antennas to capture the light energy and transfer it to the phthalocyanine core via efficient excitation energy transfer. The excited phthalocyanine is subsequently quenched by the electron-deficient AQ units through electron transfer. Femtosecond transient absorption spectroscopy provides clear evidence for the singlet-singlet energy transfer from the photo-excited ZnTPPS to the phthalocyanine core with a rate constant (kENT ) in the order of 109 s-1 . The population of phthalocyanine radical cations indicates the occurrence of electron transfer from the excited phthalocyanine to the AQ moieties, forming a charge-separated state.

Evaluation of the Effect of Conventional and Stabilized Nitrogen Fertilizers on the Nutritional Status of Several Maize Cultivars (Zea mays L.) in Critical Growth Stages Using Plant Analysis

The study presents the results of a three year field trial aimed at assessing the nutritional status of maize in critical growth stages by means of a plant analysis in the cultivation of three maize cultivars differing in their agronomic and genetic profile. The main research problem was to demonstrate whether the availability of nitrogen from stabilized fertilizers for “stay-green” maize varieties is consistent with the dynamics of the demand for this component. This is very important from both the economic and agronomic aspect of maize cultivation. The research showed a significant response of the maize cultivars to different nitrogen fertilizer formulations, which was observed in the period from the five-leaf stage to the full flowering stage. The advantage of the fertilizer, UltraGran stabilo, over other nitrogen fertilizers in the BBCH 15 stage was demonstrated only for the cultivar, ES Metronom, which produced a greater aerial mass while maintaining the nitrogen concentration at the level of the other two maize cultivars. The nitrogen and potassium content shaped the kernel weight in the ear in the flowering stage, confirming the importance of the interaction of these two elements in forming this feature of maize as the main predictor of the grain yield. This trait (expressed by the R2 coefficient) manifested each year of the study, but especially in the years with optimal weather patterns (i.e., the first year). The response of the maize cultivars to nitrogen fertilizers, especially the cultivar, ES Metronom, was manifested by an increase in the content of nutrients and chlorophyll in the ear leaf, that is considered a predictive organ for grain yield. The fertilizers, Super N-46 and UltraGran stabilo, had a positive effect on the chlorophyll content (CCI parameter) and increased its efficiency of excitation energy transfer (the F0 parameter).

Manifestation of Hydrogen Bonding and Exciton Delocalization on the Absorption and Two-Dimensional Electronic Spectra of Chlorosomes.

Chlorosomes are supramolecular aggregates that contain thousands of bacteriochlorophyll molecules. They perform the most efficient ultrafast excitation energy transfer of all natural light-harvesting complexes. Their broad absorption band optimizes light capture. In this study, we identify the microscopic sources of the disorder causing the spectral width and reveal how it affects the excited state properties and the optical response of the system. We combine molecular dynamics, quantum chemical calculations, and response function calculations to achieve this goal. The predicted linear and two-dimensional electronic spectra are found to compare well with experimental data reproducing all key spectral features. Our analysis of the microscopic model reveals the interplay of static and dynamic disorder from the molecular perspective. We find that hydrogen bonding motifs are essential for a correct description of the spectral line shape. Furthermore, we find that exciton delocalization over tens to hundreds of molecules is consistent with the two-dimensional electronic spectra.

Ln-MOF Based Ratiometric Luminescent Sensor for the Detection of Potential COVID-19 Drugs.

Countless people have been affected by the COVID-19 pandemic on a global scale. Favipiravir, has shown potential as an effective drug for SARS-CoV-2, attracting scientists' attention. However, overuse of Favipiravir easily leads to serious side effects, requiring real-time monitoring in body fluids. Given this, a new lanthanide metal-organic framework (MOF) was prepared under solvothermal conditions from either Eu (Eu-MOF or (1)) or Tb (Tb-MOF or (2)) using the highly delocalized imidazoledicarboxylic acid linker H2 L (H2 L=5-(4-(imidazol-1-yl) phenyl) isophthalic acid) and could be successfully applied to selective optical detection of Favipiravir. In this MOF framework, the organic linker H2 L provides a high excitation energy transfer efficiency that can sensitize luminescence in lanthanides. In addition, through deliberate tuning of Eu/Tb molar ratio and reaction concentration in the lanthanide framework, ratiometric recyclable luminescent Eux Tb1-x -MOF nanoparticles with open metal sites have been constructed, which present a high detection sensitivity (Ksv =1×107 [M-1 ], detection limit is 4.63 nM) for Favipiravir. The detection mechanism is discussed with the help of Density Functional Theory (DFT) calculations that sheds light over the selective sensing of Favipiravir over other related COVID-19 drug candidates. Finally, to explore the practical application of Favipiravir sensing, MOF based thin films have been used for visual detection of Favipiravir and recycled 5 times.

Intramolecular charge-transfer enhances energy transfer efficiency in carotenoid-reconstituted light-harvesting 1 complex of purple photosynthetic bacteria

In bacterial photosynthesis, the excitation energy transfer (EET) from carotenoids to bacteriochlorophyll a has a significant impact on the overall efficiency of the primary photosynthetic process. This efficiency can be enhanced when the involved carotenoid has intramolecular charge-transfer (ICT) character, as found in light-harvesting systems of marine alga and diatoms. Here, we provide insights into the significance of ICT excited states following the incorporation of a higher plant carotenoid, β-apo-8′-carotenal, into the carotenoidless light-harvesting 1 (LH1) complex of the purple photosynthetic bacterium Rhodospirillum rubrum strain G9+. β-apo-8′-carotenal generates the ICT excited state in the reconstituted LH1 complex, achieving an efficiency of EET of up to 79%, which exceeds that found in the wild-type LH1 complex.

Biochemical and spectroscopic characterizations of the oligomeric antenna of the coral symbioticSymbiodiniaceae Fugacium kawagutii.

Light-harvesting antennas in photosynthesis capture light energy and transfer it to the reaction centers (RCs) where photochemistry takes place. The sustainable growth of the reef-building corals relies on a constant supply of the photosynthates produced by the endosymbiotic dinoflagellate, belonging to the family of Symbiodiniaceae. The antenna system in this group consists of the water-soluble peridinin-chlorophyll a-protein (PCP) and the intrinsic membrane chlorophyll a-chlorophyll c2-peridinin protein complex (acpPC). In this report, a nonameric acpPC is reported in a dinoflagellate, Fugasium kawagutii (formerly Symbiodinium kawagutii sp. CS-156). We found that extensive biochemical purification altered the oligomerization states of the initially isolated nonameric acpPC. The excitation energy transfer pathways in the acpPC nonamer and its variants were studied using time-resolved fluorescence and time-resolved absorption spectroscopic techniques at 77K. Compared to the well-characterized trimeric acpPC, the nonameric acpPC contains an 11nm red-shifted terminal energy emitter and substantially altered excited state lifetimes of Chl a. The observed energetic overlap of the fluorescence terminal energy emitters with the absorptionof RCs is hypothesized to enable efficient downhill excitation energy transfer. Additionally, the shortened Chl a fluorescence decay lifetime in the oligomeric acpPC indicate a protective self-relaxation strategy. We propose that the highly-oligomerized acpPC nonamer represents an intact functional unit in the Symbiodiniaceae thylakoid membrane. They perform efficient excitation energy transfer (to RCs), and are under manageable regulations in favor of photoprotection.

Intramolecular Energy and Solvent-Dependent Chirality Transfer within a BINOL-Perylene Hetero-Cyclophane.

Multichromophoric macrocycles and cyclophanes are important supramolecular architectures for the elucidation of interchromophoric interactions originating from precise spatial organization. Herein, by combining an axially chiral binaphthol bisimide (BBI) and a bay‐substituted conformationally labile twisted perylene bisimide (PBI) within a cyclophane of well‐defined geometry, we report a chiral PBI hetero‐cyclophane (BBI‐PBI) that shows intramolecular energy and solvent‐regulated chirality transfer from the BBI to the PBI subunit. Excellent spectral overlap and spatial arrangement of BBI and PBI lead to efficient excitation energy transfer and subsequent PBI emission with high quantum yield (80–98 %) in various solvents. In contrast, chirality transfer is strongly dependent on the respective solvent as revealed by circular dichroism (CD) spectroscopy. The combination of energy and chirality transfer affords a bright red circularly polarized luminescence (CPL) from the PBI chromophore by excitation of BBI.

Intramolecular Energy and Solvent‐Dependent Chirality Transfer within a BINOL‐Perylene Hetero‐Cyclophane

AbstractMultichromophoric macrocycles and cyclophanes are important supramolecular architectures for the elucidation of interchromophoric interactions originating from precise spatial organization. Herein, by combining an axially chiral binaphthol bisimide (BBI) and a bay‐substituted conformationally labile twisted perylene bisimide (PBI) within a cyclophane of well‐defined geometry, we report a chiral PBI hetero‐cyclophane (BBI‐PBI) that shows intramolecular energy and solvent‐regulated chirality transfer from the BBI to the PBI subunit. Excellent spectral overlap and spatial arrangement of BBI and PBI lead to efficient excitation energy transfer and subsequent PBI emission with high quantum yield (80–98 %) in various solvents. In contrast, chirality transfer is strongly dependent on the respective solvent as revealed by circular dichroism (CD) spectroscopy. The combination of energy and chirality transfer affords a bright red circularly polarized luminescence (CPL) from the PBI chromophore by excitation of BBI.

Ultrafast energy transfer between self-assembled fluorophore and photosynthetic light-harvesting complex 2 (LH2) in lipid bilayer.

Photosynthetic light-harvesting (LH) systems consist of photosynthetic pigments, which are non-covalently self-assembled with protein scaffolds in many phototrophs and attain highly efficient excitation energy transfer via ultrafast dynamics. In this study, we constructed a biohybrid LH system composed of an LH complex (LH2) from Rhodoblastus acidophilus strain 10050 and a hydrophobic fluorophore ATTO647N (ATTO) as an extrinsic antenna in the lipid bilayer. Through the addition of ATTOs into a solution of LH2-reconstituted lipid vesicles, ATTOs were incorporated into the hydrophobic interior of the lipid bilayer to configure the non-covalently self-assembled biohybrid LH. Steady-state fluorescence spectroscopy clearly showed efficient energy transfer from ATTO to B850 bacteriochlorophylls in LH2. Femtosecond transient absorption spectroscopy revealed that the energy transfer took place in the time range of 3-13ps, comparable to that of the covalently linked LH2-ATTO that we previously reported. In addition, the biohybrid LH system exhibited a much higher antenna effect than the LH2-ATTO system because of the higher loading level of ATTO in the membrane. These findings suggest that the facile self-assembled biohybrid LH system is a promising system for constructing LH for solar-energy conversion.

Template synthesis of luminescent oligoperoxide coated YBO3 nanoparticles doped with Ce3+, Tb3+ and Eu3+ ions

The template synthesis with different concentrations of heterofunctional oligoperoxide NVP-co-VEP-co-GMA (2-tert-butylperoxy-5-methyl-1-hexene-3-yne) was performed to obtain inorganic nanoparticles of controlled size. An increase of polymer concentration provides the decrease of nanoparticle size and polydispersity index. As a result of template synthesis, the polymer molecules were adsorbed unto the nanoparticle surface forming irreversibly attached functional shell protecting the nanoparticles from aggregation. Such the polymer coated nanoparticles showed significantly lower aggregation even after high-temperature annealing, which is necessary to increase their luminescence efficiency. The luminescence spectral-kinetic study of YBO3–Ce, YBO3–Ce, Tb and YBO3–Ce,Tb, Eu nanoparticles revealed an efficient nonradiative transfer of excitation energy from Ce to Tb ions in YBO3–Ce, Tb and from Ce to Tb to Eu in YBO3–Ce,Tb, Eu nanoscale host. The potential use of YBO3–Ce, YBO3–Ce, Tb and YBO3–Ce,Tb, Eu nanoparticles for biological imaging was demonstrated by the luminescence microscopy.

Influence of the light excitation on energy transfer in a multi-pigments light-harvesting model of photosynthesis

Most studies on quantum effects in the process of excitation energy transfer in photosynthesis system are based on the single-excitation initial state hypothesis, which can well describe the initial state of some photosynthesis systems that people are concerned about. But for natural and artificial photosynthesis systems that do not meet the above hypothesis, the excitation process has a non-negligible impact on the system dynamics. Based on a multi-pigments model excited by Gaussian pulse, the effects of the excitation pulse width and the excitation interval on system dynamics and excitation energy transfer efficiency are studied. First, the kinetic equations for the overall evolution of the donor system and the acceptor system that can theoretically contain any number of pigments are derived. Afterwards, the relationship between the excitation energy transfer efficiency and the related parameters of the system, as well as the optimal range of the corresponding parameters are demonstrated by numerical simulation. It is found that under the condition of donor pigments being excited by a single Gaussian pulse, there exists optimal pulse width, and the optimal range of the pigment molecule numbers, the coupling strength as well as the dephasing rate can be modulated by the pulse width. The mechanism of the above modulation is also analyzed and presented. Under the condition of donor pigments being excited by two Gaussian pulses sequentially, there exists an optimal combination of pulse width and pulse interval. The kinetic equations obtained in this paper can be extended to other forms of excitation pulses. The numerical results and the related optimal design principles obtained have reference significance for the optimal design of artificial photosynthesis systems under different light conditions.

Strong Eu3+ luminescence in Lа1-x-yErx/2Eux/2CayVO4 nanocrystals: The result of co-doping optimization

Co-doped with Ca2+ and Er3+ ions LаVO4:Eu crystalline nanoparticles are synthesized and investigated with a goal to clarify the mechanisms of Ca2+ and Er3+ impurities effects on Eu3+ ions luminescence and to find compositions with enhanced luminescence intensity. The XRD analysis reveals dependence of crystal structure on dopants concentration: monoclinic crystal phase is observed for low dopant concentrations and content of tetragonal crystal phase increases with dopant concentrations increase. The SEM investigation reveals formation of nanoparticles with two types of shapes. Photoluminescence spectra consist of lines caused by f-f transitions in the Er3+ and Eu3+ ions. It has been shown that dependence of the Eu3+ ions luminescence intensity on the Er3+ and Ca2+ concentrations is caused by cumulative effects of dopants on crystal lattice structure, on defects in the first coordination sphere of the Eu3+ ions and on efficiency of excitation energy transfer. The maximal luminescence intensity is found for the Lа0.8Er0.05Eu0.05Ca0·1VO4 composition. The corresponded intensity is as much as 19 ± 2 and 8 ± 2 times higher than luminescence intensity of the Lа0.95Eu0.05VO4 and Lа0.9Eu0.05Ca0·05VO4 compounds, respectively. Conclusion is made that Er3+ and Ca2+ ions co-doping is a promising way to increase luminescence efficiency of the Eu3+ ions in the LaVO4 nanocrystals.

SORPTION-LUMINESCENT DETERMINATION OF OROTIC ACID IN MEDICINAL DRUGS

Luminescent properties of orotic acid (vitamin B13), known bioactive substance, have been evaluated in this research. It has been shown that inside a coordination complex of orotic acid with terbium (III) an intermollecular excitation energy transfer from a ligand to a lanthanide ion occurs which causes sensitization of terbium (III) ion luminescence. Intensity of the terbium (III) ion luminescence (ILum) increases in the presence of anionic and cationic surfaceactive agents as a result of displacement of water molecules from coordination sphere of the complex. As a consequence of this process, a non-radiative deactivation of excitation energy decreases and more efficient excitation energy transfer from a ligand to a lanthanide ion occurs. It has been established that after absorption of analyte of interest onto a polymer matrix of a solid phase extraction sorbent with subsequent increasing of its molecular rigidity more efficient excitation energy transfer is observed followed by elevation of luminescence (ILum) intensity of the coordination complex being studied. Intensity of luminescence of coordination complex of orotic acid with terbium (III) in the form of a sorbate salt has been estimated involving different types of sorbents (Phosphalugel, SFG-75, Calflo E, Celite 545, Silicagel Merck). Most suitable results have been achieved by the use of Silica gel Merck as a solid-phase matrix (sorbent). The removal rate of the complex from the solution in this case reaches to 97%. The most effective conditions for determination of orotic acid have been specified. The highest values of luminescence intensity is obtained by conducting of sorption using 5 mL of solution and 100 mg of sorbent. Luminescence intensity of the complex in the form of a sorbate salt, during a sorption process, increases in presence of ethonium, cationic dimeric surface-active agent. Decrease in luminescence intensity of the complexes in the form of a sorbate salt in presence of other surface-active agents may be caused by solubilization of the complex in the solution and thereby reduced level of its sorption. On the basis of presented research work a new analytical procedure has been developed for the solid-phase luminescence determination of orotic acid and orotic acid salts in pharmaceutical drugs. Determination of orotic acid salts has been performed in pharmaceutical drugs ‘Magnerot’ (magnesium orotate) and ‘Potassium orotate’. The proposed analytical procedure for determination of orotic acid salts is remarkable by good metrological characteristics and relative simplicity of performance. The relative standard deviation, Sr, is 3,6 - 4,3%.

Direct Energy Transfer from Allophycocyanin-Free Rod-Type CpcL-Phycobilisome to Photosystem I.

Phycobilisomes (PBSs) are photosynthetic antenna megacomplexes comprising pigment-binding proteins (cores and rods) joined with linker proteins. A rod-type PBS that does not have a core is connected to photosystem I (PSI) by a CpcL linker protein, which stabilizes a red-form of the phycocyanobilin (red-PCB) in the rod. However, quantitative information on the energy transfer from red-type PBS to PSI has not been determined. Herein, the isolated supercomplex of the rod-type PBS and the PSI tetramer from Anabaena sp. PCC 7120 were probed by time-resolved spectroscopy at 77 K and by decay-associated spectral analysis to show that red-PCB mediates the fast and efficient (time constant = 90 ps, efficiency = 95%) transfer of excitation energy from PCB to chlorophyll a (Chl a). According to the Förster energy transfer mechanism, this high efficiency corresponds to a 4 nm distance between red-PCB and Chl a, suggesting that β-84 PCB in the rod acts as red-PCB.