New Acceptor-Donor-Acceptor Systems Based on Bis-(Imino-1,8-Naphthalimide).

In this paper, six novel symmetrical bis-(imino-1,8-naphthalimides) differing in core and N-substituent structure were synthesized, and their thermal (TGA, DSC), optical (UV-Vis, PL), electrochemical (DPV, CV) properties were evaluated. The compounds were stable to 280 °C and could be transferred into amorphous materials. Electrochemical investigations showed their ability to occur reductions and oxidations processes. They exhibited deep LUMO levels of about -3.22 eV and HOMO levels above -5.80 eV. The optical investigations were carried out in the solutions (polar and non-polar) and in films and blends with PVK:PBD. Bis-(imino-1,8-naphthalimides) absorbed electromagnetic radiation in the range of 243-415 nm and emitted light from blue to yellow. Their capacity for light emission under voltage was preliminarily tested in devices with an active layer consisting of a neat compound and a blend with PVK:PBD. The diodes emitted green or red light.

Carbazole effect on ground- and excited-state properties of rhenium(i) carbonyl complexes with extended terpy-like ligands.

The ground- and excited-state properties of three novel complexes [ReCl(CO)3(Ln-κ2N)] bearing 2,2':6',2''-terpyridine, 2,6-di(thiazol-2-yl)pyridine and 2,6-di(pyrazin-2-yl)pyridine functionalized with 9-carbazole attached to the central pyridine ring of the triimine core via phenylene linkage were investigated by spectroscopic and electrochemical methods and were simulated using density functional theory (DFT) and time-dependent DFT. To get a deeper and broader understanding of structure-property relationships, the designed Re(i) carbonyl complexes were compared with previously reported analogous systems - without any groups attached to the phenyl ring and bearing pyrrolidine instead of 9-carbazole. The results indicated that attachment of the N-carbazolyl substituent to the triimine core has less influence on the nature of the triplet excited state of [ReCl(CO)3(Ln-κ2N)] than the pyrrolidine group. Additionally, the impact of the ligand structural modifications on the light emission of the Re(i) complexes under external voltage was preliminarily examined with electroluminescence spectra of diodes containing the synthesized new molecules in an active layer.

Influence of initial pH on the production of volatile fatty acids and hydrogen during dark fermentation of kitchen waste.

The purpose of this work was to determine the effect of initial pH on the production of volatile fatty acids (VFA) and hydrogen (H2) in the dark fermentation processes of kitchen waste. The study was conducted in batch bioreactors of working volume 1 L for different initial pH in the range from 5.5 to 9.0. The dark fermentation processes were carried out for 4 days at 37°C. Initial organic load of the kitchen waste in all bioreactors amounted to 25.5 gVS/L. Buffering of pH during the fermentation process was carried out with the use of ammonia contained mainly in digested sludge. The optimal conditions for the production of VFA and H2 were achieved at the initial pH of 8. Production of VFA and H2 in these conditions was, respectively, 13.9 g/L and 72.4 mL/gVS. The main produced components of VFA were acetic and butyric acids. The production of ethanol and lactic acid was at very low levels due to the high ratio of the volatile fatty acids to total organic content of 0.86. With the optimal initial pH of 8 the yield of CO2 production was 0.30 gC/gC. High initial pH value (above 8) extended the lag phase duration in the course of H2 production. The dominant groups of micro-organisms at the most favourable initial pH of 8 for the production of VFA and H2 were Bacteroidetes, Firmicutes, Spirochaetes and Waste Water of Evry 1 (WWE1) at the phylum level.

Photoluminescence enhancement of Re(i) carbonyl complexes bearing D-A and D-π-A ligands.

Three Re(i) carbonyl complexes [ReCl(CO)3(Ln)] bearing 2,2'-bipyridine, 2,2':6',2''-terpyridine, and 1,10-phenanthroline functionalized with diphenylamine/or triphenylamine units (L1-L3) were synthesized to explore the impact of highly electron donating units appended to the imine ligand on the thermal and optoelectronic properties of Re(i) systems. Additionally, for comparison, the ligands L1-3 and parent complexes [ReCl(CO)3(bipy)], [ReCl(CO)3(phen)] and [ReCl(CO)3(terpy-κ2N)] were investigated. The thermal stability was evaluated by differential scanning calorimetry. The ground- and excited-state electronic properties of the Re(i) complexes were studied by cyclic voltammetry and differential pulse voltammetry, absorption and emission spectroscopy, as well as using density-functional theory (DFT). The majority of the compounds form amorphous molecular materials with high glass transition temperatures above 100 °C. Compared to the unsubstituted complexes [ReCl(CO)3(bipy)], [ReCl(CO)3(phen)] and [ReCl(CO)3(terpy-κ2N)], the HOMO-LUMO gap of the corresponding Re(i) systems bearing modified imine ligands is reduced, and the decrease in the value of the ΔEH-L is mainly caused by the increase in HOMO energy level. In relation to the parent complexes, all designed Re(i) carbonyls were found to show enhanced photoluminescence, both in solution and in solid state. The investigated ligands and complexes were also preliminarily tested as luminophores in light emitting diodes with the structures ITO/PEDOT:PSS/compound/Al and ITO/PEDOT:PSS/PVK:PBD:compound/Al. The pronounced effect of the ligand chemical structure on electroluminescence ability was clearly visible.

Production of volatile fatty acids and H2 for different ratio of inoculum to kitchen waste.

The aim of this study was to evaluate the effect of different inoculum ratio on the dark fermentation of kitchen waste in terms of volatile fatty acids (VFAs) and H2 production. The experiments were performed in batch bioreactors of effective volume 1 L without pH regulation. The ratio between the DS and KW was being increased from 0.11 to 0.51 on a volatile solids (VS) basis, while the initial content of KW was equal to 34.1 g VS/L. Increase of the DS/KW ratio from 0.11 to 0.28 resulted in the rise of VFAs and H2 production. Further increase in the amount of added DS did not cause a significant change in the production of VFAs and H2. In the bioreactor with the DS/KW ratio of 0.28, the production of VFAs and H2 was equal to 16.0 g/L and 68.1 mL/g VS, respectively. Acetic and butyric acids were produced in the largest amount and their content, for DS/KW ratio of 0.28, were equal 37% and 43%, respectively. At the ratio of DS/KW above 0.4, the caproic acid content attained the level of 25%. Based on the DS and KW microbiological analysis, it was observed that dominant bacteria were Bacteroidetes, Firmicutes, Proteobacteria, Spirochaetes and WWE1 at the phylum level.

Energy Transfer from Photosystem I to Thermally Reduced Graphene Oxide.

The energy transfer from photosynthetic complex photosystem I to thermally reduced graphene oxide was studied using fluorescence microscopy and spectroscopy, and compared against the structure in which monolayer epitaxial graphene was used as the energy acceptor. We find that the properties of reduced graphene oxide (rGO) as an energy acceptor is qualitatively similar to that of epitaxial graphene. Fluorescence quenching, which in addition to shortening of fluorescence decay, is a signature of energy transfer varies across rGO substrates and correlates with the transmission pattern. We conclude that the efficiency of the energy transfer depends on the number of rGO layers in the flakes and decreases with this number. Furthermore, careful analysis of fluorescence imaging data confirms that the energy transfer efficiency dependence on the excitation wavelength, also varies with the number of rGO flakes.

Wide-Field Fluorescence Microscopy of Real-Time Bioconjugation Sensing.

We apply wide-field fluorescence microscopy to measure real-time attachment of photosynthetic proteins to plasmonically active silver nanowires. The observation of this effect is enabled, on the one hand, by sensitive detection of fluorescence and, on the other hand, by plasmonic enhancement of protein fluorescence. We examined two sample configurations with substrates being a bare glass coverslip and a coverslip functionalized with a monolayer of streptavidin. The different preparation of the substrate changes the observed behavior as far as attachment of the protein is concerned as well as its subsequent photobleaching. For the latter substrate the conjugation process is measurably slower. The described method can be universally applied in studying protein-nanostructure interactions for real-time fluorescence-based sensing.

Spectrally selective fluorescence imaging of Chlorobaculum tepidum reaction centers conjugated to chelator-modified silver nanowires.

A polyhistidine tag (His-tag) present on Chlorobaculum tepidum reaction centers (RCs) was used to immobilize photosynthetic complexes on a silver nanowire (AgNW) modified with nickel-chelating nitrilo-triacetic acid (Ni-NTA). The optical properties of conjugated nanostructures were studied using wide-field and confocal fluorescence microscopy. Plasmonic enhancement of RCs conjugated to AgNWs was observed as their fluorescence intensity dependence on the excitation wavelength does not follow the excitation spectrum of RC complexes in solution. The strongest effect of plasmonic interactions on the emission intensity of RCs coincides with the absorption spectrum of AgNWs and is observed for excitation into the carotenoid absorption. From the absence of fluorescence decay shortening, we attribute the emission enhancement to increase of absorption in RC complexes.

The effect of initial organic load of the kitchen waste on the production of VFA and H2 in dark fermentation.

Dark fermentation of kitchen wastes was studied in batch bioreactors, with no pH adjustment, to evaluate the effect of the initial organic load on the process performance in terms of volatile fatty acids and H2 production. Initial organic load of the kitchen wastes ranged from 4.1 to 48.2gVS/L. Acetic and butyric acids were produced in the largest amount. At the initial organic load of 48.2KWgVS/L the highest concentration of volatile fatty acids was 9.81g/L. The maximum production yield of H2 (76.1mL/gVS) was found for the initial organic load of kitchen wastes at 14.3gVS/L. The carbon balance calculation showed that the maximum CO2 yield of 0.34 gC/gC was attained in the bioreactor with the initial organic load of 14.3gVS/L. The microbiological analysis revealed that the predominant microorganisms in the dark fermentation process were Bacteroidetes, Firmicutes, Spirochaetes and WWE1 at phyla level.

PsbS is required for systemic acquired acclimation and post-excess-light-stress optimization of chlorophyll fluorescence decay times in Arabidopsis.

Systemic acquired acclimation (SAA) is an important light acclimatory mechanism that depends on the global adjustments of non-photochemical quenching and chloroplast retrograde signaling. As the exact regulation of these processes is not known, we measured time-resolved fluorescence of chlorophyll a in Arabidopsis thaliana leaves exposed to excess light, in leaves undergoing SAA, and in leaves after excess light episode. We compare the behavior induced in wild-type plants with null mutant of non-photochemical quenching (npq4-1). The wild type rosettes exhibit a small reduction of fluorescence decay times in leaves directly exposed to excess light and in leaves undergoing SAA in ambient low light. However in npq4-1 exposition to excess light results in much faster fluorescence decay, which is insensitive to excitation power. At the same time npq4-1 leaves undergoing SAA displayed intermediate fluorescence decay. The npq4-1 plants also lost the ability to optimize florescence decay, and thus chlorophyll a dynamics up to 2 h after excess light episode. The fluorescence decay dynamics in both WT and npq4-1 can be described by a set of 3 maximum decay times. Based on the results, we concluded that functional PsbS is required for optimization of absorbed photon fate and optimal light acclimatory responses such as SAA or after excess light stress.