Fluorescence and photophysical properties of D-π-A push-pull systems featuring a 4,5-dicyanoimidazole unit

Absorption and fluorescence spectra and fluorescence quantum yields of 18 D-;π-A push-pull compounds were measured. The investigated chromophores consist of 4,5-dicyanoimidazole — bearing donor — substituted and systematically extended π-conjugated spacers. The influence of temperature and solvent polarity on the spectral and photophysical properties was investigated. Employing INDO/S calculations, the structure-property relationships were discussed.     

Fischer aminocarbene complexes of chromium and iron: Anomalous electrochemical reduction of p-carbonyl substituted derivatives

This contribution shows how a small change of a remote substituent (COOCH₃ for e.g. OCH₃) on Fischer aminocarbene complexes can change totally the LUMO location, and thus electron distribution, extent of π-electron delocalization and, consequently, redox properties of these potential catalysts. During investigation of redox properties of extended series of title compounds, an exceptionally positive reduction potential was observed (non fitting the LFER plot) for p-COOR substituents. This effect is caused by a strong intramolecular electronic interaction, which is specific for p-phenylene dicarbonyl compounds. In this context, the CN bond in aminocarbene moiety has a double bond character and resembles carbonyl function. The interpretation was proved by DFT calculations.     

DockVis: Visual Analysis of Molecular Docking Trajectories

Computation of trajectories for ligand binding and unbinding via protein tunnels and channels is important for predicting possible protein–ligand interactions. These highly complex processes can be simulated by several software tools, which provide biochemists with valuable information for drug design or protein engineering applications. This paper focuses on aiding this exploration process by introducing the DockVis visual analysis tool. DockVis operates with the multivariate output data from one of the latest available tools for the prediction of ligand transport, CaverDock. DockVis provides the users with several linked views, combining the 2D abstracted depictions of ligands and their surroundings and properties with the 3D view. In this way, we enable the users to perceive the spatial configurations of ligand passing through the protein tunnel. The users are initially visually directed to the most relevant parts of ligand trajectories, which can be then explored in higher detail by the follow-up analyses. DockVis was designed in tight collaboration with protein engineers developing the CaverDock tool. However, the concept of DockVis can be extended to any other tool predicting ligand pathways by the molecular docking. DockVis will be made available to the wide user community as part of the Caver Analyst 3.0 software package ( www.caver.cz ).     

Colloidally stable polypeptide-based nanogel: Study of enzyme-mediated nanogelation in inverse miniemulsion

The current work presents a pivotal study of the nanogelation of the linear poly(N⁵-2-hydroxypropyl-L-glutamine) polymer precursor containing tyramine (TYR) units in an inverse miniemulsion by horseradish peroxidase/H₂O₂-mediated crosslinking. The effects of various n_H2O2/n_TYR ratios on the kinetics of nanogelation in the inverse miniemulsion and on the reaction time are investigated by linear sweep voltammetry, while the formation of dityramine crosslinking is explored by fluorescence spectroscopy. The study is completed using dynamic light scattering measurements, nanoparticle tracking analysis, and cryogenic transmission electron microscopy to acquire comprehensive information about the formed nanoparticulate systems. With the optimal ratio n_H2O2/n_TYR = 2, the strategy yields in the high-quality ~ 130 nm poly(amino acid)-based nanogel, which is prepared in 2 h. The nanogel is colloidally stable under different temperature and pH conditions for over 168 h. Moreover, the demonstrated nanogel is noncytotoxic for HeLa cells and human primary fibroblasts and is quickly enzymatically hydrolyzed into small fragments during a biodegradation study in human blood plasma. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48725.     

Electronic interactions between "pea" and "pod": the case of oligothiophenes encapsulated in carbon nanotubes

One of the most challenging strategies to achieve tunable nanophotonic devices is to build robust nanohybrids with variable emission in the visible spectral range, while keeping the merits of pristine single-walled carbon nanotubes (SWNTs). This goal is realized by filling SWNTs ("pods") with a series of oligothiophene molecules ("peas"). The physical properties of these peapods are depicted by using aberration-corrected high-resolution transmission electron microscopy, Raman spectroscopy, and other optical methods including steady-state and time-resolved measurements. Visible photoluminescence with quantum yields up to 30% is observed for all the hybrids. The underlying electronic structure is investigated by density functional theory calculations for a series of peapods with different molecular lengths and tube diameters, which demonstrate that van der Waals interactions are the bonding mechanism between the encapsulated molecule and the tube.     

Effect of the talc filler content on the mechanical properties of polypropylene composites

This research examines the effect of a microsize/nanosize talc filler on the physicochemical and mechanical properties of filled polypropylene (108MF10 and 33MBTU from Saudi Basic Industries Corp. and HE125MO grade from Borealis) composite matrices. A range of mechanical properties were measured [tensile properties, bending properties, fracture toughness, notched impact strength (at the ambient temperature and ?20°C), strain at break, and impact strength] along with microhardness testing and thermal stability testing from 40 to 600°C as measured by differential thermal analysis and thermogravimetric analysis. Increasing filler content lead to an increase in the mechanical strength of the composite material with a simultaneous decrease in the fracture toughness. The observed increase in tensile strength ranged from 15 to 25% (the maximum tensile strength at break was found to be 22 MPa). The increase in mechanical strength simultaneously led to a higher brittleness, which was reflected in a decrease in the mean impact strength from the initial 18 kJ/m² (for the virgin polypropylene sample) to 14 kJ/m², that is, a 23% decrease. A similar dependency was also obtained for the samples conditioned at ?20°C (a decrease of 12.5%). With increasing degree of filling of the talc–polypropylene composite matrix, the thermooxidative stability increased; the highest magnitude was obtained for the 20 wt % sample (decomposition temperature = 482°C, cf. 392°C for the virgin polymer). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Economic contradictions of the waste-to-energy concept and emissions reduction plan (case study,Czech Republic)

According to the latest waste-to-energy concept, the corporate operators of urban heating systems (UHS) in European Union (EU) should replace fossil fuels by incineration of mixed municipal solid waste (MMSW, following 2008/98/EC Waste Framework Directive that implements mandatory waste separation system for at least paper, plastic, glass, and metal packaging since 31 of December 2014). However, there are indications that MMSW incineration will be counterproductive to the existing Directive on reducing national emissions of certain atmospheric pollutants. Material flow analysis for comparing the environmental impacts of the incineration of lignite, natural gas, and waste in UHS was carried out on a commercial scale. Results showed that replacing lignite by MMSW can lead to an increase in emissions of nitrogen oxides and other negative environmental impacts. However, it is proposed that co-combustion MMSW with natural gas could be a better alternative.     

Magnetically modified spent coffee grounds for dyes removal

Large amounts of spent coffee grounds are discharged from food industries, for example, during the instant coffee manufacture. Although part of them is reused as compost and animal feed, most of the coffee grounds are burned as a waste. However, this material can be used as a biosorbent for xenobiotics removal. Spent coffee grounds were magnetically modified by contact with water-based magnetic fluid. This new type of magnetically responsive biocomposite materials can be easily separated by means of commercially available magnetic separators or strong permanent magnets. Magnetic coffee grounds can be used as an inexpensive magnetic adsorbent for the removal of water-soluble dyes. Seven dyes (crystal violet, malachite green, amido black 10B, Congo red, Bismarck brown Y, acridine orange and safranin O) were used to study the adsorption process. The dyes adsorption could be described with the Langmuir isotherm. The maximum adsorption capacities reached the value 73.4 mg of dye per g of dried magnetically modified coffee grounds for acridine orange; it corresponds to 276.6 μmol g⁻¹. This adsorbent can also be used for magnetic solid-phase extraction of crystal violet from extremely diluted solutions. To conclude, magnetic modification of spent coffee grounds resulted in the formation of a new, promising adsorbent for selected xenobiotics removal.     

Impact of selected factors – Cultivar,storage, cooking and baking on the content of anthocyanins in coloured-flesh potatoes

The impact of selected factors – cultivar, storage, cooking and baking on the content of total anthocyanins (TAC) in coloured-flesh potato cultivars has been studied. TAC ranged from 248.5 to 2257.8 mg kg⁻¹ dry matter (DM). TAC difference between cultivars was statistically significant. Cold storage (4 °C) influenced TAC differentially. In the Violette and Highland Burgundy Red cultivars TAC increased by 18.5% and 12.1% respectively, and in the Valfi cultivar it decreased by 33.9%. Baking increased TAC 3.34 times whereas cooking in boiled water increased it 4.22 times. Correlation between antioxidant activity (AOA) and TAC (r² = 0.659) has been found. The Violette, Vitelotte and Highland Burgundy Red cultivars with the highest TAC showed high AOA and the Shetland Black cultivar and the cultivars Salad Blue and Blue Congo with a “marbled” texture showed the lowest TAC and AOA. Individual anthocyanidins are fingerprints of colour-fleshed potato cultivars.     

Performance of “ductless” personalized ventilation in conjunction with displacement ventilation: Impact of disturbances due to walking person(s)

The performance of the novel “ductless” personalized ventilation in conjunction with displacement ventilation (DV) was compared with the performance of DV alone under realistic conditions involving disturbances due to walking of one or two persons. An office room with two workstations was arranged in a full-scale test room. Two thermal manikins were used as sedentary occupants at the workstations. Two pollution sources, namely exhaled air by one of the manikins and passive pollution on the table in front of the same manikin were simulated. The performance of the ventilation systems was evaluated with regard to the quality of inhaled air and thermal comfort of the seated “occupants”. The walking person(s) caused mixing of the clean and cool air near the floor with the polluted and warmer air at higher levels and disturbed the displacement principle which resulted in a decrease of the inhaled air quality. The performance of the “ductless” PV under the tested conditions was better as opposed to DV alone. Thus in practice the “ductless” PV will be superior to DV alone as regards perceived quality of inhaled air. The location of a walking person was found to be important. Person(s) walking close to the displacement diffuser will cause greater disturbance.