Katarína Kráľová

Metal Nanoparticles and Plants / Nanocząstki Metaliczne I Rośliny

Abstract Metal nanoparticles (MNPs) belong mostly to the engineered type of nanoparticles and have not only unique physical and chemical properties but also different biological actions. In recent years, noble MNPs and their nano-sized agglomerates (collectively referred to as nanoparticles or particles in the subsequent sections) have been the subjects of much focused research due to their unique electronic, optical, mechanical, magnetic and chemical properties that can be significantly different from those of bulk materials. To enhance their use, it is important to understand the generation, transport, deposition, and interaction of such particles. Synthesis of MNPs is based on chemical or physical synthetic procedures and by use of biological material (“green synthesis” as an environmentally benign process) including bacteria, algae and vascular plants (mainly metallophytes). In biological methods for preparation of metal nanoparticles mainly leaf reductants occurring in leaf extracts are used. MNPs can be formed also directly in living plants by reduction of the metal ions absorbed as a soluble salt, indicating that plants are a suitable vehicle for production of MNPs. These methods used for preparation of MNPs are aimed to control their size and shape. Moreover, physicochemical properties of MNPs determine their interaction with living organisms. In general, inside the cells nanoparticles might directly provoke either alterations of membranes and other cell structures or activity of protective mechanisms. Indirect effects of MNPs depend on their physical and chemical properties and may include physical restraints, solubilization of toxic nanoparticle compounds or production of reactive oxygen species. Toxic impacts of MNPs on plants is connected with chemical toxicity based on their chemical composition (eg release of toxic metal ions) and with stress or stimuli caused by the surface, size and shape of these nanoparticles. Positive effects of MNPs were observed on the following plant features: seed germination, growth of plant seedlings, stimulation of oxygen evolution rate in chloroplasts, protection of chloroplasts from aging for long-time illumination, increase of the electron transfer and photophosphorylation, biomass accumulation, activity of Rubisco, increase of quantum yield of photosystem II, root elongation, increase of chlorophyll as well as nucleic acid level and increase in the shoot/root ratio. However, it should be stressed that MNPs impact on human and environmental health remains still unclear. Abstrakt Ze względu na unikalne właściwości fizyczne i chemiczne, ale także różne działanie biologiczne nanocząstek metali (MNPS) są obiektem zainteresowania nowo powstałej inżynierii tych materiałów. W ostatnich latach MNPS metali szlachetnych (zbiorowo określane w dalszej części tekstu jako nanocząstki lub cząstki) były poddawane wielu badaniom ze względu na ich unikalne właściwości elektroniczne, optyczne, mechaniczne, magnetyczne i chemiczne, które mogą być znacząco różne od właściwości materiałów litych. Synteza MNPS polega na procesach chemicznych lub fizycznych oraz na wykorzystaniu materiału biologicznego („zielona synteza” - proces przyjazny środowisku), w tym bakterii, glonów i roślin naczyniowych (głównie metalofitów). W biologicznych metodach wytwarzania nanocząstek metali używane są głównie substancje redukujące, występujące w ekstraktach z liści. MNPS również mogą być utworzone bezpośrednio w żywych roślinach przez redukcję jonów metali absorbowanych w postaci rozpuszczalnych soli, co wskazuje, że rośliny są odpowiednim środkiem produkcji MNPS. Metody te pozwalają na kontrolę rozmiarów i kształtu cząstek. Jest to ważne, ponieważ właściwości fizykochemiczne MNPS określają ich oddziaływanie z żywymi organizmami. Zwykle w komórkach nanocząstki mogą bezpośrednio wywoływać zmiany w błonach komórkowych albo w innych strukturach oraz mogą wpływać na aktywność komórek lub na ich mechanizmy ochronne. Pośrednio skutki działania MNPS zależą od ich właściwości fizycznych i chemicznych. Skutki te mogą obejmować ograniczenia fizyczne, rozpuszczanie toksycznych MNPS lub wytwarzanie reaktywnych form tlenu. Toksyczny wpływ MNPS na rośliny jest związany z toksycznością chemiczną, uzależnioną od składu chemicznego (np. uwalnianie toksycznych jonów metali) oraz ze stymulacją lub napięciami wywołanymi przez kontakt z powierzchnią. Istotne są także rozmiary i kształt nanocząstek. Pozytywne wpływy MNPS obserwowano na: kiełkowanie nasion, wzrost siewek roślin, stymulację tempa przemiany tlenu w chloroplastach, ochronę przed starzeniem chloroplastów wywołanym przez długotrwałe oświetlanie, zwiększenie transferu elektronów i fotofosforylacji, gromadzenie biomasy, aktywność RuBisCO, wzrost wydajności kwantowej fotosystemu II, wzrost korzeni, wzrost chlorofilu, jak również poziomu kwasów nukleinowych i stosunku długości pędów i korzeni. Jednak należy podkreślić, że wpływ MNPS na zdrowie ludzi i na środowisko jest nadal niejasny.

Substituted N-Benzylpyrazine-2-carboxamides: Synthesis and Biological Evaluation

A series of twelve amides was synthesized via aminolysis of substituted pyrazinecarboxylic acid chlorides with substituted benzylamines. Compounds were characterized with analytical data and assayed in vitro for their antimycobacterial, antifungal, antibacterial and photosynthesis-inhibiting activity. 5-tert-Butyl-6-chloro-N-(4-methoxybenzyl)pyrazine-2-carboxamide (12) has shown the highest antimycobacterial activity against Mycobacterium tuberculosis (MIC = 6.25 µg/mL), as well as against other mycobacterial strains. The highest antifungal activity against Trichophyton mentagrophytes, the most susceptible fungal strain tested, was found for 5-chloro-N-(3-trifluoromethylbenzyl)-pyrazine-2-carboxamide (2, MIC = 15.62 µmol/L). None of the studied compounds exhibited any activity against the tested bacterial strains. Except for 5-tert-butyl-6-chloro-N-benzylpyrazine-2-carboxamide (9, IC50 = 7.4 µmol/L) and 5-tert-butyl-6-chloro-N-(4-chlorobenzyl)pyrazine-2-carboxamide (11, IC50 = 13.4 µmol/L), only moderate or weak photosynthesis-inhibiting activity in spinach chloroplasts (Spinacia oleracea L.) was detected.

Principles of classification of medicinal plants as hyperaccumulators or excluders

Strategies of plants, known as metallophytes, in response to metal excess are explored. Specific features of medicinal plants related to metal exposition are discussed. Different parameters used for metallophyte classification are discussed. Bioaccumulation and translocation factors are characterized. Chamomile (Matricaria recutita L.), one of the most important medicinal plants, is presented as a case history. Based on actual knowledge of plant response to metal excess and published data related to chamomile, it has been concluded that this plant species is Cd hyper/accumulator. Thus, chamomile can manifest high potential for cleaning-up (phytoremediation) of the soils contaminated with cadmium. However, it should be stressed that cultivation of this medicinal plant under natural conditions for pharmaceutical use should be carefully supervised.

Effect of zinc and cadmium on physiological and production characteristics in Matricaria recutita

Effects of zinc (12–180 μM) alone and in mixtures with 12 μM Cd on metal accumulation, dry masses of roots and shoots, root respiration rate, variable to maximum fluorescence ratio (FV/FM), and content of photosynthetic pigments were studied in hydroponically cultivated chamomile (Matricaria recutita) plants. The content of Zn in roots and shoots increased with the increasing external Zn concentration and its accumulation in the roots was higher than that in the shoots. While at lower Zn concentrations (12 and 60 μM) the presence of 12 μM Cd decreased Zn accumulation in the roots, treatment with 120 and 180 μM Zn together with 12 μM Cd caused enhancement of Zn content in the root. Presence of Zn (12–120 μM) decreased Cd accumulation in roots. On the other hand, Cd content in the shoots of plants treated with Zn + Cd exceeded that in the plants treated only with 12 μM Cd. Only higher Zn concentrations (120 and 180 μM) and Zn + Cd mixtures negatively influenced dry mass, chlorophyll (Chl) and carotenoid content, FV/FM and root respiration rate. Chl b was reduced to a higher extent than Chl a.

Application Of Nanotechnology In Agriculture And Food Industry, Its Prospects And Risks

Abstract Nanoagrochemicals, such as nanopesticides, nanofertilizers or plant growth stimulating nanosystems, were primarily designed to increase solubility, enhance bioavailability, targeted delivery, controlled release and/or protection against degradation resulting in the reduced amount of applied active ingredients and finally in a decrease of dose-dependent toxicity/burden. This paper is a comprehensive up-to-date review related to the preparation and the biological activity of nanoformulations enabling gradual release of active ingredient into weeds and the body of pests and controlled release of nutrients to plants. The attention is also devoted to the decrease of direct environmental burden and economic benefits due to application of nanoformulations, where less amount of active ingredient is needed to achieve the same biological effect in comparison with bulk. The application of nanotechnology in the areas such as food packaging, food security, encapsulation of nutrients and development of new functional products is analysed. The use of nanoparticles in biosensors for detection of pathogens and contaminants as well as in DNA and gene delivery is discussed as well. Benefits and health risks of nanoagrochemicals are highlighted, and special attention is given to nanoecotoxicology and guidelines and regulatory documents related to the use of nanoformulations in agriculture and food industry.

Synthesis and Biological Evaluation of Quinazoline-4-thiones

Several 2,2-dimethyl-3-phenyl-1,2-dihydroquinazoline-4(3H)-thiones and 2-methyl-3-phenylquinazoline-4(3H)-thiones were synthesized and tested for their antimycobacterial, photosynthesis-inhibiting, and antialgal activity. Antimycobacterially active compounds were found among the 6-chloro substituted compounds. 6-Chloro-3-(4-isopropylphenyl)-2-methylquinazoline-4(3H)-thione exhibited higher activity than the isoniazid standard against Mycobacterium avium and M. kansasii. Most of the compounds possessed photosynthesis-inhibiting activity. 6-Chloro-2,2-dimethyl-3-phenyl-1,2-dihydro-quinazoline-4(3H)-thione and its 3´-chloro- and 3´,4´-dichloro analogs were most effective in the inhibition of oxygen evolution rate in spinach chloroplasts. Of compounds selected for toxicological screening, 6-chloro-3-(4-isopropylphenyl)-2-methyl-quinazoline-4(3H)-thione was the only one active in the brine shrimp bioassay.

5-Bromo- and 3,5-dibromo-2-hydroxy-N-phenylbenzamides — inhibitors of photosynthesis

Abstract5-Bromo-(Br-PBA) and 3,5-dibromo-2-hydroxy-N-phenylbenzamides (Br2-PBA) inhibited photosynthetic electron transport (PET) and their inhibitory efficiency depended on the compound lipophilicity as well as on the electronic properties of the R substituent in the N-phenyl moiety. Br-PBA showed higher PET inhibiting activity than Br2-PBA with the same R substituent. The most effective inhibitors in the tested series were the derivatives with R = 3-F (Br-PBA; IC50 = 4.3 μmol dm−3) and R = 3-Cl (Br2-PBA; IC50 = 8.6 μmol dm−3). Bilinear dependence of the PET inhibiting activity on the lipophilicity of the compounds as well as on the Hammett constant, σ, of the R substituent was observed for both investigated series. Using EPR spectroscopy it was found that the site of action of the tested compounds in the photosynthetic apparatus is situated on the donor side of PS 2, in D· or in the Z·/D· intermediates. Interaction of the studied compounds with chlorophyll a and aromatic amino acids present in the pigment-protein complexes mainly in photosystem 2 was documented by fluorescence spectroscopy.

New polyfluorothiopropanoyloxy derivatives of 5β-cholan-24-oic acid designed as drug absorption modifiers

A series of final six propanoyloxy derivatives of 5β-cholan-24-oic acid (tridecafluoroctylsulfanyl- and tridecafluoroctylsulfinylethoxycarbonylpropanoyloxy derivatives) as potential drug absorption promoters (skin penetration enhancers, intestinal absorption promoters) was generated by multistep synthesis. Structure confirmation of all generated compounds was accomplished by (1)H NMR, (13)C NMR, IR and MS spectroscopy methods. All the prepared compounds were analyzed using RP-TLC, and their lipophilicity (RM) was determined. The hydrophobicity (log P), solubility (logS), polar surface area (PSA) and molar volume (MV) of the studied compounds were also calculated. All the target compounds were tested for their in vitro transdermal penetration effect and as potential intestinal absorption enhancers. The cytotoxicity of all the evaluated compounds was evaluated against normal human skin fibroblast cells. Their anti-proliferative activity was also assessed against human cancer cell lines: T-lymphoblastic leukaemia cell line and breast adenocarcinoma cell line. One compound showed high selective cytotoxicity against human skin fibroblast cells and another compound possessed high cytotoxicity against breast adenocarcinoma cell line and skin fibroblast cells. Only one compound expressed anti-proliferative effect on leukaemia and breast adenocarcinoma cells without affecting the growth of normal cells, which should be promising in potential development of new drugs. Most of the target compounds showed minimal anti-proliferative activity (IC50>37μM), indicating they would have moderate cytotoxicity when administered as chemical absorption modifiers. The relationships between the lipophilicity/polarity and the chemical structure of the studied compounds as well as the relationships between their chemical structure and penetration enhancement effect are discussed in this article.

Plant-Heavy Metal Interaction: Phytoremediation, Biofortification and Nanoparticles

Contamination of ecosystems and action of toxic metals to plants is one of the major problems of all over the world. Most of these metals are present in the environment as a consequence of geological and/or anthropogenic activities. Metal contamination in agricultural environments can originate from atmospheric pollution, pesticide applications, contamination by chemical fertilizers, and irrigation with wastewater of poor quality. Although, some of metals are bioelements (macroand micronutrients) at normal concentration, they can cause harmful effects on the plants in excess. Moreover, these metals have strong impact on human health through the food chain. Toxic metals or metals, as bioelements in higher than normal concentrations, are group of substances belonging to the xenobiotics. Frequently is also used term heavy metals, that are metals with specific weight higher than 5 gcm-3, e.g. Cd, Hg, Pb, Cr, Ag and Sn (di Toppi & Gabbrielli, 1999). Knowledge of dominant fluxes of metals in the soil-root-shoot continuum can also help agronomic strategy to address the problem of crop growth under metal-excess, biomass production and food quality. In addition to the highly toxic heavy metals, light metals (e.g. Mg, Al) and metalloids (e.g. As and Se) are of great environmental and health significance. Extraordinarily dangerous for both humans and plants are mainly metals that attack activity of the enzymes containing –SH group (e.g. Cd, Hg and Pb). These metals can initiate acute or more dangerous and frequently occurring chronic diseases. Therefore, new and environmental-friendly technologies, such phytoremediation appeared to remove the harmful metals from the environment. Based on their strategy, plants growing on soil containing metal can be classified as accumulators and excluders. Later the following groups of plants were suggested: metal excluders and metal non-excluders (indicators, hyperaccumulators) (in detail see Masarovicova et al., 2010).

Effect of different Fe(III) compounds on photosynthetic electron transport in spinach chloroplasts and on iron accumulation in maize plants

Synthesis and spectral characteristics of [Fe(nia)3Cl3] and [Fe(nia)3(H2O)2](ClO4)3 are described. The effect of these compounds as well as of FeCl3·6H2O on photosynthetic electron transport in spinach chloroplasts was investigated using EPR spectroscopy. It was found that due to the interaction of these compounds with tyrosine radicals situated at the 161st position in D1 (TyrZ) and D2 (TyrD) proteins located at the donor side of photosystem (PS) II, electron transport between the photosynthetic centres PS II and PS I was interrupted. In addition, the treatment with [Fe(nia)3(H2O)2](ClO4)3 resulted in a release of Mn(II) from the oxygen evolving complex situated on the donor side of PS II. Moreover, the effect of the Fe(III) compounds studied on some production characteristics of hydroponically cultivated maize plants and on Fe accumulation in plant organs was investigated. In general, the production characteristic most inhibited by the presence of Fe(III) compounds was the leaf dry mass and [Fe(nia)3(H2O)2](ClO4)3 was found to be the most effective compound. The highest Fe amount was accumulated in the roots, and the leaves treated with Fe(III) compounds contained more Fe than the stems. The treatment with FeCl3·6H2O caused the most effective translocation of Fe into the shoots. Comparing the effect of nicotinamide complexes, [Fe(nia)3(H2O)2](ClO4)3 was found to facilitate the translocation of Fe into the shoots more effectively than [Fe(nia)3Cl3]. This could be connected with the different structure of these complexes. [Fe(nia)3(H2O)2](ClO4)3 has ionic structure and, in addition, coordinated H2O molecules can be easily substituted by other ligands.