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In this study, a novel supramolecular composite, "photogels", was synthesized by mixing of cysteine-silver sol (CSS) and methylene blue (MB). A complex of modern physico-chemical methods of analysis such as viscosimetry, UV spectroscopy, dynamic and electrophoretic light scattering, scanning electron microscopy and energy-dispersive X-ray spectroscopy showed that MB molecules are uniformly localized mainly in the space between fibers of the gel-network formed by CSS particles. Molecules of the dye also bind with the surface of CSS particles by non-covalent interactions. This fact is reflected in the appearance of a synergistic anticancer effect of gels against human squamous cell carcinoma even in the absence of light irradiation. A mild toxic influence of hydrogels was observed in normal keratinocyte cells. Photodynamic exposure significantly increased gel activity, and there remained a synergistic effect. The study of free-radical oxidation in cells has shown that gels are not only capable of generating reactive oxygen species, but also have other targets of action. Flow cytometric analysis allowed us to find out that obtained hydrogels caused cell cycle arrest both without irradiation and with light exposure. The obtained gels are of considerable interest both from the point of view of academics and applied science, for example, in the photodynamic therapy of superficial neoplasms.

We studied the recovery of the growth and physiological parameters of Scots pine seedlings after long-term zinc toxicity. The removal of excess zinc from the nutrient solution resulted in the rapid recovery of primary root growth but did not promote the initiation and growth of lateral roots. The recovery of root growth was accompanied by the rapid uptake of manganese, magnesium, and copper. Despite the maximum rate of manganese uptake by the roots, the manganese content in the needles of the recovering plants did not reach control values during the 28 days of the experiment, unlike magnesium, iron, and copper. In general, the recovery of ion homeostasis eliminated all of the negative effects on the photosynthetic pigment content in the needles. However, these changes, along with recovery of the water content in the needles, were not accompanied by an increase in the weight gain of the recovering seedlings compared with that of the Zn-stressed seedlings. The increased accumulation of phenolic compounds in the needles persisted for a long period after excess zinc was removed from the nutrient solution. The decreased lignin content in the roots and needles is a characteristic feature of Zn-stressed plants. Moreover, the removal of excess zinc from the nutrient solution did not lead to an increase in the lignin content in the organs.

Supramolecular hydrogels based on low-molecular-weight compounds are a unique class of so-called "soft" materials, formed by weak non-covalent interactions between precursors at their millimolar concentrations. Due to the variety of structures that can be formed using different low-molecular-weight gelators, they are widely used in various fields of technology and medicine. In this study, we report for the first time an unusual self-assembly process of mixing a hydrosol obtained from L-cysteine and silver nitrate (cysteine-silver sol-CSS) with sodium halides. Modern instrumental techniques such as viscosimetry, UV spectroscopy, dynamic light scattering, zeta potential measurements, SEM and EDS identified that adding fluoride anions to CSS is able to form stable hydrogels of a thixotropic nature, while Cl - , Br - and I - lead to precipitation. The self-assembly process proceeds using a narrow concentration range of F - . An increase in the fluoride anion content in the system leads to a change in the gel network morphology from elongated structures to spherical ones. This fact is reflected in a decrease in the gel viscosity and a number of gel-sol-gel transition cycles. The mechanism of F - 's interaction with hydrosol includes the condensation of anions on the positive surface of the CSS nanoparticles, their binding via electrostatic forces and the formation of a resulting gel carcass. In vitro analysis showed that the hydrogels suppressed human squamous carcinoma cells at a micromolar sample concentration. The obtained soft gels could have potential applications against cutaneous malignancy and as carriers for fluoride anion and other bioactive substance delivery.

Forest trees are subjected to multiple stressors during their long lifetime and therefore require effective and finely regulated stress-protective systems. Stressors can induce protective systems either directly or with the involvement of stress memory mechanisms. Stress memory has only begun to be uncovered in model plants and is unexplored in coniferous species. Therefore, we studied the possible role of stress memory in the regulation of the accumulation of stress-protective compounds (heat shock proteins, dehydrins, proline) in the needles of naturally grown Scots pine and Norway spruce trees subjected to the subsequent action of long-term (multiyear) and short-term (seasonal) water shortages. Although the water deficit was relatively mild, it significantly influenced the pattern of expression of stress memory-related heat shock factor (HSF) and SWI/SNF genes, indicating the formation of stress memory in both species. In spruce, dehydrin accumulation was increased by water shortage in a manner compatible with Type II stress memory. The accumulation of HSP40 in spruce needles was positively influenced by long-term water shortage, but this increase was unlikely to be of biological importance due to the concomitant decrease in HSP70, HSP90 and HSP101 accumulation. Finally, proline accumulation was negatively influenced by short-term water deficit in spruce. In pine, no one protective compound accumulated in response to water stress. Taken together, the results indicate that the accumulation of stress-protective compounds was generally independent of stress memory effects both in pine and in spruce., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Masson SAS. All rights reserved.)

Delayed or incomplete recovery of gas exchange after water stress relief limits assimilation in the post-drought period and can thus negatively affect the processes of post-drought recovery. Abscisic acid (ABA) accumulation and antagonistic action between ABA and cytokinins (CKs) play an important role in regulation of stomatal conductance under water deficit. Specifically, in pine species, sustained ABA accumulation is thought to be the main cause of delayed post-drought gas exchange recovery, although the role of CKs is not yet known. Therefore, we aimed to study the effects of ABA and CKs on recovery of stomatal conductance in greenhouse-grown 3-year-old Scots pine saplings recovering from water stress. We analysed both changes in endogenous ABA and CK contents and the effects of treatment with exogenous CK on stomatal conductance. Drought stress suppressed stomatal conductance, and post-drought stomatal conductance remained suppressed for 2 weeks after plant rewatering. ABA accumulated during water stress, but ABA levels decreased rapidly after rewatering. Additionally, trans -zeatin/ABA and isopentenyladenine/ABA ratios, which were decreased in water-stressed plants, recovered rapidly in rewatered plants. Spraying plants with 6-benzylaminopurine (0.1-100 µM) did not influence recovery of either stomatal conductance or needle water status. It can be concluded that the delayed recovery of stomatal conductance in Scots pine needles was not due to sustained ABA accumulation or a sustained decrease in the CK/ABA ratio, and CK supplementation was unable to overcome this delayed recovery.

Copper(II) complexes with 2,5-bis(methylthio)-1,3,4-thiadiazole (tda) formulated as [Cu(tda) n X 2 ] (n=2, X=Cl - , Br - , C 2 N 3 - ; n= 1, X=C 2 N 3 - ) have been isolated and fully characterized. The crystal structures of all compounds have been determined using single-crystal X-ray diffraction (SCXRD). A study of the magnetic susceptibility in the range 1.77-300 K has shown that magnetic properties of the [Cu(tda) 2 Cl 2 ] and [Cu(tda) 2 Br 2 ] complexes match those of 1D chains of antiferromagnetically-coupled Cu 2+ ions. The intrachain interaction J in [Cu(tda) 2 Cl 2 ] turns out to be ∼1.2 times weaker than in its bromide analogue. In its turn, [Cu(tda) 2 (C 2 N 3 ) 2 ] exhibits J being an order of magnitude smaller and of the opposite ferromagnetic sign. Halogen bonding (HB) between adjacent complexes is much stronger than the H-bonds or π-π interactions between tda ligands according to the DFT calculations., (© 2023 Wiley-VCH GmbH.)

Extracellular vesicles induced by exercise have emerged as potential mediators of tissue crosstalk. Extracellular vesicles and their cargo miRNAs have been linked to dysglycemia and obesity in animal models, but their role in humans is unclear., Aim: The aim of the study was to characterize the miRNA content in plasma extracellular vesicle isolates after acute and long-term exercise and to study associations between extracellular vesicle miRNAs, mRNA expression in skeletal muscle and adipose tissue, and cardiometabolic risk factors., Methods: Sedentary men with or without dysglycemia and overweight underwent an acute bicycle test and a 12-week exercise intervention with extensive metabolic phenotyping. Gene expression in m. vastus lateralis and subcutaneous adipose tissue was measured with RNA sequencing. Extracellular vesicles were purified from plasma with membrane affinity columns or size exclusion chromatography., Results: Extracellular vesicle miRNA profiling revealed a transient increase in the number of miRNAs after acute exercise. We identified miRNAs, such as miR-652-3p, that were associated to insulin sensitivity and adiposity. By performing explorative association analyses, we identified two miRNAs, miR-32-5p and miR-339-3p, that were strongly correlated to an adipose tissue macrophage signature., Conclusion: Numerous miRNAs in plasma extracellular vesicle isolates were increased by exercise, and several miRNAs correlated to insulin sensitivity and adiposity. Our findings warrant future studies to characterize exercise-induced extracellular vesicles and cargo miRNA to clarify where exercise-induced extracellular vesicles originate from, and to determine whether they influence metabolic health or exercise adaptation., (© 2022 The Authors. Acta Physiologica published by John Wiley & Sons Ltd on behalf of Scandinavian Physiological Society.)

Manganese deficiency is a serious plant nutritional disorder, resulting in the loss of crop productivity in many parts of the world. Despite the progress made in the study of angiosperms, the demand for Mn in gymnosperms and the physiological responses to Mn deficiency remain unexplored. We studied the influence of Mn deficiency for 24 weeks on Pinus sylvestris L. seedling growth, ion homeostasis, pigment contents, lipid peroxidation, chlorophyll fluorescence indices and the transcript levels of photosynthetic genes and genes involved in chlorophyll biosynthesis. It was shown that Mn-deficient plants demonstrated suppressed growth when the Mn content in the needles decreased below 0.34 µmol/g DW. The contents of photosynthetic pigments decreased when the Mn content in the needles reached 0.10 µmol/g DW. Mn deficiency per se did not lead to a decrease in the nutrient content in the organs of seedlings. Photoinhibition of PSII was observed in Mn-deficient plants, although this was not accompanied by the development of oxidative stress. Mn-deficient plants had an increased transcript abundance of genes ( psbO , psbP , psbQ , psbA and psbC ), encoding proteins directly associated with the Mn cluster also as other proteins involved in photosynthesis, whose activities do not depend on Mn directly. Furthermore, the transcript levels of the genes encoding the large subunit of Rubisco, light-dependent NADPH-protochlorophyllide oxidoreductase and subunits of light-independent protochlorophyllide reductase were also increased in Mn-deficient plants.

The tight connection between the deterioration of xylem function and plant mortality under drought is well recognized. However, a lack of mechanistic understanding of how substantial conductivity loss influences plant performance under drought and during post-drought recovery hinders our ability to model tree responses to drought stress. We artificially induced a loss of 50% of xylem conducting area in Scots pine and Norway spruce saplings by stem notching and investigated plant performance under drought and during post-drought recovery. Plant mortality, xylem hydraulic conductivity, leaf water status and stomatal conductance were measured. We observed no preferential mortality of top plant parts (above the notches) compared to basal plant parts (below the notches), and no consistent trend in hydraulic conductivity loss was observed between top and basal parts of dying plants. Stem hydraulic conductivity, water status of the needles and stomatal conductance changed similarly between the top and basal parts during drought and post-drought recovery, which indicated the substantial hydraulic overcapacity of the stems. The recovery of stomatal conductance demonstrated prominent hysteresis due to non-hydraulic stomatal limitations. The results obtained are highly important for modelling the influence of plant hydraulic impairment on plant performance under drought and during post-drought recovery., (© 2022 Scandinavian Plant Physiology Society.)

The deterioration of plant mineral nutrition during drought is a significant factor in the negative influence of drought on plant performance. We aimed to study the effects of seasonal and multiyear water shortages on nutrient supply and demand in Scots pine and Norway spruce. We studied pine and spruce trees naturally grown in the Bryansk region (Russia). The dynamics of several nutrients (K, Ca, Mg, P, Fe, Mn, Zn, and Ca) in wood, needles, and bark of current-year twigs and the dynamics of the available pools of these elements at different soil depths were analysed. To assess the physiological consequences of changes in element concentrations, lipid peroxidation products and photosynthetic pigments were measured in the needles. Water shortage increased the wood concentrations of all elements except for Mn. In pine, this increase was mainly due to seasonal water deficit, whereas in spruce, multiyear differences in water supply were more important. This increased availability of nutrients was not observed in soil-based analyses. In needles, quite similar patterns of changes were found between species, with Mg increasing almost twofold and Fe and Mn decreasing under water shortage, whereas the remainder of the elements did not change much under differing water supplies. Neither the concentrations of photosynthetic pigments nor the contents of lipid peroxidation products correlated with element dynamics in needles. In summary, water shortage increased the availability of all elements except Mn for the plant; however, needle element contents were regulated independently of element availability for plants.

The present article reports the in situ preparation of silver nanoparticles (AgNPs) homogeneously distributed in the gel matrix formed using only L-cysteine (CYS) as a bio-reducing agent. The physicochemical methods of analysis confirmed the formation of a gel-network from aggregates consisting of spherical/elliptical cystine-stabilized AgNPs (core) and cysteine/Ag + complexes (shell) regardless of the used silver salt - AgNO 3 , AgNO 2 or AgOOCCH 3 . CYS/AgNO 3 and CYS/AgOOCCH 3 aqueous solution systems needed the addition of electrolytes (Cl - and SO 4 2- ) for the gelation process, but the gel-formation in CYS/AgNO 2 occurred in one stage without any additional components. The AgNP sizes were about 1-5 nm in diameter for CYS/AgNO 3 , 5-10 nm for CYS/AgOOCCH 3 and 20-40 nm for CYS/AgNO 2 systems. The zeta-potential values varied from +60 mV for CYS/AgNO 3 to +25 mV for the CYS/AgNO 2 system. The MTT-test showed that the obtained composites suppressed the MCF-7 breast cancer cells and the CYS/AgNO 3 system possessed the highest activity. Flow cytofluorimetry confirmed that the cell death occurred by apoptosis and this effect was the strongest for the CYS/AgNO 3 system. All systems were non-toxic to fibroblast cells. The novel simplest "green chemistry" approach, combining the knowledge of organic, inorganic, physical and supramolecular chemistry could open possibilities for the creation of the newest soft gel materials used in various fields of our life.

Effects of irradiation with visible light on the process of self-assembly in an aqueous l-cysteine-silver solution (CSS) and hydrogels based on were investigated using a set of physico-chemical methods. It was found that the exposure to light of CSS and hydrogels based on l-cysteine and silver acetate colors them firstly into yellow and subsequently to brown, which is due to the plasmon resonance of free electrons at the surface of resulting silver nanoparticles (AgNPs). A mechanism involving participation of AgNPs was proposed for the self-assembly in CSS and hydrogel., (© Springer Science+Business Media LLC 2022.)

We report a new and the most simple strategy for the synthesis of silver molybdate functional composite microspheres based on low molecular weight gelators -amino acids, silver salts and heptamolybdate ions. The resulting material shows a high photocatalytic activity with respect to the methylene blue dye degradation at neutral pH.