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A series of novel non-symmetric neutral N,N′,O-chelating ligands derived from the α-iminopyridine 2-(C(R1)[double bond, length as m-dash]N(C6H3-2,6-iPr2))-6-(R2R3P[double bond, length as m-dash]O)C5H3N (L1: R1 = H, R2 = R3 = Ph; L2: R1 = Me, R2 = R3 = Ph; L3: R1 = H; R2 = Ph, R3 = EtO; L4: R1 = Me, R2 = Ph, R3 = EtO; L5: R1 = H, R2 = R3 = iPrO; L6: R1 = Me, R2 = R3 = iPrO) were synthesized. Ligands L1–6 were reacted with SnCl2 and Sn(OTf)2 with the aim of studying the influence of different R2R3P[double bond, length as m-dash]O functional groups on the Lewis base mediated ionization of SnCl2 and Sn(OTf)2. While all ligands L1–6 provided the corresponding ionic tin(II) complexes [L1–6 → SnCl]+[SnCl3]− (1–6), only ligands L1, L4 and L6 were able to stabilize tin(II) dications [L1,4,6 → Sn(H2O)][OTf]2 (7–9). The auto-ionized compounds [L3–6 → SnCl]+[SnCl3]− possessing ethylphenyl phosphinate and diisopropylphosphite substituents undergo elimination of EtCl and iPrCl, respectively, yielding compounds 10–13. Thesecan either be interpreted as neutral tin(II)phosphinate chloride (10, 11) and tin(II)phosphonate chloride (12, 13), respectively, containing Sn–O and Sn–Cl bonds, and a P[double bond, length as m-dash]O → SnCl2 interaction, or as zwitterionic compounds, where the positive charge of the central tin atom is compensated by an [OSnCl2]− anion. Finally, DFT studies were performed to better understand the steric and electronic properties of the ligands L1–6 as well as the nature of the bonds in the resulting products, with a particular focus on complexes 10–13.

Based on reconstruction of the spatial context of causewayed enclosures and long barrows of the Proto- and Early Eneolithic period, we attempt to model the phenomenon of the ritual landscape in Central and North Bohemia. Discussing the purpose and meaning of the long barrows and enclosures, they are being described as funerary and religious structures related to the cult of ancestors. An alternative explanation views them primarily, in economic terms, as territorial markers delineating the areas controlled by different communities. It seems likely that both of these interpretations are valid and well characterise the true nature of such structures. Both types of monuments should not be perceived as isolated structures, but just the opposite as they are part of a pattern of regional and super-regional identity of communities and individuals. In fact, they are crucial elements of the overall system of structuring of the prehistoric landscape.

Reactivity studies of the GeII→B complex L(Cl)Ge⋅BH3 (1; L=2-Et2NCH2-4,6-tBu2-C6H2) were performed to determine the effect on the GeII→B donation. N-coordinated compounds L(OtBu)Ge⋅BH3 (2) and [LGe⋅BH3]2 (3) were prepared. The possible tuning of the GeII→B interaction was proved experimentally, yielding compounds 1-PPh2-8-(LGe)-C10H6 (4) and L(Cl)Ge⋅GaCl3 (5) without a GeII→B interaction. In 5, an unprecedented GeII→Ga coordination was revealed. The experimental results were complemented by a theoretical study focusing on the bonding in 1−5. The different strength of the GeII→E (E=B, Ga) donation was evaluated by using energy decomposition analysis. The basicity of different L(X)Ge groups through proton affinity is also assessed.

Peri-substituted naphthalene 1-PPh2-8-SnL-C10H6 (1) [L = 2,6-(Me2NCH2)2C6H3] was used as a ligand for the complexation of transition metals (TMs). The presence of two donor atoms provided rigid κ2P,Sn-coordinated complexes of TM. Correspondingly, reactions of 1 with binuclear Mn2(CO)10 and Co2(CO)8 yielded ionic complexes [(κ2-1)Mn(CO)4]+ [Mn(CO)5]− (2) and [(κ2-1)Co(CO)3]+ [Co(CO)4]− (3), first examples of Sn-coordinated Mn(CO)4+ and Co(CO)3+ cations. The reactivity of 1 toward TM–Cl complexes is quite different. During these reactions, transmetallation with subsequent elimination of L(Cl)Sn was observed. However, L(Cl)Sn remained in the coordination sphere of the TM, yielding P-coordinated heterobimetallic TM complexes 1-PPh2-8-[Rh(COD){Sn(Cl)L}]C10H6 (7), 1-PPh2-8-[Ir(COD){Sn(Cl)L}]C10H6 (8), and 1-PPh2-8-[Pd(Cl){Sn(Cl)L}]-C10H6 (9) with additional Sn→TM intermolecular coordination. These transmetallations may be kinetically driven, as suggested by density functional theory calculations and isolation of the κ2P,Sn-coordinated complex of PtCl2, [(κ2-1)PtCl2] (10). Thus, the reactivity of 1 clearly deviates from the P,Sn-based ligands studied so far.

Determining pharmaceutical levels in fish plasma represents an increasingly valuable approach for environmental assessments of pharmaceuticals. These fish plasma observations are compared to human therapeutic plasma doses because of the high evolutionary conservation of many drug targets among vertebrates. In the present study, we initially identified highly variable information regarding plasma sampling practices in the literature and then tested the hypothesis that fish plasma levels of selected pharmaceuticals and per- and polyfluoroalkyl substances (PFASs) would not change with time to process samples from the field. After common carp were placed in a wastewater-fed pond for one month, we immediately sampled fish plasma nonlethally in the field or after transferring fish to clean water and held them under these conditions for either 3 or 20 h. We then quantitated pharmaceuticals in water, and pharmaceuticals and PFASs in plasma by LC-MSMS. Whereas plasma levels of most pharmaceuticals decreased even after 3 h that fish spent in clean water, plasma concentrations of the PFASs examined here remained stable over 20 h. Collectively, our examination of these time-dependent sampling approaches and associated findings highlight the importance of appropriate and consistent sampling for bioaccumulation studies, biomonitoring activities, and aquaculture product safety evaluations.

The drive to develop maximal atom-efficient catalysts coupled to the continuous striving for more sustainable reactions has led to an ever-increasing interest in single-atom catalysis. Based on a periodic conceptual density functional theory (cDFT) approach, fundamental insights into the reactivity and adsorption of single late transition metal atoms supported on a fully hydroxylated amorphous silica surface have been acquired. In particular, this investigation revealed that the influence of van der Waals dispersion forces is especially significant for a silver (98 %) or gold (78 %) atom, whereas the oxophilicity of the Group 8–10 transition metals plays a major role in the interaction strength of these atoms on the irreducible SiO2 support. The adsorption energies for the less-electronegative row 4 elements (Fe, Co, Ni) ranged from −1.40 to −1.92 eV, whereas for the heavier row 5 and 6 metals, with the exception of Pd, these values are between −2.20 and −2.92 eV. The deviating behavior of Pd can be attributed to a fully filled d-shell and, hence, the absence of the hybridization effects. Through a systematic analysis of cDFT descriptors determined by using three different theoretical schemes, the Fermi weighted density of states approach was identified as the most suitable for describing the reactivity of the studied systems. The main advantage of this scheme is the fact that it is not influenced by fictitious Coulomb interactions between successive, charged reciprocal cells. Moreover, the contribution of the energy levels to the reactivity is simultaneously scaled based on their position relative to the Fermi level. Finally, the obtained Fermi weighted density of states reactivity trends show a good agreement with the chemical characteristics of the investigated metal atoms as well as the experimental data.

Autor opracowania wybiera z wielu zagadnień poruszanych w Liście 22 św. Hieronima temat dziewictwa rozumianego jako ustawiczna walka dla Pana i analizuje fundamenty biblijne tej idei. Próbuje najpierw ustalić cel, jaki przyświecał św. Hieronimowi, piszącemu ten list, czyli ukazanie, w świetle Biblii, z jednej strony racji i piękna życia w dziewictwie, z drugiej zaś trudów i wyrzeczeń, które trzeba nieustannie podejmować, aby wytrwać w tym stanie. Zajmuje się następnie odnośnymi tekstami biblijnymi, pochodzącymi głównie z Nowego Testamentu, zwłaszcza z Ewangelii i z listów św. Pawła apostoła; analizuje ich użycie, wybrane zwroty i wyrażenia (pochodzące niekiedy ze świata sportowców i żołnierzy) oraz ich kontekst literacki i doktrynalny. Podaje następnie konkretne elementy duchowej walki podejmowanej przez dziewicę dla Chrystusa (modlitwa, rozważanie Pisma świętego, milczenie, post, pozostawanie w domu, różne umartwienia dotyczące ciała i ducha), który osobiście dał nam dowody najwyższej miłości, ubóstwa i wytrwałości w znoszeniu cierpień. Pyta na zakończenie, w kontekście ciągle aktualnej debaty dotyczącej dziewictwa i małżeństwa, o znaczenie omawianego Listu 22 św. Hieronima dla tego tematu w perspektywie biblijnej, chrystologicznej, eklezjologicznej i eschatologicznej. St. Jerome deals with many themes in his Letter 22 to Eustochium, but the author focuses on virginity interpreted as a constant struggle for the Lord, and he analyses the Biblical foundations of this exposition. He first tries to clarify St. Jerome’s purpose as he wrote this letter, that is, the articulation, in the light of the Bible, on the one hand of the reason and beauty of life in virginity, and on the other hand the difficulties and renunciations that have to be constantly undertaken so as to persevere in this state. He then discusses the pertinent Biblical references, primarily from the New Testament and in particular from the Gospels and the letters of the apostle St. Paul. He analyses their use, the chosen expressions and terms (sometimes taken from the vocabulary of sportsmen and soldiers) and their literary and doctrinal context. He then lists concrete elements of the spiritual struggle undertaken by the virgin for Christ (prayer, meditating of the Sacred Scriptures, silence, fasting, remaining at home, various mortifications pertaining to the body and spirit), as the Lord has personally given us proofs of supreme love, poverty and perseverance in the withstanding of sufferings. Finally, in the context of the continuously actual debate about virginity and marriage, he questions the value of the discussed Letter 22 of St. Jerome for this theme within a Biblical, Christological, ecclesiological and eschatological perspective.

The growing importance of aquaculture products for human health also raises the question of product sustainability and decreasing its costs. Insects are considered as novel feed ingredients and source of proteins. In this study, a twelve-week feeding trial with replacement of 25% fishmeal by a mixture of house cricket (Acheta domesticus) and superworm (Zophobas morio) in the fish feed was conducted with perch (Perca fluviatilis). There were no significant differences in this feeding trial, regarding survival, but decreased fish growth and increased feed conversion between the control and the experimental fed groups. Hepatic cytochrome P450 (CYP1A and CYP3A-like) activity and fatty acid (FA) composition were assessed in perch also. No significant effects were observed on cytochrome P450 activity associated with presence of toxic compounds in fish. Feeding with insect pellets resulted in significant increasing of linoleic FA and an increase of the total content of n-6 FA in fish fillets, compared to the fish fillets from control group. However, changes in FA composition were only minor and did not affect the nutritional value of the fish with insect-based diet for human consumption. Further evaluation should be conducted with different ratios or different insect species.

Beer is not only a favourite drink for many archaeologists, but is increasingly the subject of their research. Brewing and beer consumption have played a significant role in prehistoric human cultures around the world. Beer was a tasty, nutritious food, a substance affecting the mind, medicine, a religious symbol, as well as a social medium and an accelerator. Alcohol relieved the pain and prevented the spread of infection. Beer was a safe and healthy drink compared to contaminated water. At the time when our ancestors began to domesticate agricultural crops, they commonly produced not only bread but also beer. It is probable that the first ceramic vessels in the Near East were created precisely out of the need to more effectively control the technological process of beer production. Similarly, in the Central European Copper Age, beer production and its growing social significance influenced the emergence of the set Ceramic complex that lasted continuously for more than three millennia. Beer has entered almost all aspects of social life, from everyday consumption and social interactions to initiation ceremonies and major religious celebrations. The study of beer and other fermented beverages sheds light on many aspects of the biocultural development of humans on this planet.

Freshwater protected areas are designated parts of the inland waters that restrict human activities. They were created as a mechanism to combat the decline of fauna and flora of the world. Some authors have questioned their actual effectiveness in terms of the purpose of protecting endangered fauna and flora. We conducted an experiment in Lipno reservoir in the Czech Republic to evaluate the impact of protection against angling pressure on the fish community. We selected data from two years of gill netting and analyzed the difference between areas of low anthropogenic impact (LAI) and those of high anthropogenic impact (HAI) in terms of abundance, biomass, standard length, and diversity indices. Three groups of fish were found to prefer protected areas with low anthropogenic pressure: 1. YOY (Young-of-the-year) perch (Perca fluviatilis), the dominant of the young-of-the-year fish community. 2. Pike (Esox lucius), wels catfish (Silurus glanis) and rudd (Scardinius erythrophthalmus), which were not found in HAI areas at all. 3. Larger individuals of pikeperch (Stizostedion lucioperca), which survived better in LAI areas. Some factors may affect LAI, such as illegal poaching or setting out food bait to attract the fish outside. Another factor that can be considered is the migration of fish, either to forage or to reproduce, since the LAI areas are open to the reservoir. The areas of LAI act as protective habitats for heavily exploited predatory fish species and increase fish diversity indexes. The example of the protected and low-impact areas of Lipno should be followed in other water bodies with high fishing pressure and anthropogenic impact.

A stable ionic κ2Sn,P-coordinated Ru complex shows excellent catalytic activity in aerobic oxidations of benzylamine and benzyl alcohol. This complex is stabilized by a stannylene-phosphine peri-substituted naphthalene ligand, which can act as either a reducing agent for a Ru(III) complex or as a κ2Sn,P-chelating ligand for Ru(II) compounds.

Alpha-Iminopyridine ligands L-1(2-(CH=N(C6H2-2,4,6-Ph-3))C5H4N), L-2 (2-(CH=N(C6H2-2,4,6-tBu(3)))C5H4N) and L-3 (1,2-(C5H4N-2-CH=N)(2)CH2CH2) differing by the steric demand of the substituent on the imine CH=N group and by the number of donating nitrogen atoms were utilized to initiate a Lewis base mediated ionization of SnCl2 in an effort to prepare ionic tin(II) species [L1-3 -> SnCl][SnCl3]. The reaction of L-1 and L-2 with SnCl2 led to the formation of neutral adducts [L-1 -> SnCl2] (2) and [L-2 -> SnCl2] (3). The preparation of the desired ionic compounds was achieved by subsequent reactions of 2 and 3 with an equivalent of SnCl2 or GaCl3. In contrast, ligand L-3 containing four donor nitrogen atoms showed the ability to ionize SnCl2 and also Sn(OTf)(2), yielding [L-3 -> SnCl][SnCl3] (7) and [L-3 -> Sn(H2O)][OTf](2) (8). The study thus revealed that the reaction is dependent on the type of the ligand. The prepared complexes 4-8 together with the previously reported [{2-((CH3)C=N(C6H3-2,6-iPr(2)))-6-CH3O-C5H3N}SnCl][SnCl3] (1) were tested as catalysts for the ROP of L-lactide, which could operate via an activated monomer mechanism. Finally, a DFT computational study was performed to evaluate the steric and electronic properties of the ionic tin(II) species 1 and 4-8 together with their ability to interact with the L-lactide monomer. Alfa-iminopyridinové ligandy L-1(2-(CH=N(C6H2-2,4,6-Ph-3))C5H4N), L-2 (2-(CH=N(C6H2-2,4,6- tBu(3)))C5H4N) a L-3 (1,2-(C5H4N-2-CH=N)(2)CH2CH2) lišící se stericitou substituentu na iminové skupině CH=N a počtem donorových atomů dusíku byly použity k autoionizaci SnCl2 zprostředkované Lewisovou bází ve snaze připravit cínaté iontové komplexy [L1-3 -> SnCl][SnCl3]. Reakce L-1 a L-2 se SnCl2 vedla ke vzniku neutrálních aduktů [L-1 -> SnCl2] (2) a [L-2 -> SnCl2] (3). Příprava požadovaných iontových sloučenin byla dosažena následnými reakcemi s ekvivalentem SnCl2 nebo GaCl3. Naproti tomu ligand L-3 obsahující čtyři donorové atomy dusíku vykazoval schopnost ionizovat SnCl2 a také Sn(OTf)(2), čímž vznikl [L-3 -> SnCl][SnCl3] (7) a [L-3 -> Sn(H20)][OTf](2) (8). Studie tak odhalila, že reakce je závislá na typu ligandu. Připravené komplexy 4-8 spolu s dříve uvedeným [{2-((CH3)C=N(C6H3-2,6-iPr(2)))-6-CH3O-C5H3N}SnCl][SnCl3] (1) byly testovány jako katalyzátory pro ROP L-laktidu prostřednictvím mechanismu aktivovaného monomeru. Nakonec byla provedena výpočetní DFT studie, aby se vyhodnotily sterické a elektronické vlastnosti cínatých iontových komplexů 1 a 4-8 spolu s jejich schopností interagovat s monomerem L-laktidu.

α-Iminopyridine ligands L

Les façons dont le « package campaniforme » a été diffusé dans la majeure partie de l’Europe centrale et occidentale ont probablement été différentes d’une région à l’autre. Des artefacts prestigieux circulaient par échange, migration par infiltration, mariages interrégionaux et mobilité d’individus. Mais cela n’explique pas pourquoi des personnes qui se trouvaient dans des régions géographiquement et culturellement éloignées ont subitement partagé un style et un système symbolique uniformes. Le nouveau système symbolique ainsi que le set d’artefacts significatifs contribuaient à renforcer l’identité collective en maintenant une série d’activités spirituelles. Au sein de pratiques funéraires individualisées, l’importance de la communication avec les ancêtres est soulignée, le statut social des défunts mis en lumière, au même titre qu’une hiérarchie sociale, se trouve confirmée et un système de descendance basé sur la richesse héréditaire d’individus et de familles est renforcé. Cet article soutient l’hypothèse selon laquelle cette uniformisation et la diffusion rapide d’une uniformité commune surviennent à ce moment-là à cause d’une idéologie commune qui se servait du nouvel ensemble du set campaniforme en tant qu’expression officielle d’une unité symbolique et cosmologique. The ways in which the “Bell Beaker package” spread across most of Central and Western Europe may have been different from region to region. Prestigious artefacts circulated through exchange, migration by infiltration, interregional marriages and mobility of individuals. This, however, does not explain why people from geographically and culturally distant regions suddenly shared a distinct uniform style and symbolic system. The new symbolic system and the package of significant artefacts helped to reinforce collective identity and maintained a range of spiritual activities. Within these individualised funerary practices people emphasised communication with their ancestors and a display of their social status, as well as confirmation of social hierarchy and reinforcement of a genealogical system of hereditary wealth of individuals and families. I believe that this unification and rapid spread of shared uniformity occurred as a result of a common ideology that used the new assemblage of the Bell Beaker package as a formal expression of symbolical and cosmological unity.

Autor artykułu podejmuje temat polemiki św. Hieronima z herezjami w świetle jego Homilii o Psalmie 82 (seria II). Omawia najpierw niektóre cechy ogólne tej polemiki, a następnie te jej elementy, które odnoszą się do konkretnych autorów, czyli Maniego, Marcjona, Ariusza, Walentyna i Bazylidesa. Ukazuje w tym kontekście św. Hieronima jako obrońcę jedności całego Pisma św., twierdzącego, że Nowy Testament jest logiczną kontynuacją i dopełnieniem Starego Testamentu. Przedstawia autora Wulgaty jako opowiadającego się zdecydowanie za prawdziwym bóstwem Chrystusa, przeciwko wszystkim tym, którzy widzieli w Nim jedynie stworzenie. Wreszcie prezentuje księcia egzegetów głoszącego absolutne panowanie Boga Najwyższego nad światem i wszystkimi stworzeniami, przeciwko twórcom nauki o neonach i ich rzekomo szczególnej mocy. Z opracowania wynika, że św. Hieronim mógł przejąć niektóre elementy polemiki z dzieł Orygenesa, jednak wykazuje on dużą kreatywność także w sporze z tymi heretykami, którzy nie byli znani w czasach autora O zasadach. The article deals with the polemic of St. Jerome against the heresies in the light of his Homily on Psalm 82 (series II). First, it discusses some general characteristics of this polemic and then those fragments of it that refer to specific authors, that is, to Manes, Marcion, Arius, Valentine and Basilides. In this context, St. Jerome is presented as the defender of the unity of the entire Scriptures, because he claimed that the New Testament is a logical continuation and fulfilment of the Old Testament. It is shown that the translator of the Vulgate decisively professed the true divinity of Christ against all those who saw in Him only a creature. Finally, the prince of the exegetes is presented as claiming the absolute dominion of Almighty God over the world and all creatures, this being against those who invented the teaching on the neons and their supposed particular power. The study demonstrates that St. Jerome could have taken certain elements of the polemic from the writings of Origen; nevertheless, he has manifested ample creativity also in the conflict with those heretics who were unknown in the times when the author of The Principles wrote.

With increasing population growth and climate change, de facto reuse practices are predicted to increase globally. We investigated a longitudinal gradient within the Uhlava River, a representative watershed, where de facto reuse is actively occurring, during Fall and Spring seasons when instream flows vary. We observed human pharmaceutical levels in the river to continuously increase from the mountainous areas upstream to downstream locations and a potable intake location, with the highest concentrations found in small tributaries. Significant relationship was identified between mass flow of pharmaceuticals and the size of human populations contributing to wastewater treatment plant discharges. Advanced ozonation and granular activated carbon filtration effectively removed pharmaceuticals from potable source waters. We observed a higher probability of encountering a number of targeted pharmaceuticals during colder Spring months when stream flows were elevated compared to warmer conditions with lower flows in the Fall despite a dilution paradigm routinely applied for surface water quality assessment and management efforts. Such observations translated to greater water quality hazards during these higher Spring flows. Future water monitoring efforts should account for periods when higher chemical uses occur, particularly in the face of climate change for regions experiencing population growth and de facto reuse.

The reactions of monomeric C,N-chelated organogermanium(II) hydride L(H)Ge⋅BH3 with organolithium salts RLi yielded lithium hydrogermanatoborates (Li(THF)2 {BH3 [L(H)GeR]})2 . Compound (Li(THF)2 {BH3 [L(H)GePh]})2 was used as a source of LiH for the reduction of organic C=O or C=N bonds in nonpolar solvents accompanied by the elimination of a neutral complex L(Ph)Ge⋅BH3 . The interaction of (Li(THF)2 {BH3 [L(H)GePh]})2 with the polar C=O bond was further investigated by computational studies revealing a plausible geometry of a pre-reactive intermediate. The experimental and theoretical studies suggest that, although the Li atom of (Li(THF)2 {BH3 [L(H)GePh]})2 coordinates the C=O bond, the GeH fragment is the active species in the reduction reaction. Finally, benzaldehyde was reduced by a mixture of L(H)Ge⋅BH3 with PhLi in nonpolar solvents.

Treatment of N,C,N-chelated organopnictogen(I) compounds ArE (1-3) (Ar=2,6-(RN=CH)2 C6 H3 , E/R=As/Dmp (1), Sb/tBu (2), and Bi/tBu (3), where Dmp=2,6-Me2 C6 H3 ) with various electron-deficient alkynes RC≡CR' (R/R'=CO2 Me (DMAD), R/R'=H/CO2 Me, or R/R'=NC5 F4 ) affords different types of heterocyclic compounds. In these reactions, 1-3 act as hidden dienes and participate in hetero-Diels-Alder (DA) reactions, a feature that has been only rarely reported for heavier pnictogen compounds. In this way, reactions of 1 furnished the set of 1-arsanaphthalenes 4-6. The most likely mechanism involves two steps, that is, an arsa-DA reaction giving a 1-arsa-1,4-dihydro-iminonaphthalene, followed by CH→NH proton migration. In contrast, this reaction sequence terminates at the first step in the case of the antimony analogue 2, thus giving the 1-stiba-1,4-dihydro-iminonaphthalenes 7 and 8. Reactions of the bismuth congener 3 gave one of two products depending on the alkyne used. Reaction of 3 with DMAD gave 1-bisma-1,4-dihydro-iminonaphthalene 9, whilst its reaction with two equivalents of HC≡C(CO2 Me) gave bismacyclohexadiene (10). All compounds have been characterized by NMR, IR, and Raman spectroscopies and X-ray diffraction analysis. The experimental data were complemented by a computational study, including a description of the reaction profiles of the hetero-DA reactions and an assessment of the aromaticities of the heterocyclic naphthalene derivatives.

Aquaculture is increasing at the global scale, and beneficial reuse of wastewater is becoming crucial in some regions. Here we selected a unique tertiary treatment system for study over a one-year period. This experimental ecosystem-based approach to effluent management included a treated wastewater pond (TWP), which receives 100% effluent from a wastewater treatment plant, and an aquaculture pond (AP) that receives treated water from the TWP for fish production. We examined the fate of a wide range of pharmaceutically active compounds (PhACs) in this TWP-AP system and a control pond fed by river water using traditional grab sampling and passive samplers. We then employed probabilistic approaches to examine exposure hazards. Telmisartan, carbamazepine, diclofenac and venlafaxine, exceeded ecotoxicological predicted no effect concentrations in influent wastewater to the TWP, but these water quality hazards were consistently reduced following treatment in the TWP-AP system. In addition, both grab and passive sampling approaches resulted in similar occurrence patterns of studied compounds, which highlights the potential of POCIS use for water monitoring. Based on the approach taken here, the TWP-AP system appears useful as a tertiary treatment step to reduce PhACs and decrease ecotoxicological and antibiotic resistance water quality hazards prior to beneficial reuse in aquaculture.

Monitoring the contamination level in aquatic environments and assessing the impact on aquatic life occurs throughout the world. In the present study, an approach based on a combination of biomarkers and the distribution of various industrial and municipal pollutants was used to investigate the effect of aquatic environmental contamination on fish. Monitoring was performed in ten rivers in the Czech Republic (Berounka, Dyje, Elbe, Lužnice, Odra, Ohře, Otava, Sazava, Svratka, and Vltava rivers, with one or two locations in each river) at the same sites that were regularly monitored within the Czech National Monitoring Program in 2007–2011. Health status, hepatic ethoxyresorufin-O-deethylase (EROD) activity, total cytochrome P450 content, and the plasma vitellogenin concentration were assessed in wild chub (Squalius cephalus) males caught at the monitored sites. The contamination level was the highest in the Svratka River downstream of Brno. Among all measured persistent organic pollutants (POPs), polychlorinated biphenyls and dichlorodiphenyltrichloroethane and its metabolites were the major contributors of POPs in fish muscle. Elbe, Odra, and Svratka rivers were identified as the most polluted. Fish from these locations showed reduced gonad size, increased vitellogenin concentration in male plasma, EROD, and total cytochrome P450 content. These biomarkers can be used for future environmental monitoring assessments. Overall, this study improves our understanding of the relationship between human activities and pollutant loads and further contributes to the decision to support local watershed managers to protect water quality in this region.

Sewage treatment plants (STPs) are one of the major source of pharmaceuticals and personal care products in the aquatic environment. Generally, the effects of individual chemicals on fish are studied under laboratory conditions, which leads to results that are potentially not realistic regarding the effects of these chemicals under environmental conditions. Therefore, in this study, common carps were held in exposed pond that receive water from STP effluents for 360 days under natural conditions. Elimination of xenobiotics starts in the fish intestine, in which the microbial community strongly influences its function. Moreover, the fish intestine functions as crucial organ for absorbing lipids and fatty acids (FA), with consequent transport to the liver where their metabolism occurs. The liver is the primary organ performing xenobiotic metabolism in fish, and therefore, the presence of pollutants may interact with the metabolism of FA. The catalytic activity of CYP1A and CYP3A-like enzymes, their gene expression, FA composition and intestinal microbiome consortia were measured. The catalytic activity of enzymes and their gene and protein expression, were induced in hepatic and intestinal tissues of fish from the exposed pond. Also, fish from the exposed pond had different compositions of FA than those from the control pond: concentration of 18:1 n-9 and 18:2 n-6 were significantly elevated and the longer chain n-3 FA 20:5 n-3, 22:5 n-3 and 22:6 n-3 were significantly lowered. There were clear differences among microbiome consortia in fish intestines across control and exposed groups. Microbiome taxa measured in exposed fish were also associated with those found in STP activated sludge. This study reveals that treated STP water, which is assumed to be clean, affected measured biomarkers in common carp.

Generating monovalent pnictogens within NCN pincers has resulted in the isolation of three distinct types of 1,2-azaheteroles, highly aromatic nitrogen analogues like pyrazole-based 5, aromatic yet fluxional P- and As-derived bell-clappers 1 and 2, and hypervalent Sb and Bi derivatives 3 and 4, which are supported by 3-center, 4-electron N-E-N bonds. Careful analysis of the solid-state structures of 1-5/[5-Me][OTf] in combination with NICS calculations (at the GIAO/M06/cc-pVTZ(-PP) level) and other computational methods (NBO) suggest that simpler NC chelates may support new phosphorus- and arsenic-containing heterocycles. Indeed, reduction of ECl2 (E = P or As) derivatives supported by N-Dipp (Dipp = 2,6-diisopropylphenyl) substituted NC bidentate ligands produced 1,2-benzoazaphosphole 11 and 1,2-benzoazaarsole 12. NICS calculations revealed 11 and 12 had aromatic character on par with that of pyrazole-based 5.

The fate of fourteen target perfluoroalkyl substances (PFASs) are described within a small stream affected by a sewage treatment plant (STP) effluent. Concentrations of target PFASs in samples of water, benthic macroinvertebrates and brown trout (Salmo trutta) are presented. Two hundred brown trout individuals originating from clean sites within the same stream were tagged and stocked into an experimental site affected by the STP's effluent. As a passive sampling approach, polar organic chemical integrative samplers (POCIS) were deployed in the water to reveal the water-macroinvertebrates-fish biotransformation processes of PFASs. Bioconcentration/bioaccumulation of target compounds was monitored one, three, and six months after stocking. Twelve of the fourteen target PFASs were found in concentration above the LOQ in at least one of the studied matrices. The compound pattern varied significantly between both the studied species and water samples. Concerning the accumulation of PFASs in fish, the highest concentrations were found in the liver of individuals sampled after three months of exposure. These concentrations rapidly decreased after six months although the water concentrations were slightly increasing during experiment.

Although pharmaceuticals are frequently studied contaminants, their fate in the environment is still not completely clear. During a one year study, a complex approach including water, sediment and fish sampling was used to describe the behaviour of pharmaceuticals and their metabolites (PTMs) in the environment. Eighteen pharmaceuticals and seven of their metabolites were determined in a pond used for the tertiary treatment of wastewater effluent. A liquid chromatography-tandem mass spectrometry method was applied to determine the PTMs concentrations in all matrices. Seasonal variations in concentrations were evaluated. The partitioning of contaminants between pond compartments was estimated by means of solid water distribution coefficients (Kd) and bioaccumulation factors (BAF) for the livers of fish. Kd values were almost stable throughout the year, which may be a sign of the continuous transport of PTMs between water and sediment under the experimental conditions. Almost all of the studied compounds, with exception of sertraline (BAF of 6200), were found to not be bioaccumulative in fish livers. The pond removal efficiency was calculated for all PTMs, and favourable conditions for natural pharmaceutical removal were proposed. Further aspects regarding fish pharmaceutical exposure need to be studied.

N,C,N-Chelated pnictinidenes ArE [where E = As, Sb or Bi; Ar = 2,6-(tBuN[double bond, length as m-dash]CH)2C6H3] were used as ligands for the coordination of various gold(i) complexes. Thus, the reaction of ArE with [AuCl(Me2S)] gave complexes [AuCl(ArE)] [where E = As (1) or Sb (2)] that exhibited only limited stability in solution. By contrast, the reaction of ArBi with [AuCl(Me2S)] led to the immediate deposition of gold metal and the oxidation of the bismuth atom giving ArBiCl2. The treatment of a tetrameric gold alkynyl complex [Au(C[triple bond, length as m-dash]CPh)]4 with ArAs and ArSb gave ionic compounds [Au(ArAs)2]+[Au2(C[triple bond, length as m-dash]CPh)3]- [denoted as 3+[Au2(C[triple bond, length as m-dash]CPh)3]-] and [Au(ArSb)2]+[Au(C[triple bond, length as m-dash]CPh)2]- [denoted as 4+[Au(C[triple bond, length as m-dash]CPh)2]-], respectively. Finally, the reaction of ArE with the carbene gold(i) complex [Au(IPr)(MeCN)]+[BF4]- [where IPr = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene, MeCN = acetonitrile] produced ionic complexes [Au(IPr)(ArE)]+[BF4]- [for cations: E = As (5+), Sb (6+) or Bi (7+)]. All complexes were characterized using 1H and 13C NMR, high mass accuracy electrospray ionization mass spectrometry (ESI-MS), IR and Raman spectroscopy and (except for 1) by single-crystal X-ray diffraction analysis. Furthermore, the structure and bonding of both neutral and ionic complexes with different coordination patterns have also been investigated in detail using a Density Functional Theory (DFT) computational approach.

Sadly, aggression is still one of the most common features of human behaviour; it is an instinct to promote and survive our own genes against the genes of others. Human intraspecific aggression has gradually become part of human culture over the last 40,000 years and has been institutionalized in various forms of social activities. Particularly in the post-glacial period, the level of social relations has developed dramatically in the context of population growth and the growth of human communities. In the time of Neolithic and Chalcolithic European agricultural populations, the motive of control over farming land became highly important. Also the control of main means of production and social power was increasingly maintaining the intragroup competition and aggression. Thus, violence was employed within the community in order to obtain and maintain individual or collective social status, but also against other communities in an effort to protect property and territory. Particularly the intracommunity aggression was soon transformed into variety of different formal ways of symbolic fighting, which usually did not lead to the unwanted death of a defeated member of the community. The symbolic struggle between members of the community as well as the defense against external aggression were gradually formalized in the form of introduction of specialized weapons designed for combat between people and creation of fortifications. During the Neolithic period a new phenomenon arose in human culture: warfare.

The synthesis of the monomeric organogermanium(II) hydrides {(LGeH)M(CO)5} (M = Cr (4), W (5)) utilizing the C,N-chelated ligand L (L is [2-(CH2NEt2)-4,6-tBu2-C6H2]-) is reported. The stabilization of the GeH terminal bond in 4 and 5 is accompanied by the combination of the electronic and steric protection of the ligand L. The reactivity of the GeH terminal bond was also investigated and attempts to reduce the polar C≡N bond in tBuNC provided unexpected N-C bond cleavage reaction yielding organogermanium(II) cyanides {(LGeCN)M(CO)5} (M = Cr (6), W (7)) instead of hydrogermylation reaction

Ionic and nutrient compositions of throughfall, tributaries and lake outlet were analysed in the Plesne catchment-lake system (an unmanaged mountain forest in Central Europe) from 1997 to 2016. The aim was to evaluate changes in surface water chemistry after natural forest dieback. In the 2004–2008, 93% of the Norway spruce trees were killed by bark beetle outbreak, and all dead biomass remained in the catchment. Forest dieback changed the chemistry of all water fluxes, and the magnitude, timing, and duration of these changes differed for individual water constituents. The most pronounced decreases in throughfall concentrations occurred for K+, dissolved organic carbon (DOC), Ca2+ and Mg2+, i.e. elements mostly originating from canopy leaching, while concentrations of NH4+ and soluble reactive phosphorus (SRP) remained almost unaffected. In tributaries, the most rapid changes were increases in NO3−, K+, H+ and ionic aluminium (Ali) concentrations, while terrestrial export of DOC and P forms started more slowly. Immediately after the forest dieback, increase in NO3− concentrations was delayed by elevated DOC availability in soils. NO3− became the dominant anion, with maximum concentrations up to 346 μeq L− 1 within 5–7 years after the bark beetle outbreak, and then started to decrease. Terrestrial exports of Ali, K+, H+, Mg2+, and Ca2+ accompanied NO3− leaching, but their trends differed due to their different sources. Elevated losses of SRP, DOC, and dissolved organic nitrogen continued until the end of the study. In the lake, microbial processes significantly decreased concentrations of NO3−, organic acid anions, H+ and Ali, and confounded the chemical trends observed in tributaries. Our results suggest that terrestrial losses of elements and the deterioration of waters after forest dieback are less pronounced in unmanaged than managed (clear-cut) catchments.