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The structures and interactions in four new hydrates of substituted piperidines have been studied using X-ray crystallography and quantum chemistry. The piperidine ring substitution leads to a significant reduction in the number of hydrates compared with the parent amine, with 4-methylpiperidine yielding a hemihydrate and a trihydrate; 4-chloropiperidine a monohydrate and a trihydrate, (where the architecture is similar to 4-methylpiperidine trihydrate). Despite many attempts, it did not prove possible to crystallize hydrates with higher molar amine : water ratios. Therefore, trihydrates are probably the most hydrated crystals to be obtained at ambient pressure for both amines. Both trihydrates create identical water layers of the L4(6)5(7)6(8) type and the main structural difference is the arrangement of hydrogen bonds between water layers and amines. Despite this, both trihydrates have the same melting temperature (263 K) and as supported by lattice energy calculations. Chlorine⋯chlorine contacts have no significant impact on the stabilization of the 4-chloropiperidine monohydrate or the 4-chloropiperidine trihydrate. Periodic DFT-D3 calculations show that the energies of the water layers are identical in both cases, and the summed hydrogen bond energies (although arranged differently) are similar. Moreover, in the case of trihydrates, which have a 2-D topology of water⋯water interactions, it is possible to perform DFT calculations for separate layers and to determine the contribution of those interaction energies to the cohesive energy of the whole crystals. [ABSTRACT FROM AUTHOR]

Spirituality has remained a controversial subject matter of psychological research. In spite of this fact, the volume of research grows alongside the development of civilization processes in the Western world. Mostly, these are analyses of spirituality in the substantial approach, particularly that recognizing spirituality as what the research subjects consider it to be. The views of psychologists of interest in the present analysis can be divided into: overt and hidden ones. The first kind includes concepts of philosophical, psychoanalytic, and humanistic origins (usually not subjected to operationalization); the second kind are those whose authors were not in need of recognizing them as theories of spirituality; nevertheless, they seem to have much in common with spirituality. The proposed solution is spirituality as the process of a unique transformation whose outcome is a more or less successful coping with an existential situation. Since it is possible to distinguish provisionally two types of these situations: one of an ultimate character (transience), and one of a non-ultimate (the existential limitations are more or less harmful); likewise there are two types of possible transformation. In both cases, the transformation is a self-creation unique for a particular kind of an existential situation. The understanding of spirituality as a transformation allows for its operationalization through measuring this experience assumed here to be a marker of the feeling of sacredness. One can measure this experience before a particular situation takes place as well as after the period considered the endpoint of coping with this situation occurs. Spirituality - the transcendence of limitations - is a process occurring within a unique existential context. At the end of the article, the features of a spiritual transformation have been described in order to show a wider account of the process. [ABSTRACT FROM AUTHOR]

Abundant and stratigraphically well positioned fossil material of two small mustelids, stoat and weasel, from Biśnik Cave was studied to investigate size variation. Size was found to be correlated with temperature: during cold periods individuals of both species were smaller than during warm periods. The weasel measurements varied much more, compared to the stoat. Weasel males varied more than females. The largest weasel individuals came from the late Middle Pleistocene layers of Biśnik Cave, while the smallest, dwarf specimens were typical of the cold periods of the last glaciation. [ABSTRACT FROM AUTHOR]

Abstract: A unique record of faunal changes from the late Middle Pleistocene until the end of the late Pleistocene was provided by rodent assemblages from Biśnik Cave in Poland. The 17 rodent assemblages, of different qualitative and quantitative composition, included a total of 25 species of various ecological requirements and associated with five types of climate, represented by over 8500 individuals. For biostratigraphic analysis, the following indices were used: the ratio of enamel thickness on anterior and posterior edges of tooth loops in the genus Arvicola (SDQ), and morphological teeth changeability of Microtus oeconomus and Dicrostonyx. All three biostratigraphic methods are consistent, and made it possible to determine the stratigraphic position of the rodent assemblages. The layers from 19 to 14 were deposited in Middle Pleistocene, and the layers from 13 to 1 were deposited in the Late Pleistocene. The layers 14 and 13 constitute the border between the Middle and Late Pleistocene. Climatic and environmental conditions (temperature and humidity, duration of vegetation season) during the deposition were reconstructed, based on the assemblages representing the late Middle Pleistocene (layers 19–14; MIS 7-6), the Eemian interglacial (layers 14, 13; MIS 5e), and the Vistulian (Weichselian) glaciation (layers 12–1; MIS 5d-2). The analysis of bioclimatic indices made it possible to determine the most probable climate during the deposition of the respective assemblages. The environmental preferences allowed reconstruction of the prevailing biomes in the environments of Biśnik Cave. The results of quantitative bioclimatic analysis indicate that the deposition of same of the assemblages may be associated with cold temperature climate. The values of 11 climatic indices show the oscillations of two types of climate, temperate and boreal, with oceanic and continental influence. Reconstruction values of 11 climatic parameters shows an interesting pattern of relative stability in almost all the climatic parameters. Only drought length shows a remarkable change across Middle and Late Pleistocene sediment sequences from Biśnik Cave. [Copyright &y& Elsevier]

Abstract: Biśnik Cave is situated in the limestone rock, 7m above the bottom of the presently dry Wodąca valley. It is located in the Smoleń–Niegowonice Range in the southern part of the Częstochowa Upland. To date, an area of 260m2 has been explored, to the depth of 150–850cm. The results of sedimentological, geomorphological, palaeozoological and archaeological investigations provided the basis for the reconstruction of the history of habitation at the Biśnik Cave, in the background of palaeoenvironmenal transformations. Throughout about 300,000 years of occupation, the cave was surrounded by a changing and widely diversified natural environment, with steppe, tundra and forest ecosystems, and marshland and aquatic biotopes. This, combined with the opportunity to exploit varied ecological niches, made the cave a particularly attractive habitation site. As a result, the cave has remnants of a number of habitation phases: ten in the Middle Palaeolithic, one in the Upper Palaeolithic and at least five in the period between the Neolithic and the Middle Ages. The importance of the Biśnik Cave stems from the fact that it has the longest sequence of cave sediments in Poland, seventeen cultural levels including remnants of the oldest Palaeolithic in this part of Europe and the oldest dwelling structures ever discovered in Poland. The history of environment changes was reconstructed based on sedimentological and palaeozoological data. The multiproxy palaeoecology and climatology data are extremely significant for the reconstruction of palaeogeography of Central Europe in the Middle and Upper Pleistocene as well as human occupation history. [Copyright &y& Elsevier]

Aluminum garnets display exceptional adaptability in incorporating mismatching elements, thereby facilitating the synthesis of novel materials with tailored properties. This study explored Ce3+-doped Tb3Al5−xScxO12 crystals (where x ranges from 0.5 to 3.0), revealing a novel approach to control luminescence and photoconversion through atomic size mismatch engineering. Raman spectroscopy confirmed the coexistence of garnet and perovskite phases, with Sc substitution significantly influencing the garnet lattice and induced A1g mode softening up to Sc concentration x = 2.0. The Sc atoms controlled sub-eutectic inclusion formation, creating efficient light scattering centers and unveiling a compositional threshold for octahedral site saturation. This modulation enabled the control of energy transfer dynamics between Ce3+ and Tb3+ ions, enhancing luminescence and mitigating quenching. The Sc admixing process regulated luminous efficacy (LE), color rendering index (CRI), and correlated color temperature (CCT), with adjustments in CRI from 68 to 84 and CCT from 3545 K to 12,958 K. The Ce3+-doped Tb3Al5−xScxO12 crystal (where x = 2.0) achieved the highest LE of 114.6 lm/W and emitted light at a CCT of 4942 K, similar to daylight white. This approach enables the design and development of functional materials with tailored optical properties applicable to lighting technology, persistent phosphors, scintillators, and storage phosphors. [ABSTRACT FROM AUTHOR]

Determining the age of late Middle and Late Pleistocene (MIS 8-MIS 3) Neanderthal sites can be difficult as radiometry has limitations. Biostratigraphic methods can be used to overcome these difficulties. A species useful in these analyses is Alexandromys oeconomus (Pallas, 1776), which has a wide modern geographical distribution in the Northern Hemisphere. During the Pleistocene, its range significantly increased, occurring in large numbers both in interglacials and glacials. We distinguished Middle Pleistocene from Late Pleistocene and modern populations of this species based on temporal variation in the morphological structure of the first lower molar (m1) occlusion surface, and the relative proportions of the typical “oeconomus” and atypical “gud,” “nivalis,” and “malei” morphotypes. Our results showed that the mean values of metric parameters of the occlusion surface m1 of A. oeconomus varied over time. We found that this variation distinguisheed between populations of species from the late Middle Pleistocene (MIS 8-MIS 6) and early Late Pleistocene (MIS 5) from those from the Late Pleistocene (MIS 4-MIS 2), and some measurements and coefficients were correlated with climate-environmental changes. Using variation in A. oeconomus m1 morphology can be used as a tool in biostratigraphy requires further research including, among others, studies on how morphology varies between regions. [ABSTRACT FROM AUTHOR]

β-Hydroxy sulfones are important in organic synthesis. The simplest method of β-hydroxy sulfones synthesis is the hydrogenation of β-keto sulfones. Herein, we report the reducing properties of alkyl aluminum compounds R3Al (R = Et, i-Bu, n-Bu, t-Bu and n-Hex); i-Bu2AlH; Et2AlCl and EtAlCl2 in the hydrogenation of β-keto sulfones. The compounds i-Bu2AlH, i-Bu3Al and Et3Al are the at best reducing agents of β-keto sulfones to β-hydroxy sulfones. In reactions of β-keto sulfones with aluminum trialkyls, hydroalumination products with β-hydroxy sulfone ligands [R2AlOC(C6H5)CH2S(O)2(p-R1C6H4]n [where n = 1,2; 2aa: R = i-Bu, R1 = CH3; 2ab: R = i-Bu, R1 = Cl; 2ba: R = Et, R1 = CH3; 2bb: R = Et, R1 = Cl] and {[Et2AlOC(C6H5)CH2S(O)2(p-ClC6H4]∙Et3Al}n3bb were obtained. These complexes in the solid state have a dimeric structure, while in solutions, they appear as equilibrium monomer–dimer mixtures. The hydrolysis of both the isolated 2aa, 2ab, 2ba, 2bb and 3bb and the postreaction mixtures quantitatively leads to pure racemic β-hydroxy sulfones. Hydroalumination reaction of β-keto sulfones with alkyl aluminum compounds and subsequent hydrolysis of the complexes is a simple and very efficient method of β-hydroxy sulfones synthesis. [ABSTRACT FROM AUTHOR]

t‐Butyl derivatives play a significant role in the organometallic chemistry of group 13 metals. It was shown on the basis of reactions of t‐Bu3Al·OEt2 with [p‐RC6H4S(O)2C(H)2C(Ph) = O] (where R = CH3, Cl) β‐keto sulfones that the structure of the reaction products depends on the purity of the aluminum compound used. In the reactions, in addition to the expected complexes [p‐RC6H4S(O2)C(H) = C (Ph)‐OAl(t‐Bu)2] [where R = CH3 (2); R = Cl (4)] possessing β‐keto sulfone ligands, complexes with β‐hydroxy sulfone ligands [p‐RC6H4S(O2)C(H)2‐C (Ph)‐OAl(t‐Bu)2] [where R = CH3 (1); R = Cl (3)] were formed. Compounds 1 and 3 were the result of the hydroalumination reaction of the β‐keto sulfone ligands with t‐Bu2AlH, which is an impurity of t‐Bu3Al. These compounds are obtained, for the first time, as intermediate products in the hydrogenation reaction of β‐keto sulfones. In this work, during t‐Bu3Al·OEt2 production t‐Bu2AlH·OEt2 formed as a by‐product. Re‐examination of reaction conditions of AlCl3 with t‐BuMgCl resulted in a control of the t‐Bu2AlH·OEt2 by‐product content in t‐Bu3Al·OEt2. [ABSTRACT FROM AUTHOR]

Knowledge on the Eemian (MIS 5e) fauna of Poland is based on vertebrate remains from 16 open-air localities and 8 cave sites. Considering the short period of time covered by MIS 5e, the amount of data is surprisingly large. There is still an ongoing debate on whether the age of some assemblages is Eemian, latest Saalian or even earliest Weichselian. There are faunal assemblages or stratigraphically isolated finds with some disputable evidence. The full picture of the evolution of the Eemian vertebrate fauna in the present-day territory of Poland is still far from being complete. The finds of various groups of vertebrates (fishes, amphibians, reptiles, birds and mammals) from the Eemian Interglacial of Poland are analysed in terms of their environmental preferences. A number of thermophilic species or forms which preferred temperate climate conditions are known from this period. Among them, Clethrionomys glareolus, Glis glis, Meles meles, Martes martes, Lynx lynx, Felis silvestris, Sus scrofa, Palaeoloxodon antiquus, and Stephanorhinus kirchbergensis indicate a forest environment. The presence of species that preferred more open environments (Cricetus cricetus, Mammuthus primigenius, Coelodonta antiquitatis, and Equus ferus) is also recorded for the Eemian Interglacial of Poland. Characteristic was the presence of the large broad-toothed and flat-headed Ursus arctos taubachensis, which additionally often outnumbered remains of Ursus spelaeus sensu lato in the contemporary layers. The Eemian vertebrate fauna of Poland consisted of about 150 species (representing 61 genera and 26 families), most of which were recorded earlier from other localities of this age in central and eastern Europe. [ABSTRACT FROM AUTHOR]

Complexes containing aminophenolate ligands are considered as very efficient initiators of ring-opening polymerization (ROP). Our systematic studies of the reactions of two selected aminophenols, 2-[( p-tolylamino)methyl]-4-(2,4,4-trimethylpentan-2-yl)phenol (L'H2) and 2-cyclohexylaminomethyl-4-methylphenol (L″H2), with alkyl compounds of aluminium, gallium and zinc resulted in the formation of a variety of products depending on the type of metallic centre and alkyl groups bonded to metal atoms. New trinuclear aluminium complexes (Me5Al3(L′)2 ( 1) and Me5Al3(L″)2 ( 2)), monomeric aluminium ( tBu2Al(L'H) ( 3) and tBu2Al(L″H) ( 5)) and gallium ( tBu2Ga(L'H) ( 4) and tBu2Ga(L″H) ( 6)) compounds, and dinuclear gallium (Et2Ga(L″H)·Et3Ga ( 7)) and zinc ( tBuZn(L″H)]2 ( 8)) complexes were isolated and characterized. The molecular and crystal structures of 7 and 8 were determined on the basis of an X-ray diffraction study. Polymerization tests showed that only three complexes ( 6- 8) had activity in the ROP of ε-caprolactone, whereas 1- 5 were inactive in ROP. [ABSTRACT FROM AUTHOR]

2-Mercapto-1,3-benzothiazole (mbztH) may act as a chelating or bridging ligand. In this study, reactions of mbztH with Me3Ga and Me3In were examined. The products were characterized by NMR spectroscopy, elemental analyses, melting point, and molecular weight determinations. Formation of mononuclear chelating complexes Me2M(mbzt) (M = Ga, In) was observed in solutions. Crystallization of Me2M(mbzt) yielded uncommon non-symmetrical dinuclear complexes Me4M2(mbzt)2, in which one metal is bonded to two sulfurs and the other to two nitrogens. [ABSTRACT FROM PUBLISHER]

This study provided the first in-depth investigation of the effects of large dopant incompatibility (Pr3+ and La3+ ions) on the small host lattice element (Lu3+) in Lu 3 Al 5 O 12 (LuAG) single crystal. The growth of such complex crystals from the melt presented many challenges. By engineering the ionic radius ratio of RE- and M-site cations, a single-crystal phase stabilized by configurational entropy was achieved. This investigation elucidated the crystallization behavior of configurationally disordered rare-earth aluminum garnet oxide (Lu 1−x−y Pr x La y) 3 Al 5 O 12 from the melt and characterized its functional properties, including microstructural, optical, photoluminescence, and scintillation properties, between 5 and 300 K. Relaxation of the imposed strain energy led to local perturbations and destabilization of the garnet structure. Multielemental EDS mapping, micro-Raman spectroscopy, and thermoluminescence revealed the mechanism by which atomic size mismatch drove a smooth transition from the garnet to the perovskite phase in high entropy garnets. The optical, photoluminescence, and scintillation measurements provided fundamental insights into property changes driven by incompatibility doping. Standard and modified Judd-Ofelt theory analysis of absorption spectra determined the phenomenological Judd-Ofelt parameters Ω λ and radiative lifetimes. Atomic size mismatch engineering offers a promising approach to overcoming the limitations of conventional eutectic synthesis methods. • Perovskite inclusions, driven by atomic size mismatch, extend from rim to core. • Controlled incompatible La3+,Pr3+ codoping in LuAG modify functional properties. • Scintillation light yield improved up to 30% in La3+ codoped LuAG:Pr crystals. • (La,Pr)AlO 3 perovskite forms due to size mismatch of La3+ and Pr3+ with Lu3+. • Lattice disorder affects the intensity ratio of Pr³⁺ 5d→4 f and 4 f→4 f emissions. [ABSTRACT FROM AUTHOR]

Cesium lead bromide (CsPbBr 3 , CPB) powder formed by micro-, nanocrystals (MC, NC) and quantum dots (QD) was synthesized as free-standing and polystyrene covered. Luminescence was multicomponent, in general, ranging from below 1.9 eV up to about 2.6 eV. The ultrafast decay kinetics exhibited strong decay time component with the value of 260 ps. Electron paramagnetic resonance (EPR) revealed surface defects like O 2 − and some spin transitions most likely originating from some complex defect, supposedly F-V k (H) dimer center under the constant ultraviolet (UV) light irradiation at the temperature T = 10 K. The thermal release of the electrons from the O 2 − center was correlated with the 117 K thermally stimulated luminescence (TSL) peak. Coating with polystyrene resulted in the about doubly increased decay time of luminescence. The O 2 − and F-V k (H) EPR resonances were not observed as well. The TSL peak which might be ascribed to the O 2 − was not clearly detected anymore. The glow curve was composed of one very broad peak typical for the amorphous materials. At the same time, the polystyrene prevented the MCs creation. The existence of charge/energy transfer between the CPB and polystyrene due to the chemical bonding was assumed and confirmed also by calculations. [Display omitted] • EPR, TSL and RL study of charge trapping and luminescence in CsPbBr 3. • Charge/energy transfer was detected. • O 2 − -related electron trapping center was revealed in these crystals. • TSL peak was correlated to the release of electrons from the O 2 − surface center. • Complex bromine vacancy-related charge trapping center was observed. [ABSTRACT FROM AUTHOR]

Surgical and endovascular revascularization of ischemic legs in patients with peripheral arterial disease (PAD) can damage the arterial wall (endothelial and smooth muscle cells). Hemostatic factors released during endothelial dysfunction can lead to restenosis. 1. Determination of selected endothelial hemostatic factors in PAD patients and a reference group. 2. Prospective observation of new restenosis appearance in PAD patients after endovascular revascularization. 3. Comparison of selected endothelial hemostatic factors between non-restenotic and restenotic PAD patients. 150 PAD patients after endovascular revascularization - 90 men and 60 women, aged 44-88 (mean 65.5) years - were examined. During one-year observation after the revascularization procedures in 38 PAD patients restenosis occurred, when blood samples were also collected. The reference group consisted of 53 healthy persons - 44 men and 9 women, aged 20-56 years. Blood was drawn in the morning into 3.2% sodium citrate at a ratio of 9:1. Tissue factor (TF), tissue factor pathway inhibitor (TFPI), thrombomodulin (TM), von Willebrand factor (vWF) and tissue plasminogen activator (t-PA) were measured in plasma with commercial tests using the enzyme immunoassay. In the plasma of PAD patients after revascularization, the concentrations of TF and vWF were significantly higher, TM lower, TFPI and t-PA similar compared to the reference group. Six months after revascularization the level of TF had increased and vWF had significantly decreased. The endothelial hemostatic factors before and after restenosis did not significantly differ except TF, which after restenosis was higher. Increased TF and vWF levels in PAD patients indicate arterial endothelial cell damage, by atherosclerotic and revascularization processes. In PAD patients with restenosis compared to these patients before restenosis the determined endothelial hemostatic factors, except TF level, did not significantly differ. Perhaps TF participates in restenosis formation. [ABSTRACT FROM AUTHOR]

Rodent remains are potentially a powerful tool in paleoecological reconstructions. Rodents are a worldwide group of mammals inhabiting all climatic zones, from arctic tundra to tropical forests. Some of their representatives have narrow ranges of environmental tolerance, while others have cosmopolitan distributions. Additionally, rodent remains are well preserved and numerous in cave sediments, and are easily identified to the species level. The species composition of rodent assemblage from the specific cave gives valuable data on ecosystem status around the site. Moreover, isotopic composition (C, N) of rodent remains provides information on some environmental factors, e.g. type of vegetation, soil activity, precipitation, and temperature. The material for this study was collected from the sediments of the Biśnik Cave (Poland). The cave is known from its sediment sequence deposited during the middle and late Pleistocene and Holocene, containing a rich collection of the Pleistocene fauna remains and archeological artifacts. The stratigraphy of the sediment sequence previously was based on archeological findings and several radiometric dates. In this study, we applied U–Th dating method to bone collagen, rodent tooth enamel, and cave bear tooth enamel. Finally, we revised the chronology of sediment sequence from the Biśnik Cave based on these new data. We found significantly higher variability of nitrogen and carbon isotopic composition in the lemming than in the common vole. However, both species show the same trends in isotopic composition of nitrogen in time. At the beginning of the record, δ 15 N values were relatively high, suggesting intensive soil activity and, indirectly, mild climate. After that, from a stratigraphic layer dated to the early Würm glaciation, lower δ 15 N values point to lower soil activity. Deterioration of ecosystem productivity and climate conditions were also confirmed by higher δ 13 C. This indicates lower canopy effect and suggests conversion of vegetation around the cave. The isotopic record suggests high instability of the environmental conditions during the Würm glaciations, with significantly warmer periods before and after the Last Glacial Maximum. [ABSTRACT FROM AUTHOR]

Evidence of mobiliary art and body augmentation are associated with the cultural innovations introduced by Homo sapiens at the beginning of the Upper Paleolithic. Here, we report the discovery of the oldest known human-modified punctate ornament, a decorated ivory pendant from the Paleolithic layers at Stajnia Cave in Poland. We describe the features of this unique piece, as well as the stratigraphic context and the details of its chronometric dating. The Stajnia Cave plate is a personal 'jewellery' object that was created 41,500 calendar years ago (directly radiocarbon dated). It is the oldest known of its kind in Eurasia and it establishes a new starting date for a tradition directly connected to the spread of modern Homo sapiens in Europe. [ABSTRACT FROM AUTHOR]

Abstract: The Crimean Mountains are well known from the abundance of Middle and Late Palaeolithic sites and palaeontological remains recovered from cultural layers in caves and rockshelters. The fossil-bearing deposits of Emine-Bair-Khosar Cave, located at the elevation of 1000 m on the Chatyrdag Plateau, yielded a very diverse and numerous vertebrate remains that widen the knowledge of Late Pleistocene faunal diversity in the Crimea. The assemblage comprised in total almost 50 species of vertebrates. Studies included geomorphological, geological and stratigraphic analyses as well AMS 14C dating. Faunal remains were present in ten palaeontological sites. The main bone accumulation (section Ba2) was deposited during Middle Valdai or Vytachiv (MIS 3) interstadial, and including a long time gap, to the end of the Pleistocene and the Holocene. Comparison of the Emine-Bair-Khosar fauna with vertebrate faunas of other Crimean sites showed a remarkable stability in the faunal composition and frequency during the whole MIS 3 interstadial. Steppe and other open-country species dominated in the compared assemblages, while boreal-tundra species were far less numerous. Inhabitants of forests, including red deer and some rodents, were stable members of fossil assemblages. [Copyright &y& Elsevier]

There is a widespread belief that the abrupt warming at 14.7 ka had a profound impact on the environment. However, the direct correlation between the global climatic event and changes in local environments is not obvious. We examined faunal succession in an intra-mountain basin of the Western Carpathians to assess the potential influence of the climatic change between Greenland Stadial-2a and Greenland Interstadial-1e on the local environment. We investigated three vertebrate assemblages (total number of identified specimens = 18,745; minimum number of individuals = 7515; 138 taxa) from Obłazowa Cave (western entrance) and a Rock overhang in Cisowa Rock, radiocarbon dated to the period before and after the global warming, between ca. 17.0 and 14.0 ka. Our data revealed that the major abrupt warming that occurred 14.7 ka had little impact on the local environment, which could suggest that ecosystems in Central Europe were resilient to the abrupt global climate changes. The increase in fauna population sizes and species diversities in local biotopes was gradual and began long before the temperature increase. This was supported by the analysis of ancient DNA of Microtus arvalis, which showed a gradual increase in effective population size after 19.0 ka. The results of palaeoclimatic reconstruction pointed out that the compared sites were characterized by similar climatic conditions. According to our calculations, the differences in the annual mean temperatures did not exceed 0.5 °C and mean annual thermal amplitude changed from 22.9 to 22.4 °C. The environmental changes before 14.7 ka had no impact on the activity of Final Palaeolithic hunters in the studied area. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • The 13C CPMAS NMR studies of β-glucosides and a-mannosides. • New X-ray structures of aryl β-glucosides and a-mannoside. • The low-energy conformers by the grid search method with a genetic algorithm. • The influence of aryl aglycone rotation on the aryl- O -glycosides structure. Abstract The X-ray structures of 2,6-dimethylphenyl and phenyl 2,3,4,6-tetra- O -acetyl β-glucosides (1 and 3) and phenyl α-mannoside (6) were obtained. The independent part of the unit cell of the glycosides 1 and 6 was formed by one molecule, and for the glucoside 3, two molecules in the crystal cell were observed. In deacetylated glycosides 4 and 6 the crystal structure was established by a hydrogen bond network formed between the sugar hydroxyls and solvent molecules. The 13C CPMAS NMR spectra of aryl glycosides 1 – 6 were analysed. In the spectrum of 3 , doubling of the C4 aryl signal was observed which confirmed the presence of two independent molecules in the solid sample. The GAAGS (Genetic Algorithm-Assisted Grid Search) method was used to determine the low-energy conformers of α-mannosides and β-glucosides. The orientation of the aryl pendant group was calculated using Molecular Mechanics (MMFF94) as well as Quantum Mechanics theory (DFT, B3LYP/6-31 + G(d,p)). [ABSTRACT FROM AUTHOR]

Although cave bear remains have been described since the end of 18th century, recent discoveries and methods provide new knowledge about the typical representative of Pleistocene megafauna, which did not survive the Last Glacial Maximum. Genetic studies supplemented by morphometric analyses showed that this mammal differentiated in the Late Pleistocene into two main forms called Ursus spelaeus and U. ingressus. The latter is regarded more expansive and replaced the native U. spelaeus in some areas of Western Europe. Taking into account the differences between these bears, it is interesting to determine if these forms became extinct at different or similar times. Therefore, we assessed their extinction times, applying seven methods using 205 dated records of cave bear ascribed to these two forms. The average extinction time of U. spelaeus was about 25,600 cal. yr BP (Before Present) and of U. ingressus about 24,800 cal. yr BP. The estimations showed that that U. ingressus could survive up to ca. 1,000 years longer than its relative U. spelaeus. The longer survival of the former could be related to its greater morphological variability and better adaptation to arid continental environments, as well as a stronger tendency to occasional omnivory. Both bears became extinct within the coldest phase of the last glacial period, Greenland Stadial 3, which implies that climate cooling was the main factor of their extinction. The climate deterioration decreased vegetation productivity, and could also have had negative consequences on the prolonged hibernation period when the bears were more susceptible to the activity of humans and predators. [ABSTRACT FROM AUTHOR]

Reactions of the chiral alcohol rac 6,7-dihydro-5H-pyrrolo[1,2- a ]imidazol-7-ol [(R,S)-LH] with R 3 Al (R = t Bu, Et) have been studied. An influence of reaction conditions on the product structures and distributions was found. The dimeric products (Al 2 R 4 L 2 ) [R = t Bu ( 1 ), R = Et ( 2 )] were formed in the reactions of R 3 Al with one equivalent of (R,S)-LH as mixtures of the heterochiral (R,S) and homochiral (R,R) and (S,S) diastereomers. The X-ray diffraction measurements of the (R,S)- 1 and (R,S)- 2 showed dinuclear complexes with bridging ON ligands and 10-membered C 4 N 2 O 2 Al 2 central cycles. The molecules contain two chiral ligands demonstrating (R) and (S) configurations of CO carbon atoms. Polymerization tests showed that the complexes 1 and 2 have activity in the ROP of ε-caprolactone. Kinetic studies revealed first order reaction of polymerization. [ABSTRACT FROM AUTHOR]

In order to explore temporal trends of morphological variation in the narrow-headed vole ( Microtus gregalis ) traditional morphometric methods were used to quantify enamel differentiation quotient (SDQ), tooth size (L) and tooth proportion (A/L) in over 800 first lower molars from two sites in Central Europe. Our results suggest that SDQ values in late Middle Pleistocene assemblages are significantly lower than those in Late Pleistocene populations. A greater chronostratigraphic variation in SDQ occurs across the Late Pleistocene compared to the late Middle Pleistocene. This probably indicates repeated extinctions and re-colonisations, most likely from Eastern Europe or Asia, during MIS 3 and MIS 2. However, it is unclear whether this pattern represents a local phenomenon or whether the SDQ changes took place across a large geographical scale. Further studies on fossil and recent populations of the species are necessary to identify the determinants of SDQ variation in Microtus gregalis and to confirm the usefulness of the index for the Pleistocene stratigraphy. [ABSTRACT FROM AUTHOR]

The reaction of the N- tert -butyl amide of succinic acid with t Bu 3 M (M = Al, Ga) resulted in the formation of the new complexes [Al t Bu 2 {N(H)( t Bu)C(O)CH 2 CH 2 COO}] ( 1 ), [M t Bu 2 {N(H)( t Bu)C(O)CH 2 CH 2 COO}( t Bu 3 M)] [M = Al ( 2 ), M = Ga ( 3 ), and [Ga t Bu 2 {N(H)( t Bu)C(O)CH 2 CH 2 COO}] 2 ( 4 ). The aluminum complexes 1 and 2 contained seven-membered C 4 O 2 Al rings with the Al atom bonded to the oxygen atom and coordinated to the nitrogen atom. The reaction of t Bu 3 Ga with the N- tert -butyl amide of succinic acid resulted in the formation of a mixture of 3 and 4 . The gallium complex 3 was isostructural to 2 , whereas the gallium atoms in the dinuclear compound 4 were bonded to the carboxylate oxygens only forming a central Ga 2 C 2 O 4 ring. X-ray studies showed that the crystalline solid obtained after crystallization from the post-reaction mixture was composed of crystals of compound 3 and co-crystals of 3 and 4 . In all reactions, only the OH protons of the ligand reacted with t BuM groups with an alkane evolution, while NH protons remained unreactive. The reaction of t Bu 3 Ga with the N- tert -butyl amide of succinic acid in a 2:1 M ratio of the reagents in the presence of water proceeded with the formation of the unprecedented compound [(Ga t Bu 2 ) 2 (OH){N(H)( t Bu)C(O)CH 2 CH 2 COO}] ( 5 ) as the only product. Compound 5 was also obtained in the hydrolysis reaction of the mixture of compounds 3 and 4 isolated from the post-reaction mixture of t Bu 3 Ga with the N- tert -butyl amide of succinic acid. The molecular and molecular packing in the crystal structures of 1 – 3 and 5 were determined by single-crystal X-ray diffraction. Crystal structure examinations showed laminar structures of 1 , 3 , and 5 and a packed crystal network of 2 . [ABSTRACT FROM AUTHOR]

Recent palaeogenetic studies indicate a highly dynamic history in collared lemmings ( Dicrostonyx spp.), with several demographical changes linked to climatic fluctuations that took place during the last glaciation. At the western range margin of D. torquatus, these changes were characterized by a series of local extinctions and recolonizations. However, it is unclear whether this pattern represents a local phenomenon, possibly driven by ecological edge effects, or a global phenomenon that took place across large geographical scales. To address this, we explored the palaeogenetic history of the collared lemming using a next-generation sequencing approach for pooled mitochondrial DNA amplicons. Sequences were obtained from over 300 fossil remains sampled across Eurasia and two sites in North America. We identified five mitochondrial lineages of D. torquatus that succeeded each other through time across Europe and western Russia, indicating a history of repeated population extinctions and recolonizations, most likely from eastern Russia, during the last 50 000 years. The observation of repeated extinctions across such a vast geographical range indicates large-scale changes in the steppe-tundra environment in western Eurasia during the last glaciation. All Holocene samples, from across the species' entire range, belonged to only one of the five mitochondrial lineages. Thus, extant D. torquatus populations only harbour a small fraction of the total genetic diversity that existed across different stages of the Late Pleistocene. In North American samples, haplotypes belonging to both D. groenlandicus and D. richardsoni were recovered from a Late Pleistocene site in south-western Canada. This suggests that D. groenlandicus had a more southern and D. richardsoni a more northern glacial distribution than previously thought. This study provides significant insights into the population dynamics of a small mammal at a large geographical scale and reveals a rather complex demographical history, which could have had bottom-up effects in the Late Pleistocene steppe-tundra ecosystem. [ABSTRACT FROM AUTHOR]

Mikolaj Urbanowski disagrees with this Author Correction. Correction to: I Scientific Reports i https://doi.org/10.1038/s41598-020-71504-x, published online 08 September 2020 Marjolein D. Bosch was omitted from the author list in the original version of this Article. The Author contributions section now reads: "W.N., A.N. and S.T. designed research; A.P., M.H., W.N., S.B., M.U., A.M., H.F., M.D.B., P.S., K.S., M.Z., A.W., A.N. and S.T. performed research; A.P., M.H., W.N., S.B., M.U., A.M., H.F., M.D.B., P.S., K.S., M.Z., A.W., A.N. and S.T. analysed data; A.P., M.H., S.T., W.N. and S.B. wrote the paper with the collaboration of all the co-authors.". [Extracted from the article]

The Author contributions section now reads: "S.T. W.N. and A.N. conceived the project; S.T., W.N., A.P., M.B., S.C., M.D., H.F., A.M., M.D. B., D.P., M.P.R., C.M.R., V.S-M., G.M.S., P.S., M.S., K.S., A.V., F.W., H.W., A.W., M.Z., S.B., A.N., J-J. H., performed research; S.T., A.P., W.N., M.B., M.D.B., S.C., M.D., H.F., A.M., D.P., M.P.R., C.M.R., V.S-M., G.M.S., P.S., M.S., K.S., A.V., F.W., H.W., A.W., M.Z., S.B., A.N., J-J. H. analysed all archaeological data; S.T. and A.P. wrote the paper with the collaboration of all the co-authors." Correction to: I Scientific Reports i https://doi.org/10.1038/s41598-021-01221-6, published online 25 November 2021 The original version of this Article contained errors in the author list where Marjolein D. Bosch was omitted from the author list, and Mikolaj Urbanowski was incorrectly listed as an author of the original Article, and has subsequently been removed. The original article can be found online at https://doi.org/10.1038/s41598-021-01221-6. [Extracted from the article]

Introduction. Inflammation plays a central role in the pathophysiology and progression of atherosclerosis, also in patients with peripheral arterial disease (PAD). Revascularization is a risk factor which intensifies this process sometimes leading to newly developed restenosis. Aim. To determine the levels offibrinogen, C-reactive protein (CRP), interleukin 6 (IL-6), interleukin 10 (IL-10), basic fibroblast growth factor (bFGF) and transforming growth factor-beta 1 (TGF-β1) in the blood of patients with PAD after endovascular revascularization of lower limbs and in patients with new restenosis. Material and methods. The study included 150 patients with PAD (90 men and 60 women), aged 50-88 (mean 65.5) years after successful peripheral angioplasty (PTA) and/or stenting. Within 12 months after revascularization procedure in 38 PAD patients restenosis occurred. Control group for cytokines consisted of 15 clinically healthy subjects without limb ischaemia aged 60-83 years. Fasting blood was drawn in the morning and put into 3.2% sodium citrate in a 9:1 proportion (for determination offibrinogen and CRP), and 2.6 ml of blood was mixed with EDTA for determination of cytokines: IL-6, IL-10, bFGF and TGF-β1. All parameters were measured in the plasma of patients with commercial kits for enzyme immunoassay; fibrinogen and CRP levels were measured with coagulometer. Results. In the plasma of patients with PAD after revascularization, the levels offibrinogen and CRP were significantly higher than in controls. These markers increased within 12 months of observation: CRP level increased almost two-fold and fibrinogen only by about 10%. All examined cytokines in PAD patients with restenosis were higher than in those without restenosis, but the difference was significant only for IL-10 and bFGF. But increased cytokines in patients with restenosis were within the laboratory norms specified by reagent producers except of TGF-β1. Conclusions. 1. In PAD patients after endovascular revascularization the levels of CRP and fibrinogen during one year observation significantly increased. 2. In these patients, significant correlation was observed between pro-inflammatory CRP and anti-inflam matory IL-10. 3. The concentrations of CRP, fibrinogen and cytokines (IL-6, bFGF, TGF-β1 and IL-10) were also higher in PAD patients with restenosis indicating the involvement of low-grade inflammation in this process. [ABSTRACT FROM AUTHOR]

Abstract: The Emine-Bair-Khosar Cave (EBK), situated on the northern edge of the Lower Plateau of the Chatyrdag Massif (Crimean Mountains) is rich in palaeontological material accumulated over most of the Pleistocene. mtDNA was isolated from bones of three specimens of red deer (Cervus elaphus) dated to the late Pleistocene (MIS 3). These are the first ancient DNA sequences obtained for this species. The position of the three red deer individuals on the phylogeographic tree is based on mtDNA sequences of contemporary representatives of the Cervinae inhabiting the Northern Hemisphere. The results confirm the notion that the Crimean Peninsula was the north-easternmost refugium in Europe, and that during and after the Late Pleistocene it played a major role in recolonisation and dispersal of temperate species in the whole Eurasian continent. [Copyright &y& Elsevier]

Abstract: An ornamented artefact made of antler, found in the environs of Świdwin (Pomerania, NW Poland), was subject to structural and environmental analysis. Radiocarbon dating (10 700±60 BP or 10 910–10 680 cal. BC) places it in the Final Palaeolithic, at the end of Weichselian (boundary of the Allerød and Younger Dryas). The surface of the artefact bears a complex ornament of zigzag lines and an anthropomorphic drawing, representing most probably a woman with spread legs. Palynological analysis of the deposit in which the object was found indicates forest communities (pine-birch forests) with some open areas, in a cool climate. Ultrastructural examination points to the elk Alces alces (Linnaeus, 1758) as the source species; the antler was at the stage of intense growth which indicates that the elk was killed or died in the spring-summer period. The antler was large, and the object made of it was used for a long time, playing a role in rituals and symbolic culture of a hunting group. The ornamentation shows an affinity to the early Mesolithic art and makes it possible to better trace the relations between the hunters of the late Pleistocene and those of the early Holocene. [ABSTRACT FROM AUTHOR]

Identification of volcanic signals preserved in paleoenvironmental records can provide key insights into the timing and consequences of explosive volcanism. Yet the eruption record is incomplete and this confounds our ability to link volcanic eruptions to their impacts on climate and environments. Studies have suggested that stalagmite records can help to address these gaps, through the identification of transient geochemical variability associated with incorporation of elements derived from erupted material. However, the utility of stalagmites for tracing volcanism is poorly constrained globally. Here, we present a high-resolution geochemical dataset for stalagmite NIED08–05 from Niedźwiedzia Cave (Poland). We do this with two primary aims: (1) to test the suitability of NIED08–05 as a record of volcanism since 3 ka BP, and (2) to ascertain whether stalagmites grown in temperate regions preserve volcanic signals with success comparable to those grown in tropical regions. We find transient enrichments of 16 trace elements and the rare-earth-elements Y, La, Nd, which coincide with the timing of some known eruption events. Using Principal Component Analysis (PCA) we find that elements atypically incorporated into calcite (e.g., Fe) co-vary. Similarly, filtering PC1 (17% of the dataset variability) for high magnitude deviations from a baseline signal yields tentative agreement between PC scores and some known large eruptions with tephra found in Poland. We use our analysis to discuss the complexities involved in associating volcanic signals with stalagmite chemistry in temperate regions far from the source of large eruptions. The transport pathway from volcanic source to stalagmite growth surfaces includes the complex Niedźwiedzia Cave hydrological system and is influenced by dense forest above the cave site. Together these factors increase the potential for attenuation of volcanic-derived chemical signals prior to reaching the stalagmite, and so make it difficult to unambiguously link trace element enrichments in NIED08–05 to volcanic eruptions. Our results provide strong evidence that in a temperate depositional environment far from active volcanoes, climate and hydrology conspire to mute the strength of volcanic geochemical signals. Therefore, this work provides important incentives for future research in this area by highlighting that stalagmites grown in a comparatively simple hydrological regime and grown in caves overlain by thin vegetation and soil cover , may preserve volcanic signatures with greater success than those grown in temperate environments. • An exploratory analysis of the geochemical composition of a mid-latitude, temperate stalagmite grown in SW Poland between 0 and 3 ka BP. • Transient enrichments of 16 trace elements and the rare-earth-elements Y, La, Nd coincide with the timing of some known eruption events. • However, it is difficult to unambiguously link trace element enrichments to volcanic eruptions. • We suggest this is linked to four key factors: (1) distal location relative to active volcanoes, (2) regional climate, (3) depth within the cave, (4) lack of an extremely precise chronology. • Our results suggest that not all stalagmites are suitable for tephrochronology. [ABSTRACT FROM AUTHOR]

The Micoquian is the broadest and longest enduring cultural facies of the Late Middle Palaeolithic that spread across the periglacial and boreal environments of Europe between Eastern France, Poland, and Northern Caucasus. Here, we present new data from the archaeological record of Stajnia Cave (Poland) and the paleogenetic analysis of a Neanderthal molar S5000, found in a Micoquian context. Our results demonstrate that the mtDNA genome of Stajnia S5000 dates to MIS 5a making the tooth the oldest Neanderthal specimen from Central-Eastern Europe. Furthermore, S5000 mtDNA has the fewest number of differences to mtDNA of Mezmaiskaya 1 Neanderthal from Northern Caucasus, and is more distant from almost contemporaneous Neanderthals of Scladina and Hohlenstein-Stadel. This observation and the technological affinity between Poland and the Northern Caucasus could be the result of increased mobility of Neanderthals that changed their subsistence strategy for coping with the new low biomass environments and the increased foraging radius of gregarious animals. The Prut and Dniester rivers were probably used as the main corridors of dispersal. The persistence of the Micoquian techno-complex in South-Eastern Europe infers that this axis of mobility was also used at the beginning of MIS 3 when a Neanderthal population turnover occurred in the Northern Caucasus. [ABSTRACT FROM AUTHOR]