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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.

In recent years, the economic situation in Poland has undergone dynamic changes. These changes had an impact on the standard of living of Poles, by affecting their financial situation. The article presents and analyzes the characteristics of changes in the structure of polish household budgets in 2008-2018. Issues such as income and expenditure, expenditure structure, tendency and dynamics of changes, including demographic and economic factors, has been discused in this article. In addition to analyzing the data on the structure of household budgets, the causes responsible for such and not other directions of changes has been also identified. W ostatnich latach sytuacja gospodarcza w Polsce podlegała dynamicznym zmianom. Zmiany te oddziaływały na poziom życia Polaków poprzez wpływ na ich sytuację finansową. Artykuł przedstawia oraz analizuje charakterystykę zmian w strukturze budżetów gospodarstw domowych w latach 2008–2018. Omówione zostały zagadnienia, takie jak poziom dochodów i wydatków, struktura wydatków, tendencja oraz dynamika zmian z uwzględnieniem czynników demograficznych i ekonomicznych. Oprócz przeanalizowania danych dotyczących struktury budżetów gospodarstw domowych, zidentyfikowane zostały również przyczyny odpowiadające za takie, a nie inne kierunki zmian.

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.

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.

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)).

α-Tocopheryl succinate (α-TOS) is a very promising anticancer agent; however, the mechanism of its action and the role of the succinic moiety in biological activity still remains unclear. This paper, presents the first determination of the X-ray structure of α-TOS and 2,2,5,7,8-pentamethylchroman-6-yl succinate (PMCS). The X-ray data indicated high out of planarity deformation of the aryl ring in the chroman-6-ol system. α-TOS and PMCS differed in angle θ value (28.4° vs. 21.5°, respectively) and in their heterocyclic ring conformations: 2-endo-3-exo in PMCS, and 2-endo-3-exo and 2-exo-3-endo in α-TOS. Due to their strong intermolecular hydrogen bonds, both succinates form cyclically repeated dimeric structures in well assembled crystal supramolecular structures.A population analysis of α-tocopherol (α-TOC), 2,2,5,7,8-pentamethylchroman-6-ol (PMC) and their acyl derivatives was performed at B3LYP/6-31G(d,p)/CPCM level of theory using a natural bond orbital (NBO) analysis within the Gaussian 09 program package. For all compounds, relaxed scans were performed along torsion angle γ, and for low-energy conformers the Fukui functions were calculated: electron donor (ƒ−(r)), electron acceptor (ƒ+(r)), free radical (ƒo(r)) and dual descriptor (ƒ2(r)).In general, the differences observed between α-TOC and its acyl derivative structures result from the non-bonding lone pair of the phenolic oxygen and its interaction with aromatic system π electrons. Keywords: α-Tocopheryl succinate, X-ray, Natural Bond Orbital, DFT calculation, Fukui function

In this Article, a number of single crystal structures of piperidine hydrates are presented. While the lower hydrates, i.e., containing 1/2 or 2 water molecules per amine, present features characteristic for well-defined structures of cocrystals, the higher hydrates (8.1, 9 3/4, 11) have properties more similar to clathrate hydrates with the organic molecules enclosed in cages. However, in these systems some weak hydrogen bonds between piperidine and the water framework exist; thus they cannot be considered as pure host–guest structures. The property of piperidine to crystallize with water giving full enclathration of the amine is compared with the ability of nonionic chaotropes to generate clathrate hydrate-like structures. According to the obtained crystal structures of higher hydrates of piperidine, this amine behaves more like a chaotrope. This finding is supported by Raman spectra in the solid state.

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.

In this study, five new complexes containing deferiprone (dfp) and N,N-donor ligands [bipyridine (bpy), 1,10-phenanthroline (phen) and ethylenediamine (en)] were synthesized: [Fe(dfp)2(bpy)](PF6) (1), [Fe(dfp)2(phen)](PF6) (2), [Cu2(dfp)2(bpy)2](PF6)2 (3), [Ga(dfp)2(bpy)](PF6) (4), and [Fe(dfp)2(en)](PF6) (5). Characterization of these complexes was carried out through elemental analysis and FT-IR, and single-crystal X-ray crystallography was used to determine their structures. Whilst the polyhedron has a distorted octahedral geometry in 1, 2, 4, and 5, it adopts a distorted square-pyramidal geometry in 3. Interaction of these compounds with human serum albumin (HSA) has been investigated through electronic absorption and fluorescence titration techniques. Emission quenching was performed separately for each complex at three different temperatures and thermodynamic parameters were calculated using binding constants to better understand the power of different binding forces with the HSA. Results demonstrated that compounds interact strongly with the HSA with a static quenching mechanism. Our evaluation of the cytotoxicity of complexes against the breast cancer MCF-7 cell line showed that complex 2 presents a better cytotoxicity than the standard cis-Pt. Finally, using the AutoDock 4.2 program, simulations to analyze the mechanism of complex–HSA interactions and their binding mode were carried out. Results showed that the best binding mode is located in subdomain IB for 1, 2, and 4, in I/II for 3, and in IA/IIA for 5. Communicated by Ramaswamy H. Sarma

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.

Reactions of the chiral alcohol rac 6,7-dihydro-5H-pyrrolo[1,2-a]imidazol-7-ol [(R,S)-LH] with R3Al (R = tBu, Et) have been studied. An influence of reaction conditions on the product structures and distributions was found. The dimeric products (Al2R4L2) [R = tBu (1), R = Et (2)] were formed in the reactions of R3Al 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 C4N2O2Al2 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 e-caprolactone. Kinetic studies revealed first order reaction of polymerization.

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.

Robust chronologies are crucial for the correct interpretation of climate proxy records and for detailed reconstructions of palaeoclimate. Stalagmites have garnered strong interest as recorders of past climate in part due to their amenability to U-series dating. However, many stalagmites are not dateable using this technique due to low 238U and/or high detrital Th concentrations (e.g., many tropical cave systems (Adkins et al., 2013)), and occasionally these issues affect stalagmites across wide geographical regions (e.g., large parts of Australia (Green et al. 2013)) complicating the use of stalagmites in these areas. Radiocarbon (14C) offers an alternative method of dating stalagmites, but issues associated with the ‘dead carbon fraction’ (DCF) have historically hindered this approach. Here, a novel 14C-based method for dating stalagmites is presented and discussed. The technique calculates a best-fit growth rate between a time-series of stalagmite 14C data and known atmospheric 14C variability. The new method produces excellent results for stalagmites that satisfy four requirements: i) the absence of long-term secular variability in DCF (i.e., stalagmite DCF varies around a mean value with no long-term trend), ii) stalagmite growth rate does not vary significantly (the technique identifies stalagmites with substantial growth rate variability), iii) the stalagmite record is long enough that measurable 14C decay has occurred, and iv) one ‘anchor’ point exists where the calendar age is known. The model produces good results for a previously U–Th dated stalagmite from Heshang Cave, China, and is then applied to an undated stalagmite from southern Poland. The new method will not replace high-precision U–Th measurements, because the precision of the technique is difficult to quantify. However, it provides a means for dating certain stalagmites undateable by conventional U–Th methods and for refining coarse U–Th chronologies.

The reaction of the N-tert-butyl amide of succinic acid with tBu3M (M = Al, Ga) resulted in the formation of the new complexes [AltBu2{N(H)(tBu)C(O)CH2CH2COO}] (1), [MtBu2{N(H)(tBu)C(O)CH2CH2COO}(tBu3M)] [M = Al (2), M = Ga (3), and [GatBu2{N(H)(tBu)C(O)CH2CH2COO}]2 (4). The aluminum complexes 1 and 2 contained seven-membered C4O2Al rings with the Al atom bonded to the oxygen atom and coordinated to the nitrogen atom. The reaction of tBu3Ga 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 Ga2C2O4 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 tBuM groups with an alkane evolution, while NH protons remained unreactive. The reaction of tBu3Ga 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 [(GatBu2)2(OH){N(H)(tBu)C(O)CH2CH2COO}] (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 tBu3Ga 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.

5-[2-(N,N-dimethylamino)ethoxy]-4,7-dimethylcoumarin (1) and 6-acetyl-5-[2-(N,N-dimethylamino)ethoxy]-4,7-dimethylcoumarin (2), structurally related, were synthesized using both conventional and microwave-assisted approach. An impact of acetyl groups on the molecular structure of coumarin derivatives has been examined. Crystals of 2 were investigated using single crystal and powder X-ray diffraction techniques. Compound 2 crystallizes forming two polymorphs (denoted as 2_1 and 2_2), both belonging to P21/c space group. Both polymorphs are comparably stable and can be formed simultaneously during crystallization process. The solid state structure was also analysed using the fully resolved 13C CP/MAS NMR. The double signals with the intensity ratio of about 1:1 which were observed in the 13C CP/MAS NMR spectrum of compound 1 must arise due to the presence of two conformers of 1. In contrast, NMR spectrum recorded for powder mixture of two polymorphs of compound 2 displays no signal splitting. This is related to structural similarities of molecules in both polymorphs.

Background. In patients with peripheral artery disease (PAD) a hypercoagulable state and thromboembolic complications occur. Revascularization procedures increase this state, sometimes leading to restenosis. Restenosis following balloon angioplasty (PTA)and stent implantation is ≥ 50% of artery stenosis. Objectives. To determine the concentration of tissue factor (TF), tissue factor pathway inhibitor (TFPI), thrombin–antithrombin (TAT) complexes, fibrinogen and D-dimers in the blood of patients with PAD after peripheral endovascular revascularization of the lower legs and in PAD patients with restenosis. Material and Methods. The study included 150 patients with PAD, 90 men and 60 women, aged 44–88 (mean 65.5) years, after successful peripheral angioplasty (PTA) and/or with stenting. During the 6 months after the revascularization procedures, restenosis occurred in 27 patients. 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% natrium citrate at a ratio of 9 : 1. The concentration of TF, TFPI, TAT complexes and D-dimers were measured in plasma with commercial tests using an enzyme immunoassay. Fibrinogen was determined with coagulometer. Results. In the plasma of patients with PAD after endovascular revascularization, the concentrations of TF, TAT complexes, fibrinogen and D-dimers were significantly higher compared to the reference group. During the six months of observation, 27 patients developed restenosis. The results of hemostatic factors in patients with restenosis were compared with the same patients before restenosis and the group of 123 PAD patients after endovascular revascularization. TF and fibrinogen levels in the 27 patients with restenosis were significantly higher than in the group of PAD patients before restenosis. Conclusions. Statistically significantly higher levels of tissue factor (TF) and fibrinogen in PAD patients with new restenosis, compared to those without restenosis after endovascular revascularization, indicate they can participate in the formation of restenosis (Adv Clin Exp Med 2015, 24, 1, 93–98).

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 e-caprolactone, whereas 1–5 were inactive in ROP.

The Stajnia Cave is one of the most important archaeological sites due to the finds of the first remains of Neanderthals in Poland, and several tens of thousands of flint artefacts from the Middle Palaeolithic. Based on geological, geochemical, palaeobotanical, palaeozoological, archaeological and isotope analyses, coupled with absolute age determinations (OSL, U-Th and C 14 ), 15 lithostratigraphic layers were distinguished and palaeoenvironmental conditions during the sedimentation of these beds were determined. The cave loams accumulated through weathering, aeolian and fluvial processes. Their age may be correlated with an interval from the Early Glacial to the Late Pleniglacial of the Visulian (Weichselian) Glaciation. Archaeological relics related to the Neanderthals have been discovered in layer D with an absolute age of about 52,000–45,000 years BP and correlated with MIS 3 – the Middle Plenivistulian (Interplenivistulian). Climate oscillations in the Vistulian are reflected by the type of the sediments and their physical-chemical features, allowing determining warmer interstadial and colder stadial periods. Generally, the climate was cold, characteristic of tundra areas with a typical vegetation and fauna, and with the mean temperature of the warmest month not exceeding 12°C. Based on multi-proxy studies it can be concluded that from layer E1 upwards, the climate conditions became progressively drier. At that time, the climate was cold with continental features enhancing tundra domination. This conclusion is confirmed by palaeontological investigations and the record of stable oxygen isotopes in the teeth of reindeer. The studies have also indicated seasonal migration of reindeer on the tundra that surrounded the cave. Probably, short-term slight climate warmings occurred during the Middle Plenivistulian (Interplenivistulian).

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.

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, δ15N values were relatively high, suggesting intensive soil activity and, indirectly, mild climate. After that, from a stratigraphic layer dated to the early Wurm glaciation, lower δ15N values point to lower soil activity. Deterioration of ecosystem productivity and climate conditions were also confirmed by higher δ13C. 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 Wurm glaciations, with significantly warmer periods before and after the Last Glacial Maximum.

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.

Climate changes that occurred during the Late Pleistocene have profound effects on the distribution of many plant and animal species and influenced the formation of contemporary faunas and floras of Europe. The course and mechanisms of responses of species to the past climate changes are now being intensively studied by the use of direct radiocarbon dating and genetic analyses of fossil remains. Here, we review the advances in understanding these processes by the example of four mammal species: woolly mammoth (Mammuthus primigenius), cave bear (Ursus spelaeus s. l.), saiga antelope (Saiga tatarica) and collared lemmings (Dicrostonyx ssp.). The cases discussed here as well as others show that the migrations, range shifts and local extinctions were the main responses to climate changes and that the dynamics of these climate driven processes were much more profound than it was previously thought. Each species reacted by its individual manner, which depended on its biology and adaptation abilities to the changing environment and climate conditions. The most severe changes in European ecosystems that affected the largest number of species took place around 33–31 ka BP, during the Last Glacial Maximum 22–19 ka BP and the Late Glacial warming 15–13 ka BP.

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.

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.

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.

The fossil-bearing deposits of Żabia Cave (Czestochowa Upland, Poland) yielded a diverse vertebrate fauna (75 taxa in total) of middle Early Pleistocene age. The assemblage comprises 5 amphibian, 10 reptilian and 6 bird taxa. Small mammals are represented by13 insectivorous species, 6 taxa of bats, 2 lagomorphs and 18 rodents. Large mammals include 15 species of carnivores, an unidentified horse, and 3 even-toed ungulates. The assemblage contains few Pliocene relict forms (e.g. Mioproteus wezei, Asoriculus gibberodon, Beremendia fissidens, Mimomys pitymyoides, Pannonictis ardea) and numerous Early Pleistocene newcomers (e.g. Sorex runtonensis, Ochotona zabiensis, Prolagurus ternopolitanus, early Microtus, Gulo schlosseri, Lutra simplicidens, Cervalces carnutorum). The assemblage documents migration of species associated with cool climate into Central Europe in the middle Early Pleistocene.

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 Allerod 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.

Biśnik Cave is situated in the limestone rock, 7 m above the bottom of the presently dry Wodąca valley. It is located in the Smolen–Niegowonice Range in the southern part of the Czestochowa Upland. To date, an area of 260 m 2 has been explored, to the depth of 150–850 cm. 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.

An upper second permanent molar from a human was found alongside numerous tools of the Micoquian tradition and was excavated in Stajnia Cave, which is located over 100 km North of the Carpathian Mountains in southern Poland. The age of these finds has been established within a time-span of late Saalian to early Weichselian, most likely to OIS 5c or 5a, according to the palaeontological, geological, archaeological and absolute dating of the layer from which they were obtained. An examination of the morphology of the human molar indicates that this tooth exhibits many traits frequently occurring in Neanderthal upper molars. Although the occurrence of derived Neanderthal traits in the Stajnia molar cannot be firmly established because of degradation of its cusps, the presence of the above-mentioned features allows the assertion that this tooth belonged to a Neanderthal. The age of the Stajnia tooth and the archaeological context of this find also indicate that this molar is of Neanderthal origin.

Mineralization of teeth and bones of the cave bear (Ursus spelaeus) from the Biśnik Cave, Southern PolandThe studied bones and teeth of the cave bear (Ursus spelaeus) come from the Biśnik Cave, located in the Częstochowa Upland (Southern Poland). The specimens originate from different geological layers formed since the Odra Glaciation (250-270 thousand years BP). The fossilized bones and teeth were studied using optical microscopy, scanning electron microscopy, X-ray diffraction, FTIR spectroscopy, and INAA. They are built of recrystallized carbonate-rich apatite-(CaOH) and/or apatite-(CaOH). The teeth additionally contain some apatite-(CaF). The lack of collagen and minor REE contents suggest rapid burial and collagen decay in the early stage of diagenesis. The bones and teeth have only limited mineral infillings. In some teeth, Mn-Fe (hydroxy)oxides were found in the dentine canaliculi and in bones, some osteocyte lacunae contain Fe (hydroxy)oxides with admixture of Mn. In one bone specimen, calcite infillings are present in Haversian canals. The infillings formed during later stages of diagenesis and were succeeded by non-filled cracks.

Biśnik Cave is situated in a limestone rock about 50 km northeast of Krakow, southern Poland. Its importance stems from the fact that it is one of the few sites in Europe, and the only one in Poland, with 300,000-year-long sequence of uninterrupted sediments, that cover the time span from before the Saalian to the Holocene. The excavations yielded about 200,000 animal bones and more than 4,000 stone, bone and antler artifacts. Bird remains from Biśnik Cave consist of nearly 1,600 skeletal fragments of at least 96 taxa that represent a minimum of 285 individuals. The majority of the remains belong to Galliformes; relatively numerous are also Corvidae, Falconiformes, Anseriformes and the genus Turdus. The remains include one extinct taxon (Falco tinnunculus atavus) and four species new for the Polish fossil avifauna (Aquila heliaca, Pinicola enucleator, Loxia pytyopsittacus and Carduelis flammea). Avian remains indicate a mosaic of various habitats in the surroundings of Biśnik Cave. Some kind of mature forest or at least sparsely growing trees, as well as water bodies, marshes, wet meadows, steppe and tundra habitats must have been present during the entire time of sedimentation. It is postulated that the Krakow-Czestochowa Upland was a local refugium for the forest fauna during the Saalian and Vistulian glaciations.