Light-Induced Structural Dynamics and Charge Transport in Layered Halide Perovskite Thin Films.

The dynamic nature of the metal halide perovskite lattice upon photoexcitation plays a vital role in their properties. Here we report an observation of light-induced structure dynamics in quasi-2D Ruddlesden-Popper phase perovskite thin films and its impact on the carrier transport properties. By a time-resolved X-ray scattering technique, we observe a rapid lattice expansion upon photoexcitation, followed by a slow relaxation over the course of 100 ns in the dark. Theoretical modeling suggests that the expansion originates from the lattice's thermal fluctuations caused by photon energy deposition. Power dependent optical spectroscopy and photoconductivity indicate that high laser powers triggered a strong local structural disorder, which increased the charge dissociation activation energy that results in localized transport. Our study investigates the impact of laser energy deposition on the lattices and the subsequent carrier transport properties, that are relevant to device operations.

Accessing One-Dimensional Chains of Halogenoindates(III) in Organic-Inorganic Hybrids.

Organic-inorganic hybrids of halogenoindates(III) are typically represented by one of the zero-dimensional units: InX4-, InX52-, InX63-, or In2X115-. Higher dimensional anionic forms, although not forbidden, have remained almost elusive. Here we report for the first time In3+-based organic-inorganic hybrids, (C4H5N2S)2InCl5 and (C4H5N2S)2InBr5, with 1D anionic chains of trans-halide-bridged InX6 octahedra whose formation is guided by 2-mercaptopyrimidinium cations (C4H5N2S+). The chains are characterized by the significant ease of deformation, which is reflected in the elongation of the bridging bonds or the displacement of In3+ ions. The materials show a robust band gap predominantly governed by C4H5N2S+ cations. Dielectric relaxation processes in (C4H5N2S)2InBr5 arise from the cations' dynamics and suggest the ability of the brominated system to accommodate even larger cations. Our work represents a successful attempt to expand the structural diversity of halogenoindates(III) and opens a pathway to reach multifunctional 1D In3+-based hybrids.

Near-Room-Temperature Magnetoelectric Coupling via Spin Crossover in an Iron(II) Complex.

Magnetoelectric coupling is achieved near room temperature in a spin crossover FeII molecule-based compound, [Fe(1bpp)2 ](BF4 )2 . Large atomic displacements resulting from Jahn-Teller distortions induce a change in the molecule dipole moment when switching between high-spin and low-spin states leading to a step-wise change in the electric polarization and dielectric constant. For temperatures in the region of bistability, the changes in magnetic and electrical properties are induced with a remarkably low magnetic field of 3 T. This result represents a successful expansion of magnetoelectric spin crossovers towards ambient conditions. Moreover, the observed 0.3-0.4 mC m-2 changes in the H-induced electric polarization suggest that the high strength of the coupling obtained via this route is accessible not just at cryogenic temperatures but also near room temperature, a feature that is especially appealing in the light of practical applications.

Work instability and associated factors among patients with rheumatoid arthritis in Greater Poland.

OBJECTIVES: Rheumatoid arthritis (RA) affects patients' capacity to work. The Rheumatoid Arthritis Work Instability Scale (RA-WIS) is a reliable method to measure work instability (WI) (1-3). We lack data on the relationship between RA and work instability among Polish patients. Our study aimed to assess WI and associated factors among patients with RA. MATERIAL AND METHODS: The authors conducted a multi-centre cross-sectional observational study. 315 patients from three rheumatology centres were enrolled and filled in questionnaires, including demographic and self-reported clinical data, RA-WIS, and the Health Assessment Questionnaire (HAQ). Swollen and tender joint counts (SJC, TJC) were assessed by the attending physician, and current erythrocyte sedimentation rate (ESR) and C-reactive protein (CRP) were collected. We excluded 41 patients due to an incorrectly filled in form and analysed questionnaires of 274 patients. DAS28 (Disease Activity Score in 28 joints) and DAS28-CRP were calculated. We performed statistical analysis with Statistica v. 13.3 using the Mann-Whitney U test, χ2 test, and Spearman's correlation. RESULTS: 140 (51%) patients were currently employed and their characteristics were analysed. In univariable analysis we identified the following risk factors for high risk WI: moderate-to-high disease activity (DAS28 ≥ 3.2 - OR 2.29, 95% CI 1.06-4.96, p = 0.033; DAS28-CRP ≥ 3.2 - OR 2.34, 95% CI 1.04-5.27, p = 0.038), ESR ≥ 30 mm/h in women and ≥ 20 mm/h in men (OR 2.65, 95% CI 1.20-5.89, p = 0.010), CRP ≥ 1 mg/dl (OR 4.02, 95% CI 1.78-9.10, p < 0.001), HAQ-DI > 1.0 (OR 2.23, 95% CI 1.04-4.81, p = 0.037) and at least moderate pain on the visual analogue scale (VAS p ≥ 4.5 cm - OR 5.31, 95% CI 2.36-11.96, p < 0.001).Correlations were moderate between RA-WIS and VASp (RS = 0.59, p < 0.001) and HAQ-DI (RS = 0.52, p < 0.001) but weak with disease activity indices (DAS28 [RS = 0.31, p < 0.001]; DAS28-CRP [RS = 0.28, p < 0.001]). CONCLUSIONS: Pain and disability are the main factors strongly associated with work instability among patients with RA.

Comparative analysis of 13 HPV genotypes diagnosed in urine sediment cells vs. desquamated cervical epithelial cells

INTRODUCTION: The human papilloma virus (HPV) belongs to double-stranded, DNA circular viruses which infect the epithelial cells. The highest incidence of HPV is identified in malignant processes which affect the uterine cervix, as well as vulvar, penile, rectal and pharyngeal regions. GOAL OF STUDY: An attempt to find correlations between HPV incidence rates in urine sediment cells and in desquamated epithelial cells of the uterine cervix in a group of patients with frequent, recurrent cystitis. MATERIALS AND METHODS: HPV presence was studied, both in urine sediment cells and in uterine cervix epithelial cells of 77 patients. RESULTS: An analysis of urinary sediments brought a total of twenty (25.97%) positive and 57 (74.03%) negative results. In turn, an evaluation of uterine cervix material samples revealed 17 (22.08%) positive and 60 (77.92%) negative results. CONCLUSIONS: The study enabled a comparison between HPV prevalence rates in urine sediment cells and in uterine cervix epithelial cells of an examined patient. The performed observations are likely to trigger a further analysis of the studied issue; however, the obtained results provide arguments for different natural histories of the infection processes.

Redox-Active Macrocycles for Organic Rechargeable Batteries.

Organic rechargeable batteries, composed of redox-active molecules, are emerging as candidates for the next generation of energy storage materials because of their large specific capacities, cost effectiveness, and the abundance of organic precursors, when compared with conventional lithium-ion batteries. Although redox-active molecules often display multiple redox states, precise control of a molecule's redox potential, leading to a single output voltage in a battery, remains a fundamental challenge in this popular field of research. By combining macrocyclic chemistry with density functional theory calculations (DFT), we have identified a structural motif that more effectively delocalizes electrons during lithiation events in battery operations-namely, through-space electron delocalization in triangular macrocyclic molecules that exhibit a single well-defined voltage profile-compared to the discrete multiple voltage plateaus observed for a homologous macrocyclic dimer and an acyclic derivative of pyromellitic diimide (PMDI). The triangular macrocycle, incorporating three PMDI units in close proximity to one another, exhibits a single output voltage at 2.33 V, compared with two peaks at (i) 2.2 and 1.95-1.60 V for reduction and (ii) 1.60-1.95 and 2.37 V for oxidation of the acyclic PMDI derivative. By investigating the two cyclic derivatives with different conformational dispositions of their PMDI units and the acyclic PMDI derivative, we identified noticeable changes in interactions between the PMDI units in the two cyclic derivatives under reducing conditions, as determined by differential pulse voltammetry, solution-state spectroelectrochemistry, and variable-temperature UV-Vis spectra. The numbers and relative geometries of the PMDI units are found to alter the voltage profile of the active materials significantly during galvanostatic measurements, resulting in a desirable single plateau for the triangular macrocycle. The present investigation reveals that understanding and controlling the relative conformational dispositions of redox-active units in macrocycles are key to achieving high energy density and long cycle-life electrodes for organic rechargeable batteries.

A Boat-Shaped Tetracationic Macrocycle with a Semiconducting Organic Framework.

We report the synthesis of a tetracationic macrocycle which contains two N,N'-bis(methylene)naphthalenediimide units inserted in between the pyridinium rings of the bipyridinium units in cyclobis(paraquat-p-phenylene) (CBPQT4+ or "blue box") and describe the investigation of its potential use in materials for organic electronics. The incorporation of the two naphthalenediimide (NDI) units into the constitution of CBPQT4+ , not only changes the supramolecular properties of the tetracation in the solid state, but also has a profound influence on the electrochemical and electronic behavior of the resulting tetracationic macrocycle. In particular, the solid-state (super)structure, investigated by single-crystal X-ray diffraction, reveals the formation of a three-dimensional (3D) supramolecular framework with ca. 2.8 nm diameter one-dimensional (1D) hexagonal channels. Electrochemical studies on solid-state thin films of the macrocycle show that they exhibit semiconducting properties with a redox-conductivity of up to 7.6×10-4  S m-1 . Moreover, EPR and ENDOR spectroscopies show that charge is equally shared between the NDIs within the one-electron reduced state of the NDI-based macrocycle on the time scale of these techniques.

Linking drought indices to atmospheric circulation in Svalbard, in the Atlantic sector of the High Arctic.

Based on long-term climatological data from Ny-Ålesund, Svalbard Airport-Longyearbyen and the Polish Polar Station at Hornsund, we undertook an analysis of drought indices on Spitsbergen Island, Svalbard, for the period 1979-2019. The features and causes of spatiotemporal variability of atmospheric drought in Svalbard were identified, as expressed by the standardized precipitation evapotranspiration index (SPEI). There were several-year periods with SPEI indicating the dominance of drought or wet conditions. The long-term variability in the annual and half-year (May-October) SPEI values showed a prevalence of droughts in the 1980s and the first decade of the twenty-first century, while wet seasons were frequent in the 1990s and in the second decade of the twenty-first century. The seasonal SPEIs were characteristic of interannual variability. In MAM and JJA, droughts were more frequent after 2000; during SON and DJF of the same period, the frequency of wet seasons increased. The most remarkable changes in the scale of the entire research period occurred in autumn when negative values of SPEI occurred more often in the first part of the period, and positive values dominated in the last 20 years. The long-term pattern of the variables in consecutive seasons between 1979 and 2019 indicates relationships between the SPEI and anomalies of precipitable water and somewhat weaker relationships with anomalies of sea level pressure. The three stations are located at distances of more than 200 km from each other in the northern (Ny-Ålesund), central (Longyearbyen) and southern parts of Svalbard (Hornsund), and the most extreme values of drought conditions depended on the atmospheric circulation which could have been modified by local conditions thus droughts developed under various circulation types depending on the station. However, some similarities were identified in the atmospheric circulation patterns favouring drought conditions at Ny-Ålesund and Hornsund, both having more maritime climates than Longyearbyen. Extremely dry seasons were favoured by anticyclonic conditions, particularly a high-pressure ridge (type Ka) centred over Svalbard, air advection from the eastern sector under an influence of cyclone and negative precipitable water anomalies. During wet seasons anomalies of precipitable water were positive and cyclonic conditions dominated. These results were corroborated by the frequency of regional circulation types during JJA and DJF with the lowest and highest values of SPEI.

Expression of Foxp3 in Fibromas and Fibrosarcomas of Skin and Subcutaneous Tissue in Dogs.

BACKGROUND/AIM: Foxp3 is a transcription factor responsible for the formation of T regulatory lymphocytes. Foxp3 expression can be associated with either neoplastic progression or regression. The aim of the study was to evaluate Foxp3 expression in soft tissue tumours (fibromas and fibrosarcomas) of skin and subcutaneous tissue in dogs and to describe its relationship with tumour malignancy grade. MATERIALS AND METHODS: The study was conducted on 71 skin and subcutaneous tumours including 31 fibromas and 40 fibrosarcomas. The samples underwent histological and immunohistochemical evaluation using anti-Foxp3, anti-Ki, and vimentin antibodies. RESULTS: Cytoplasmic expression of Foxp3 protein in the cutaneous and subcutaneous fibrosarcomas in dogs was confirmed. Moreover, a positive relationship between the expression of Foxp3 and tumour malignancy grade and between Foxp3 and Ki-67 expression was noted. CONCLUSION: A positive correlation between the Foxp3 expression intensity and malignancy grade suggests a significant role of Foxp3 in the carcinogenesis of skin and subcutaneous fibrosarcomas in dogs. Increased expression of Foxp3 may have a positive effect on the progression of cancer.

[A comparison of biochemical and genetic classification of propionibacterium acnes strains isolated from skin lesions of patients with acne]. / Porównanie biochemicznej i genetycznej klasyfikacji szczepów Propionibacterium acnes izolowanych ze zmian skórnych od osób z tradzikiem mlodzienczym.

INTRODUCTION: Propionibacterium acnes is dominating group of resident bacteria in skin biocenosis. These bacteria participate in autosterilisation of skin with the process of decomposition of triglycerides into free fatty acids and by keeping the pH of skin on the level 5.5. When the process goes out of control the excess of fatty acids in sebaceous glands leads to necrosis and inflammation. Apart of the presence on the skin P acnes also are present in mucous membranes of intestinal tract, eyes, internal ears channels, and in upper respiratory tracts. Traditionally they are regarded as anaerobes, but they tolerate oxygen atmosphere and are resistant to phagocytosis, surviving even in macrophages. These bacteria produce a number of enzymes and proinflammatory factors activating monocytes, stimulating mitogenic activity of lymphocytes T. According to common opinion they are responsible for disease acne vulgaris, but there are also researchers claiming their low pathogenicity. The list of the P acnes related diseases is not short, some of these diseases may be facilitated by predisposing factors as surgery interventions, diagnostic, or cosmetic procedures. The aim of the study was to compare standard biochemical analysis of P acnes strains to genotypic typing basing on the results from MP-PCR analyses. Relations of hemolysis activity to biochemical types or genetic types were also analysed. METHODS: The analysis of 66 P acnes strains isolated from skin lesions of patients with acne vulgaris was performed. A collection of the strains was analysed biochemically according to Pulverer, Sourek and Hoffler method modified by Kasprowicz, and typed genetically by MP-PCR method. Relations of biochemical and genetic types to beta-hemolysis of strains were studied. RESULTS: Dominating biochemical type was type number I grouping 79% of all isolates, and dominant genotype was A which was detected in 75% of all collected strains. Beta-hemolysis was a feature present in 34% of strains, more frequently in type I (40%) than in type II (12%). beta-hemolysis was present only in A-genotype strains, but A-genotype by itself does not determine that reaction: 53% of A-genotype strains does not exhibit beta-hemolysis. All type I strains represent A-genotype. Type II was genotypicaly differentiated: all genotypes A, A', B, and C were present. CONCLUSIONS: The results obtained show genotypic heterogenity of P acnes strains and relations to biochemical types. Hemolysis was detected independently to biotype or genotype representation. The results confirm biochemical and genetic heterogenities of P acnes, but the observations also indicate necessity of further microbiological-molecular investigation of that bacteria group using other molecular techniques to the study.

Towards ferroelectricity-inducing chains of halogenoantimonates(iii) and halogenobismuthates(iii).

In halogenoantimonate(iii) and halogenobismuthate(iii) organic-inorganic hybrids, chains of trans-connected octahedra, trans-[MX5]∞, are considered attractive anionic structures for inducing ferroelectricity. The latter is realized by displacing the bridging halogen atoms along the chain direction - the process that changes the polarity of the whole unit. Advances in the identification of such materials have been hindered, however, by substantial difficulty in obtaining such structures. Here we investigate structural and dielectric properties of three families of compounds based on 2-mercaptopyrimidinium, 2-aminopyrimidinium, and 2-amino-4-methylpyrimidinium cations in which 8 out of 12 compounds show trans-[MX5]∞ chains in their crystal structures. Two of the compounds adopt a polar P21 space group and are potentially ferroelectric. We perform a detailed structural analysis of all compounds with trans-[MX5]∞ chains discovered by far to understand the factors that lead to the chains' formation. We reveal that the size of a cation predominantly defines the accessibility of structures with this anionic form and we provide rules for designing hybrids with trans-[MX5]∞ chains to help guide future efforts to engineer materials with interesting non-linear electrical properties.

The Usefulness of Cell-Based and Liquid-Based Urine Tests in Clarifying the Diagnosis and Monitoring the Course of Urothelial Carcinoma. Identification of Novel, Potentially Actionable, RB1 and ERBB2 Somatic Mutations.

Bladder cancer is one of the most common cancers in global statistics. One of the issues associated with this disease is the high incidence of cases with delayed diagnosis and what factors correlate with worse treatment outcomes. A possible reason for this may be the rather limited availability of non-invasive diagnostic tools. This short communication presents a case of a 68 year old male patient after an ineffective therapy, carried on for several years with symptoms commonly associated with prostate overgrowth that masked a carcinoma in situ of the urinary bladder. Implementation of several diagnostic techniques, including urine sediment cytology, immunocytochemistry, the fluorescence in situ hybridisation technique, the Bladder EpiCheck test and whole-genome sequencing, enabled the establishment of a correct diagnosis, implementation of appropriate treatment and provision of patient-friendly monitoring. The described case emphasises the usefulness of cell-based and liquid-based urine tests in bladder cancer diagnostic procedures.

Effect of Drought and Heavy Metal Contamination on Growth and Photosynthesis of Silver Birch Trees Growing on Post-Industrial Heaps.

Silver birch trees (Betula pendula Roth) are a pioneering species in post-industrial habitats, and have been associated with an expansive breeding strategy and low habitat requirements. We conducted ecophysiological and dendroclimatological studies to check whether there are any features of which the modification enables birch trees to colonise extreme habitats successfully. We characterised the efficiency of the photosynthetic apparatus, the gas exchange, the content of pigments in leaves, and the growth (leaf thickness and tree-ring width) of birch trees on a post-coal mine heap, a post-smelter heap, and a reference site. Birch growth was limited mainly by temperature and water availability during summer, and the leaves of the birch growing on post-industrial heaps were significantly thicker than the reference leaves. Moreover, birch trees growing on heaps were characterised by a significantly higher content of flavonols and anthocyanins in leaves and higher non-photochemical quenching. In addition, birches growing on the post-coal mine heap accumulated a concentration of Mn in their leaves, which is highly toxic for most plant species. Increasing the thickness of leaves, and the content of flavonols and anthocyanins, as well as efficient non-photochemical quenching seem to be important features that improve the colonization of extreme habitats by birches.

Re-activation of landslide in sub-Arctic areas due to extreme rainfall and discharge events (the mouth of the Great Whale River, Nunavik, Canada).

Climate change is impacting surficial geomorphic processes, especially in sensitive areas such as the sub-Arctic. One of the most common examples involves landslides, which often develop in glacio-isostatically raised marine clays in northeastern Canada. One of these sites, an expansive area of complex landslide terrain located at the mouth of the Great Whale River in Nunavik, has already been studied due to its age and morphology. We present new data, based on the multidisciplinary research including geomorphic, dendrochronological, and hydroclimatological analyses, allowing us to determine how contemporary climate change has affected landslide reactivation during the last 80 years. Our research included collecting 60 cores from Picea glauca trees, growing on the marginal zone of a landslide deposit, as well as from a reference site. The tilted trees formed eccentric growth-ring patterns, which provided us with reliable dates on the landslide events. In addition to these dendrochronological data, we studied these landslides using repeated aerial photography, which showed changes in river channel constrictions in the period 1969-2019. Based on the eccentricity index of the tree ring data, we recognized disturbance events due to landslides. We compared these data with the hydroclimatological conditions and found clearly visible correlations between heavy rainfall and discharge (>95th percentile) of the Great Whale River. The increased landslide activity over the past several years can be linked to an increase in extreme summertime rainfall events. Increased landslide activity poses a real threat, through its input of large amounts of fine-grained sediment to the river, causing it to narrow.

The low-temperature phase of morpholinium tetra-fluoro-borate.

The crystal structure of the low-temperature form of the title compound, C(4)H(10)NO(+)·BF(4) (-), was determined at 80 K. Two reversible phase transitions, at 158/158 and 124/126 K (heating/cooling), were detected by differential scanning calorimetry for this compound, and the sequence of phase transitions was subsequently confirmed by single-crystal X-ray diffraction experiments. The asymmetric unit at 80 K consists of three BF(4) (-) tetra-hedral anions and three morpholinium cations (Z' = 3). Hydrogen-bonded morpholinium cations form chains along the [100] direction. The BF(4) (-) anions are connected to these chains by N-H⋯F hydrogen bonds. In the crystal structure, two different layers perpendicular to the [001] direction can be distinguished, which differ in the geometry of the hydrogen bonds between cationic and anionic species.

Flexible ferroelectric organic crystals.

Flexible organic materials possessing useful electrical properties, such as ferroelectricity, are of crucial importance in the engineering of electronic devices. Up until now, however, only ferroelectric polymers have intrinsically met this flexibility requirement, leaving small-molecule organic ferroelectrics with room for improvement. Since both flexibility and ferroelectricity are rare properties on their own, combining them in one crystalline organic material is challenging. Herein, we report that trisubstituted haloimidazoles not only display ferroelectricity and piezoelectricity-the properties that originate from their non-centrosymmetric crystal lattice-but also lend their crystalline mechanical properties to fine-tuning in a controllable manner by disrupting the weak halogen bonds between the molecules. This element of control makes it possible to deliver another unique and highly desirable property, namely crystal flexibility. Moreover, the electrical properties are maintained in the flexible crystals.

Investigation of structure-properties relationship in a novel family of halogenoantimonates(III) and halogenobismuthates(III) with morpholinium cation: [NH2(C2H4)2O]MX4. Crystal structure, phase transitions and dynamics of molecules.

Three new organic-inorganic hybrids based on halogenoantimonates(III) and halogenobismuthates(III) with the morpholinium cation, [NH2(C2H4)2O]SbCl4, [NH2(C2H4)2O]SbBr4 and [NH2(C2H4)2O]BiBr4, have been prepared and characterized with DSC, TGA, DTA and single-crystal X-ray diffraction. The common feature of the crystal structures of the studied compounds is the presence of polyanionic ([MX4]∞(-)) and morpholinium (head-to-tail configuration) chains, which expand themselves parallel to each other. The antimonate derivatives are isomorphous, crystallizing in a centrosymmetric orthorhombic Pbca space group and show no phase transitions (PTs) between 110 and 370 K. On the other hand, [NH2(C2H4)2O]BiBr4 undergoes two first-order structural PTs: I ↔ II at 321/343 K (cooling/heating) and II ↔ III at 285/289 K (cooling/heating). The mechanism of the PTs is discussed on the basis of crystallographic data and (1)H NMR and infrared spectroscopy. The PT at 343 K is accompanied by a spectacular switching of the spin-lattice T1 relaxation pathway. Structural parameters analysis has been performed to discuss a structure-properties relationship.

[NH2(C2H4)2O]MX5: a new family of morpholinium nonlinear optical materials among halogenoantimonate(III) and halogenobismuthate(III) compounds. Structural characterization, dielectric and piezoelectric properties.

This paper presents the structural features of ionic complexes formed by morpholine and metal ions which belong to group VA, namely Sb(III) and Bi(III). A series of target inorganic-organic hybrid compounds of the general formula [NH(2)(C(2)H(4))(2)O](2)MX(5) (where M = Sb, Bi; X = Cl, Br) has been synthesized by incorporating the organic component (morpholine) into the highly polarizable one-dimensional halogenoantimonate(III)/halogenobismuthate(III) chain network. Among the studied compounds, four were found to crystallize in the room temperature phase in the piezoelectric, orthorhombic space group P2(1)2(1)2(1), Z = 4, the feature being confirmed by the powder second harmonic generation of light and piezoelectric measurements. Dielectric dispersion studies between 200 Hz and 2 MHz disclosed a relaxation process below room temperature well described by the Cole-Cole equation. Based on crystal structures available in Cambridge Structural Database (version 5.32, November 2010) we attempt to show a relationship between the acentric symmetry of compounds and the type of anionic network within the R(2)MX(5)-subgroup (where R denotes organic cation) of halogenoantimonates(III) and halogenobismuthates(III).