The In Vitro Cytotoxicity of Eremothecium oil and Its Components-Aromatic and Acyclic Monoterpene Alcohols.

The microscopic fungi Eremothecium ashbyi and E. gossypii are known for their ability to synthetize essential oil, which has a composition similar to that of rose oil. The development of Eremothecium oil technology enables the production of rose-scented products, which are demanded by pharmaceutical, food, and perfumery industries. This study focuses on assessing the in vitro cytotoxicity of Eremothecium oil, in comparison with that of rose oil, using a combination of methods and two cell types (3T3 mouse fibroblast cell line and bone-marrow-derived mesenchymal stromal cells (BM-MSCs)). The Eremothecium oil samples possessed cytotoxic effects that varied among strains and batches. The revealed cytotoxicity level may be used to tailor the qualitative and quantitative composition of Eremothecium oil to achieve a particular quality in its end products. These results require further analysis using other cell types and assays based on measuring other cell functions.

Synthesis, Structure, Spectral-Luminescent Properties, and Biological Activity of Chlorine-Substituted N-[2-(Phenyliminomethyl)phenyl]-4-methylbenzenesulfamide and Their Zinc(II) Complexes.

New azomethine compounds of 2-(N-tosylamino)benzaldehyde or 5-chloro-2-(N-tosylamino)benzaldehyde and the corresponding chlorine-substituted anilines, zinc(II) complexes based on them have been synthesized. The structures of azomethines and their complexes were determined by elemental analysis, IR, 1H NMR, X-ray spectroscopy, and X-ray diffraction. It is found that all ZnL2 complexes have a tetrahedral structure according to XAFS and X-ray diffraction data. The photoluminescent properties of azomethines and zinc complexes in methylene chloride solution and in solid form have been studied. It is shown that the photoluminescence quantum yields of solid samples of the complexes are an order of magnitude higher compared to the solutions and range from 11.34% to 48.3%. The thermal properties of Zn(II) complexes were determined by thermal gravimetric analysis (TGA) and differential scanning calorimetry. The TGA curves of all the compounds suggest their high thermal stability up to temperatures higher than 290 °C. The electrochemical properties of all complexes were investigated by the cyclic voltammetry method. The multilayered devices ITO/PEDOT:PSS/NPD/Zn complex/ TPBI/LiF/Al with wide electroluminescence (EL) color range spanning the range from bluish-green (494 nm) to green (533 nm) and the high values of brightness, current and power efficiency were fabricated. The biological activity of azomethines and zinc complexes has been studied. In the case of complexes, the protistocidal activity of the zinc complex with azomethine of 5-chloro-2-(N-tosylamino)benzaldehyde with 4-chloroaniline was two times higher than the activity of the reference drug toltrazuril.

Main sources controlling atmospheric burdens of persistent organic pollutants on a national scale.

National long-term monitoring programs on persistent organic pollutants (POPs) in background air have traditionally relied on active air sampling techniques. Due to limited spatial coverage of active air samplers, questions remain (i) whether active air sampler monitoring sites are representative for atmospheric burdens within the larger geographical area targeted by the monitoring programs, and thus (ii) if the main sources affecting POPs in background air across a nation are understood. The main objective of this study was to explore the utility of spatial and temporal trends in concert with multiple modelling approaches to understand the main sources affecting polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in background air across a nation. For this purpose, a comprehensive campaign was carried out in summer 2016, measuring POPs in background air across Norway using passive air sampling. Results were compared to a similar campaign in 2006 to assess possible changes over one decade. We furthermore used the Global EMEP Multi-media Modeling System (GLEMOS) and the Flexible Particle dispersion model (FLEXPART) to predict and evaluate the relative importance of primary emissions, secondary emissions, long-range atmospheric transport (LRAT) and national emissions in controlling atmospheric burdens of PCB-153 on a national scale. The concentrations in air of both PCBs and most of the targeted OCPs were generally low, with the exception of hexachlorobenzene (HCB). A limited spatial variability for all POPs in this study, together with predictions by both models, suggest that LRAT dominates atmospheric burdens across Norway. Model predictions by the GLEMOS model, as well as measured isomeric ratios, further suggest that LRAT of some POPs are dictated by secondary emissions. Our results illustrate the utility of combining observations and mechanistic modelling approaches to help identify the main factors affecting atmospheric burdens of POPs across a nation, which, in turn, may be used to inform both national monitoring and control strategies.

Tetranuclear Lanthanide Complexes Containing a Hydrazone-type Ligand. Dysprosium [2 × 2] Gridlike Single-Molecule Magnet and Toroic.

A multidentate hydrazone-type ligand (Z,Z)-bis(1-(pyridin-2-yl)-1-amino-methylidene)oxalohydrazide (H2L) was utilized in the synthesis of three new isomorphous tetranuclear complexes of the general formula [Ln4(HL)4(H2L)2(NO3)4](NO3)4·4CH3OH (Ln = GdIII, 1, TbIII, 2, DyIII, 3) with the gridlike [2 × 2] topology. The analysis of the static magnetic data revealed weak anti-ferromagnetic interaction among lanthanide(III) atoms, whereas dynamic magnetic data led to the observation of the single-molecule magnet behavior in zero static magnetic field for the Dy4 compound 3 with Ueff = 42.6 K and τ0 = 1.50 × 10-5 s. The theoretical CASSCF calculations supported also the presence of the net toroidal magnetic moment, which classifies compound 3 also as a single-molecule toroic.

Assessing polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in air across Latin American countries using polyurethane foam disk passive air samplers.

A passive air sampling network has been established to investigate polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) at Global Atmospheric Passive Sampling (GAPS) sites and six additional sites in the Group of Latin American and Caribbean Countries (GRULAC) region. The air sampling network covers background, agricultural, rural, and urban sites. Samples have been collected over four consecutive periods of 6 months, which started in January 2011 [period 1 (January to June 2011), period 2 (July to December 2011), period 3 (January to June 2012), and period 4 (July 2012 to January 2013)]. Results show that (i) the GAPS passive samplers (PUF disk type) and analytical methodology are adequate for measuring PCDD/F burdens in air and (ii) PCDD/F concentrations in air across the GRULAC region are widely variable by almost 2 orders of magnitude. The highest concentrations in air of Σ4-8PCDD/Fs were found at the urban site São Luis (Brazil, UR) (i.e., 2560 fg/m3) followed by the sites in São Paulo (Brazil, UR), Mendoza (Argentina, RU), and Sonora (Mexico, AG) with values of 1690, 1660, and 1610 fg/m3, respectively. Very low concentrations of PCDD/Fs in air were observed at the background site Tapanti (Costa Rica, BA), 10.8 fg/m3. This variability is attributed to differences in site characteristics and potential local/regional sources as well as meteorological influences. The measurements of PCDD/Fs in air agree well with model-predicted concentrations performed using the Global EMEP Multimedia Modeling System (GLEMOS) and emission scenario constructed on the basis of the UNEP Stockholm Convention inventory of dioxin and furan emissions.

Lanthanide(III) SMMs with cationic and anionic complex fragments formed by a Schiff base: structure, luminescence, magnetic properties and ab initio calculations.

The syntheses, structures, luminescence and magnetic properties of a new series of Ln(III) complexes of the formula [Ln(L)(H2O)2(DMF)2][Ln(L)2] (in which H2L is N,N'-ethylaminebis[1-phenyl-3-methyl-4-formylimino-2-pyrazoline-5-one]; Ln(III) - Gd (1), Tb (2), or Dy (3) ions). The crystal structures were determined by single-crystal X-ray diffraction measurements for all the above-mentioned complexes. The crystals of these compounds consist of cationic [Ln(L)(H2O)2(DMF)2]+ and anionic [Ln(L)2] moieties which form a 3D supramolecular architecture by the H-bonds and electrostatic forces. Luminescence emission in the visible range was observed for Tb(III) and Dy(III) compounds upon ligand sensitization, with moderate quantum yields of 3.2% for the Dy complex and 24.2% for the Tb analogue. Moreover the Tb(III) complex demonstrates triboluminescence activity. The dynamic magnetization studies revealed that 1 and 2 demonstrate field-induced magnetic relaxation with effective energy barriers, ΔE|kB = 24 K (for 1) and 85 K (for 2), while the Dy complex 3 exhibits slow relaxation of magnetization in zero field with an activation energy of 256 K.

Zinc Complexes of Fluorosubstituted N-[2-(Phenyliminomethyl)phenyl]-4-methylbenzenesulfamides: Synthesis, Structure, Luminescent Properties, and Biological Activity.

Mono-, di-, and trifluorophenyl substituted in different positions of amine fragments bis [2-[[(E)-((fluorophenyl)iminomethyl]-N-(p-tolylsulfonyl)anilino]zinc(II) complexes were synthesized. Their crystal structure, photo- and electroluminescent properties, and protistocidal, fungistatic, and antibacterial activities were studied. It has been shown that the introduction of fluorine atoms and an increase in their number in the ligand structure of the resulting metal complexes promote the luminescence quantum yields and values of performance and brightness in EL cells compared to their previously studied chlorine-substituted analogs.

Photo- and electroluminescent properties europium complexes using bistriazole ligands.

Luminescent properties of two heteroleptic dibenzoylmethanate europium(III) complexes with 1,3-bis(5-pyridin-2-yl-1,2,4-triazol-3-yl)propane (H2L1) and 1,4-bis(5-pyridin-2-yl-1,2,4-triazol-3-yl)butane (H2L2) as ancillary ligands are described. The two double-layer-type electroluminescent cells with the structures: (1) ITO/NPB(40 nm)/Eu(DBM)2HL1 (40 nm)/LiF (1 nm)/Al (100 nm) and (2) ITO/NPB(40 nm)/Eu(DBM)2HL2 (40 nm)/LiF (1 nm)/Al (100 nm) emit red light originating from the europium complexes. The device 2 gives the maximum brightness of 455 cd/m2 at 19.2 V.

Synthesis, structure and luminescence studies of Eu(III), Tb(III), Sm(III), Dy(III) cationic complexes with acetylacetone and bis(5-(pyridine-2-yl)-1,2,4-triazol-3-yl)propane.

Studies concerning synthesis, structure and luminescence of eight-coordinate Eu, Tb, Sm and Dy complexes of the type [Ln(acac)2(L)]Cl (Hacac = pentanedione-2,4 and L = bis(5-(pyridine-2-yl)-1,2,4-triazol-3-yl)propane) are reported in detail. The obtained complexes were investigated by various means including elemental- and thermogravimetric analysis, IR- and electron transition spectroscopy. The structure of the Tb complex was determined by single-crystal X-ray crystallography: Tb is eight-coordinate, and L acting only as a tetradentate chelate together with two bidentate acac ligands. Photophysical studies of the complexes were carried out. The Tb(III) and Eu(III) complexes show strong emissions both in solid state and solution. The intensity of the luminescence of Dy(III) and Sm(III) are relatively weak. The factors determining the intensity of the photoluminescence are discussed.

Anionic lanthanide complexes with 3-methyl-1-phenyl-4-formylpyrazole-5-one and hydroxonium as counter ion.

A series of [H3O]+[LnL4]-·nH2O complexes (n = 1-3, Ln = Nd, (1), Sm (2), Eu (3), Tb (4); HL = 3-methyl-1-phenyl-4-formylpyrazole-5-one) were synthesized and characterized. The structures of the SmIII and EuIII complexes were investigated by X-ray diffraction. The isostructutal crystalls 2 and 3 consist the tetrakis [LnL4]- anions which are linked by H-bonding with the hydroxonium counter-ion and water molecules. The lanthanide ion is situated in the center of distorted tetragonal antiprism formed by eight oxygen atoms of 4-formyl-5-hydroxypyrazolonate anions. The TbIII and SmIII complexes show strong luminescence in solid state, whereas the EuIII and NdIII complexes show low luminescence activity.

Mononuclear copper(I) complexes bearing a 3-phenyl-5-(pyridin-4-yl)-1,2,4-triazole ligand: synthesis, crystal structure, TADF-luminescence, and mechanochromic effects.

Three new mononuclear heteroleptic copper(I) halide complexes, [CuL(PPh3)2X] (X = Cl, Br, I), based on 3-phenyl-5-(pyridin-4-yl)-1,2,4-triazole (L) and triphenylphosphine (PPh3) ligands, have been prepared by reaction of CuX (X = Cl, Br, I), L and PPh3 in a molar ratio of 1 : 1 : 2 in MeCN solutions. The synthesized complexes exhibit blue light emission in solutions and bright green emission in the crystal state with quantum yields of up to 100%. The luminescence decay analysis and density functional theory calculations revealed that the emission of solid samples at room temperature corresponds to the thermally activated delayed fluorescence, while that at 77 K is assigned to phosphorescence. Utilizing the studied complexes in OLED heterostructures resulted in high-performing green-emitting devices with an external quantum efficiency of up to 13.4%.

Structure and emission properties of dinuclear copper(i) complexes with pyridyltriazole.

A new series of five highly emissive binuclear heteroleptic pyridyltriazole-Cu(i)-phosphine complexes 1-5 was synthesized and examined by different experimental (IR, elemental and thermogravimetric analysis, single crystal X-ray diffraction technique, UV-vis and fluorescence spectroscopy) and quantum chemical aproaches. Complexes 1-5 exhibited excellent stimuli-responsive photoluminescent performance in the solid state at room temperature (quantum yield (QY) = 27.5-52.0%; lifetime (τ) = 8.3-10.7 µs) and when the temperature was lowered to 77 K (QY = 38.3-88.2; τ = 17.8-134.7 µs). The highest QY was examined for complex 3 (52%) that can be explained by the small structural changes between the ground S0 and exited S1 and T1 states leading to the small S1-T1 triplet gap and efficient thermally-activated delayed fluorescence. Moreover, complex 4 demonstrates reversible mechanochromic and excitation dependent luminescence.

Structural and photophysical studies on ternary Sm(III), Nd(III), Yb(III), Er(III) complexes containing pyridyltriazole ligands.

Two bidentate pyridine-triazole ligands (3-(pyridine-2-yl)-5-phenyl-1,2,4-triazole (L1) and 5-phenyl-2-(2'-pyridyl)-7,8-benzo-6,5-dihydro-1,3,6-triazaindolizine (L2)), have been synthesized and used for Ln(Dbm)3 (Ln = Sm(III), Nd(III), Yb(III) and Er(III)) coordination. The structures of the ligands and resulting Sm(III) complex were determined in the solid state by X-ray diffraction. The title complexes were characterized by UV, fluorescent, IR-spectroscopy and thermogravimetric and elemental analyses. Photophysical studies on the Ln(III) complexes were carried out showing luminescence in the region typical for Ln(III). The effect of various factors on the enhancement luminescence of complexes is discussed.

Tubular Duplication of the Esophagus in a Newborn, Treated by Thoracoscopy.

We present a case of tubular esophageal duplication in a 3-day-old female newborn (38 weeks, 2,500 g) without concomitant abnormal development. Esophageal duplication was diagnosed based on the clinical picture, direct laryngoscopy, esophagography and computed tomography. The duplicated esophagus was resected by thoracoscopy leaving the orthotopic esophagus in place. Isolation from the pharynx was performed via a separate cervical incision. After a follow-up period of 20 months, the child returned to normal growth and development.

Features of the Preparation and Luminescence of Langmuir-Blodgett Films Based on the Tb(III) Complex with 3-Methyl-1-phenyl-4-stearoylpyrazol-5-one and 2,2'-Bipyridine.

In this study, we investigated the effect of terbium ions (Tb3+) on the subphases of the limiting area of the molecule for the complex compound (CC) TbL3∙bipy (where HL is 3-methyl-1-phenyl-4-stearoylpyrazol-5-one and bipy is 2,2'-bipyridine). We examined the Langmuir monolayer and the change in the luminescence properties of TbL3∙bipy-based Langmuir-Blodgett films (LBFs). The analysis of the compression isotherms, infrared, and luminescence spectra of TbL3∙bipy LBFs was performed by varying the concentration of Tb3+ in the subphases. Our results demonstrate the partial dissociation of the CC at concentrations of C(Tb3+) < 5 × 10-4 M.

Clinical, Morphological, and Immunohistochemical Justification of Surgery for Chronic Appendicitis in Children.

Objective: Chronic appendicitis (CA) is a diagnosis characterized by long-standing right lower quadrant pain. We analyzed clinical, morphological, and immunohistochemical studies of the appendix to confirm the adequacy of surgery for CA in children with chronic right lower quadrant pain. Patients and Methods: We carried out comparative studies of clinical presentations and results of morphological and immunohistochemical studies of remote appendicitis in 55 children with chronic recurrent lower quadrant pain (CRLQP). Results: Morphological and immunohistochemical studies revealed three types of changes in the appendix. Type 1 (n = 21)-chronic inflammation. Inflammatory leukocyte infiltration was localized within the mucous membrane of the appendix. An immunohistochemical study revealed a significant (P < .01) increase in the expression of CD106 (vascular cell adhesion molecule 1) and in the number of matrix metalloproteinase 9 (MMP-9) positive cells. Type 2 (n = 20)-lymphoid hyperplasia. Morphological changes were characterized by lymphoid infiltration of the mucosa and submucosa of the appendix. Immunological changes were characterized by an increase (P < .01) in the expression and number of MMP-9, expression of CD106 positive cells, an increase in the expression of collagen IIIα in combination with a decrease in the expression and number of positive vascular endothelial growth factor (VEGF) and vasoactive intestinal peptide cells. Type 3 (n = 12)-catarrhal inflammation. Morphological changes were characterized by impaired blood circulation only in the mucous membrane, without destructive or inflammatory changes. Immunological changes were characterized by an increase (P < .01) in the expression and number of VEGF-positive cells, which may indicate a response to local hypoxia of the appendix and explain neovascularization in a chronic condition. The abdominal syndrome after appendectomy was noted to disappear in 89% of patients. The established changes in remote appendicitis, other than acute inflammation, make it possible to consider reasonable appendectomy a way of treating CRLQP in children. Conclusions: We have identified immunohistochemical and morphological changes pointing to autoimmune and vascular mechanisms of appendix damage in children with CRLQP. Laparoscopic appendectomy helps to eliminate abdominal pain in most CA patients.

Surgical Treatment of Patients with Full Tracheal Rings: Our Experience.

Introduction: Complete tracheal rings are a rare pathology occurring in 1 out of 100,000 live births. It is rare isolated tracheal or tracheobronchial anomaly resulting from abnormal cartilage growth, forming a complete ring, and leading to airway stenosis. A sliding tracheoplasty, primarily described by Tsang et al. and later widely presented by Grillo et al., overlaps the tracheal stenosing segments and shortens the trachea itself, and thus increases the diameter and circumference of the stenosing area double up. Materials and Methods: We have performed four slide tracheoplasties in the period between February 2019 and December 2020 in children who underwent medical treatment in the department of thoracic surgery in our center. Median age was 10 ± 5.5 months (2 months-1 year 6 months). Median weight was 6.9 ± 1.9 kg (4.5-9 kg). Slide tracheoplasty was performed using central venoarterial extracorporeal membrane oxygenation in 3 cases and using cardiopulmonary bypass in 1 case. Results: Patients were on artificial lung ventilation for 2-6 days in the postoperative period. Patients were discharged 14-18 days after the surgery. There were no lethal outcomes in our study. Discussion: Long segment congenital tracheal stenosis is an often and serious life-threatening anatomical malformation that bounded the length of trachea >50%. There is no unique treatment strategy for patients with such pathology. Sliding tracheoplasty can be recommended for all, but not for the shortest segments of stenosis, as it creates permissible voltage fluctuations during tracheal anastomosis. Excellent results in management of such severe patients can be achieved only through the collaboration of multidisciplinary team of specialists sharing organized and consistent patient-oriented approach.

The footprint of dioxins in globally traded pork meat.

The bioaccumulation of polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs), known as dioxins, in fatty meat is one of primary pathways of entry into the human body, but levels of human exposure to dioxins in fatty meat subject to global trade are unknown. We show high dioxin estimated dietary intake (EDI) via pork consumption in Europe, the United States, and China, owing to stronger dioxin environmental contamination and high pork consumption in these countries. The dioxin risk transfer embodied in pork trade is mostly significant in high-latitude countries and regions of Canada, Russia, and Greenland because these regions with low dioxin environmental levels import large amounts of pork meat from more severely dioxin-contaminated Europe and the United States. We demonstrate that global pig feed trading decreases the exposure of pork consumers to dioxins via the import of feed from countries with low dioxin environmental contamination by pig breeding countries.

Synthesis, Photoluminescence and Electrical Study of Pyrazolone-Based Azomethine Ligand Zn(II) Complexes.

New luminescent zinc complexes were obtained by reaction of pyrazolone-based azomethine ligands with Zn(CH3COO)2·2H2O. Complexes fully characterized by elemental analysis, FTIR, ES-MS, NMR, and single crystal X-ray analysis. Title complexes in the solid state demonstrate tunable luminescence from blue to orange by varying of substituents on the aromatic ring. Quantum yields are in the 0.03 to 0.49 range. TGA data shows that obtained complexes demonstrate high thermal stability and can be used as electroluminescent materials. The electrical properties of the complexes under study were considered in the ITO-Zncomplex-Al "sandwich" structure.

Structure and excitation-dependent emission of novel zinc complexes with pyridyltriazoles.

A series of Zn(ii) complexes with 5-(4-R-phenyl)-3-(pyridin-2-yl)-1,2,4-triazoles have been synthesized and subsequently characterized by single crystal X-ray diffraction, 1H-NMR, FT-IR spectroscopy, elemental analyses, ESI-MS, and PXRD. The X-ray diffraction analyses revealed that the complexes have a similar molecular structure and their supramolecular frameworks are constructed by hydrogen bonds and π⋯π interaction scaffolds. Upon irradiation with UV light, the studied complexes display deep blue emission at 396-436 nm in the solid state. The compounds show an unexpected excitation-dependent emission phenomenon which is detected by a change in the emission color (from blue to yellow) upon increase of the excitation wavelength. The conducted quantum-chemical calculations indicate that supramolecular differences in the single-crystal architecture of the synthesized complexes play a crucial role for this photophysical behaviour.