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Complexes of chlorogenic acid (5-CQA) with copper(II) and iron(III) were synthesized in a solid state and examined by means of FT-IR, thermogravimetric, and elemental analyses. The molar stoichiometric ratios of metal:ligand for the solid forms of the complexes were established as Cu(II):L = 1:2 and Fe(III):L = 2:3 (L: 5-CQA), with the possible coordination through the carboxylate group and the hydroxyl group from the catechol moiety. In an aqueous solution at pH = 7.4, the composition of the complexes was Cu(II):L = 1:1, and Fe(III):L = 1:1 and 1:2. The Cu(II) and Fe(III) complexes with 5-CQA showed lower antioxidant properties, as estimated by the spectrophotometric methods with DPPH•, ABTS•+, and HO• radicals, than the ligand alone, whereas in the lipid peroxidation inhibition assay, the metal complexes revealed a higher antioxidant activity than 5-CQA. Cu(II) 5-CQA showed the highest pro-oxidant activity in the Trolox oxidation assays compared to the other studied compounds. The lipophilic parameters of the compounds were estimated using the HPLC method. 5-CQA and its complexes with Fe(III) and Cu(II) were not toxic to HaCaT cells in a tested concentration range of 0.15–1000 nM after a 24 h incubation time.

Solvothermal reactions of lanthanide (III) salts with 1,2-phenylenediacetic acid in N,N′-dimethylformamide (DMF) solvent lead to the formation of the metal complexes of the general formula Ln2(1,2-pda)3(DMF)2, where Ln(III) = Pr(1), Sm(2), Eu(3), Tb(4), Dy(5), and Er(6), 1,2-pda=[C6H4(CH2COO)2]2−. The compounds were characterized by elemental analysis, powder and single-crystal X-ray diffraction methods, thermal analysis methods (TG-DSC and TG-FTIR), infrared and luminescence spectroscopy. They exhibit structural similarity in the two groups (Pr, Sm, and Eu, Tb, Dy, and Er), which was reflected in their thermal behaviours and spectroscopic properties. Single-crystal X-ray diffraction studies reveal that Sm(2) and Eu(3) complexes form 2D coordination polymers with four crystallographically independent metal centers. Every second lanthanide ion is additionally coordinated by two DMF molecules. The 1,2-phenylenediacetate linker shows different denticity being: penta- and hexadentate while carboxylate groups exhibit bidentate-bridging, bidentate-chelating, and three-dentate bridging-chelating modes. The infrared spectra reflect divergence between these two groups of complexes. The complexes of lighter lanthanides contain in the structure coordinated DMF molecules, while in the structures of heavier complexes, DMF molecules appear in the inner and outer coordination sphere. Both carboxylate groups are deprotonated and engaged in the coordination of metal centers but in different ways in such groups of complexes. In the groups, the thermal decomposition of the isostructural complexes occurs similarly. Pyrolysis of complexes takes place with the formation of such gaseous products as DMF, carbon oxides, ortho-xylene, ethers, water, carboxylic acids, and esters. The complexes of Eu and Tb exhibit characteristic luminescence in the VIS region, while the erbium complex emits NIR wavelength.

Four isostructural lanthanide coordination polymers of the formula [Ln2(1,3-pda)3(H2O)]·H2O where Ln = Gd(1), Dy(2), Er(3), Lu(4) and 1,3-pda = 1,3-phenylenediacetate were hydrothermally synthesized and characterized by vibrational spectroscopy, thermal analysis, powder and single-crystal X-ray diffraction methods. All 1,3-phenylenediacetates act as μ4-linkers and connect the eight-coordinate lanthanide ions into the 3-D coordination networks. Carboxylate groups in the ligands molecules exhibit diverse conformations: both trans or trans and cis. Changes of Ln–O bond lengths among the investigated compounds point out to the lanthanide contraction. Infrared and Raman spectra confirmed that both carboxylic groups of ligand were deprotonated. The presence of the band of non-hydrogen bonded hydroxyl group from water molecule in the infrared spectra was discussed. Thermal behaviour of the complexes was investigated by the TG-DSC and TG-FTIR methods. The investigated complexes are thermally stable in air and nitrogen atmosphere up to 106–135 °C. Further heating of the complexes leads to dehydration and decomposition. Water, carbon oxides, m-xylene and methane are main volatile products of complexes thermal decomposition in nitrogen.

OBJECTIVE. To investigate rural-urban differences in severity of injuries, by means of age, sex and duration of hospitalization of injured children in northeastern Poland. METHODS. The study included children admitted to the Department of Pediatric Orthopaedics and Traumatology in between 2002-2005 (1322 patients) and 2012-2013 (1725 patients) due to injury. We applied the rural-urban division on the base of number of inhabitants (rural – below, urban – over 25000). We divided injuries into four categories based on severity. Statistical analysis was performed to compare the risk of hospitalization due to different types of injuries among children in different age and sex groups, living in rural and urban areas RESULTS. Children from urban areas have a higher risk of hospitalization compared to their peers living in rural areas due to two least severe categories of injuries. Children from rural areas had much higher risk of hospitalization due to most severe injuries. Results were consistent for both time intervals.. The average duration of hospitalization was significantly longer among rural populations. However, in both rural and urban areas the mean length of stay has been shortened in comparison with the years 2002-2005. The average age of urban patients has been reduced over the years and remained stable among rural population. In both groups boys comprised the majority of patients with all kinds of injuries. CONCLUSIONS. Analysis of the risk of hospitalization among children from rural and urban areas brings constructive conclusions only after applying the division based on severity of injuries. Children living in rural areas and small towns are at a higher risk of suffering severe injuries that pose a risk of permanent disability, and of longer hospitalization because of them, compared to children living in larger cities.

The structure of the Zn(II) complex of 5-caffeoylquinic acid (chlorogenic acid, 5-CQA) and the type of interaction between the Zn(II) cation and the ligand were studied by means of various experimental and theoretical methods, i.e., electronic absorption spectroscopy UV/Vis, infrared spectroscopy FT-IR, elemental, thermogravimetric and density functional theory (DFT) calculations at B3LYP/6-31G(d) level. DPPH (2,2-diphenyl-1-picrylhydrazyl), ABTS (2,2&prime, azino-bis(3-ethylbenzothiazoline-6-sulfonic acid), FRAP (ferric reducing antioxidant power), CUPRAC (cupric reducing antioxidant power) and trolox oxidation assays were applied in study of the anti-/pro-oxidant properties of Zn(II) 5-CQA and 5-CQA. The antimicrobial activity of these compounds against Escherichia coli, Pseudomonas aeruginosa, Bacillus subtilis, Staphylococcus aureus, Salmonella enteritidis and Candida albicans was tested. An effect of Zn(II) chelation by chlorogenic acid on the anti-/pro-oxidant and antimicrobial activities of the ligand was discussed. Moreover, the mechanism of the antioxidant properties of Zn(II) 5-CQA and 5-CQA were studied on the basis of the theoretical energy descriptors and thermochemical parameters. Zn(II) chlorogenate showed better antioxidant activity than chlorogenic acid and commonly applied natural (L-ascorbic acid) and synthetic antioxidants (butylated hydroxyanisol (BHA) and butylated hydroxytoluene (BHT)). The pro-oxidant activity of Zn(II) 5-CQA was higher than the ligand and increased with the rise of the compound concentration The type of Zn(II) coordination by the chlorogenate ligand strongly affected the antioxidant activity of the complex.

The DFT studies were carried out with the B3LYP method utilizing the 6-31G and 6-311++G(d,p) basis sets depending on whether the aim of calculations was to gain the geometry at equilibrium, or to calculate the optimized molecular structure of (benzylthio)acetic acid (Hbta) in the forms of monomer and dimer. The minimum conformational energy search was followed by the potential energy surface (PES) scan of all rotary bonds existing in the acid molecule. The optimized geometrical monomeric and dimeric structures of the title compound were compared with the experimental structural data in the solid state. The detailed vibrational interpretation of experimental infrared and Raman bands was performed on the basis of theoretically simulated ESFF-scaled wavenumbers calculated for the monomer and dimer structures of Hbta. The electronic characteristics of Hbta is also presented in terms of Mulliken atomic charges, frontier molecular orbitals and global reactivity descriptors. Additionally, the MEP and ESP surfaces were computed to predict coordination sites for potential metal complex formation.

The metal–organic frameworks of the formula Ln(bta)·nH2O where n = 3, 4, 5 or 6; bta = benzene-1,3,5-triacetate ion: [C9H9(COO)3]3−; Ln = La(III), Nd(III), Eu(III), Tb(III), Ho(III), Tm(III), Lu(III) were synthesized by the reaction of LnCl3·xH2O with ammonium salt of H3bta acid in water solution. Insoluble water compounds crystallize in the monoclinic or triclinic crystal system, and they are stable up to 30 °C. When heated, they decompose up to 160–200 °C in two stages to stable anhydrous compounds. The dehydrated compounds Ln(bta) are still crystalline and stable up to about 350 °C. When heated above 350 °C, they undergo decomposition where the intermediate products are Ln2O2CO3 or Tb4O6CO3 and the residues are: Ln2O3 or Tb4O7. The interpretation of IR spectra of title compounds was made taking into consideration the experimental and theoretical wavenumbers obtained for H3bta specie. The XPS spectra of H3bta and its complexes were recorded. The way of metal–carboxylate group of ligand coordination was discussed. This work presents the results of the XPS analyses, which allowed to determine the binding energies (E b) for the main lines of Ln3d, Ln4d, Ln5p, C1s, O1s spectra, spin–orbital splitting and full width at half maximum complexes.

(Benzylthio)acetic acid (Hbta) was synthesized with 78% yield from benzyl chloride and thiourea as substrates. Well-shaped crystals of Hbta were grown by slow solvent evaporation technique from pure methanol. The compound was investigated by single-crystal X-ray and powder diffraction techniques and was also characterized by other analytical methods, like ATR-FTIR, 1H and 13C NMR and TG/DSC. The acid molecule adopts bent conformation in the solid state. The crystal structure of Hbta is stabilized by numerous intermolecular interactions, including O–H···O, C–H···O, C–H···S and C–H···π contacts. Thermal decomposition of the obtained material takes place above 150 °C.

Autonomic nervous system of the pelvis is still poorly understood. Every year more and more pelvic procedures are carried out on patients suffering from different pelvic disorders what leads to numerous pelvic dysfunctions. Authors tried to review, starting from historical and clinical background, the most important reports on anatomy of the pelvic autonomic plexuses. We also pay attention to complete lack of knowledge of students of medicine on the autonomic nervous structures in the area studied. We present anatomical description of the pelvic plexuses including their visceral branches and anatomy of surrounding pelvic tissues which still remains unclear. More and more attention is paid to the topography of the plexuses specially because of new pain releasing techniques - neurolysies.

A novel 4,4′-disubstituted biphenyl derivative featuring two acetic acid side arms symmetrically attached to a biphenyl system, that is biphenyl-4,4′-diacetic acid (H2bpda), has been successfully synthesized by means of the three-stage organic strategy. The synthesis product was characterized by elemental analysis, various spectroscopic techniques including FT-IR, Raman, 1H and 13C NMR as well as thermogravimetric and TG–FT-IR coupled measurements. The phase purity of material was verified on the basis of the X-ray powder diffraction. The studied compound crystallizes in the monoclinic P21/c space group with half of the molecule in the asymmetric unit. Structural studies indicate intermolecular O H⋯O hydrogen bonding between the carboxylic groups of the adjacent molecules of H2bpda. The occurrence of intermolecularly associated carboxylic groups can also be clearly seen in the vibrational spectra of the acid. On thermal analysis both in air and nitrogen an anhydrous compound demonstrates considerable thermal stability.

The series of isostructural lanthanide coordination polymers with the empirical formula [Ln2(PDA)3(H2O)]·2H2O, where PDA = 1,4-phenylenediacetate anion = [C8H8(COO)2]2−; Ln = La-Lu(III), and Y(III) were produced in the reaction of LnCl3·nH2O with ammonium salt of 1,4-phenylenediacetic acid in water solution. The compounds were characterised structurally using powder X-ray diffraction, elemental and thermogravimetric analyses as well as FT-IR spectroscopy. Thermogravimetric analyses show that in the range 60–170 °C the dehydration process occurs. The thermal stability of dehydrated compounds, Ln2(PDA)3 increased from about 200–350 °C in the whole series of complexes. Single-crystal X-ray diffraction analysis for the Gd(III) complex revealed that the compound crystallizes in the monoclinic P21/c space group with a = 21.863(2) A, b = 10.035(1) A, c = 13.854(1) A, β = 91.53(1)° and V = 3,038.5(4) A3. The complex contains one-dimensional gadolinium-carboxylato chains, which are connected with the –CH2–C6H4–CH2– spacers of PDA ligand to the three-dimensional metal–organic framework.

The influence of synthesis conditions on the structural and thermal properties of solid lanthanide 1,2,3,4,5,6-benzenehexacarboxylates (mellitates) was investigated. The general formula of the complexes is Ln 2 (C 12 O 12 )· n H 2 O (where Ln = Nd(III) and Er(III), n = 10 for Nd, and n = 14 for Er – mild conditions; n = 6 for Nd and Er – hydrothermal synthesis). They were characterized by elemental analysis, X-ray diffraction methods, IR spectroscopy and thermal analysis methods (TG-DSC and TG-FTIR). The prepared complexes are crystalline but not isostructural. The IR spectra confirm deprotonation of all carboxylic groups in all investigated complexes. Their thermal stability as well as pathway of thermal decomposition differ significantly.

Pyridine-2,5-dicarboxylic acid, known as isocinchomeric acid is one of six isomers containing two carboxylic groups. Light lanthanide (III) complexes with pyridine-2,5-dicarboxylic acid with general formula Ln2L3·nH2O, where n = 8, 9, were obtained. Their thermal and spectroscopic properties were studied. Sodium salt was obtained as Na2L·H2O. Hydrated complexes of La(III), Ce(III), Pr(III), Nd(III), Sm(III), Eu(III) and Gd(III) are stable to 313–333 K, whereas Na2L·H2O is stable to about 333 K. Dehydration process for all compounds runs in one stage, next they decompose into appropriate lanthanide oxalates, oxocarbonates carbonates and finally to metal oxides. Bands of νCOOH vibrations at 1736 and 1728 cm−1 disappear on complex spectra and νas and νs of COO− groups appear thus indicating that complexation process took place.

The complexes of rare earth elements with 2,3-naphthalenedicarboxylic acid of the formula: Ln2(C12H6O4)3·nH2O, where Ln = La(III)-Lu(III) and Y(III); n = 3 for La(III), Ce(III); n = 6 for Pr(III)-Yb(III) and Y(III) and n = 5 for Lu(III) have been synthesized and characterized by elemental analysis, IR spectroscopy, thermal analysis (TG, DTG, DTA and TG-FTIR) and X-ray analysis. They are sparingly soluble in water and stable at room temperature. During heating in air atmosphere, they lose all water molecules in several steps, generally in two or three steps, except for the La(III) and Ce(III) complexes which lose all water molecules in one step. The anhydrous compounds are stable up to about 773 K and then decompose to corresponding oxides. The thermal decomposition is connected with the release of water molecules (443 K), carbon dioxide (713 K) and hydrocarbons.

Rare earth complexes with 2,2 0 -biphenyldi- carboxylic acid (diphenic acid = H2dpa) were obtained as hydrated precipitates of the general formula Ln2(C14H8O4)3� nH2O, where n = 3 for the of Y(III) and Ce(III)-Er(III) and n = 6 for La(III), Tm(III), Yb(III) and Lu(III) complexes. On heating in air atmosphere complexes lose all water molecules in the temperature range 30-210 C in one step and form anhydrous compounds, which are stable up to 315- 370 C. During further heating they decompose to oxides. The trihydrated compounds are crystalline powders whereas the hexahydrated are amorphous solids. The trihydrated complexes crystallize in the monoclinic (Pr(III) and Ce(III) complexes) and triclinic (Y(III) and Nd(III)-Er(III) com- plexes) crystal systems.

The study concerned the possibility of using superficial skeletal muscles of the thorax as a power source to a bio-pump used for supporting the hemodynamically insufficient heart muscle. Having thoroughly analyzed the topography, ways and sources of blood supply to the muscles, the pectoralis minor muscle was selected as the most suitable one for this purpose.

The aim of this study was to present review on pelvic plexuses in males and females with some referrals to clinical practice, specially to the methods including nerve stimulation.Anatomy of pelvic plexuses is still confusing. Much attention should be paid to further studies on the arrangement of pelvic plexuses specially because of nerve stimulation techniques.

The DFT calculations (B3LYP method with 6-311++G(d,p) mixed with LanL2DZ for transition metals basis sets) for different conformers of 2,5-dihydroxybenzoic acid (gentisic acid), sodium 2,5-dihydroxybenzoate (gentisate) and copper(II) and cadmium(II) gentisates were done. The proposed hydrated structures of transition metal complexes were based on the results of experimental findings. The theoretical geometrical parameters and atomic charge distribution were discussed. Moreover Na, Cu(II) and Cd(II) gentisates were synthesized and the composition of obtained compounds was revealed by means of elemental and thermogravimetric analyses. The FT-IR and FT-Raman spectra of gentisic acid and gentisates were registered and the effect of metals on the electronic charge distribution of ligand was discussed.

International audience; The molecular structure of Mn(II), Cu(II), Zn(II), Cd(II) and Ca(II) ferulates (4-hydroxy-3-methoxycinnamates) was studied. The selected metal ferulates were synthesized. Their composition was established by means of elementary and thermogravimetric analysis. The following spectroscopic methods were used: infrared (FT-IR), Raman (FT-Raman), nuclear magnetic resonance (13C, 1H NMR) and ultraviolet–visible (UV/VIS). On the basis of obtained results the electronic charge distribution in studied metal complexes in comparison with ferulic acid molecule was discussed. The microbiological study of ferulic acid and ferulates toward Escherichia coli, Bacillus subtilis, Candida albicans, Pseudomonas aeruginosa, Staphylococcus aureus and Proteus vulgaris was done.

The paper deals with anatomy of human cervical spine. It shows close relation between knowledge on the normal structure and methods of treatment of different kinds of spine injuries. It describes detailed anatomy and mechanical features of cervical vertebral column, including the structure of distinct vertebrae, their joints and arrangement of muscles. It reviews also historical methods of treatment of fractures in this region considering current methods.

Anatomical and clinical descriptions of variations in arteries are based solely on anatomical terminology. New diagnostic techniques depend on terms such as the anterior, posterior, superior, inferior, medial, and lateral location of arteries and their branches or bifurcations, trifurcations, and fenestrations. However, these methods may be obsolete and such a simplistic approach is inadequate, especially for procedures that require precise morphological and morphometrical descriptions in 3D space. This is critical for neruonavigational surgery and interventional vascular radiology.This paper presents a new system for the accurate location and description of structural variations in vessels which is based on the alpha, beta, and gamma direction cosines. The algorithm can be summarized in the following steps: acquisition of the point coordinates in 3D space, interpolation, recovery of the 3D point coordinates, and calculation of the interpolated trajectory.New parameters (cos alpha, beta, and gamma, the tortuous index TI, and the deviation index DI) were calculated for the spatial description of vessels.By using this new method, new vascular descriptive methods have been proposed. It is possible that new categories as well as vessel variations may be found. The curvature and tortuosity of the vascular segments can also be considered more effective when incorporated into the description of vessels, especially in cases where pathologies such as tumors have altered the vessel in some way.

The lanthanide biphenyl-4,4 0 -dicarboxylates (bpdc) series of the general formulae Ln2(bpdc)3� nH2O, where Ln = lanthanides from La(III) to Lu(III); bpdc = C12H5(COO)2- ; n = 4, 5 or 6 have been obtained by the conventional precipitation method. All prepared complexes were characterized by elemental analysis, simultaneous thermal analyses thermogravimetric-differential scanning calorimetry (TG-DSC) and TG-FT-IR, FT-IR, and FT- Raman spectroscopy as well as X-ray diffraction patterns measurements. In the whole series of analyzed complexes the bpdc 2- ligand is completely deprotonated. In view of that, four carboxylate oxygen atoms are engaged in the coordination of Ln(III) ions. The synthesized compounds are polycrystalline and insoluble in water. They crystallize in the low symmetry crystal systems, like monoclinic and triclinic. Heating in the air atmosphere resulted in the multi-steps decomposition process, namely endothermic dehydration and strong exothermic decomposition pro- cesses. The dehydration process leads to the formation of stable anhydrous Ln2bpdc3 compounds which subsequently decompose to the corresponding lanthanide oxides.

The reaction of sodium hydroxide with 2-aminoterephthalic acid leads to the formation of a complex of the general formula: [Na2(atpt)(H2O)5]·H2O, where atpt = [NH2C6H3(COO)2]2−. Sodium 2-aminoterephthalate was synthesized and characterized by single-crystal X-ray diffraction, FT-IR spectroscopy, thermal analysis and coupled TG–FT-IR technique. Crystallographic study of the sodium complex reveals that the compound crystallizes in the triclinic system, the space group P-1 with a = 7.983(3) A, b = 8.405(3) A, c = 11.311(5) A, α = 70.74(3)°, β = 76.57(3)°, γ = 83.12(3)° and V = 696.1(5) A3. On heating in air atmosphere the compound in question loses all water molecules in two steps in the temperature range 30–205 °C. The anhydrous form of the complex is stable up to 370 °C and then decomposes to sodium carbonate.