Diphenyltin(IV) complexes of the 2-quinolinecarboxaldehyde Schiff bases of S-methyl- and S-benzyldithiocarbazate (Hqaldsme and Hqaldsbz): X-ray crystal structures of Hqaldsme and two conformers of its diphenyltin(IV) complex

New organometallic tin(IV) complexes of the empirical formula Sn(NNS)Ph2Cl (NNS = anionic forms of the 2-quinolinecarboxaldehyde Schiff bases of S-methyl- and S-benzyldithiocarbazate) have been prepared and characterized by IR, electronic, I H NMR and ES mass spectroscopic techniques. The molecular structures of the 2-quinolinecarboxaldehyde Schiff base of S-methyldithiocarbazate (Hqaldsme) and its diphenyltin(IV) complex, Sn(qaldsme)Ph2Cl, have been determined by X-ray diffraction. In the solid state, the ligand remains as the thione tautomer in which the dithiocarbazate chain adopts an E,E configuration and is almost coplanar with the quinoline ring. The Sn(qaldsme)Ph2Cl complex crystallizes in two distinctly different conformationally isomeric forms, each having the same space group but different lattice parameters. X-ray analysis shows that in each polymorph, the tin atom adopts a distorted octahedral geometry with the Schiff base coordinated to it as a uninegatively charged tridentate chelating agent via the quinoline nitrogen atom, the azomethine nitrogen atom and the thiolate sulfur atom. The two phenyl groups occupy axial positions and the chloride ligand occupies the sixth coordination position of the tin atom. The deprotonated ligand adopts an E,E,Z configuration in the complex. (C) 2004 Elsevier Ltd. All rights reserved.

Crystal structure and magnetic behaviour of a five-coordinate iron(III) complex of pyridoxal-4-methylthiosemicarbazone

The crystal structure and magnetic properties of a penta-coordinate iron(III) complex of pyridoxal-4-methylthiosemicarbazone, [Fe(Hmthpy)Cl](CHCHSO), are reported. The synthesised ligand and the metal complex were characterised by spectroscopic methods (H NMR, IR, and mass spectroscopy), elemental analysis, and single crystal X-ray diffraction. The complex crystallises as dark brown microcrystals. The crystal data determined at 100(1) K revealed a triclinic system, space group P over(1, ¯) (Z = 2). The ONSCl geometry around the iron(III) atom is intermediate between trigonal bipyramidal and square pyramidal (t = 0.40). The temperature dependence of the magnetic susceptibility (5-300 K) is consistent with a high spin Fe(III) ion (S = 5/2) exhibiting zero-field splitting. Interpretation of these data yielded: D = 0.34(1) cm and g = 2.078(3). © 2007 Elsevier B.V. All rights reserved.

Caesium bis­(5-bromo­salicyl­aldehyde thio­semicarbazonato-κ3O,N,S)ferrate(III): supramolecular arrangement of low-spin FeIII complex anions mediated by Cs+ cations

The synthesis and crystal structure determination (at 293 K) of the title complex, Cs[Fe(C8H6BrN3OS)2], are reported. The compound is composed of two dianionic O,N,S-tridentate 5-bromo­salicyl­aldehyde thio­semicarbazonate(2-) ligands coord­inated to an FeIII cation, displaying a distorted octa­hedral geometry. The ligands are orientated in two perpendicular planes, with the O- and S-donor atoms in cis positions and the N-donor atoms in trans positions. The complex displays inter­molecular N-H...O and N-H...Br hydrogen bonds, creating R44(18) rings, which link the FeIII units in the a and b directions. The FeIII cation is in the low-spin state at 293 K.

Compositional Geometry and Programming

Report published in the Proceedings of the National Conference on "Education and Research in the Information Society", Plovdiv, May, 2014

Geochemistry of sheeted dike complex minerals of ODP Hole 140-504B

Diabases were recovered during Legs 137 and 140 at Hole 504B from depths between 1621.5 and 2000.4 meters below seafloor in the lower sheeted dike complex. The samples contain multiple generations of millimetric to centimetric veins. The orientation of the measured veins suggests that two main vein sets exist: one characterized by shallow dipping and the other by random trend. Thermal contraction during rock cooling is considered the main mechanism responsible for fracture formation. Vein infill is related to the circulation of hydrothermal fluids near the spreading axis. Some veins are surrounded by millimeter-sized alteration halos due to fluid percolation from the fractures through the host rock. Vein-filling minerals are essentially amphibole, chlorite, and zeolites. Amphibole composition is controlled by the microstructural site of the rock. Actinolite is the main amphibole occurring in the veins and also in the groundmass away from the halos. In the alteration halos, amphibole shows composition of actinolitic hornblende and Mg-hornblende. Late-stage tension gashes and interstitial spaces in some amphibole-bearing veins are filled with zeolites, suggesting that the veins likely suffered multiple opening stages that record the cooling history of the circulating fluids. Evidence of deformation recorded by the recovered samples seems to be restricted to veins that clearly represent elements of weakness of the rock. On the basis of vein geometry and microstructure we infer structural interpretations for the formation mechanism and for deformation of veins.

Mechanical properties and cellular response of novel electrospun nanofibers for ligament tissue engineering: Effects of orientation and geometry

Electrospun nanofibers are a promising material for ligamentous tissue engineering, however weak mechanical properties of fibers to date have limited their clinical usage. The goal of this work was to modify electrospun nanofibers to create a robust structure that mimics the complex hierarchy of native tendons and ligaments. The scaffolds that were fabricated in this study consisted of either random or aligned nanofibers in flat sheets or rolled nanofiber bundles that mimic the size scale of fascicle units in primarily tensile load bearing soft musculoskeletal tissues. Altering nanofiber orientation and geometry significantly affected mechanical properties; most notably aligned nanofiber sheets had the greatest modulus; 125% higher than that of random nanofiber sheets; and 45% higher than aligned nanofiber bundles. Modifying aligned nanofiber sheets to form aligned nanofiber bundles also resulted in approximately 107% higher yield stresses and 140% higher yield strains. The mechanical properties of aligned nanofiber bundles were in the range of the mechanical properties of the native ACL: modulus=158±32MPa, yield stress=57±23MPa and yield strain=0.38±0.08. Adipose derived stem cells cultured on all surfaces remained viable and proliferated extensively over a 7 day culture period and cells elongated on nanofiber bundles. The results of the study suggest that aligned nanofiber bundles may be useful for ligament and tendon tissue engineering based on their mechanical properties and ability to support cell adhesion, proliferation, and elongation.

Advanced numerical modeling of masonry vaulted structures based on BIM parametric geometry generation

Vaults are an architectural element which during construction history have been built with a great variety of different materials, shapes, and sizes. The shape of these structural elements was often dependent by the necessity to cover complex spaces, by the needed loading capacity, or by architectural aesthetics. Within this complex scenario masonry patterns generates also different effects on loading capacity, load percolation and stiffness of the structure. These effects were been extensively investigated, both with empirical observations and with modern numerical methods. While most of them focus on analyzing the load bearing capacity or the texture effect on vaulted structures, the aim of this analysis is to investigate on the effects of the variation of a single structural characteristic on the load percolation in the vault. Moreover, an additional purpose of the work is related to the coding of a parametrical model aiming at generating different masonry vaulted structures. Nevertheless, proposed script can generate different typology of vaulted structure basing on some structural characteristics, such as the span and the length to cover and the dimensions of the blocks.

Flow of Complex Fluids in Geological Fractures

In this study, the lubrication theory is used to model flow in geological fractures and analyse the compound effect of medium heterogeneity and complex fluid rheology. Such studies are warranted as the Newtonian rheology is adopted in most numerical models because of its ease of use, despite non-Newtonian fluids being ubiquitous in subsurface applications. Past studies on Newtonian and non-Newtonian flow in single rock fractures are summarized in Chapter 1. Chapter 2 presents analytical and semi-analytical conceptual models for flow of a shear-thinning fluid in rock fractures having a simplified geometry, providing a first insight on their permeability. in Chapter 3, a lubrication-based 2-D numerical model is first implemented to solve flow of an Ellis fluid in rough fractures; the finite-volumes model developed is more computationally effective than conducting full 3-D simulations, and introduces an acceptable approximation as long as the flow is laminar and the fracture walls relatively smooth. The compound effect of shear-thinning fluid nature and fracture heterogeneity promotes flow localization, which in turn affects the performance of industrial activities and remediation techniques. In Chapter 4, a Monte Carlo framework is adopted to produce multiple realizations of synthetic fractures, and analyze their ensemble statistics pertaining flow for a variety of real non-Newtonian fluids; the Newtonian case is used as a benchmark. In Chapter 5 and Chapter 6, a conceptual model of the hydro-mechanical aspects of backflow occurring in the last phase of hydraulic fracturing is proposed and experimentally validated, quantifying the effects of the relaxation induced by the flow.

Albumin Is Synthesized In Epididymis And Aggregates In A High Molecular Mass Glycoprotein Complex Involved In Sperm-egg Fertilization.

The epididymis has an important role in the maturation of sperm for fertilization, but little is known about the epididymal molecules involved in sperm modifications during this process. We have previously described the expression pattern for an antigen in epididymal epithelial cells that reacts with the monoclonal antibody (mAb) TRA 54. Immunohistochemical and immunoblotting analyses suggest that the epitope of the epididymal antigen probably involves a sugar moiety that is released into the epididymal lumen in an androgen-dependent manner and subsequently binds to luminal sperm. Using column chromatography, SDS-PAGE with in situ digestion and mass spectrometry, we have identified the protein recognized by mAb TRA 54 in mouse epididymal epithelial cells. The ∼65 kDa protein is part of a high molecular mass complex (∼260 kDa) that is also present in the sperm acrosomal vesicle and is completely released after the acrosomal reaction. The amino acid sequence of the protein corresponded to that of albumin. Immunoprecipitates with anti-albumin antibody contained the antigen recognized by mAb TRA 54, indicating that the epididymal molecule recognized by mAb TRA 54 is albumin. RT-PCR detected albumin mRNA in the epididymis and fertilization assays in vitro showed that the glycoprotein complex containing albumin was involved in the ability of sperm to recognize and penetrate the egg zona pellucida. Together, these results indicate that epididymal-derived albumin participates in the formation of a high molecular mass glycoprotein complex that has an important role in egg fertilization.

Effects Of Partial Inhibition Of Respiratory Complex I On H2o 2 Production By Isolated Brain Mitochondria In Different Respiratory States.

The aim of this work was to characterize the effects of partial inhibition of respiratory complex I by rotenone on H2O2 production by isolated rat brain mitochondria in different respiratory states. Flow cytometric analysis of membrane potential in isolated mitochondria indicated that rotenone leads to uniform respiratory inhibition when added to a suspension of mitochondria. When mitochondria were incubated in the presence of a low concentration of rotenone (10 nm) and NADH-linked substrates, oxygen consumption was reduced from 45.9 ± 1.0 to 26.4 ± 2.6 nmol O2 mg(-1) min(-1) and from 7.8 ± 0.3 to 6.3 ± 0.3 nmol O2 mg(-1) min(-1) in respiratory states 3 (ADP-stimulated respiration) and 4 (resting respiration), respectively. Under these conditions, mitochondrial H2O2 production was stimulated from 12.2 ± 1.1 to 21.0 ± 1.2 pmol H2O2 mg(-1) min(-1) and 56.5 ± 4.7 to 95.0 ± 11.1 pmol H2O2 mg(-1) min(-1) in respiratory states 3 and 4, respectively. Similar results were observed when comparing mitochondrial preparations enriched with synaptic or nonsynaptic mitochondria or when 1-methyl-4-phenylpyridinium ion (MPP(+)) was used as a respiratory complex I inhibitor. Rotenone-stimulated H2O2 production in respiratory states 3 and 4 was associated with a high reduction state of endogenous nicotinamide nucleotides. In succinate-supported mitochondrial respiration, where most of the mitochondrial H2O2 production relies on electron backflow from complex II to complex I, low rotenone concentrations inhibited H2O2 production. Rotenone had no effect on mitochondrial elimination of micromolar concentrations of H2O2. The present results support the conclusion that partial complex I inhibition may result in mitochondrial energy crisis and oxidative stress, the former being predominant under oxidative phosphorylation and the latter under resting respiration conditions.

A New Platinum Complex With Tryptophan: Synthesis, Structural Characterization, Dft Studies And Biological Assays In Vitro Over Human Tumorigenic Cells.

A new platinum(II) complex with the amino acid L-tryptophan (trp), named Pt-trp, was synthesized and characterized. Elemental, thermogravimetric and ESI-QTOF mass spectrometric analyses led to the composition [Pt(C11H11N2O2)2]⋅6H2O. Infrared spectroscopic data indicate the coordination of trp to Pt(II) through the oxygen of the carboxylate group and also through the nitrogen atom of the amino group. The (13)C CP/MAS NMR spectroscopic data confirm coordination through the oxygen atom of the carboxylate group, while the (15)N CP/MAS NMR data confirm coordination of the nitrogen of the NH2 group to the metal. Density functional theory (DFT) studies were applied to evaluate the cis and trans coordination modes of trp to platinum(II). The trans isomer was shown to be energetically more stable than the cis one. The Pt-trp complex was evaluated as a cytotoxic agent against SK-Mel 103 (human melanoma) and Panc-1 (human pancreatic carcinoma) cell lines. The complex was shown to be cytotoxic over the considered cells.

Management of a complex dentoalveolar trauma: a case report

This paper describes the case of a 12-year-old male patient who presented a severe lateral luxation of the maxillary central incisors due to a bicycle fall. Treatment involved suture of the soft tissues lacerations, and repositioning and splinting of the injured teeth, followed by endodontic treatment and periodontal surgery. After a 2-year follow-up, clinical and radiographic evaluation revealed that the incisors presented satisfactory esthetic and functional demands.

Rhinometric evaluation of nasal cavity geometry and its relation to the upper arch transverse distance

The objective of this study was to evaluate children's respiratory patterns in the mixed dentition, by means of acoustic rhinometry, and its relation to the upper arch width development. Fifty patients were examined, 25 females and 25 males with mean age of eight years and seven months. All of them were submitted to acoustic rhinometry and upper and lower arch impressions to obtain plaster models. The upper arch analysis was accomplished by measuring the interdental transverse distance of the upper teeth, deciduous canines (measurement 1), deciduous first molars (measurement 2), deciduous second molars (measurement 3) and the first molars (measurement 4). The results showed that an increased left nasal cavity area in females means an increased interdental distance of the deciduous first molars and deciduous second molars and an increased interdental distance of the deciduous canines, deciduous first and second molars in males. It was concluded that there is a correlation between the nasal cavity area and the upper arch transverse distance in the anterior and mid maxillary regions for both genders.

Overview of the taxonomy and of the major secondary metabolites and their biological activities related to human health of the Laurencia complex (Ceramiales, Rhodophyta) from Brazil

In Brazil, the Laurencia complex is represented by twenty taxa: Laurencia s.s. with twelve species, Palisada with four species (including Chondrophycus furcatus now that the proposal of its transference to Palisada is in process), and Osmundea and Yuzurua with two species each. The majority of the Brazilian species of the Laurencia complex have been phylogenetically analyzed by 54 rbcL sequences, including five other Rhodomelacean species as outgroups. The analysis showed that the Laurencia complex is monophyletic with high posterior probability value. The complex was separated into five clades, corresponding to the genera: Chondrophycus, Laurencia, Osmundea, Palisada, and Yuzurua. A bibliographical survey of the terpenoids produced by Brazilian species showed that only six species of Laurencia and five of Palisada (including C. furcatcus) have been submitted to chemical analysis with 48 terpenoids (47 sesquiterpenes and one triterpene) isolated. No diterpenes were found. Of the total, 23 sesquiterpenes belong to the bisabolane class and eighteen to the chamigrene type, whose biochemical precursor is bisabolane, two are derived from lauranes and four are triquinols. Despite the considerable number of known terpenes and their ecological and pharmacological importance, few experimental biological studies have been performed. In this review, only bioactivities related to human health were considered.