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The purpose of the study was to evaluate the influence of extremities length improvement in the form of special shoe orthoses on the walking energy cost of the leading Polish representative in race walking. Before a proper study, the aerobic capacity of the subject was evaluated. The test consisted of two walking efforts performed on a mechanical treadmill. The subject was walking for 12 minutes with shoe orthoses at constant speed (12 km/h) and then the rest phase allowed for the total covering of the oxygen debt. Then the trial was repeated without orthoses. Simultaneously with measuring physiological variables, there was made 3D recording of the athlete's movements on the treadmill applying the Vicon system. There were chosen vertical oscillations of the body center of gravity and work of the subject's system of motion connected with kinetic and potential energy changes regarding the movements of COM during gait. The energy cost of walking at speed related to anaerobic threshold (starting) using shoe orthoses was slightly lower compared to energy expenditure during gait without improvement. No significant differences were noticed in the range of summary vertical COM oscillations during walking in both variants of the measurement. However, considerable asymmetries appeared in the value of COM kinetic energy changes that were lower for the right leg. This testifies to a strongly fixed asymmetrical scheme of individual athlete's technique.
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PMID:The evaluation of energy cost of effort and changes of centre of mass (COM) during race walking at starting speed after improving the length of lower extremities. 1842 44

The new cerium(III), lanthanum(III) and neodymium(III) complexes were synthesized in view of their application as cytotoxic agents. The complexes were characterized by different physicochemical methods: elemental analysis, mass spectrometry, (1)H NMR, (13)C NMR and IR spectroscopy. The spectra of the complexes were interpreted on the basis of comparison with the spectrum of the free ligand. The vibrational analysis showed that in the complexes the ligand coordinates to the metal ion through both deprotonated hydroxyl groups, however participation of the carbonyl groups in the coordination to the metal ion was also suggested. Geometry optimization of 3,3'-(ortho-pyridinomethylene)di-[4-hydroxycoumarin] H(2)(o-pyhc), (H(2)L) and its dianionic forms, o-pyhc(2-), (L(2-)) were carried out at AM1 and PM3 levels as well as using density functional theory with Becke's three parameter hybrid method and correlation functional of Lee, Yang and Parr (B3LYP) with 6-31G(d) basis set. The optimized geometries of the neutral ligand isomers were stabilized by two asymmetrical intramolecular O-H...O hydrogen bonds (HBs). The conformational search showed four low-energy dianionic species (o-pyhc(2-)) on the potential energy surface. Molecular electrostatic potential calculations showed that the most preferred sites for electrophilic attack in H(2)(o-pyhc) and o-pyhc(2-) are the carbonyl oxygen atoms. The evaluation of the cytotoxic activity of the novel lantanide complexes on HL-60 myeloid cells revealed, that they are potent cytotoxic agents. The cerium complex was found to exhibit superior activity in comparison to the lanthanum, and neodymium species, the latter being the least active. Taken together our data give us a reason to conclude that the newly synthesized lanthanide complexes should be a subset to further more detailed pharmacological and toxicological evaluation.
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PMID:Theoretical, spectral characterization and antineoplastic activity of new lanthanide complexes. 1856 22

We report a case of repair of the postinfarction ventricular septal perforation (VSP), using an equine pericardium tailored in an asymmetrical conical shape for exclusion (modified sack technique) and an additional direct patch closure of VSP. An asymmetrical conical patch is easily sutured to the normal septum away from the VSP edge by using the longer part of the cone border. The postoperative left ventriculogram 1.5 months after surgery revealed a minor leakage from the patch to the excluded left ventricle. However, no residual left to the right shunt was found in calculation from the oxygen saturation in blood samples. Echocardiography 1 year after surgery showed no residual patch leakage at all. We suggest that this modified sack technique is a simple and easy method by which to exclude the VSP.
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PMID:Repair of ventricular septal perforation with asymmetrical conical patch exclusion. 1857 2

Reactive nitrogen oxygen species (RNOS) contribute to the deleterious effects attributed to reacting with biomolecules. The mechanisms of the nitration and nitrosation of dimethylamine (DMA), which is the simplest secondary amine by N2O4, a member of RNOS, have been investigated at the CBS-QB3 level of theory. The nitration and nitrosation proceed via different pathways. The nitration of DMA follows three pathways. The first is the abstraction of the hydrogen atom of the amino group of DMA by the NO2 radical followed by a recombination reaction of the resulting aminyl radical with another NO2 radical. The second is DMA directly reacting with symmetrical O2NNO2 leading to dimethylnitramine via a concerted and a stepwise mechanism. The third is the reaction of DMA with asymmetrical ONONO2. By computation, the main pathway for the formation of dimethylnitramine in the gas phase is by DMA directly reacting with asymmetrical ONONO2. As to the nitrosation, a concerted mechanism for the reaction of DMA with asymmetrical ONONO2 plays a major role in nitrosodimethylamine (NDMA) formation. In addition, the solvent effect on these nitration and nitrosation reactions has been also studied by using the implicit polarizable continuum model. Two major pathways of the formation of dimethylnitramine in water were found, and they are the radical process involving NO2 and the concerted mechanism starting from symmetrical O2NNO2. The result of the nitrosation of DMA in water is consistent with that in the gas phase. Comparison of the energy barriers of each mechanism leads to the conclusion that the nitrosation is more favorable than the nitration in the reaction of DMA with N2O4. This conclusion is in good agreement with the experimental results. The results obtained here will help elucidate the mechanism of the lesions of biomolecules by RNOS.
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PMID:Theoretical investigation of nitration and nitrosation of dimethylamine by N2O4. 1861 60

The bacterial phosphotriesterase (PTE) from Pseudomonas diminuta catalyzes the hydrolysis of organophosphate esters at rates close to the diffusion limit. X-ray diffraction studies have shown that a binuclear metal center is positioned in the active site of PTE and that this complex is responsible for the activation of the nucleophilic water from solvent. In this paper, the three-dimensional structure of PTE was determined in the presence of the hydrolysis product, diethyl phosphate (DEP), and a product analogue, cacodylate. In the structure of the PTE-diethyl phosphate complex, the DEP product is found symmetrically bridging the two divalent cations. The DEP displaces the hydroxide from solvent that normally bridges the two divalent cations in structures determined in the presence or absence of substrate analogues. One of the phosphoryl oxygen atoms in the PTE-DEP complex is 2.0 A from the alpha-metal ion, while the other oxygen is 2.2 A from the beta-metal ion. The two metal ions are separated by a distance of 4.0 A. A similar structure is observed in the presence of cacodylate. Analogous complexes have previously been observed for the product complexes of isoaspartyl dipeptidase, d-aminoacylase, and dihydroorotase from the amidohydrolase superfamily of enzymes. The experimentally determined structure of the PTE-diethyl phosphate product complex is inconsistent with a recent proposal based upon quantum mechanical/molecular mechanical simulations which postulated the formation of an asymmetrical product complex bound exclusively to the beta-metal ion with a metal-metal separation of 5.3 A. This structure is also inconsistent with a chemical mechanism for substrate hydrolysis that utilizes the bridging hydroxide as a base to abstract a proton from a water molecule loosely associated with the alpha-metal ion. Density functional theory (DFT) calculations support a reaction mechanism that utilizes the bridging hydroxide as the direct nucleophile in the hydrolysis of organophosphate esters by PTE.
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PMID:Structure of diethyl phosphate bound to the binuclear metal center of phosphotriesterase. 1870 30

Chiral pesticides with an asymmetrical center in their molecular structures possess enantioselectivity, not only in their pesticidal activities toward targeted organisms but also in toxicities to nontargeted organisms. Despite the fact that chiral pesticides deserve particular attention because of their ubiquitous presence in living and working environments, there has been limited research into their enantioselectivity in chronic toxicity. The immunotoxicity of chiral pesticides with respect to enantioselectivity has not been studied before. In this study, the role of enantioselectivity in the immunotoxicity of acetofenate (AF), an organochlorine insecticide, was investigated in an in vitro macrophage cell line model. Results of the cytotoxicity assay showed a clear dose-dependent growth inhibition effect of AF with enantioselectivity on RAW264.7 cells. S-(+)-AF was clearly more toxic to macrophages than R-(-)-AF and rac-AF. This work also demonstrated that S-(+)-AF possesses the strongest effects in induction of intracellular reactive oxygen species, DNA damage, and upregulation of p53 gene expression. These results, for the first time, show stark selectivity between enantiomers in their ability to induce macrophage-involved immunotoxicity of AF. These results suggest that assessment of the environmental safety and health risk of chiral contaminants should consider the role of enantioselectivity in immunotoxicity. In addition, our study will improve the knowledge of the role of enantioselectivity in immunotoxicity of chiral contaminants.
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PMID:Enantioselectivity in the immunotoxicity of the insecticide acetofenate in an in vitro model. 1893 38

Potentiometric titrations of metal ions with EDTA have been carried out with a platinum or graphite electrode and the Fe(III)/Fe(II) redox system. In the absence of oxygen and for pH < 2 the titration curves may be described by an equation similar to that given previously for titrations with silver and mercury electrodes. Titration curves for bismuth and indium, which are more strongly complexed than iron, are asymmetrical and useful for analytical purposes. When the titrated ions are complexed less strongly than iron(III) ions the kinetics of metal complexation have a pronounced effect. The titration curves of thorium and copper, which react more rapidly than iron, are analytically useful. The curves recorded rapidly after titrant additions have a better end-point break than those which correspond to thermodynamic equilibrium. When a metal, e.g., nickel, is weakly bound by EDTA, and reacts more slowly than iron, a very small end-point break or none at all is observed.
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PMID:Titration curves in complexometric titrations with the redox system Fe(III)/Fe(II). 1896 Aug 80

The oldest known fossil hominin in southern Asia was recovered from Hathnora in the Narmada Basin, central India in the early 1980's. Its age and taxonomic affinities, however, have remained uncertain. Current estimates place its maximum age at >236ka, but not likely older than the early middle Pleistocene. The calvaria, however, could be considerably younger. We report recent fieldwork at Hathnora and associated Quaternary type-sections that has provided new geological and archaeological insights. The portion of the exposed 'Boulder Conglomerate' within the Surajkund Formation, which forms a relict terrace and has yielded the hominin fossils, contains reworked and stylistically mixed lithic artifacts and temporally mixed fauna. Three mammalian teeth stratigraphically associated with the hominin calvaria were dated by standard electron spin resonance (ESR). Assuming an early uranium uptake (EU) model for the teeth, two samples collected from the reworked surface deposit averaged 49+/-1ka (83+/-2ka, assuming linear uptake [LU]; 196+/-7ka assuming recent uptake [RU]). Another sample recovered from freshly exposed, crossbedded gravels averaged 93+/-5ka (EU), 162+/-8ka (LU) or 407+/-21ka (RU). While linear uptake models usually provide the most accurate ages for this environment and time range, the EU ages represent the minimum possible age for fossils in the deposit. Regardless, the fossils are clearly reworked and temporally mixed. Therefore, the current data constrains the minimum possible age for the calvaria to 49+/-1ka, although it could have been reworked and deposited into the Hathnora deposit any time after 160ka (given the LU uptake ages) or earlier (given the RU ages). At Hathnora, carbonaceous clay, bivalve shells, and a bovid tooth recovered from layers belonging to the overlying Baneta Formation have yielded (14)C ages of 35.66+/-2.54cal ky BP, 24.28+/-0.39cal ky BP, and 13.15+/-0.34ky BP, respectively. Additional surveys yielded numerous lithics and fossils on the surface and within the stratigraphic sequence. At the foot of the Vindhyan Hills 2km from the river, we recovered a typologically Early Acheulean assemblage comprised of asymmetrical bifaces, large cleavers with minimal working, trihedral picks, and flake tools in fresh condition. These tools may be the oldest Acheulean in the Narmada Valley. Several lithics recovered from the Dhansi Formation may represent the first unequivocal evidence for an early Pleistocene hominin presence in India. In situ invertebrate and vertebrate fossils, pollen, and spores indicate a warm, humid climate during the late middle Pleistocene. High uranium concentrations in the mammalian teeth indicate exposure to saline water, suggesting highly evaporative conditions in the past. Late Pleistocene sediment dated between 24.28+/-0.39cal ky BP and 13.15+/-340ky BP has yielded pollen and spores indicating cool, dry climatic conditions corresponding to Oxygen Isotope Stage 2 (OIS 2). An early Holocene palynological assemblage from the type locality at Baneta shows evidence for relatively dry conditions and a deciduous forest within the region. The Dhansi Formation provisionally replaces the Pilikarar Formation as the oldest Quaternary formation within the central Narmada Basin. The Baneta Formation, previously dated at 70ka to 128ka, correlates with the late Pleistocene and early Holocene. Our results highlight the need for further Quaternary geological and paleoanthropological research within the Narmada Basin, especially because dam construction threatens these deposits.
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PMID:New geochronological, paleoclimatological, and archaeological data from the Narmada Valley hominin locality, central India. 1911 67

Dinucleoside polyphosphates (Np(n)N's; where N and N' are nucleosides and n = 3-6 phosphate residues) are naturally occurring compounds that may act as signaling molecules. One of the most successful approaches to understand their biological functions has been through the use of Np(n)N' analogs. Here, we present the results of studies using novel diadenosine polyphosphate analogs, with an oxymethylene group replacing one or two bridging oxygen(s) in the polyphosphate chain. These have been tested as potential substrates and/or inhibitors of the symmetrically acting Ap(4)A hydrolase [bis(5'-nucleosyl)-tetraphosphatase (symmetrical); EC 3.6.1.41] from E. coli and of two asymmetrically acting Ap(4)A hydrolases [bis(5'-nucleosyl)-tetraphosphatase (asymmetrical); EC 3.6.1.17] from humans and narrow-leaved lupin. The six chemically synthesized analogs were: ApCH(2)OpOCH(2)pA (1), ApOCH(2)pCH(2)OpA (2), ApOpCH(2)OpOpA (3), ApCH(2)OpOpOCH(2)pA (4), ApOCH(2)pOpCH(2)OpA (5) and ApOpOCH(2)pCH(2)OpOpA (6). The eukaryotic asymmetrical Ap(4)A hydrolases degrade two compounds, 3 and 5, as anticipated in their design. Analog 3 was cleaved to AMP (pA) and beta,gamma-methyleneoxy-ATP (pOCH(2)pOpA), whereas hydrolysis of analog 5 gave two molecules of alpha,beta-oxymethylene ADP (pCH(2)OpA). The relative rates of hydrolysis of these analogs were estimated. Some of the novel nucleotides were moderately good inhibitors of the asymmetrical hydrolases, having K(i) values within the range of the K(m) for Ap(4)A. By contrast, none of the six analogs were good substrates or inhibitors of the bacterial symmetrical Ap(4)A hydrolase.
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PMID:Novel diadenosine polyphosphate analogs with oxymethylene bridges replacing oxygen in the polyphosphate chain: potential substrates and/or inhibitors of Ap4A hydrolases. 1921 May 43

Plants survive against myriad environmental odds while remaining rooted to a single spot. The time scale over which plant cells can respond to environmental cues is seldom appreciated. Fluorescent protein-assisted live imaging of peroxisomes reveals that they respond within seconds of exposure to hydrogen peroxide and hydroxyl radicals by producing dynamic extensions called peroxules. Observations of the Arabidopsis flu mutant and treatments with xenobiotics eliciting singlet oxygen and superoxide reactive oxygen species suggest that the observed responses are specific for hydroxyl radicals. Prolonged exposure to hydroxyl radicals inhibits peroxule extension, and instead causes motile and spherical peroxisomes in a cell to become immotile and elongate several-fold. Expression of photo-convertible EosFP-PTS1 demonstrates that vermiform peroxisomes result from rapid stretching of individual peroxisomes, while the subsequent 'beads-on-a-string' morphology results from differential protein distribution within an elongated tubule. Over time, the beads in elongated peroxisomes also extend peroxules randomly before undergoing asynchronous, asymmetrical fission. Peroxule extension does not appear to involve cytoskeletal elements directly, but is closely aligned with and reflects the dynamics of ER tubules. Peroxisomal responses reveal a rapidly invoked subcellular machinery that is involved in recognition of hydroxyl stress thresholds, and its possible remediation locally through extension of peroxules or globally by increasing peroxisome numbers. A matrix protein retro-flow mechanism that supports peroxisome-ER connectivity in plant cells is suggested.
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PMID:Peroxule extension over ER-defined paths constitutes a rapid subcellular response to hydroxyl stress. 1982 Mar 26


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