Computational Study of the Fe(CN)(2)CO Cofactor and Its Binding to HypC Protein.

In the intricate maturation process of [NiFe]-hydrogenases, the Fe(CN)2CO cofactor is first assembled in a HypCD complex with iron coordinated by cysteines from both proteins and CO is added after ligation of cyanides. The small accessory protein HypC is known to play a role in delivering the cofactor needed for assembling the hydrogenase active site. However, the chemical nature of the Fe(CN)2CO moiety and the stability of the cofactor–HypC complex are open questions. In this work, we address geometries, properties, and the nature of bonding of all chemical species involved in formation and binding of the cofactor by means of quantum calculations. We also study the influence of environmental effects and binding to cysteines on vibrational frequencies of stretching modes of CO and CN used to detect the presence of Fe(CN)2CO. Carbon monoxide is found to be much more sensitive to sulfur binding and the polarity of the medium than cyanides. The stability of the HypC–cofactor complex is analyzed by means of molecular dynamics simulation of cofactor-free and cofactor-bound forms of HypC. The results show that HypC is stable enough to carry the cofactor, but since its binding cysteine is located at the N-terminal unstructured tail, it presents large motions in solution, which suggests the need for a guiding interaction to achieve delivery of the cofactor.

Identification of the overtone of the Fe-CO stretching mode in heme proteins: a probe of the heme active site.

Two CO-isotope sensitive lines have been detected in the overtone region of the resonance Raman spectra of CO-bound hemeproteins. One line is assigned as the overtone of the Fe-CO stretching mode and is located in the 1000- to 1070-cm-1 region. The other line is found in the 1180- to 1210-cm-1 region and is assigned as a combination between a porphyrin mode, nu 7, and the Fe-CO stretching mode. The high intensities of these lines, which in the terminal oxidase class of proteins are of the same order as those of the fundamental stretching mode, indicate that the mechanism of enhancement for modes involving the Fe-CO moiety is different from that for the modes of the porphyrin macrocycle and call for reexamination of Raman theory of porphyrins as applied to axial ligands. The anharmonicity of the electronic potential function was evaluated, revealing that in the terminal oxidases the anharmonicity is greater than in the other heme proteins that were examined, suggesting a distinctive interaction of the bound CO with its distal environment in this family. Furthermore, the anharmonicity correlates with the frequency of the C-O stretching mode, demonstrating that both of these parameters are sensitive to the Fe-CO bond energy. The overtone and combination lines involving the bound CO promise to be additional probes of heme protein structural properties.

Discovery of "isolated" co-moving T Tauri stars in Cepheus

Context. During the course of a large spectroscopic survey of X-ray active late-type stars in the solar neighbourhood, we discovered four lithium-rich stars packed within just a few degrees on the sky. Although located in a sky area rich in CO molecular regions and dark clouds, the Cepheus-Cassiopeia complex, these very young stars are projected several degrees away from clouds in front of an area void of interstellar matter. As such, they are very good "isolated" T Tauri star candidates. Aims. We present optical observations of these stars conducted with 1-2 m class telescopes. We acquired high-resolution optical spectra as well as photometric data allowing us to investigate in detail their nature and physical parameters with the aim of testing the "runaway" and "in-situ" formation scenarios. Their kinematical properties are also analyzed to investigate their possible connection to already known stellar kinematic groups. Methods. We use the cross-correlation technique and other tools developed by us to derive accurate radial and rotational velocities and perform an automatic spectral classification. The spectral subtraction technique is used to infer chromospheric activity level in the Hα line core and clean the spectra of photospheric lines before measuring the equivalent width of the lithium absorption line. Results. Both physical (lithium content, chromospheric, and coronal activities) and kinematical indicators show that all stars are very young, with ages probably in the range 10-30 Myr. In particular, the spectral energy distribution of TYC4496-780-1 displays a strong near-and far-infrared excess, typical of T Tauri stars still surrounded by an accretion disc. They also share the same Galactic motion, proving that they form a homogeneous moving group of stars with the same origin. Conclusions. The most plausible explanation of how these "isolated" T Tauri stars formed is the "in-situ" model, although accurate distances are needed to clarify their connection with the Cepheus-Cassiopeia complex. The discovery of this loose association of "isolated" T Tauri stars can help to shed light on atypical formation processes of stars and planets in low-mass clouds.

Adolescent Trajectories of Depressive Symptoms : co-development of Behavioral and Academic Problems

Purpose: Increasing evidence suggests the existence of heterogeneity in the development of depressive symptoms during adolescence, but little remains known regarding the implications of this heterogeneity for the development of commonly co-occurring problems. In this study, we derived trajectories of depressive symptoms in adolescents and examined the codevelopment of multiple behavioral and academic problems in these trajectories. Methods: Participants were 6,910 students from secondary schools primarily located in disadvantaged areas of Quebec (Canada) who were assessed annually from the age 12 to 16 years. Trajectories were identified using growth mixture modeling. The course of behavioral (delinquency, substance use) and academic adjustment (school liking, academic achievement) in trajectories was examined by deriving latent growth curves for each covariate conditional on trajectory membership. Results: We identified five trajectories of stable-low (68.1%), increasing (12.1%), decreasing (8.7%), transient (8.7%), and stable-high (2.4%) depressive symptoms. Examination of conditional latent growth curves revealed that the course of behavioral and academic problems closely mirrored the course of depressive symptoms in each trajectory. Conclusions: This pattern of results suggests that the course of depressive symptoms and other adjustment problems over time is likely to involve an important contribution of shared underlying developmental process(es).

Adolescent Trajectories of Depressive Symptoms : co-development of Behavioral and Academic Problems

Purpose: Increasing evidence suggests the existence of heterogeneity in the development of depressive symptoms during adolescence, but little remains known regarding the implications of this heterogeneity for the development of commonly co-occurring problems. In this study, we derived trajectories of depressive symptoms in adolescents and examined the codevelopment of multiple behavioral and academic problems in these trajectories. Methods: Participants were 6,910 students from secondary schools primarily located in disadvantaged areas of Quebec (Canada) who were assessed annually from the age 12 to 16 years. Trajectories were identified using growth mixture modeling. The course of behavioral (delinquency, substance use) and academic adjustment (school liking, academic achievement) in trajectories was examined by deriving latent growth curves for each covariate conditional on trajectory membership. Results: We identified five trajectories of stable-low (68.1%), increasing (12.1%), decreasing (8.7%), transient (8.7%), and stable-high (2.4%) depressive symptoms. Examination of conditional latent growth curves revealed that the course of behavioral and academic problems closely mirrored the course of depressive symptoms in each trajectory. Conclusions: This pattern of results suggests that the course of depressive symptoms and other adjustment problems over time is likely to involve an important contribution of shared underlying developmental process(es).

Description and chemical composition of manganese nodules in a core located in the Nares Abyssal Plain, Atlantic Ocean

Three nodules from a core taken north of Puerto Rico are composed chiefly of an x-ray amorphous, hydrated, iron-manganese oxide, with secondary goethite, and minor detrital silicates incorporated during growth of the nodules. No primary manganese mineral is apparent. The nodules are enriched in iron and depleted in manganese relative to Atlantic Ocean averages. The formation of these nodules appears to have been contemporary with sedimentation and related to volcanic activity.

Holes, contours and surfaces : located, machined, ground, and inspected by precision methods /

Includes Woodworth circular tables.

Orbit and altimetric corrections for the ERS satellites through analysis of single and dual satellite crossovers

Due to the failure of PRARE the orbital accuracy of ERS-1 is typically 10-15 cm radially as compared to 3-4cm for TOPEX/Poseidon. To gain the most from these simultaneous datasets it is necessary to improve the orbital accuracy of ERS-1 so that it is commensurate with that of TOPEX/Poseidon. For the integration of these two datasets it is also necessary to determine the altimeter and sea state biases for each of the satellites. Several models for the sea state bias of ERS-1 are considered by analysis of the ERS-1 single satellite crossovers. The model adopted consists of the sea state bias as a percentage of the significant wave height, namely 5.95%. The removal of ERS-1 orbit error and recovery of an ERS-1 - TOPEX/Poseidon relative bias are both achieved by analysis of dual crossover residuals. The gravitational field based radial orbit error is modelled by a finite Fourier expansion series with the dominant frequencies determined by analysis of the JGM-2 co-variance matrix. Periodic and secular terms to model the errors due to atmospheric density, solar radiation pressure and initial state vector mis-modelling are also solved for. Validation of the dataset unification consists of comparing the mean sea surface topographies and annual variabilities derived from both the corrected and uncorrected ERS-1 orbits with those derived from TOPEX/Poseidon. The global and regional geographically fixed/variable orbit errors are also analysed pre and post correction, and a significant reduction is noted. Finally the use of dual/single satellite crossovers and repeat pass data, for the calibration of ERS-2 with respect to ERS-1 and TOPEX/Poseidon is shown by calculating the ERS-1/2 sea state and relative biases.

Location and ages of terrestrial peatlands located on continental shelves and in coastal sediments

This synthesis dataset contains records of freshwater peat and lake sediments from continental shelves and coastal areas. Information included is site location (when available), thickness and description of terrestrial sediments as well as underlying and overlying sediments, dates (when available), and references.

Spatiotemporal control over the co-conformational switching in pH-responsive flavylium-based multistate pseudorotaxanes

A multistate molecular dyad containing flavylium and viologen units was synthesized and the pH dependent thermodynamics of the network completely characterized by a variety of spectroscopic techniques such as NMR, UV-vis and stopped-flow. The flavylium cation is only stable at acidic pH values. Above pH ≈ 5 the hydration of the flavylium leads to the formation of the hemiketal followed by ring-opening tautomerization to give the cis-chalcone. Finally, this last species isomerizes to give the trans-chalcone. For the present system only the flavylium cation and the trans-chalcone species could be detected as being thermodynamically stable. The hemiketal and the cis-chalcone are kinetic intermediates with negligible concentrations at the equilibrium. All stable species of the network were found to form 1 : 1 and 2 : 1 host : guest complexes with cucurbit[7]uril (CB7) with association constants in the ranges 10(5)-10(8) M(-1) and 10(3)-10(4) M(-1), respectively. The 1 : 1 complexes were particularly interesting to devise pH responsive bistable pseudorotaxanes: at basic pH values (≈12) the flavylium cation interconverts into the deprotonated trans-chalcone in a few minutes and under these conditions the CB7 wheel was found to be located around the viologen unit. A decrease in pH to values around 1 regenerates the flavylium cation in seconds and the macrocycle is translocated to the middle of the axle. On the other hand, if the pH is decreased to 6, the deprotonated trans-chalcone is neutralized to give a metastable species that evolves to the thermodynamically stable flavylium cation in ca. 20 hours. By taking advantage of the pH-dependent kinetics of the trans-chalcone/flavylium interconversion, spatiotemporal control of the molecular organization in pseudorotaxane systems can be achieved.

Co-occurrence of Helicobacter pylori with faecal bacteria in Nairobi river basin: public health implications.

Introduction: Overwhelming evidence implicates Helicobacter pylori (H. pylori) as an etiologic agent of gastrointestinal diseases including gastric cancer. The mode of transmission of this pathogen remains poorly understood. Objective: This investigation is to establish the presence of H. pylori in the waters of the Nairobi river basin and the predictive value the presence of fecal indicator bacteria would have for H. pylori. Methodology: Physical, chemical and biological assessment of water quality of rivers in Nairobi were carried out using standard methods. H. pylori DNA in water was detected using highly specific primers of glmM gene (294pb). Results: There was high presence of faecal bacteria in the waters sampled. H. pylori DNA was detected in two domestic wells and one river. The wells were located in two different regions of the water basin but influenced by similar human activities. Conclusion: The high presence of faecal bacteria in the waters sampled did not parallel the H. pylori detection in the same waters. H. pylori was detected in the Nairobi river basin, but there was no relationship between the numerical levels of fecal bacteria and H. pylori.

Gonadal Hormones Modulate The Responsiveness To Local β-blocker-induced Antinociception In The Temporomandibular Joint Of Male And Female Rats.

We have previously demonstrated that blockade of β-adrenoreceptors (β-AR) located in the temporomandibular joint (TMJ) of rats suppresses formalin-induced TMJ nociceptive behaviour in both male and female rats, but female rats are more responsive. In this study, we investigated whether gonadal hormones modulate the responsiveness to local β-blocker-induced antinociception in the TMJ of rats. Co-administration of each of the selective β1 (atenolol), β2 (ICI 118.551) and β3 (SR59230A)-AR antagonists with equi-nociceptive concentrations of formalin in the TMJ of intact, gonadectomized and hormone-treated gonadectomized male and female rats. Atenolol, ICI 118.551 and SR59230A significantly reduced formalin-induced TMJ nociception in a dose response fashion in all groups tested. However, a lower dose of each β-AR antagonist was sufficient to significantly reduce nociceptive responses in gonadectomized but not in intact and testosterone-treated gonadectomized male rats. In the female groups, a lower dose of β1 -AR antagonist was sufficient to significantly reduce nociceptive responses in gonadectomized but not in intact or gonadectomized rats treated with progesterone or a high dose of oestradiol; a lower dose of β2 -AR antagonist was sufficient to significantly reduce nociceptive responses in gonadectomized but not in intact and gonadectomized rats treated with low or high dose of oestradiol. Gonadal hormones may reduce the responsiveness to local β-blocker-induced antinociception in the TMJ of male and female rats. However, their effect depends upon their plasma level, the subtype of β-AR and the dose of β-blockers used.

Estudo inicial da degradação in vivo de poli(L-co-D,L ácido lático), sintetizado em laboratório, aplicado como prótese tibial em coelhos

The copolymer poly (L-co-D,L lactic acid), PLDLA, has gained prominence in the field of temporary prostheses due to the fact that their time of degradation is quite compatible with the requirement in the case of osseous fracture. In this work the in vivo degradation of devices from copolymer, as a system of plates and screws, used in fixation of the tibia of rabbits was studied. The devices were implanted in 15 adult rabbits, albinos, New Zealand race, and they were used as control devices of alloys of titanium (Ti-6Al-4V/ V grade). The use of copolymers, synthesized in the laboratory, was tested in the repair of fracture in rabbits'tibias, being assessed in the following times: 2 weeks, 2 months and 3 months. Morphological analysis of tissue surrounding the plate and screw system, for 2 weeks of implantation, showed the presence of osteoblasts, indicating a pre bone formation. After 2 months there was new bone formation in the region in contact with the polymer. This bone growth occurred simultaneously with the process of PLDLA degradation, invading the region where there was polymer and after 3 months there was an intense degradation of the copolymer and hence greater tissue invasion compared to 2 months which characterized bone formation in a region where the polymer degraded. The in vivo degradation study of the devices for PLDLA by means of histological evaluations during the period of consolidation of the fracture showed the efficiency of plate and screw system, and it was possible to check formation of bone tissue at the implantation site, without the presence of inflammatory reaction

Cation size effects-modified phase and PTCR development in Er3+ and Ca2+ co-doped BaTiO3 ceramics during sintering

Development of the positive temperature coefficient of resistivity (PTCR) in Er3+ and Ca2+ co-doped ferroelectric BaTiO3 was studied in this work, with Er3+ being used to act as a donor doping. Irrespective of all the materials showing high densities after sintering at 1200 to 1300 ºC, these revealed insulator at the lowest sintering temperature, changing to semiconducting and PTCR-type materials only when the sintering temperature was further increased. Observations from X-ray diffraction help correlating this effect with phase development in this formulated (Ba,Ca,Er)TiO3 system, considering the formation of initially two separated major (Ba,Ca)TiO3- and minor (Ca,Er)TiO3-based compounds, as a consequence of cation size-induced stress energy effects. Thus, appearance and enhancement here of the semiconducting and PTCR responses towards higher sintering temperatures particularly involve the incorporation of Er3+ into the major phase, rendering finally possible the generation and "percolative-like" migration of electrons throughout the whole material.

Óxidos do tipo perovskita para reação de redução de no com CO

In this work, the perovskite-type oxides LaNiO3, LaMnO3, La0,7Sr0,3NiO3 and La0,7Sr0,3MnO3 were prepared by co-precipitation and tested in the NO reduction with CO at 400 and 500 ºC for 10 h. The catalysts were characterized by X-ray diffraction, temperature programmed reduction with hydrogen, nitrogen adsorption and chemical analysis. The nonstoichiometric oxygen was quantified by temperature programmed reduction, and the catalytic tests showed that the La0,7Sr0,3MnO3 catalyst presented the higher performance for the reduction reaction of NO with CO. The partial substitution of lanthanum by strontium increased the NO conversion and the N2 yield.