RESUMO
In this study we investigate the crystallographic structure of the Rh(1 0 0)-([Formula: see text])-2O phase by quantitative low energy electron diffraction (LEED) and scanning tunnelling microscopy as well as the energetics of the system applying density functional theory calculations (DFT). The ([Formula: see text]) structure forms upon exposing the clean Rh(1 0 0) surface to 1200 L of oxygen at 520 K. A full-dynamical LEED intensity analysis (Pendry R-factor [Formula: see text]) reveals an oxygen-induced shifted row-reconstruction of the rhodium top layer where every third Rh-row is displaced by half a surface lattice parameter along the [0 1 1]-direction. There are two oxygen atoms within the unit cell which assume threefold coordinated sites on both sides of the shifted Rh-row with one bond to the shifted and two bonds to the unshifted rows. DFT calculations yield a total energy gain of 0.27 eV per oxygen atom compared to adsorption on the unreconstructed surface. This by far overcompensates the energetic penalty of 0.10 eV per oxygen atom for shifting the Rh-row and thus drives the substrate reconstruction. A coadsorption of oxygen at remaining regular sites of the substrate is not observed in experiment and is found to be energetically unfavorable.
RESUMO
Female mice were immunized intravaginally with gonococcal outer membrane vesicles (OMVs) plus microencapsulated interleukin-12 (IL-12), and challenged using an established model of genital infection with Neisseria gonorrhoeae. Whereas sham-immunized and control animals cleared the infection in 10-13 days, those immunized with OMV plus IL-12 cleared infection with homologous gonococcal strains in 6-9 days. Significant protection was also seen after challenge with antigenically distinct strains of N. gonorrhoeae, and protective anamnestic immunity persisted for at least 6 months after immunization. Serum and vaginal immunoglobulin G (IgG) and IgA antibodies were generated against antigens expressed by homologous and heterologous strains. Iliac lymph node CD4+ T cells secreted interferon-γ (IFNγ), but not IL-4, in response to immunization, and produced IL-17 in response to challenge regardless of immunization. Antigens recognized by immunized mouse serum included several shared between gonococcal strains, including two identified by immunoproteomics approaches as elongation factor-Tu (EF-Tu) and PotF3. Experiments with immunodeficient mice showed that protective immunity depended upon IFNγ and B cells, presumably to generate antibodies. The results demonstrated that immunity to gonococcal infection can be induced by immunization with a nonliving gonococcal antigen, and suggest that efforts to develop a human vaccine should focus on strategies to generate type 1 T helper cell (Th1)-driven immune responses in the genital tract.
Assuntos
Vacinas Bacterianas/imunologia , Vesículas Extracelulares/metabolismo , Gonorreia/imunologia , Interleucina-12/imunologia , Neisseria gonorrhoeae/imunologia , Porinas/metabolismo , Células Th1/imunologia , Animais , Anticorpos Antivirais/sangue , Carga Bacteriana , Células Cultivadas , Modelos Animais de Doenças , Vesículas Extracelulares/imunologia , Feminino , Humanos , Imunização , Interferon gama/metabolismo , Ativação Linfocitária , Camundongos , Camundongos Endogâmicos BALB C , Camundongos Endogâmicos C57BL , Camundongos Transgênicos , Fator Tu de Elongação de Peptídeos/imunologia , Porinas/imunologiaRESUMO
Cobalt oxide nanomaterials show high activity in several catalytic reactions thereby offering the potential to replace noble metals in some applications. We have developed a well-defined model system for partially reduced cobalt oxide materials aiming at a molecular level understanding of cobalt-oxide-based catalysis. Starting from a well-ordered Co3O4(111) film on Ir(100), we modified the surface by deposition of metallic cobalt. Growth, structure, and adsorption properties of the cobalt-modified surface were investigated by scanning tunneling microscopy (STM), low-energy electron diffraction (LEED), and infrared reflection absorption spectroscopy (IRAS) using CO as a probe molecule. The deposition of a submonolayer of cobalt at 300 K leads to the formation of atomically dispersed cobalt ions distorting the surface layer of the Co3O4 film. Upon annealing to 500 K the Co ions are incorporated into the surface layer forming ordered two-dimensional CoO islands on the Co3O4 grains. At 700 K, Co ions diffuse from the CoO islands into the bulk and the ordered Co3O4(111) surface is restored. Deposition of larger amounts of Co at 300 K leads to formation of metallic Co aggregates on the dispersed cobalt phase. The metallic particles sinter at 500 K and diffuse into the bulk at 700 K. Depending on the degree of bulk reduction, extended Co3O4 grains switch to the CoO(111) structure. All above structures show characteristic CO adsorption behavior and can therefore be identified by IR spectroscopy of adsorbed CO.
RESUMO
Iron oxides play an increasingly prominent role in heterogeneous catalysis, hydrogen production, spintronics, and drug delivery. The surface or material interface can be performance-limiting in these applications, so it is vital to determine accurate atomic-scale structures for iron oxides and understand why they form. Using a combination of quantitative low-energy electron diffraction, scanning tunneling microscopy, and density functional theory calculations, we show that an ordered array of subsurface iron vacancies and interstitials underlies the well-known (â2 × â2)R45° reconstruction of Fe3O4(001). This hitherto unobserved stabilization mechanism occurs because the iron oxides prefer to redistribute cations in the lattice in response to oxidizing or reducing environments. Many other metal oxides also achieve stoichiometry variation in this way, so such surface structures are likely commonplace.
RESUMO
Epitaxial cobalt oxide films on Ir(100) exhibit a rich scenario of different structural phases which are reviewed in this paper. The great majority of phases could be, as a rare case, crystallographically described by the joint application of atomically resolved STM and quantitative LEED, whereby structural surprises were more the rule than the exception. So, the oxide grows in the polar (111) orientation for both the Co3O4 and CoO stoichiometry on the bare Ir substrate in spite of the latter's square symmetry. Moreover, the film orientation can be tuned to non-polar (100) growth when one or several pseudomorphic Co layers are introduced as an interface between oxide and Ir substrate. By using the nanostructured Ir(100)-(5 × 1)-H phase as a template a nanostructured Co film can be formed whose oxidation leads to a nanostructured oxide. The nominally polar films circumvent the polarity problem by appropriate surface terminations. That of CoO(111) is, again as a surprise, realized by a switch from rocksalt-type to wurtzite-type stacking near the surface, by which the latter becomes metallic. The stepwise oxidation of a pseudomorphic Co layer on the bare Ir substrate leads to the sequential formation of rocksalt-type tetrahedral Co-O building blocks (with intermediate BN-type blocks) whereby the Co species more and more assume positions determined by the inner-oxidic binding.
RESUMO
The usefulness of two quantitative real-time PCR assays (qrt-PCRmip targeting Legionella pneumophila, and qrt-PCR16S targeting all Legionella species) performed on lower respiratory tract (LRT) samples for diagnostic and prognostic purposes in 311 patients hospitalized for community-acquired pneumonia (CAP) in Rhône-Alpes (France) was evaluated. The Now Legionella urinary antigen test (UAT) from Binax (Portland, ME, USA) was used as a reference test. Samples were divided into two groups. Group A included 255 CAP patients admitted to Chambery hospital in 2005 and 2006. The Now Legionella UAT was positive in 14 patients. Sensitivities, specificities, positive predictive and negative predictive values for both qrt-PCR tests were 63.6, 98.7, 77.7 and 97.4%, respectively. Group B included 56 consecutive legionellosis patients diagnosed during a 4-year period (2003-2006) at the Grenoble University Hospital. The qrt-PCR16S and qrt-PCRmip displayed a sensitivity of 82.14 and 80.4%, respectively. Among the 70 legionellosis cases, L. pneumophila serogroup 1 was isolated in 15; qrt-PCRmip was positive in another 36, suggesting L. pneumophila infection, whereas the Legionella species involved could not be determined in the remaining 19 cases. The Legionella burden in LRT samples at the time of admission was determined in 46 patients using qrt-PCR16S tests, 44 for qrt-PCR mip groups A and B patients. It varied from 1.9 to 8.35 log(10) DNA copies/mL of LRT sample for qrt-PCR16S and from 1.9 to 8.11 log(10) DNA copies/mL of sample for qrt-PCRmip. High bacterial loads in LRT samples at hospital admission were significantly associated with higher Fine classes, the need for hospitalization in an intensive care unit and for prolonged hospitalization.
Assuntos
Legionelose/diagnóstico , Reação em Cadeia da Polimerase/métodos , Adolescente , Adulto , Idoso , Infecções Comunitárias Adquiridas/microbiologia , DNA Bacteriano/análise , Humanos , Legionella/genética , Pessoa de Meia-Idade , Pneumonia/microbiologia , Sensibilidade e Especificidade , Adulto JovemRESUMO
The stability of various point defects in NiAl(100) has been investigated by first-principles calculations. For Al-rich surfaces, Ni vacancies within the first Al layer are energetically most favourable. For Ni-rich surfaces, so-called double defects, consisting of both Ni-antisite atom in the first Al layer and a Ni vacancy within the second Ni layer, form the configuration of lowest energy, superior to singular Ni antisites. An additional and significant energy gain is found in both cases by mutual lateral interaction of the defects, when they are arranged in the diagonal direction. Respective [Formula: see text] ordered configurations were found as the most stable structures. A 50:50 mixture of both defect types turns out to be even lower in energy than the ideal Al-terminated NiAl(100) surface, proving the latter to be metastable only. This is in line with the often reported inability in experiments to prepare ideal NiAl(100) surfaces.
RESUMO
Cobalt oxides on the unreconstructed Ir(100) surface were prepared by reactive deposition of Co established by simultaneous oxygen flux at about 50 °C and subsequent annealing. The films were investigated by low-energy electron diffraction (LEED), scanning tunnelling microscopy (STM) and thermal desorption spectroscopy (TDS). We show that in spite of the quadratic unit mesh of the substrate, oxide films of (111) orientation develop. As long as oxygen-rich conditions are maintained they are of spinel-type Co(3)O(4)(111). They are non-pseudomorphic and transform to rocksalt-type CoO(111) when oxygen loss is induced by annealing at elevated temperatures. Thin films of CoO(111) are commensurate, and so, in order to realize that, they exhibit a slightly distorted unit cell when below a thickness equivalent to about seven cobalt monolayers. With increasing film thickness the uniaxial strain accompanied by the commensurability is gradually relieved by the insertion of dislocations so that eventually the film assumes ideal hexagonality. All CoO(111)-type surfaces are reconstructed at low sample temperatures equivalent to a [Formula: see text] superstructure. They reversibly transform into a (1 × 1) phase at about 50 °C.
RESUMO
A substoichiometric monolayer of cobalt oxide has been prepared by deposition and oxidation of slightly less than one monolayer of cobalt on the unreconstructed surface of Ir(100). The ultrathin film was investigated by scanning tunnelling microscopy (STM) and quantitative low-energy electron diffraction (LEED). The cobalt species of the film reside in or near hollow positions of the substrate with, however, unoccupied sites (vacancies) in a 3 × 3 arrangement. In the so-formed 3 × 3 supercell the oxide's oxygen species are both threefold and fourfold coordinated to cobalt, forming pyramids with a triangular and square cobalt basis, respectively. These pyramids are the building blocks of the oxide. Due to the reduced coordination as compared to the sixfold one in the bulk of rock-salt-type CoO, the Co-O bond lengths are smaller than in the latter. For the threefold coordination they compare very well with the bond length in oxygen terminated CoO(111) films investigated recently. The substoichiometric 3 × 3 oxide monolayer phase transforms to a stoichiometric c(10 × 2)-periodic oxide monolayer under oxygen exposure, in which, however, cobalt and oxygen species are in (111) orientation and so form a CoO(111) layer.
RESUMO
Cobalt oxide (CoO) films epitaxially grown on Ir(100) in (111) orientation were investigated by means of quantitative low-energy electron diffraction and scanning tunneling microscopy. We find with high crystallographic precision that in the bulk of the films the rocksalt structure prevails while near the surface there is a switch towards the wurtzite structure. As a consequence, nanosized CoO cannot be considered as a single structural phase. The film surfaces prove to be metallic, apparently connected with polarity compensation.
RESUMO
OBJECTIVE: Few studies have shown that aged packed red blood cells (RBC) transfusion negatively influenced the outcome of ICU patients, probably related to storage lesions which could be decreased by leukodepletion of RBC. The purpose of this study was to evaluate the impact of aged leukodepleted-RBC pack, on the outcome of ICU patients. DESIGN: Retrospective, observational, cohort study in a Medical Intensive Care Unit. PATIENTS: Consecutive patients admitted during the years 2005 and 2006, and requiring a transfusion. We recorded patient's demographic data, number of RBC unit and age of each RBC, length of ICU, mortality during ICU stay. RESULTS: Five hundred and thirty-four patients were included with global mortality was 26.6%, length of stay in ICU six days (3-14) and SAPS II 48 (35-62). RBC equaling to 5.9 were transfused per patients (22.7%<14 days and 57.3%<21 days). The number of RBC was significantly higher in the dead patients group, but the rate of RBC stored less than 21 days was not different (54% versus 60%; p=0.21). In a multivariate logistic model, independent predictors of ICU death were SAPS II (OR=1.02 per point, p<0.001), number of RBC (OR=1.08 per RBC, p<0.001), length of stay in ICU (p<0.001). Similar results were obtained while introducing the age of RBC as time dependent covariates in a multivariate Cox's model. CONCLUSIONS: RBC transfused in our ICU are old. The ICU outcome is independently associated with the number of leucodepleted RBC transfused, but not with their age.
Assuntos
Envelhecimento Eritrocítico/fisiologia , Transfusão de Eritrócitos/métodos , Eritrócitos/fisiologia , Idoso , Comorbidade , Transfusão de Eritrócitos/normas , Eritrócitos/citologia , Feminino , Humanos , Unidades de Terapia Intensiva , Tempo de Internação , Masculino , Pessoa de Meia-Idade , Estudos Retrospectivos , Sepse/mortalidade , Sepse/terapia , Choque Hemorrágico/mortalidade , Choque Hemorrágico/terapia , Análise de Sobrevida , SobreviventesRESUMO
Cobalt oxide films were prepared by oxidation of different amounts of cobalt deposited on Ir(100)-(1 × 1), where oxygen rich conditions were applied during deposition. The resulting oxide films with thicknesses of up to about 40 Å were investigated as regards their crystallographic structure and morphology, applying quantitative low energy electron diffraction (LEED) and scanning tunnelling microscopy (STM). It can be unequivocally shown that the spinel-type Co(3)O(4) phase develops, for which an excellent fit between measured and calculated LEED intensity spectra is achieved (Pendry R-factor R = 0.124). In spite of the quadratic unit cell of the substrate the oxide films are in the polar (111) orientation. Also, the native lattice parameter of the material is assumed, i.e. there is no pseudomorphic relation to the substrate. However, by means of orientational epitaxy, one of the unit-mesh vectors of the oxide and one of those of the substrate layer are aligned, leading to two mutually orthogonal domains in the oxide. The oxide is terminated by a sublayer of cobalt ions which in the bulk were tetrahedrally coordinated Co(2+) ions. There are drastic relaxations of layer spacings at and near the surface. As a consequence, the bond length between the surface terminating cobalt ions and oxygen ions below is considerably reduced, indicative of a substantial change of the ionicity of the cobalt and/or oxygen ions. This is interpreted as accounting for polarity compensation of the film, as surface reconstruction, oxygen vacancies and species adsorbed can be ruled out.
RESUMO
A 48 year old man was admitted to the intensive care unit with septicaemic shock associated with febrile jaundice and anuric renal failure. Within hours, he developed cardiogenic shock with multi-organ failure due to an acute myocarditis refractory to catecholamines and requiring intra-aortic balloon pumping. The diagnosis was an ictero-haemorrhagic leptospirosis, the outcome of which was finally favourable. Myocarditis is an underestimated complication of leptospirosis because it is often symptomless. The main signs are arrhythmias, conduction defects and ST-T wave abnormalities which have little clinical expression. The disease may progress and is sometimes fatal. Leptospirosis myocarditis should therefore be carefully considered because of its potential severity and its reversibility with appropriate antibiotic therapy and also the necessity of initial management in a specific infrastructure.
Assuntos
Miocardite/complicações , Miocardite/microbiologia , Choque Cardiogênico/etiologia , Doença de Weil/diagnóstico , Humanos , Masculino , Pessoa de Meia-IdadeRESUMO
The combination of density-functional theory (DFT) calculations of geometrically fully relaxed binary alloy surfaces with concepts from statistical physics is applied to construct a DFT-based phase diagram for a binary alloy surface. As a first example, we studied the appearance of Co antisite atoms at CoAl(100) surfaces. The structural parameters as multilayer relaxations, surface buckling, lateral order, and segregation profile of the predicted stable surface phases are in excellent agreement with experimental structure determinations applying low-energy electron diffraction.
RESUMO
A reversible switching of the easy axis of magnetization for Ni on Cu(001) from in plane to out of plane is found by changing the partial pressure of hydrogen in the gas phase around the sample, allowing even for oscillations of the magnetization direction. A quantitative low-energy electron diffraction study of the diffracted intensity versus electron energy [I(E)] shows that the hydrogen-induced spin reorientation transition is accompanied by changes of the tetragonal distortion of the topmost Ni layer upon hydrogen adsorption. Surprisingly, the orientation switch to perpendicular to the surface comes with a relaxation, i.e., reduction of the film's tetragonal distortion rather than its amplification.
RESUMO
We show that the Ir(100) surface forms a new nanostructure in a self-organized way when its reconstructed equilibrium surface is exposed to hydrogen. Scanning tunneling microscopy and quantitative low-energy electron diffraction retrieve that a long-range ordered superlattice of defect-free Ir chains with average lateral spacing of 1.36 nm and micrometer lengths develops. This can be used as a template for the formation of other nanostructures as is demonstrated.
RESUMO
PURPOSE: This article is an update of past and current data on the relationship between obstructive sleep apnea syndrome and cardiovascular diseases. CURRENT KNOWLEDGE AND KEY POINTS: Obstructive sleep apnea syndrome is a common, but under-recognised, condition and should not be considered simplistically as the association of snoring and obesity. It may be suspected by the clinical history but a definite diagnosis requires the practice of polysomnography. Numerous studies have found a significant relationship between the presence of obstructive sleep apnea syndrome and the occurrence of cardiovascular events. Nonetheless, a definite causal relationship has only been established for the occurrence of hypertension. There are multiple immediate and delayed cardiovascular responses to the apneic events and thus there are many possible physiopathological mechanisms to explain the association of obstructive sleep apnea and cardiac and vascular events, the primary one being sympathetic hyperactivity. The prognosis of obstructive sleep apnea syndrome is closely related to the incidence of cardiovascular events. FUTURE PROSPECTS AND PROJECS: The existence of an independent relationship between obstructive sleep apnea syndrome and atherosclerosis is not yet demonstrated. The beneficial effects of continuous positive airway pressure, the treatment of choice for this condition, on the incidence of cardiovascular diseases remains to be confirmed although recent studies suggest that correct treatment of obstructive sleep apnea syndrome by continuous positive airway pressure may reduce the cardiovascular risk and in particular that of hypertension.
Assuntos
Doenças Cardiovasculares/etiologia , Apneia Obstrutiva do Sono/complicações , Arteriosclerose/complicações , Arteriosclerose/etiologia , Humanos , Hipertensão/complicações , Hipertensão/etiologia , Prognóstico , Fatores de RiscoRESUMO
For the example of the B2 CoAl(100) surface, we demonstrate that even slight deviations from an ordered alloy's ideal stoichiometry in a subsurface region or in the bulk can drastically affect its surface composition. By experimental surface analysis and first-principles calculations, we show that Co antisite atoms segregate to the very surface, driven by the same strong interactions which enforce order in the bulk. Our findings are consistent with the lack of antisite segregation we found earlier for the much weaker ordering FeAl(100), and resolve contradictory reports for NiAl(100).
RESUMO
Little is known about the consequences to children of bottle feeding prolonged beyond age 1 year on caloric intake and overall dietary composition. To obtain these data, 165 children, followed up from infancy, were assessed in these respects for a 24-hour period at age 3 1/2 years. Bottle-fed children (n = 14) consumed more milk than their weaned counterparts (p < 0.001), had a higher mean daily calcium intake (p < 0.05), received fewer calories from carbohydrates (p = 0.034), and received a greater percentage of calories from protein (p = 0.033). There were no significant differences between the groups in total caloric intake, total iron intake, total volume ofjuice, or calories from fat. Pediatricians questioned about the effects of continuing to offer children nutritive liquids from bottles as well as cups (versus offering cups alone) may inform parents that this feeding practice is associated with significantly greater milk consumption and daily calcium intake. However, this study could not find evidence that prolonged bottle feeding at age 3 1/2 years is associated with a significantly decreased total daily iron intake or an increased risk for factors associated with adiposity such as a greater daily calorie intake, a higher body mass index, or greater percentage of total calories derived from fat.
Assuntos
Alimentação com Mamadeira , Dieta , Ingestão de Energia/fisiologia , Animais , Índice de Massa Corporal , Cálcio/sangue , Pré-Escolar , Estudos de Coortes , Gorduras na Dieta/administração & dosagem , Ingestão de Alimentos , Feminino , Seguimentos , Humanos , Lactente , Ferro/sangue , Deficiências de Ferro , Estudos Longitudinais , Masculino , LeiteRESUMO
OBJECTIVE: To assess longitudinally the relationship between measures of adiposity in children over the first 8 y of life with that of their parents and to explore the role of parental adiposity in the development of childhood adiposity. DESIGN: Longitudinal study of measures of adiposity in children. SUBJECTS: A community sample from three health service systems including 114 children followed annually from infancy to age 8 and their 228 biological parents. METHODS: Measurements were assessed at baseline for parents (6 months post-partum for mothers) and at regular intervals for children beginning at age 2 months. Measurements included weight, height, triceps skinfold, subscapular skinfold, midarm circumference, waist and hip. RESULTS: The major findings were: (1) significant correlations between parental body mass index (BMI), both maternal and paternal, and their biological offspring first emerged at age 7; (2) children with two overweight parents had consistently elevated BMI compared to children with either no overweight parents or one overweight parent. These differences became significant beginning at age 7. CONCLUSIONS: This study supports the hypothesis that familial factors (biological and/or environmental) affecting the development of adiposity emerge at specific ages and are related to the adiposity of both parents.