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1.
Phys Chem Chem Phys ; 19(16): 10602-10610, 2017 Apr 19.
Artigo em Inglês | MEDLINE | ID: mdl-28397886

RESUMO

The two-dimensional (2D) surface-directed self-assembly of dibenzonitrile diacetylene (DBDA) on Ag(111) under ultrahigh vacuum (UHV) conditions was investigated by combining scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS) and theoretical simulations based on density functional theory (DFT) calculations. The molecule consists of two benzonitrile groups (-C6H4-C[triple bond, length as m-dash]N) on each side of a diacetylene (-C[triple bond, length as m-dash]C-C[triple bond, length as m-dash]C-) backbone. The terminating nitrile (-C[triple bond, length as m-dash]N) groups at the meta position of the phenyl rings lead to cis and trans stereoisomers. The trans isomer is prochiral and can adsorb in the R or S configuration, leading to the formation of enantiomeric self-assembled networks on the surface. We identify two simultaneously present supramolecular networks, termed parallel and chevron phases, as well as a less frequently observed butterfly phase. These networks are formed from pure R (or S) domains, racemic mixtures (RS), and cis isomers, respectively. Our complementary data illustrates that the formation of the 2D supramolecular networks is driven by intermolecular hydrogen bonding between nitrile and phenyl groups (-C[triple bond, length as m-dash]NH-C6H3). This study illustrates that the molecular arrangement of each network depends on the geometry of the isomers. The orientation of the nitrile group controls the formation of the most energetically stable network via intermolecular hydrogen bonding.

2.
Neuroimage ; 114: 207-16, 2015 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-25891374

RESUMO

Cerebrovascular reactivity (CVR) is often defined as the increase in cerebral blood flow (CBF) produced by an increase in carbon dioxide (CO2) and may be used clinically to assess the health of the cerebrovasculature. When CBF is estimated using blood oxygen level dependent (BOLD) magnetic resonance imaging, CVR values for each voxel can be displayed using a color scale mapped onto the corresponding anatomical scan. While these CVR maps therefore show the distribution of cerebrovascular reactivity, they only provide an estimate of the magnitude of the cerebrovascular response, and do not indicate the time course of the response; whether rapid or slow. Here we describe transfer function analysis (TFA) of the BOLD response to CO2 that provides not only the magnitude of the response (gain) but also the phase and coherence. The phase can be interpreted as indicating the speed of response and so can distinguish areas where the response is slowed. The coherence measures the fidelity with which the response follows the stimulus. The examples of gain, phase and coherence maps obtained from TFA of previously recorded test data from patients and healthy individuals demonstrate that these maps may enhance assessment of cerebrovascular pathophysiology by providing insight into the dynamics of cerebral blood flow control and distribution.


Assuntos
Mapeamento Encefálico/métodos , Encéfalo/fisiologia , Encéfalo/fisiopatologia , Circulação Cerebrovascular , Transtornos Cerebrovasculares/fisiopatologia , Imageamento por Ressonância Magnética/métodos , Adulto , Encéfalo/irrigação sanguínea , Encéfalo/efeitos dos fármacos , Dióxido de Carbono/administração & dosagem , Humanos , Masculino , Pessoa de Meia-Idade , Modelos Neurológicos
3.
Langmuir ; 31(25): 7016-24, 2015 Jun 30.
Artigo em Inglês | MEDLINE | ID: mdl-25594568

RESUMO

The behavior of small molecules on a surface depends critically on both molecule-substrate and intermolecular interactions. We present here a detailed comparative investigation of 1,3,5-benzene tricarboxylic acid (trimesic acid, TMA) on two different surfaces: highly oriented pyrolytic graphite (HOPG) and single-layer graphene (SLG) grown on a polycrystalline Cu foil. On the basis of high-resolution scanning tunnelling microscopy (STM) images, we show that the epitaxy matrix for the hexagonal TMA chicken wire phase is identical on these two surfaces, and, using density functional theory (DFT) with a non-local van der Waals correlation contribution, we identify the most energetically favorable adsorption geometries. Simulated STM images based on these calculations suggest that the TMA lattice can stably adsorb on sites other than those identified to maximize binding interactions with the substrate. This is consistent with our net energy calculations that suggest that intermolecular interactions (TMA-TMA dimer bonding) are dominant over TMA-substrate interactions in stabilizing the system. STM images demonstrate the robustness of the TMA films on SLG, where the molecular network extends across the variable topography of the SLG substrates and remains intact after rinsing and drying the films. These results help to elucidate molecular behavior on SLG and suggest significant similarities between adsorption on HOPG and SLG.

4.
Br J Anaesth ; 114(3): 406-13, 2015 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-25488304

RESUMO

BACKGROUND: Current non-invasive respiratory-based methods of measuring cardiac output [Formula: see text] make doubtful assumptions and encounter significant technical difficulties. We present a new method using an iterative approach [Formula: see text], which overcomes limitations of previous methods. METHODS: Sequential gas delivery (SGD) is used to control alveolar ventilation [Formula: see text] and CO2 elimination [Formula: see text] during a continuous series of iterative tests. Each test consists of four breaths where inspired CO2 [Formula: see text] is controlled; raising end-tidal Pco2 [Formula: see text] by about 1.33 kPa (10 mm Hg) for the first breath, and then maintaining [Formula: see text] constant for the next three breaths. The [Formula: see text] required to maintain [Formula: see text] constant is calculated using the differential Fick equation (DFE), where [Formula: see text] is the only unknown and is arbitrarily assumed for the first iteration. Each subsequent iteration generates measures used for calculating [Formula: see text] by the DFE, refining the assumption of [Formula: see text] for the next test and converging it to the true [Formula: see text] when [Formula: see text] remains constant during the four test breaths. We compared [Formula: see text] with [Formula: see text] measured by bolus pulmonary artery thermodilution [Formula: see text] in seven pigs undergoing liver transplantation. RESULTS: [Formula: see text] implementation and analysis was fully automated, and [Formula: see text] varied from 0.6 to 5.4 litre min(-1) through the experiments. The bias (between [Formula: see text] and [Formula: see text]) was 0.2 litre min(-1) with 95% limit of agreement from -1.1 to 0.7 litre min(-1) and percentage of error of 32%. During acute changes of [Formula: see text], convergence of [Formula: see text] to actual [Formula: see text] required only three subsequent iterations. CONCLUSIONS: [Formula: see text] measurement is capable of providing an automated semi-continuous non-invasive measure of [Formula: see text].


Assuntos
Débito Cardíaco/fisiologia , Monitorização Fisiológica/métodos , Respiração , Animais , Gasometria/métodos , Testes Respiratórios/métodos , Dióxido de Carbono/metabolismo , Modelos Animais , Consumo de Oxigênio/fisiologia , Troca Gasosa Pulmonar/fisiologia , Reprodutibilidade dos Testes , Suínos , Termodiluição/métodos , Volume de Ventilação Pulmonar/fisiologia
5.
Neuroimage ; 92: 56-68, 2014 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-24508647

RESUMO

Cerebrovascular reactivity (CVR) is the change in cerebral blood flow (CBF) in response to a change in a vasoactive stimulus. Paradoxical reductions in CBF in response to vasodilatory stimulation ('steal') are associated with vascular pathology. However, a pathophysiological interpretation of 'steal' requires a comprehensive conceptual model linking pathology and changes in blood flow. Herein, we extend a simple model explaining steal published in the late 1960s by incorporating concepts of CBF regulation from more recent studies to generate a comprehensive dynamic model. The main elements of the model are: (a) the relationship between changes in CBF and the arterial partial pressure of carbon dioxide (PaCO2) in healthy vascular regions is sigmoidal; (b) vascular regions vasodilate to compensate for decreased perfusion pressure, leading to (c) an encroachment on vasodilatory reserve and, reduced CVR; (d) a vasodilatory stimulus may increase CBF capacity above the flow capacity of major cerebral blood vessels; and (e) this limitation induces competitive intra-cerebral redistribution of flow from territories with low vasodilatory reserve to those with high reserve. We used CVR measurements generated by applying precise, computer-controlled changes in PaCO2 as the vasoactive stimulus, and measured blood oxygen level dependent (BOLD) MRI signals as high resolution surrogates of CBF to test predictions derived from this model. Subjects were 16 healthy adults and 16 patients with known cerebral steno-occlusive diseases. We observed regional sigmoidal PaCO2-BOLD response curves with a range of slopes; graded changes in PaCO2 resulted in redistributions of BOLD signal consistent with the known underlying vascular pathology and predictions of the model. We conclude that this model can be applied to provide a hemodynamic interpretation to BOLD signal changes in response to hypercapnia, and thereby aid in relating CVR maps to pathophysiological conditions.


Assuntos
Volume Sanguíneo/efeitos dos fármacos , Encéfalo/fisiopatologia , Dióxido de Carbono/administração & dosagem , Artérias Cerebrais/fisiopatologia , Circulação Cerebrovascular/efeitos dos fármacos , Modelos Cardiovasculares , Vasodilatação/efeitos dos fármacos , Administração por Inalação , Adolescente , Adulto , Velocidade do Fluxo Sanguíneo/efeitos dos fármacos , Encéfalo/efeitos dos fármacos , Artérias Cerebrais/efeitos dos fármacos , Simulação por Computador , Feminino , Humanos , Interpretação de Imagem Assistida por Computador/métodos , Angiografia por Ressonância Magnética/métodos , Masculino , Pessoa de Meia-Idade , Modelos Neurológicos , Reprodutibilidade dos Testes , Sensibilidade e Especificidade , Vasodilatadores/administração & dosagem , Adulto Jovem
6.
Phys Chem Chem Phys ; 16(10): 4764-70, 2014 Mar 14.
Artigo em Inglês | MEDLINE | ID: mdl-24468913

RESUMO

We have performed a high-resolution synchrotron radiation photoelectron spectroscopy study of the initial growth stages of the ZnPd near-surface alloy on Pd(111), complemented by scanning tunnelling microscopy data. We show that the chemical environment for surfaces containing less than half of one monolayer of Zn is chemically distinct from subsequent layers. Surfaces where the deposition is performed at room temperature contain ZnPd islands surrounded by a substrate with dilute Zn substitutions. Annealing these surfaces drives the Zn towards the substrate top-layer, and favours the completion of the first 1 : 1 monolayer before the onset of growth in the next layer.

7.
J Physiol ; 591(23): 5809-21, 2013 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-24081155

RESUMO

Cerebrovascular reactivity is the change in cerebral blood flow in response to a vasodilatory or vasoconstrictive stimulus. Measuring variations of cerebrovascular reactivity between different regions of the brain has the potential to not only advance understanding of how the cerebral vasculature controls the distribution of blood flow but also to detect cerebrovascular pathophysiology. While there are standardized and repeatable methods for estimating the changes in cerebral blood flow in response to a vasoactive stimulus, the same cannot be said for the stimulus itself. Indeed, the wide variety of vasoactive challenges currently employed in these studies impedes comparisons between them. This review therefore critically examines the vasoactive stimuli in current use for their ability to provide a standard repeatable challenge and for the practicality of their implementation. Such challenges include induced reductions in systemic blood pressure, and the administration of vasoactive substances such as acetazolamide and carbon dioxide. We conclude that many of the stimuli in current use do not provide a standard stimulus comparable between individuals and in the same individual over time. We suggest that carbon dioxide is the most suitable vasoactive stimulus. We describe recently developed computer-controlled MRI compatible gas delivery systems which are capable of administering reliable and repeatable vasoactive CO2 stimuli.


Assuntos
Circulação Cerebrovascular/fisiologia , Encéfalo/irrigação sanguínea , Humanos , Hipercapnia/fisiopatologia , Vasodilatação/fisiologia
8.
Phys Chem Chem Phys ; 15(30): 12488-94, 2013 Aug 14.
Artigo em Inglês | MEDLINE | ID: mdl-23652296

RESUMO

We have characterized the structural properties of submonolayer amounts of Zn on Pd(111) using scanning tunneling microscopy (STM) and spot-profile analysis low energy electron diffraction (SPA-LEED). Following room temperature deposition of ≈0.06 monolayers (ML) Zn onto Pd(111), we observe the substitution of Zn for Pd in the surface layer. At ≈0.20 ML of deposited Zn, STM reveals a locally ordered phase with a (2/√3 × 2/√3)R30° unit cell located near Zn substitutions; SPA-LEED patterns reveal the same periodicity. We attribute this phase to the metastable bonding of atoms or clusters predominantly in hollow sites surrounding Zn substitutions in the surface layer. At ≈0.4 ML, STM images reveal local (√3 × âˆš3)R30° and (2 × 1) ordering on surfaces annealed to 350 K. At coverages near 0.5 ML, both STM and SPA-LEED show the onset of the formation of the (2 × 1) ordering associated with the Zn : Pd 1 : 1 alloy phase. At all coverages, the surface is dominated by island growth; the islands' size and density is shown to depend critically on annealing at temperatures as low as 350 K. These results provide insight into the structural features of a Zn/Pd(111) coverage regime that has been much debated in recent years.

9.
Acta Anaesthesiol Scand ; 57(5): 623-30, 2013 May.
Artigo em Inglês | MEDLINE | ID: mdl-23452265

RESUMO

BACKGROUND: The time to recovery from vapour anaesthesia is shortened by an increase in ventilation while maintaining normocapnia. Hypercapnia during emergence from anaesthesia in spontaneously breathing patients also increases anaesthetic clearance from the brain by increasing cerebral blood flow. We hypothesised that hypercapnia-induced hyperpnoea accelerates emergence from sevoflurane anaesthesia compared to the standard anaesthesia protocol. METHODS: After Ethics Review Board approval, 44 ASA I-III patients undergoing elective gynaecological surgery were randomised after surgery to either hypercapnic hyperpnoea or control groups. In the hypercapnic hyperpnoea group, the end-tidal CO2 was adjusted to a range of 6.0-7.3 kPa to maintain a minute ventilation of 10-15 l/min. Recovery indices were compared using unpaired t-tests and ANOVA. RESULTS: Prior to extubation, minute ventilation and end-tidal CO2 in hypercapnic hyperpnoea and control groups were 10.3 ± 1.7 l/min vs. 5.4 ± 1.2 l/min (P < 0.001) and 6.6 ± 0.6 kPa and 5.2 ± 0.5 kPa (P < 0.001), respectively. Compared to control, the study group had shorter time to extubation [4.4 ± 1.3 (SD) vs. 9.8 ± 4.4 min, P < 0.01], BIS recovery to > 75 (2.4 ± 0.9 vs. 6.1 ± 3.1 min, P < 0.01), eye opening (3.9 ± 1.6 vs. 9.8 ± 6.2 min, P < 0.01), eligibility for leaving operating room (5.1 ± 1.2 vs. 11.1 ± 4.6 min, P < 0.01), and post-anaesthesia care unit (73.9 ± 14.2 vs. 89.4 ± 22.6) CONCLUSION: Hypercapnic hyperpnoea in spontaneously breathing patients halves the time of recovery from sevoflurane-induced anaesthesia in the operating room.


Assuntos
Período de Recuperação da Anestesia , Anestésicos Inalatórios/farmacologia , Hipercapnia/fisiopatologia , Hiperventilação/fisiopatologia , Éteres Metílicos/farmacologia , Análise de Variância , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Estudos Prospectivos , Sevoflurano , Fatores de Tempo
10.
Proc Natl Acad Sci U S A ; 107(25): 11200-4, 2010 Jun 22.
Artigo em Inglês | MEDLINE | ID: mdl-20534511

RESUMO

One of the great challenges in surface chemistry is to assemble aromatic building blocks into ordered structures that are mechanically robust and electronically interlinked--i.e., are held together by covalent bonds. We demonstrate the surface-confined growth of ordered arrays of poly(3,4-ethylenedioxythiophene) (PEDOT) chains, by using the substrate (the 110 facet of copper) simultaneously as template and catalyst for polymerization. Copper acts as promoter for the Ullmann coupling reaction, whereas the inherent anisotropy of the fcc 110 facet confines growth to a single dimension. High resolution scanning tunneling microscopy performed under ultrahigh vacuum conditions allows us to simultaneously image PEDOT oligomers and the copper lattice with atomic resolution. Density functional theory calculations confirm an unexpected adsorption geometry of the PEDOT oligomers, which stand on the sulfur atom of the thiophene ring rather than lying flat. This polymerization approach can be extended to many other halogen-terminated molecules to produce epitaxially aligned conjugated polymers. Such systems might be of central importance to develop future electronic and optoelectronic devices with high quality active materials, besides representing model systems for basic science investigations.


Assuntos
Química/métodos , Polímeros/química , Tiofenos/química , Anisotropia , Catálise , Cobre/química , Dimerização , Íons , Teste de Materiais , Microscopia/métodos , Microscopia de Tunelamento/métodos , Modelos Químicos , Software , Propriedades de Superfície , Temperatura
11.
Langmuir ; 28(40): 14291-300, 2012 Oct 09.
Artigo em Inglês | MEDLINE | ID: mdl-22970746

RESUMO

Upon adsorption on the (111) facet of Ag, 4-[trans-2-(pyrid-4-yl-vinyl)] benzoic acid (PVBA) self-assembles into a highly ordered, chiral twin chain structure at submonolayer coverages with domains that can extend for micrometers in one dimension. Using polarization-dependent measurements of C and N K-shell excitations in near-edge X-ray absorption fine structure (NEXAFS) spectra, we determine the binding geometry of single PVBA molecules within this unique ensemble for both low and high coverage regimes. At submonolayer coverage, the molecule is twisted to facilitate the formation of hydrogen bonds. The gas-phase planarity is gradually recovered as the coverage is increased, with complete planarity coinciding with loss of order in the overlayer. Thermal treatment of the PVBA film results in deprotonation of the carboxyl tail of the molecule, but despite the suppression of the stabilizing hydrogen-bonds, the overlayer remains ordered.

12.
J Physiol ; 589(Pt 12): 3039-48, 2011 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-21521758

RESUMO

Carbon dioxide (CO2) increases cerebral blood flow and arterial blood pressure. Cerebral blood flow increases not only due to the vasodilating effect of CO2 but also because of the increased perfusion pressure after autoregulation is exhausted. Our objective was to measure the responses of both middle cerebral artery velocity (MCAv) and mean arterial blood pressure (MAP) to CO2 in human subjects using Duffin-type isoxic rebreathing tests. Comparisons of isoxic hyperoxic with isoxic hypoxic tests enabled the effect of oxygen tension to be determined. During rebreathing the MCAv response to CO2 was sigmoidal below a discernible threshold CO2 tension, increasing from a hypocapnic minimum to a hypercapnic maximum. In most subjects this threshold corresponded with the CO2 tension at which MAP began to increase. Above this threshold both MCAv and MAP increased linearly with CO2 tension. The sigmoidal MCAv response was centred at a CO2 tension close to normal resting values (overall mean 36 mmHg). While hypoxia increased the hypercapnic maximum percentage increase in MCAv with CO2 (overall means from76.5 to 108%) it did not affect other sigmoid parameters. Hypoxia also did not alter the supra-threshold MCAv and MAP responses to CO2 (overall mean slopes 5.5% mmHg⁻¹ and 2.1 mmHg mmHg⁻¹, respectively), but did reduce the threshold (overall means from 51.5 to 46.8 mmHg). We concluded that in the MCAv response range below the threshold for the increase of MAP with CO2, the MCAv measurement reflects vascular reactivity to CO2 alone at a constant MAP.


Assuntos
Pressão Sanguínea/fisiologia , Dióxido de Carbono/farmacologia , Dióxido de Carbono/farmacocinética , Circulação Cerebrovascular/fisiologia , Oxigênio/metabolismo , Velocidade do Fluxo Sanguíneo , Feminino , Humanos , Adulto Jovem
13.
Acta Anaesthesiol Scand ; 55(8): 995-1001, 2011 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-21770896

RESUMO

BACKGROUND: There is a concern that obesity may play a role in prolonging emergence from fat-soluble inhalational anaesthetics. We hypothesized that increased pulmonary clearance of isoflurane will shorten immediate recovery from anaesthesia and post-anaesthesia care unit (PACU) stay in obese patients. METHODS: After Ethics Review Board approval, 44 ASA I-III patients with BMI>30 kg/m(2) undergoing elective gynaecological or urological surgery were randomized after completion of surgery to either an isocapnic hyperpnoea (IH) or a conventional recovery (C) group. The anaesthesia protocol included propofol, fentanyl, morphine, rocuronium and isoflurane in air/O(2) . Groups were compared using unpaired t-test and ANOVA. RESULTS: Minute ventilation in the IH group before extubation was 22.6 ± 2.7 vs. 6.3 ± 1.8 l/min in the C group. Compared with C, the IH group had a shorter time to extubation (5.4 ± 2.7 vs. 15.8 ± 2.7 min, P<0.01), initiation of spontaneous ventilation (2.7 ± 2.3 vs. 6.5 ± 4.5 min, P<0.01), BIS recovery >75 (3.2 ± 2.3 vs. 8.9 ± 5.8 min, P<0.01), eye opening (4.6 ± 2.9 vs. 13.6 ± 7.1 min, P<0.01) and eligibility for leaving the operating room (7.1 ± 2.9 vs. 19.9 ± 11.9 min, P<0.01). There was no difference in time for eligibility for PACU discharge. CONCLUSION: Increasing alveolar ventilation enhances anaesthetic elimination and accelerates short-term recovery in obese patients.


Assuntos
Período de Recuperação da Anestesia , Anestesia por Inalação , Anestésicos Inalatórios/farmacocinética , Isoflurano/farmacocinética , Pulmão/metabolismo , Obesidade/fisiopatologia , Idoso , Manuseio das Vias Aéreas , Anestesia Geral , Cuidados Críticos , Determinação de Ponto Final , Feminino , Procedimentos Cirúrgicos em Ginecologia , Humanos , Masculino , Pessoa de Meia-Idade , Obesidade/complicações , Complicações Pós-Operatórias/epidemiologia , Náusea e Vômito Pós-Operatórios/epidemiologia , Postura , Estudos Prospectivos
14.
J Physiol ; 588(Pt 9): 1591-606, 2010 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-20194122

RESUMO

We compared the control of breathing of 12 male Himalayan highlanders with that of 21 male sea-level Caucasian lowlanders using isoxic hyperoxic ( = 150 mmHg) and hypoxic ( = 50 mmHg) Duffin's rebreathing tests. Highlanders had lower mean +/- s.e.m. ventilatory sensitivities to CO(2) than lowlanders at both isoxic tensions (hyperoxic: 2.3 +/- 0.3 vs. 4.2 +/- 0.3 l min(1) mmHg(1), P = 0.021; hypoxic: 2.8 +/- 0.3 vs. 7.1 +/- 0.6 l min(1) mmHg(1), P < 0.001), and the usual increase in ventilatory sensitivity to CO(2) induced by hypoxia in lowlanders was absent in highlanders (P = 0.361). Furthermore, the ventilatory recruitment threshold (VRT) CO(2) tensions in highlanders were lower than in lowlanders (hyperoxic: 33.8 +/- 0.9 vs. 48.9 +/- 0.7 mmHg, P < 0.001; hypoxic: 31.2 +/- 1.1 vs. 44.7 +/- 0.7 mmHg, P < 0.001). Both groups had reduced ventilatory recruitment thresholds with hypoxia (P < 0.001) and there were no differences in the sub-threshold ventilations (non-chemoreflex drives to breathe) between lowlanders and highlanders at both isoxic tensions (P = 0.982), with a trend for higher basal ventilation during hypoxia (P = 0.052). We conclude that control of breathing in Himalayan highlanders is distinctly different from that of sea-level lowlanders. Specifically, Himalayan highlanders have decreased central and absent peripheral sensitivities to CO(2). Their response to hypoxia was heterogeneous, with the majority decreasing their VRT indicating either a CO(2)-independent increase in activity of peripheral chemoreceptor or hypoxia-induced increase in [H(+)] at the central chemoreceptor. In some highlanders, the decrease in VRT was accompanied by an increase in sensitivity to CO(2), while in others VRT remained unchanged and their sub-threshold ventilations increased, although these were not statistically significant.


Assuntos
Altitude , Mecânica Respiratória/fisiologia , Dióxido de Carbono , Circulação Cerebrovascular , Humanos , Hipercapnia/fisiopatologia , Masculino , Oximetria , Oxigênio/sangue , Recrutamento Neurofisiológico , Volume de Ventilação Pulmonar/fisiologia , Adulto Jovem
15.
Adv Exp Med Biol ; 669: 221-4, 2010.
Artigo em Inglês | MEDLINE | ID: mdl-20217353

RESUMO

The example experimental results presented show how the steady state ventilatory response to hypoxia may be measured using a sequential gas delivery circuit and prospective targeting of end-tidal PCO(2) and PO(2). They also demonstrate how 3 steady state isocapnic ventilatory responses to hypoxia provide hypoxic and hyperoxic ventilatory responses to CO(2) that can be compared between individuals and between different physiological and environmental conditions as well as to modified rebreathing responses.


Assuntos
Hipóxia/fisiopatologia , Ventilação Pulmonar , Adulto , Dióxido de Carbono/farmacologia , Feminino , Humanos , Hiperóxia/fisiopatologia , Ventilação Pulmonar/efeitos dos fármacos
16.
Small ; 5(5): 592-7, 2009 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-19241417

RESUMO

The surface-mediated synthesis of epitaxially aligned and separated polyphenylene lines on Cu(110) by exploiting the Ullmann dehalogenation reaction is reported. Scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) show that the C-I bonds of 1,4-diiodobenzene and 1,3-diiodobenzene (C(6)H(4)I(2)) are catalytically cleaved when dosed onto the surface. Subsequent annealing transforms the copper-bound phenylene intermediates into covalent conjugated structures: linear chains of poly(p-phenylene) for 1,4-diiodobenzene and zigzag chains of poly(m-phenylene) as well as macrocyclic oligomers in the case of 1,3-diiodobenzene. The chains are strongly bound to the surface (likely through C--Cu bonds at the chain-ends) while the macrocycles are very mobile and can only be imaged by STM at low temperature. The detached halogens adsorb on the surface and separate the polymer chains from each other.


Assuntos
Cristalização/métodos , Nanotecnologia/métodos , Nanotubos/química , Nanotubos/ultraestrutura , Polímeros/química , Substâncias Macromoleculares/química , Teste de Materiais , Conformação Molecular , Tamanho da Partícula , Propriedades de Superfície
17.
AJNR Am J Neuroradiol ; 40(1): 45-50, 2019 01.
Artigo em Inglês | MEDLINE | ID: mdl-30573457

RESUMO

BACKGROUND AND PURPOSE: One feature that patients with steno-occlusive cerebrovascular disease have in common is the presence of white matter (WM) lesions on MRI. The purpose of this study was to evaluate the effect of direct surgical revascularization on impaired WM cerebrovascular reactivity in patients with steno-occlusive disease. MATERIALS AND METHODS: We recruited 35 patients with steno-occlusive disease, Moyamoya disease (n = 24), Moyamoya syndrome (n = 3), atherosclerosis (n = 6), vasculitis (n = 1), and idiopathic stenosis (n = 1), who underwent unilateral brain revascularization using a direct superficial temporal artery-to-MCA bypass (19 women; mean age, 45.8 ± 16.5 years). WM cerebrovascular reactivity was measured preoperatively and postoperatively using blood oxygen level-dependent (BOLD) MR imaging during iso-oxic hypercapnic changes in end-tidal carbon dioxide and was expressed as %Δ BOLD MR signal intensity per millimeter end-tidal partial pressure of CO2. RESULTS: WM cerebrovascular reactivity significantly improved after direct unilateral superficial temporal artery-to-middle cerebral artery (STA-MCA) bypass in the revascularized hemisphere in the MCA territory (mean ± SD, -0.0005 ± 0.053 to 0.053 ± 0.046 %BOLD/mm Hg; P < .0001) and in the anterior cerebral artery territory (mean, 0.0015 ± 0.059 to 0.021 ± 0.052 %BOLD/mm Hg; P = .005). There was no difference in WM cerebrovascular reactivity in the ipsilateral posterior cerebral artery territory nor in the vascular territories of the nonrevascularized hemisphere (P < .05). CONCLUSIONS: Cerebral revascularization surgery is an effective treatment for reversing preoperative cerebrovascular reactivity deficits in WM. In addition, direct-STA-MCA bypass may prevent recurrence of preoperative symptoms.


Assuntos
Revascularização Cerebral/métodos , Transtornos Cerebrovasculares/patologia , Transtornos Cerebrovasculares/cirurgia , Substância Branca/patologia , Adulto , Feminino , Humanos , Imageamento por Ressonância Magnética/métodos , Masculino , Pessoa de Meia-Idade , Resultado do Tratamento
18.
Chem Sci ; 10(19): 5167-5175, 2019 May 21.
Artigo em Inglês | MEDLINE | ID: mdl-31183070

RESUMO

Ullmann coupling of halogenated aromatics is widely used in on-surface synthesis of two-dimensional (2D) polymers and graphene nanoribbons. It stands out among other reactions for regioselectively connecting aromatic monomers into 1D and 2D π-conjugated polymers, whose final structure and properties are determined by the initial building blocks. Thanks to their exceptional electronic properties, thiophene-containing monomers are frequently used for the synthesis of various conjugated materials. On the other hand, their use in on-surface polymerization is hampered by the possibility of ring opening when adsorbed on metal surfaces. In the present work, we mapped the temperature regime for these two competing reactions by investigating the adsorption of a thiophene-based prochiral molecule using scanning tunneling microscopy, X-ray photoelectron spectroscopy and density functional theory calculations. We followed the formation of organometallic (OM) networks, their evolution into covalent structures and the competition between C-C coupling and thiophene ring opening. The effect of surface reactivity was explored by comparing the adsorption on three (111) coinage metal substrates, namely Au, Ag and Cu. While outlining strategies to minimize the ring opening reaction, we found that the surface temperature during deposition is of paramount importance for the preparation of 2D OM networks, greatly enhancing the overall ordering of the product by depositing on hot Ag surface. Notably, the same protocol permits the creation of OM structures on the air-stable Au surface, thereby allowing the synthesis and application of 2D OM networks outside the ultra-high vacuum environment.

19.
J Laryngol Otol ; 132(4): 284-292, 2018 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-29439747

RESUMO

BACKGROUND: Paediatric obstructive sleep apnoea is a common clinical condition managed by most ENT clinicians. However, despite the plethora of publications on the subject, there is wide variability, in the literature and in practice, on key aspects such as diagnostic criteria, the impact of co-morbidities and the indications for surgical correction. METHODS: A systematic review is presented, addressing four key questions from the available literature: (1) what is the evidence base for any definition of paediatric obstructive sleep apnoea?; (2) does it cause serious systemic illness?; (3) what co-morbidities influence the severity of paediatric obstructive sleep apnoea?; and (4) is there a medical answer? RESULTS AND CONCLUSION: There is a considerable lack of evidence regarding most of these fundamental questions. Notably, screening measures show low specificity and can be insensitive to mild obstructive sleep apnoea. There is a surprising lack of clarity in the definition (let alone estimate of severity) of sleep-disordered breathing, relying on what may be arbitrary test thresholds. Areas of potential research might include investigation of the mechanisms through which obstructive sleep apnoea causes co-morbidities, whether neurocognitive, behavioural, metabolic or cardiovascular, and the role of non-surgical management.


Assuntos
Síndromes da Apneia do Sono/cirurgia , Apneia Obstrutiva do Sono/diagnóstico , Apneia Obstrutiva do Sono/cirurgia , Tonsilectomia/métodos , Adolescente , Criança , Pré-Escolar , Comorbidade , Prática Clínica Baseada em Evidências , Humanos , Lactente , Polissonografia/métodos
20.
J Laryngol Otol ; 132(4): 293-298, 2018 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-29463325

RESUMO

BACKGROUND: Despite the plethora of publications on the subject of paediatric obstructive sleep apnoea, there seems to be wide variability in the literature and in practice, regarding recourse to surgery, the operation chosen, the benefits gained and post-operative management. This may reflect a lack of high-level evidence. METHODS: A systematic review of four significant controversies in paediatric ENT was conducted from the available literature: tonsillectomy versus tonsillotomy, focusing on the evidence base for each; anaesthetic considerations in paediatric obstructive sleep apnoea surgery; the objective evidence for the benefits of surgical treatment for obstructive sleep apnoea; and the medical treatment options for residual obstructive sleep apnoea after surgical treatment. RESULTS AND CONCLUSION: There are many gaps in the evidence base for the surgical correction of obstructive sleep apnoea. There is emerging evidence favouring subtotal tonsillectomy. There is continuing uncertainty around the prediction of the level of post-operative care that any individual child might require. The long-term benefit of surgical correction is a particularly fertile ground for further research.


Assuntos
Tonsila Palatina/cirurgia , Síndromes da Apneia do Sono/cirurgia , Apneia Obstrutiva do Sono/cirurgia , Tonsilectomia/métodos , Adenoidectomia/efeitos adversos , Adenoidectomia/métodos , Criança , Prática Clínica Baseada em Evidências , Humanos , Dor Pós-Operatória/patologia , Cuidados Pós-Operatórios/enfermagem , Complicações Pós-Operatórias , Síndromes da Apneia do Sono/complicações , Apneia Obstrutiva do Sono/epidemiologia , Ronco/diagnóstico , Ronco/etiologia , Tonsilectomia/efeitos adversos , Resultado do Tratamento
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